CA1088053A - Phthalocyanine dyes containing an ortho-amino- sulfanilide group, and process for preparing them - Google Patents

Abstract

Phthalocyanine dyes containing an ortho-amino-sulfanilide group, and process for preparing them Abstract of the disclosure:
Very valuable, new phthalocyanine compounds, suitable as dyestuffs, had been found which contain one or several ortho-amino-sulfanilide groups. These dyestuffs can be applied and fixed on various fiber-materials, especially in accordance with the old ice-color technique. The novel dyestuffs are fixed by treating them on the material on which they had been applied, by means of nitrous acid. The dyeings and prints thus obtained possess very good fastness properties, such as to rubbing, to washing and to light.

Description

1 0 8 ~ 0 S 3 The present invention relates to phthalocyanine com-pounds, a process for preparing them and their use as dyestuffs.
Novel phthalocyanine compounds of the general formula I
have been found R R

Pc ~ S02-NH ~ R ~I) H2N ~ R

_ _ n in which Pc represents the copper, cobalt or nickel phthalo-cyanine radical which may be substituted by substituents selected from the group halogen, such as chlorine or bromine, preferably chlorine, by phenyl, sulfo, sulfonamide, by sulfon-amide mono- or disubstituted by lower alkyl and phenyl-sulfonamide, which may be additionally N-substituted by lower alkyl, Rl, R2, R3 and R4 are the same or diEferent and each is a hydrogen atom, a halogen atom, such as chlorine or bromine, a lower alkyl group unsubstituted or substituted, for example, by hydroxy, chlorine, carboxy, sulfo, sulfato, or is a phenyl radical, or a lower alkoxy group which may be substituted in the alkyl radical, for example by lower alkoxy, or is a phenoxy, a carboxy, a carbonamide group or a carbonamide group which is mono- or disubstituted by lower alkyl, or is a phenylcarbonamide, or a cyano or carbalkoxy group of 2 to 5 carbon atoms, an alkanoyl group of 2 to 5 carbon atoms, such as acetyl or propionyl, or : : .: - : . - :: :
.
~. .. .

` ~08B053 an alkanoyloxy group of 2 to 5 carbon atoms, a lower alkenyl-sulfonyl group, a lower alkylsulfonyl group which may be sub-stituted in the alkyl radical, for example by chlorine, hydroxy, lower dialkylamino, sulfo, sulfato, phosphato, carb-oxy groups, or is a phenylsulfonyl group, a sulfo, sulfonamide, N-(lower alkyl)-sulfonamide-group which may be substituted in the alkyl radical, for example by chlorineJ hydroxy, lower dialkylamino, sulfo, sulfato, phosphato, carboxy groups, or is a N,N-di-(lower alkyl)-sulfonamide group, the two groups or prefer-ably one of them optionally being substituted in the alkyl radical, for example by chlorine, hydroxy, lower dialkylamino, sulfo, sul-fato, phosphato, carboxy, or is a trifluoromethyl or nitro group, a lower alkylsulfonylamino group which may be substituted in the alkyl radical, for example by chlorine, hydroxy, lower dialkyl-amino, sulfo, sulfato, phosphato, carboxy, or is a N-~lower alkyl)-alkylsulfonylamino group whose lower alkyl radical which is present at the sulfonyl group may be substituted, for example by chlorine, hydroxy, lower dialkylamino, sulfo, sulfato, phos-phato, carboxy, or is an alkanoylamino or alkenoylamino group having from 2 to 5 carbon atoms each, a benzoylamino group which may be substituted by 1 or 2 substituents selected from the group chlorine, lower alkyl, lower alkoxy, sulfo, sulfonamide, carboxy and sulfonamide mono- or disubstituted by lower alkyl or is a phenylsulfonylamino group, or R2 and R3 together form the group -NH-CO-NH-, with the proviso that at least oneJ pre-ferably two, especially three or four of the radicals Rl, R2, R3 and R4 stand for a hydrogen atom each, and n is a number . . :

: . ::: - ;
,~
: ~ .: :~:: . . : ::

.: . :

H E ~ I` 102 .
?0~80S3 of from 1 to 4.
The term "lower" in the above as well as in the follo-~ing pas3ages means that the alkyl or al~enyl or alkylene radical contained in the group consists of from 1 to 4 carbon atoms.
If the novel compounds contain anionic groups, they are present preferably in the form of their alkali metal salts, such as the sodium or potassium salts, or of alkaline earth metal salts, such as calcium salts, or in the form of ammoniuln salts.
Preferred compounds are those of the formula I, in which Pc represents the copper, cobalt or nickel phthalocyanine radical, e~pecially the copper phthalocyanine radical, which compounds are unsubstituted in the phthalocyanine radical or substituted by sulfo in the 3- and/or 4-position of the re-~ 15 spective aromatic carbocyclic ring in the phthalocyanine i ~ skeleton, in which n stands for a n~mber of from 1.5 to 4 an~
~ R , R2, R3 and R are identical or different and each is a hydrogen atom, a chlorine atom, a methyl, ethyl, methoxy, ethoxy, acetylamino, propionylamlno, cyano, carboxy, carb-ethoxy, carbomethoxv, carbonamide, N-methyl- or N-ethylcar-bonamide group, a N-phenylcarbonamide group, a sulfonarnide, N-methyl- or N-ethyl- or N,N-dimethyl- or N,N-diethyl- or N-methyl-N-phenyl-sulf`onamide group, a methylsulfonyl, ethyl-sulfonyl, phenylsulfonyl, acetyl, propionyl, benzoyl, phenyl, B-hydroxy-ethvlsulfonyl, ~-chloro-ethylsulfonyl, B-sulfato-ethylsulf`onyl, B-sulfoethylsulfonyl group, a vinylsulfonyl group, a sulfonamide group mono- or disubstituted at the nitroge.n atorn by a B-hydroxyethyl or B-sulfatoethyl or B-29 sulfoethyl group, or is an acetyloxy, propionyloxy, _ 4 --.. ..
. ' . ' ' ` i ' ' .~ ' '` ` . ': ' '' .' HOF, 76/~_ ~2 i0~053 benzoyloxy, phenoxy, trifluoromethyl, nitro, benzoylamino, methylsulfonylamino, ethylsulfonylamino, phellylsulfonylamino group or a phenylsulfonylamino group substituted in the nuc.l.eus by, preferably 1 or 2, substituents selected from the group lower alkyl, lower alkoxy or chlorine, with the provisn that preferably 2, especially 3 or 4 of the radicals R , R , ~3 and R represent a hydrogen atom each.
Of these novel dyestuffs, especially copper phthalocy-anine dyestuffs are interesting which contain the ortho-aminophenylene--sulfonamide radical(s) preferably in the 3-position of the carbocyclic aromatic phthalocyanine nuclei and in which one of the radicals R1, R2, R3 and R4 represents the cyano, carboxy or carbonamide group and the other three radicals stand for hydrogen, or in which each of the four radicals Rl, R2, R3 and R represents a hydrogen atom and n i8 a number of from 2 to 4.
Preference is given in particular to phthalocyanine com-pounds of the formula Pc ~ 5~2 ~ NH

. _ _ n in which Pc has one of the above-mentioned meanings and n stands for a number of from 2 to 4, of these especially the compounds in which Pc stands for the copper phthalocyanine radical having one of the above-mentioned meanings.
Particularly preferred are the compounds of Examples 3, 4, 19 and 22 with a sulfonamide radical portion of 2 to 4.

,. . . .
:: :. ~: . ..
. . .
-- :- : .

,, .~ ,. .

~lo~ 76~
~:088053 Of all the above-specified compounds of the formula (I), preference is given sspecially to those ~Jhich do not contain any anionic groups, The novel phthalocyanine compounds are prepared according to the invention by reacting 1 mole of a phthalocyanine sulfo-chloride of the general formula II

Pc ~ 502Cl) (II) m in which Pc is defined as above and m is identical with n or greater than n, however, 4 at the most, with m moles of` an atnine or less than m moles, however, with at least 1 mole of an amine of the general formula III

- R2 (I~I) Z. R
in which Rl, R2, R3 and R are defined as above and Z repre~
sents an amino group, lower alkanoylamino or benzoylamino or nitro group, and saponifying, - simultaneously in this reaction or ~ubsequently or, if Z has another meaning than the amino group, in one of the following process steps -, sulfonylchlo-ride groups which may ~till be present, into sulfonic acid groups in known analogous manner; if Z represents one of the above-mentioned acylamino groups, the condensation product obtained i9 deacylated in known analogous manner, in which process sulfonylchloride groups which may still be present are simultaneously saponified into sulfo groups, or, if Z repre-sents a nitro group, the condensation product obtained is re-duced in known analogous manner to give the compound of the ,: . : .
: . ,,, .

, . : : : . ., .~ ., ., : ,. ... .
- : :: .. : :: . -, ,., :. ,.:::.
, :, ~ , . ...
. : . .: . : :. :
. . - . : - . . .;.; : -, . :

~I ~ 76/F 1()~
~8~5~

above-s~ecified formula I, in which proces~ sul.fonylchloride groups which may still be present are simultaneously or sub-sequently saponified to give sulfo groups.
The deacylation to be optionally effected is to be carried out while considering that the sul~onamide bond having been formed in the preceding reaction, needs to be maintaine~, the deacylation is therefore carried out accordingly while applying analogous methods known for such kind of cases, for example, by heating with diluted aqueous sodium hydroxide solution at a pH value of from 8 to 10 and at a temperature in the range of from 30 to 50C.
The reduction of the nitro group to be optionally carried out may also be effected in an analogous m.anner of known pro-cesses, for-example by heating with sodium sulfide in a neu-tral or alkaline aqueous medium at a pH value of from 7 to 10 and at a temperature in the range of from 30 to 60 C.
The reaction of the phthalocyanine sulfochlorides of the general formula II with the amines of the general formula III
may be carried out in an aqueous medium. However, the reac tiOII
can also be advantageously effected in an organic solvent, such as an organic solvent miscible with water, for example, a lower alkanol, such as methanol, ethanol, in N-methyl.pyrro-li.done, dimethylformamide or dimethylsulfoxide, or in an aqueous-organic medium, the organic solvent being a solvent miscible with water, for example one of the above-mentioned solvents.
The reaction of the compounds of formula II with the amines of the formula III is advantageously carried out at a 29 temperature in the range of from about -10 C to about 110 C.

: : , . ., . .:
~, :, , - ,. ............................ :
., : : ,: ,,. .:

: ' ... .

~~OE ~ F 1~2 10~8053 In this connection it is advantageous, - depending on the reactivity and reaction rate of the sulfochloride groups - ~
to start the reaction at a low temperature, for example at a temperature of from - 10C to ~20C, especially at O to 10C, to maintain the maJor part of this reaction pro.ceeding in an exothermic manner, at this temperature and to subsequently heat up to a temperature of from 20 to 50C or, if necessary, up to about 100 C, in order to complete the reaction.
If the reaction rate of sulfochloride groups or their number is small, it is also possible to carry out the reacti.on at a starting temperature of from 20 to 55C. l`he process is then effected in an advanced dilution or under strong cooling, or one of the reaction components is added to the other slowly.
Furthermore, it is advantageous to carry out the re-action of the phthalocyanine sulfochlorides with the amines of the formula III in the presence of an acid-binding agent, for example an alkali metal hydroxide, alka.li metal carbonate, alkaline earth metal carbonate, alkali metal phosphate, a:L-kali metal acetate or a tertiary organic amine, in order to bind the hydrogen chloride being set free. As acid-binding agents of this kind there are to be mentioned in particular:
Sodium and potassium acetate, sodium and potassium bicarbo-nate, sodium and potassium carbonate, sodium-dihydrogeno-phosphate, disodium-hydrogeno-phosphate, trisodium phosphate or the corresponding potassium salts thereof. It is also possible, however, to use an excess amount of the amine of the formula III instead of one of the above-mentioned acid-bin-29 ding agents. The use of an excess amount of an amine of the . - 8 -, .. .... . ..

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~ ' ', '' ~ "' " . . ' ' ,' ,' "' :.j' " ' ' ~ ' ' , ' - ' ''- ' :: ' ' ,' ' ' .'' ~, ' ` ', ' . '., ' ',, ,, '.', . ' ' ."'' ;, ' ' .';'. ~'. '~
, . ~, ., . ., , , : , 1~0]3 ~G/i? 1~) G~

formula III is recommended in any case, if a complets reaction of all sulfochloride groups present in the compound of the formula II with the amine of the formula III is to be achieved.
The amines of t~e formula III are oxidation-sensitive~ It is therefore recommended to carry out the reaction of these amines with the phthalocyanine sulfochlorides of the formula II with the exclusion of air by superposing, for example, the reaction mixture with an inert gas, such as nitrogen. Howcver, the reaction may also be carried out in the presence of small amounts of compounds acting as antioxidants, such a~ sodiun dithionite or hydrazine.
The phthalocyanine compounds of the formula (I) of the invention are isolated according to analogous methods which are known to persons skilled in the art, for example, by se paration with filtration, if the reaction product is insoluble in the reaction medium, or by precipitation with water or an appropriate organic solvent, if the reaction product is so-luble in the other solvent used, and/or by precipitation wikh acidification with a mineral acid and subsequent filtratioll.
Z0 However, there is no need to isolate the reaction products if they are present in a dissolved form; they may be used in this form for further processing.
The phthalocyanine sulfonamide compounds thus obtained of`
the fo~mula I may be isolated in the form of the free acid if they contain acid groups, and be converted in an analogous manner known to a chemist into the salts thereof, preferably into their alkali metal salts, alkaline earth metal salts or ammonium salts.
29 The phthalocyanine compounds of the formula I may also be _ g _ ' ' :: :; -- ~,;. . -, .: . ~ ; . , . :, . ., : , ,, :
. .

~ 6 ~ ~

present in the form of their acid salts of the amino group standing in ortho-position to the sulfonamide group, for ex-ample in the form Or the hydrochlorides, sulfates or hydro-genosulfates.
The novel compounds of the formula I are excellently suitable as dyestuffs according to the invention, especially for the dyeing and printing of natural and synthetic fibrous materials, such as natural cellulose, for example cotton, linen, hemp, of regenerated cellulose, of natural polyamide fiber materials, such as wool and sillc, and of synthetic poly-amide fiber materials, such as polyamide-6, polyamide-66, poly-amide-11, of polyester fibers, for example polyesters from terephthalic acid and hexanediol, or of polyacrylonitrile fibers, as well as of mixtures of these types of fiber among each other.
In order to produce dyeings and prints by means of the compounds of the formula I, said compounds are applied in common manner, as it is known for dyeing and printing pro-; ces6es~ flom an aqueous or aqueous-organic medium onto the fibrous material and are subsequently exposed on the fiber to the action of nitrous acid, The appIication of the compounds of the formula I onto the various fibrous materials may be effected from an aqueous-alkaline, aqueous-neutral or aqueous-acid solution; the aqueous solutions may also contain an or-Z5 ganic solvent miscible with water, for example, methanol, ethanol, N-methylpyrrolidone. According to the methods common for dyeing and printing processes it is also possible to add the usual auxiliary agents and manufacturing agents to the , 29 dyestuff solution~. The fibrous materials having been treated . . :- ~ . : :. . :.- :. . :

I~OF~ 76/F 102 1~88~)53 with these soluti.ons or printing pastes of the dyestllffs of the formula I in the dye bath or preferably by padding or printing, are subsequently subjected to the action of nitr~us acid; a drying process at a temperature in the range of from 30 to 80 C may optionally be interposed before-the nitrous acid treatment.
The process for fixing the novel compounds may be carried out by treating the pre-dyed fibrous material in an aqueous bath of an alkali metal nitrite, such as sodium ni-trite, or by padding it over with an aqueous solutioll of this alkali metal nitrite, then optionally drying the material and treating it subsequently in an aqueous bath of an inorga-nic acid, such as hydrochloric, chloroacetic or sulfuric acid, preferably hydrochloric acid, the bath having a normality of from about 0.5N to 3N of this acid, at a temperature in the range of from 0 to 30 C, or by padding the material over with an acid solution of this kind. However, if the fibrous ma~
terials have been treated beforehand with allcaJ.ine solutions or printing pastes of the dyestuffs of the formuJ.a I, an al-kali metal nitrite, such as sodium nitrite, may already be added to these alkaline solutions or printing pastes, and the fibrous materials thus having been treated with the alkaline solutions or pastes are subsequently subjected, optionally after a drying process, to an acid treatment, for example in an acid bath, or by being padded over with an acid solution, for example an aqueous 0.5N to 3N hydrochloric, chloroacetic or sulfuric acid solution.
The action of the nitrous acid on the compounds of the 29 formula I during the dyeing process which occur~ in a .

, , :, ~ l02 ~088053 reaction of the ortho-amino-sulfcnanilide moiety, effects that the no~el compounds lose partially or entirely their solubility and are thus fast-fixed on or in the fibrous material. In this manner, the compounds of the formula I of the invention yield dyeings or prints which are distinguished by a good fastness to washing, to water, to rubbing, to perspiration, to chlorine and to light.
The following Examples serve to illustrate the invention.
The parts are parts by weight and the percentages are per cent by weight, unless otherwise stated. Parts by volume are to parts by wei~ht as is the lcilogram to the liter. The formula radicals CuPc, NiPc and CoPc in the Examples re-present the unsubstituted copper, nickel vr cobalt phthalo~
cyanine skeleton.

10.8 Parts of 1,2-diaminobenzene are dissolved in 300 parts of water at 50 C. 16.5 Parts of a copper phthalo-cyanine-3-sulfochloride containing about 2.5 sulfochloride groups per rnolecule on an averago, are introd~lced into thi6 solution in the form of a moist filter calce, while stirring thoroughly;

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~",,, ' _ 12 -'.

:. .: . ; : . , ......... - ~, :-' - ' , :''': '.' ~' ' ' '' ' "
' ' ' " , , ., ' "' ' " .""' 1088053 ~

s~bsequently 40 parts by volume of an aqueou~ saturated so-dium carbonate solution are added, while maint~ining a con-stant temperature of 50 C, and the reaction mixture is stirred at 50 C. Vpon completion of the reaction the precipitaterl pro-duct is filtered off, is washed thoroughly with water and dried at 60 C in the drying cabinet. 18 Parts of a darlc blue powder are obtained, the composition of which corresponds to the following formula CuPc ~ so2-NH~
S03H NH2 1~5 The compound of the invention thus obtained is soluble in water with the addition of sodium hydroxide solution.
E X A M P L E of ap~lication.
By means of the novel compound obtained in Example 1. a cotton dyeing may be prepared in the following manner:
A cotton fabric is introduced into a solution of 1 part of the dyestuff of Example 1 in 3 parts by volume o~ lN-sndiwn hydroxide solution and 20 par~s of water anfl is heated for 30 minutes at 90 C, while stirring constantly. Subsequently the fabric is rinsed for a short time with cold water, is introduced into an ~queous 40 ~ sodium nitrite solution, is left there for 30 seconds, while stirring; then the excess r nitrite solution is squeezed off and the fabric is treated for about 1 minute in an aqueous lN-hydrochloric acid. The ~; cotton fabric thus treated is thereafter rinsed with cold and hot water and is soaped at the boil. A strong turquoise blue dyeing is obtained which shows good fastness properties.

~- - 13 -~ .
,. .. . . .

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

HOE~ F 102 1~880S3 E X ~ M P L E 2-A solution OL 81 parts of 1,2-diaminobenzene in 400 parts of methanol is superposed in a closed vessel with nitrogen;
41 parts of a copper phthalocyanine-3~sulfochloride con-taining about 2.5 sulfochloride groups per molecule on an average, are added to said solution in the form of a moist filter cake, the reaction mixture being maintained at a tem-perature of 20 C by cooling. When the addition of the sulfo~
chloride has been finished, the mixture is continued to be stirred for 15 hours at room temperature and is subsequently heated to 50 C. The reaction is completed, while stirring for 5 hours at 50 C. Subsequently the precipitated novel compound is filtered off, is washed thoroughly with methanol and dried.
47 Parts of a product are obtained which has the form of a dark blue powder and is soluble in water in the presence of sodium hydroxide solution with a turquoise blue color shado.
The novel compound corresponds in its composition to the following formu a CulC ~ S0 -NH ~ ]
S3H)0 5 NH2 2 It dyes a cotton fabric according to the dyeing process ment-ioned in Example 1 in turquoise blue color shades showing good fastness properties.
E X A M P L E ~:
,~ 82 Parts of a copper phthalocyanine-3-sulfochloride con-taining about 2.5 sulfochloride groups per molecule on an average, are slowly introduced in the form of a moist filter cake into a solution of 270 parts of 1,2-diaminobenzene in . ~ ' .
~ _ 14 -.

,: , : -: ,: :: . . ,: ., , ::

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

1~01.~76~ 02 ~88053 300 parts of N-mothylpyrrolidone under a nitrogen atmosphere and at a temperature of from 5 to 10 C. The reaction mixture is stirred for 5 hours at this temperature of from 5 to 10 C, and subsequently for another 15 hours at a temperature of from 20 to 25 C. The solution is thereafter introduced into 2000 parts of n-butanol. The precipitated co~pound is filtered off, washed thoroughly with n-butanol and thereafter with methanol and is dried. 100 Parts of a dark blue powder are obtained which corresponds to a compound of the formula CuPc ~ SO~-NH ~ ~

NH2 2,5 , .
E X A M P L E of ap~lication One part Or the dyestuff prepared according to Example 3 is dissolved in 20 parts of N-methylpyrrolidone, 7 parts of water and 3 parts by volume of 1N-hydrochloric acid. A cotton fabric is introduced into this dye bath and is treated thereln for 30 minutes at 90C. Subsequently the Iabric thus obtained is rinsed for a short time with cold water, is introduced in~
to an aqueous 40 % sodium nitrite solution, and is moved there-in for 30 seconds; then the excess nitrite solution is squee-~ed off, and the fabric is treated for about 1 ~linute with an aqueous 1N-hydrochloric acid.
',~ The fabric thus dyed is then rinsed with cold and hot ~` water and is soaped at the boil. A strong turquoise blue dye-ing is obtained which shows good fastness properties.
~, .
~, - 1 5 .
, .

: ~ ` -HOE i~l` 102 1088~)53 E X A ~ P I, E, 4:
5 Parts Or sodium blcarbonate are added to a solution of 13 parts of 1,2-diaminobenzene in 70 parts of N-methylpyrroli-done ~.uperposed by nitrogen, and tho mixture i5 coolecl to 5 C.
Subs0quently 17~5 parts of copper phthalocyanine-3-trisulfo-chloride are introduced in the form of a ~ois~ filter cake, while stirring thoroughly, in which process the temperature is not allowed to rise above 10 C. The reaction mixture is con-tinued to be stirred for about 5 hours, while cooling with ice; thereafter its temperature is allowed to ris~ to 20 - 25C.
Upon completion of the reaction the mixture is introduced into 500 parts of water. The precipitated product is filtered off with suction, is washed thoroughly with water and methanol arld dried. 21 Parts of a dark blue powder are obtained which is soluble in water in the presence of alkali with Q turquoise blue shad0. It corresponds in ltS composition to the formula $ CuPc ~S02-NH~
. NH2 ' and yields on cotton according to a dyeing proces~ described ¦-- in Example 1 or 3 turquoise blue dyeings showing good fast-nesq propertieq.
E X A M_P L E S_ 5 to 18a:
,, ~
, If the preparation of the novel compounds is carried out ~; in accordance with Example 4 above, however, while using equivalent amounts of a diamine of the formuIa III specified in the following Table 1, novel compounds are obtained which are also excellently suitable for the dyeing of cotton.

_ 16 -, "
,; : ;: .

.: .

HO~ J2 lOB8053 .
: T a b l e 1:

1 2 3 4 Colour shade of thR
E~ample R R R R compound (I) obtain~
__ ._ ~
11 H CH3 H turquoise blue 6 H OCH3 CH3 H . greeil 7 H CH3 ~ H CH3 turquoise blue 8 H H . CH3 CH3 turquoise blue 9 H H . Cl H turquoise b 1UQ

H H OCH3 H . green 11 H H C2H5 H green 12 C~3 CH3 H H turquoise blue 13 H CH3 CH3 H turquoise blue 14 H CH3 H CH3 turquoise blue : 15 H Cl ~ H . turquoise blue 16 H Cl Cl H turquoise blue 17 H Cl H CH3 turquoise blue ~$ 18 H -NH-CO-C33 H H turquoise blue 18a. H -NH-CO-NH- H green , E~X A M P L_E ~
34 Parts of sodium hydrogenocarbonate are added to a solution of 86 parts of 1,2-diaminobenzene in 350 parts of N-methylpyrrolidone, and the mixture is cooled to 5 C. 97 Parts of copper phthalocyanine-3-tetrasulfochloride are slowly intro-duced in the form of a moist filter cake, while stirring thoroughly, under a nitrogen atmosphere, the temperature being maintained in the range of from 5 to 10 C. The mixture is sub-sequently stirred for 3 hours at 10 C, and thereafter for 12 ... . .. .. .

. ' , . , ' ~ ~ ', ! . ' , ~' .' ~ ' , , ' ' . ' ' ~,. ~' ,, .
. ~ , ' , ~ ' ~08B053 ~ `~?

hours at a temperature in the range of from 20 to 25 C. The reaction mixture is then introduced into 3000 parts of water, while stirring, the precipitated product is fil-tered off with suction, is washed thoroughly with water and methanol and dried. 125 Parts of a compound are obtained whic~.n corresponds i ~ to a constitution of the formula CUPC~so2~

The dark blue powder is soluble in diluted sodium hydroxide solution and yields on a cotton fabric according to the dyeing process described in Example 1 turquoise b'ue dyeings showing good fastness properties.
.- E X A M P L E 20:
A compound which is suitable as dyestuff and has good dyeing and fastness properties as those of the compound de-:, . scribed in Example 19, however, the shade being somewhat redder, is obtained if in Example 19 there is used, instead of` the ~: ~
copper phthalocyanine-3-tetrasulfochloride, the same amount of ~: copper phthalocyanine-3~4l,4'',4~ll-tetrasulfochloride and the preparati.on process is carried out otherwise in the manner described above in Example 19.
E X A M P L E 21:
. .
Compounds of the invention which are also excellently : suitable as dyestuffs, but which show a greener shade than the , dyestuff of Example 19, are obtained, if instead of the copper phthalocyanine-3-tetrasulfochloride in Example 19 there is used an equivalent amount of a nickel phthalocyanine-3-tetra-- 18 _ ~, .

... ~ .. . , .. , . " ..
- . .. . . . .

- ~; ,. ::
,. : .,~,; . :. :, .

H(~ !()2 ~08~3~53 sulfochloride or a cobal.t phthalocyanine-3-tetrasul.fochlorider E X A M P 1, E 22:
.
12.6 Parts of sodium hydrogenocarbonate are introduced ` into a solution of 40 parts of 3,4-diaminoben~onitr:ile :in 175 parts of N-methylpyrrolidone, the solution is superpose~
by nitrogen in a closed vessel and is cooled to ~5 C. Subse~
quently 43.6 parts of copper phthalocyanine-3-trisulfochloride are slowly introduced in the form of a moist filter cake, while stirring thoroughly, and the temperature is maintained in the range of from 5 to 10C; thercafter the mixture 7 S COIl tinued to be stirred for 18 hours at 20 C. The reaction mix~
ture is then introduced into 500 parts of water, the preci-: pitated novel compound is filtered off, is wash.ed t;horoughly with water and methanol and dried. 57 Parts of a compound corresponding to the constitution of the formula ':
are obtained in the form of a dark blue powder which issoluble in diluted sodium hydroxide solution and dyes cotton ~: according to a dyeing process described in Example 1 or 3 in turquoise blue shades showing good fastness properties.
~: E X A M P L E S 23 to 57:
: Compounds of the invention which show equally good dye-: stuff properties with regard to dyeing and also to the fastness of the dyeings prepared with them are obtained if in Example 22 an equivalent amount of a diamine specified in the ... .

. . . , ~:; .

.~
- . ~ ' , 10880S3 ~ !~2 followi~ Tab3e 2 correspondin~ to the formula III, in which R , R3 and R are hydrogen in each case and R is defined as in Table 2, is used instead of the 3,4-diaminobenzonitrile, ar~d the proce~s is carried out in accordance with the method of preparation described in Example 22.
T_a b l e 2 Example R2 Colour shade of the CO!ll-,. pound (I) obtained ... ~ _ ... ._ .
23 -COOH turquoiso blue 24 -COOCH3 ~~ . turquoise blue -COOC2H5 turquoise blue 26 -CONH2 turquoise blue 27 -CONH-NH turquoise blue 28 -CO-NH-CH3 . turquoise blue 29 2 CH3 turquoise blue -S2-c H turquoise blue 31 2 CH2 CH2 OH . turquoise blue 32 2 2 CH2 Cl . turquoise blue 33 -so2-cH2-cH2-oso3H turquoise blue 34 -so2-cH=cH2 turquoisc blue

2 ~ . turquoise blue 36 -S02-NH turquoise blue 37 -S02-NH-CH3 turquoise blue 38 -S02-N(CH3)2 turquoise blue 39 ~-S02-N(C2H5)2 turquoise blue -S02-NH ~ . turquoise blue 41 -502-N(CH3) ~ turquoise blue 42 -so2-NH-cH2-cH2-oH turquoise blue . , ,.. . . . ,. . .... : - ~ . ~ , , ~ , :, , . : .

: : :: ~: : . : . , : :: . . . : - -, : , . :- : :: .:. . :. .: : ~ , : ::

~TO~_ I 0;~

Example R2 ¦ Colour shade of the com-¦ poun~ (I) o~tained . . _ _ ~ ~_ 43 ~so2-NEi~cH2-cH2-oso3H turquoi.se ~lue 44 -S02-N(CH2-CH2 OH)2 turquoi.se blue -S02-N(CH2-CH2 OS03H)2 turquoise blue 46 . -CO-CH turquoise blue 47 -CO ~ turquoise blue 48 . ~ . blue green 49 ~ -0-CO-CH3 green -O-CO- ~ green 51 -O- O green 52 -CF3 turquoise blue 53 -N02 blue green 54 -NH-CO-CH3. . turquoise blue -NH-CO ~ turquoise blue 56 -NH-S02-CH turquoise blue 57 -NH-S02 ~ CH3 turquoise blue E X A M P L E~_~8-a) 16.8 Parts of sodium hydrogenocarbonate are introduced into a solution of 43~2 parts of 1,2-dianlinobenzene in 225 parts of N-methylpyrrolidone. After cooling to +5 C, 63.7 parts of tetraphenyl-copper phthalocyanine-tetrasulfochloride, the preparation of which has been described further below, are slowly added in the form of a moist filter cake under a nitrogen atmosphere, while stirring thoroughly, in the course of which the temperature of the reaction mixture is not allowed to rise above 10 C and is generally maintained in the range of from 5 to 10C. The mixture is then con-. ', `' ;- ' :
, ,. - . :~

.

10880S3 ~l~ 02 tinued to be stirred for 3 hours at 10 C and subsequently for another 18 hours at a temperature of f`rom 20 to 25 C.
The novel compound having been formed is precipitated by adding 800 parts of water, is filtered off and waslled thoroughly first with a mixture of 200 parts of N-methyl pyrrolidone and lOOO parts of water and thereafter with water alone, until it is free from starting products. After drying, 75 parts of a compound in the form of a green powder are obtained, whose constitution corresponds to the formula [ C ~) 4~502-NH~3 ~

; b) E X A_M P L E of application A printing paste is prepared for the manuf~cture of a cotton print as follows: lO parts of the dyestuff synthe-sized in Example 58 and 50 parts of urea are dissolved in lOO parts of water, while adding 14 parts of a 33 sodium hydroxide solution. 26 Parts of an aqueouA 40 sodium nitrite solution are then added and, while stirring~
300 parts of a 4 % sodium alginate thickener are intro-duced. A COttOIl fabric is then printed with the printing paste thus prepared. The print dried at 60 C is subse-quently treated for 30 seconds, while being moved, with an aqueous lN-hydrochloric acid at a temperature of from 20 to 25 C, and is then rinsed with cold and hot water and finally soaped at the boil. A brilliant bluish-green printing design is obtained which shows good fastness pro-perties.

, : " : .:

:. ~ ~ , .: . : -HOE 75/1~` 102 _ ~d8~0s3 c) Pre~e~ration of the star in~ sulfochloride 44 Parts of tetraphenyl-copper phthalocyanine are intro-duced slowly into 250 parts of chlorosulfonic acid; in the course of this process the temparature rises up to 80 C~
The mixture is then slowly heated to 100 C and is continued to be stirred for 16 hours at this temperature. Subse-; quently the mixture is cooled to 90 C, and 100 p~rts of thionylchloride are added dropwise at a temperature in the s range of from 80 to 90 C. Thereafter the reaction mix-ture ~' 10 is continued to be stirred for 4 hours at ~0 C. S~bse-quently it is cooled to room temperature, is stirred onto ice, and the precipitated tetraphenyl-copper phthalocyanine-~ tetrasulfochloride is filtered off and is washed with ice f water until neutral.
s 15 E X A M P L E 59:
~ 25.2 Parts of` sodium hydrogenocarbonate are added to a s solution of 79.8 parts of 3,4-diaminobenzonitrile in 350 parts of N-methylpyrrolidone, and the mixture is cooled to 5 C.
86.7 Parts of` cobalt phthalocyanine-3-trisulfochloride are introduced in the form of a moist filter cake, while stirring thoroughly, under a nitrogen atmosphere, the temperature being maintained at a range of from +5 to +10 C; thereafter the mix-ture is continued to be stirred for 3 hours at 10 C and then for 18 hours at a temperature in the range of from 20 to 25 C.
It is then introduced into water; tha precipitated compound is filtered off with suction, is washed at first with a mixtura of 50 parts of ~-methylpyrrolidone and 1000 parts of water and thereafter with water alone until it is free from starting 29 products, Af`ter drying, 112 parts of a dark blue powder of a - 23 _ :- - , , .

.

. .

compound are obtained which corresponds to the constitution Or the formula CoPc _~ S02-NH~--: . 2 ; The product is soluble in diluted sodium hydroxide solution :
~; and yields on cotton fabric according to the printing process indicated in Example 58 turquoise blue prints showing good fastness properties.

E X A M P L E 60: . ;
- ~
If a compound according to the invention is prepared in the manner described in Example 59, however, while using in-stead of the cobalt phthalocyanine-3-trisulfochloride an equi-valent amount of nickel phthalocyanine-3-trisulfochloride, t;he corresponding nickel phthalocyanine dyestuff is obtained which is also excellently suitable for the dyeing of cotton and which yields blue green dyeings and prints with good fastness properties.
E X_A M_P L E 61- !
If a compound according to the invention is prepared in the manner described in Example 4, however, while using in-stead of 13 parts of 1,2-diaminobenzene 5.1 parts of 3,4-di-a~inobenzonitrile and 8.6 parts of 1,2-diaminobenzene, and the product is worked up as has been described, for example, in Example 4, 19 parts of a compound are obtained which shows most probably the following constitution:

_ 24 -.. . ..

- ' .: ' , :: ' "' ~ ''; ": ''~ ': . . ` ,, ' . ". :

1088053 ~IOF 76~i~ 102 ]

CuPc NH2 2 , \\

S02-NH ~ CN

This novel compound is soluble in diluted sodium hydroxide solution and yields on cotton f`abric - for example accordjng to the printing process described in Example 58 - turquoise blue prints having good fastness properties.

12.6 Parts of sodium hydrogenocarbonate are added to asolution of 32.4 parts of 1,2-diaminobenzene in 175 parts of dimethylformamide, the solution is superposed by nitrogen and coo]ed to 5C. 43.6 Parts of copper phthalocyanino-3-tri-sulfochloride are introduced in the form of a moist filter cake, while stirring thoroughly, the temperature being main-tained at a range of from 5 to 10 C. The mixture is continu0d to be stirred for 3 hours at a temperature of 10 C and then for 18 hours at 20 to 25 C. In order to precipitate the com-pound of the invention ha~ing been formed, 600 parts of wat~r are added to the reaction mixture, the product is filtered off with suction and is washed at first with a mixture of 175 par-ts of dimethylformamide and 1000 parts of water and then with water alone until the product filtered off is free from star~
ting products. After drying, 41 parts of a co~pound are ob-,......................... .

- :

. IiOI~ 02 1088(~S3 tained which has the followin~ constitution:

, CuPc~502--N~

S03H N~2 2 The novel compound is soluble in diluted sodium hydroxide solution and yields on a cotton fabric - for example accor-ding to the printing process described in Example 58 tur-quoise blue prints showing good fastness properties.
The same compound of the invention is obtained, if in-:~ stead of the 175 parts of dimethylformamide used as solvent in this example in the sulfonamide reaction, there :is used the same amount of dimethylsulfoxide.
E X A M P L E 63:
12.6 Parts of sodium hydrogenocarbonate are added to asolution of 45 parts of 2-aminoacetanilide in 175 parts of N-methylpyrrolidone, the solution is su.perposed by nitrogen and is cool~d to 5 C. 43.6 Parts of' copper phtha].ocyanino-3-tri-sulfochloride are added in the form of a moi.st filter cake, while stirring thoroughly, and the temperature is maintained at a range of from +5 to +10 C. Subsequently tho reaction mix-ture is continued to be stirred for 3 hours at +10 C and for 18 hours at a temperature of from 20 to 25C. The reaction mixture is then mixed with 400 parts of water, and the pre-cipitated compound is filtered off, is washed first with a mixture of 175 parts of N-methylpyrrolidone and 500 parts of water and then with water alone until it is free from starting products.

26 _ : . :, :: . . ~ .

I-IOE '~ ~ 102 .~ Subsequently the mcist filter cake is boiled with 200 parts by volume of 2N-sodium hydroxide solution for 2 hourcic The mixture is then neutr~lizsd at ZOC with hydrochloric acid, in which process the compound of the invention preci-pitates. It is filtered off with suction, wa.shed thoroughly -. with ~ater and dried. 45 Parts of a dark blue po~der of a compound are obtained which corresponds according to its constitution to the formula SO~-NH ~ ~

\ NH2 1,5 (S03H)1,5 It is soluble in ~iiluted sodium hydroxide solution and yields on cotton fabric,- for example according to the printing process described in Example 58 or according to the dy~ing process described in Example 1 -,turquoise blue prints and/or dyeings which show good fastness properties.

t , .. .... . . . :

,'

Claims (14)

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

1. A phthalocyanine compound according to the formula I

(I), including the salts thereof, in which Pc is the copper, cobalt or nickel phthalocyanine radical which may be substituted by substituents selected from the group halogen, phenyl, sulfo, sulfonamide, sulfonamide mono- or disubstituted by lower alkyl, N-arylsulfonamide and N-arylsulfonamide N-substituted by lower alkyl, R1, R2, R3 and R4 are the same or different and each represents a hydrogen atom, a halogen atom, a lower alkyl group which may be substituted by hydroxy, chlorine, carboxy, sulfo or sulfato, or represents a phenyl or a lower alkoxy group which may be substituted in the alkyl radical by lower alkoxy or a phenoxy, carboxy, carbonamide group or a carbonamide group which is mono- or disubstituted by lower alkyl groups, or is a phenylcarbonamide group, a cyano or carbalkoxy group having 2 to 5 carbon atoms, an alkanoyloxy group of 2 to 5 carbon atoms, a lower alkenylsulfonyl group, a lower alkylsulfonyl group which may be substituted in the alkyl radical by chlorine, hydroxy, lower dialkylamino, sulfo, sulfato, phosphato, or carboxy groups, or a phenylsulfonyl, sulfo, sulfonamide, N-(lower alkyl)-sulfonamide group which may be substituted in the alkyl radical by chlorine, hydroxy, lower dialkylamino, sulfo, sulfato, phosphato or carboxy groups, or a N,N-di-(lower alkyl)-sulfonamide group which may be substituted in the two alkyl radicals by chlorine, hydroxy, lower dialkylamino, sulfo, sulfato, phosphato, or carboxy groups, or a trifluoromethyl or nitro group or a lower alkylsulfonylamino group which may be substituted in the alkyl radical by chlorine, hydroxy, lower dialkylamino, sulfo, sulfato, phosphato, or carboxy groups, or a N-(lower alkyl)-alkylsulfonylamino group which lower alkyl radical present at the sulfonyl group may be substituted by chlorine, hydroxy, lower dialkylamino, sulfo, sulfato, phosphato, or carboxy groups, or an alkanoylamino or alkenoylamino group having 2 to 5 carbon atoms each, a benzoylamino group optionally substituted by 1 or 2 substituents selected from the group chlorine, lower alkyl, lower alkoxy, sulfo, sulfonamide, carboxy, N-mono-(lower alkyl)-sulfonamide and sulfonamide N,N-disubstituted by lower alkyl, or is a phenylsulfonylamino group or an alkanoyl group of 2 to 5 carbon atoms, or R2 and R3 together form the group -NH-CO-NH-, with the proviso that at least one of the radicals R1, R2, R3 and R4 stands for hydrogen, and n is a number of from 1 to 4.

2. A compound according to claim 1, in which Pc is the copper, cobalt or nickel phthalocyanine radical, the phthalocyanine of which is unsubstituted or is substituted by sulfo in the 3- or 4- or 3- and 4-positions of the aromatic carbocyclic ring in the phthalocyanine skeleton, n is a number of from 1.5 to 4, R1, R2, R3 and R4 are identical or different and each is hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy, acetylamino, propionylamino, cyano, carboxy, carbethoxy, carbomethoxy, carbonamide, N-methyl- or N-ethylcarbon-amide, N-phenylcarbonamide, sulfonamide, N-methyl-, N-ethyl- or N,N-dimethyl-or N,N-diethyl- or N-methyl-N-phenyl-sulfonamide, methylsulfonyl, ethyl-sulfonyl, phenylsulfonyl, acetyl, propionyl, benzoyl, phenyl, .beta.-hydroxy-ethylsulfonyl, .beta.-chloro-ethylsulfonyl, .beta.-sulfato-ethylsulfonyl, .beta.-sulfo-ethylsulfonyl, vinylsulfonyl, sulfonamide mono- or disubstituted at the nitrogen atom by .beta.-hydroxyethyl or .beta.-sulfatoethyl or .beta.-sulfoethyl, or is acetyloxy, propionyloxy, benzoyloxy, phenoxy, trifluoromethyl, nitro, benzoylamino, methylsulfonylamino, ethylsulfonylamino, phenylsulfonylamino or phenylsulfonylamino substituted in the nucleus by substituents selected from lower alkyl, lower alkoxy and chlorine, with the proviso that two or three substituents of the group R1, R2, R3 and R4 are hydrogen each.

3. A compound according to claim 1, in which Pc is the copper, cobalt or nickel phthalocyanine radical, the phthalocyanine of which is unsubstituted or is substituted by sulfo in the 3- or 4- or 3- and 4-positions of the aro-matic carbocyclic ring in the phthalocyanine skeleton, n is a number of from 1.5 to 4, R1, R2, R3 and R4 are identical or different and each is hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy, acetylamino, cyano, carboxy, carbonamide, sulfonamide, methylsulfonyl, ethylsulfonyl and trifluoromethyl with the proviso that two or three substituents of the group R1, R2, R3 and R4 are hydrogen each.

4. A compound according to claim 1, or 3, in which Pc is the copper phthalocyanine radical defined in claim 3.

5. A compound according to claim 1, 2 or 3, in which Pc is defined as in claims 1, 2 or 3 and n stands for a number of from 2 to 4 and R1, R2, R3 and R4 each represent hydrogen.

6. A compound according to claim 1, in which Pc is the copper phthalocyanine radical defined in claim 1 and one of the substituents of R , R2, R and R4 is cyano, carboxy or carbonamide, the other are hydrogen each and n is a number of from 2 to 4.

7. A compound according to claim 6, in which R1, R2, R3 and R4 each is hydrogen.

8. A compound according to claim 1 that does not contain an anionic group.

9. A compound according to claim 1 of the formula in which Pc is the unsubstituted copper, cobalt or nickel phthalocyanine radical and n is a number of from 2 to 4.

10. A compound according to claim 9, in which Pc is the unsubstituted copper phthalocyanine radical.

11. The compound according to claim 10, in which n is 3.

12. Process for the preparation of the phthalocyanine compounds as claimed and defined in claim 1, which comprises reacting 1 mole of a phthalocyanine sulfochloride of the general formula II

(II) in which Pc is defined as in claim 1 and m is identical with n according to the definition of the latter in claim 1 or is greater than n, however, 4 at the most, with m moles of an amine or less than n moles, however, with at least 1 mole of an amine of the general formula III

(III) in which R1, R2, R3 and R4 are defined as in claim 1 and Z represents an amino group, lower alkanoylamino or benzoylamino or nitro group, and saponifying, - simultaneously in this reaction step or subsequently or, if Z has another meaning than the amino group, in one of the following process steps -, the sulfonylchloride groups which may still be present into sulfonic acid groups, and if Z represents one of the above-mentioned acylamino groups, deacylating the condensation product obtained together with simultaneous hydrolysis of sulfonylchloride groups which may still be present into sulfo groups, or, if Z represents a nitro group, reducing the conden-sation product obtained together with simultaneous or subsequent hydrolysis of sulfonylchloride groups which may still be present, to sulfo groups.

13. Process as claimed in claim 12, which comprises carrying out the reaction of the phthalocyanine sulfochlorides with the amine in the presence of an acid-binding agent.

14. A process for treating a fibrous material which comprises applying to a material a compound as defined in claim 1, in dissolved form, and sub-sequently fixing the compound on the material by subjecting the material and compound to the action of nitrous acid.