DE1544350A1 - Reactive dyes and processes for their preparation - Google Patents

Description

RATENTANWALIt

DR.I.MAAS

DR. W. PFEIFFER

DR.F. VOITHENLEiTNER

8 MUNICH 23
UNGERERSTR. 25 - TEL. 39 02 36

American Cyanamid. Company, Wayne, New Jersey, V.St.A.

Reactive! Dyes and terfabrics for their production

The invention relates to new dyes that chemically with polymeric substrates can be connected. It also relates to a process for the preparation of the new dyes.

The dyes according to the invention are characterized by that they have at least one iminobis (N-methylolpropionamide) - or iminobis (li-alkoxymethylpropionamide) residue contain.

It is known that dyes can be applied to polymeric materials in a reactive manner, in contrast to physical application in which the attraction of the dye to the polymer does not arise from any chemical combination. -Different attempts to solve the problem of ge _o suitable methods for chemical application of the dye to a substrate are known. These routes are, of course, determined by the reactivity of the polymeric substrate to be colored. For substrates which regularly recurring by re- ^ 'reactive hydrogen atoms are in ^ls> such as cellulose (either natuer Liehe or regenerated), the dye should chemically in

Documents (Art. 7 JI Abs. 2 Nr. 1 Clause 3 of the amendment of 4.9.1967t

_ 2 -

be able to enter into a condensation action. A known reactive group for the connection of The 2,4-dichlorotriazinyl radical is dye residues with cellulose. The chemical bonding of such dyes to cellulose is obtained by applying the substances under such conditions brings into contact with each other that hydrogen chloride is split off.

Another reactive group, which examines the wor is, the methyl group. When a methyl / oil-containing dye is brought into contact with cellulose under suitable conditions, water is split off and the dye is bound to the cellulose structure via an ether group. Such known reactive dyes have not yet found widespread technical application, perhaps because in practice the bond obtained with the fiber was not as stable as would be desirable for practical purposes.

The present invention relates to the field of methylolated Reactive dyes ". It is based on the discovery that the reactivity of the kethylol group with" active Hydrogen "of the polymer substrate is significantly improved by the fact that there is an activating effect between the aromatic dye and the reactive>! Ethylol radical Binding is inserted as defined below. The basic concept of an activated binding is not completely new, according to the special binding however, the invention is remarkably better able to fulfill the activating function than was previously thought possible. By modification according to the invention of the dye, an increased degree of reactivity of the dye with the polymeric substrate is obtained and when the reaction has taken place, a stronger bond with the substrate. Coloring of polymeric substrates, obtained with the modified chemically reactive dyes according to the invention have a large number better wet fastness than if the dye content was physical Application method was applied.

9 0 98-4 9/1527 BAD ORIGINAU

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wise, the dyes according to the invention are much more solid and more permanently associated with polymeric substrates than even very similar methylol-modified dyes to which the special activating bond according to the invention is absent. A great advantage of the invention is that the Dyes can be prepared under relatively mild reaction conditions, so that only minimal Damage to the chromophore or fluprophor.en. Character of; Starting material takes place. This fact helps to make the dyes according to the invention technically attractive.

The activating bond, which is the underlying discovery of the present invention, can represented by the following formula I:

CH ₂ CH ₂ CONCh ₂ OR

Y-N

CH ^ CR-COTL

CH ₂ CH ₂ CON _n T or 2

The bond itself is the best in brackets between the aromatic dye ^{radical "D" and the R f} and methylol component "CH ₂ OR", where R is a hydrogen atom or an alkyl group with 1-4 carbon atoms. This radical R ¹ is either a 'hydrogen atom or the group CH ₂ OR. In the activating bond, the symbol "Y" is intended to be a bridging group, such as a covalent bond, a sulfonyl - (- S0 ₂ -), alkylenesulfonyl - (- alk-S0 ₂ -), alkyleneoxy-C-alk-O-), Alkyltenthio-CS-alkylene-), carbonyl - (- C0-), alkylene carbonyl - (- alk-CO-) or alkylenecrtmpe represent. The alkylene radical in the case of bridging .. ·. Group should have either one or two carbon atoms. It can also be noted that the number of kethylol (or alkoxymethyl) groups can be between 1 and 4.

909849/1527

At least one such group must be present in order for the advantages according to the invention to be obtained. Up to 4 can be present, with excellent results, but such complete methylolation is sometimes difficult and often unnecessary as about 2 methylol groups have a very desirable degree of reactivity with one polymeric substrate. The methylolation step that leads to the dyes of the invention can be a Resulting reaction product, the mixtures of monomethylolated, dimethylolated, trimethylolated and tetramethylolated Contains molecules. If such mixtures' im If the following occur, they are identified by specifying the average methylation of the product. This mean is sometimes represented by a fractional number.

Compounds of the formula I. are particularly ^{suitable for dyeing polymers 1} which have a reactive hydrogen atom with which they can react. These include cellulose and its derivatives (natural forms such as cotton and paper, and synthetic forms such as rayon, acetate, etc.), polyamides (natural forms such as wool and synthetic forms such as nylon) and polyurethanes. At the current stage of polymer technology, the dyes of the invention are most notably suited for use on paper and cotton.

As indicated above, the invention is very generally applicable, regardless of the special structure of the dye. It should be noted here that the term "dye" is used herein to include fluorophoric dyes, often referred to as optical brighteners will. The classes of dyes that can be used in the present invention include acridine, Anthraquinone, azine (e.g. pyridine and quinoline dyes), Azo (mono- or poly-, metallized or non-metallized), azo-, azomethine-, cyanine-, diarylmethane-, indaain-, Indophenol, indigo, keto, amino or hydroxy, lactone,

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Methine or polymethine, nitro, nitroso, oxazine, oxazole (benzo or naphtho-), triazole (benzo- and naphtho-), phthalocyanine (and metal derivatives), quinoline, Cbinon- (benzo- or naphtho-), stilbene, sulfur, thiazine, thiazole, Triarylmethane xanthine and benzidine sulfone dyes. The aromatic components of these dyes can be mixed with the usual chromophoric and auxochromic radicals known to those skilled in the art are known to be substituted, and the latter are completely inert with respect to those conferred by the invention Responsiveness of this proportion. Most often, the dye component "D" is among the antbrachinone, azo, Nitro, phthalocyanine and triarylmethane dyes »selected because these classes are the most popular due to the range of colors in which they are available.

In preferred cases, the dyes contain solubilizing groups. These are either non-ionizing or ionizing Groups. If they are non-ionizing, such groups can represent hydrophilic radicals, such as hydroxyalkyl (including the methylol groups themselves), polyhydroxyalkyl, Carbamyl, SuIfamyl, Alkylsulfonyl, Pbosphonamyl, SuIfinamyl, SuIfenamyl and the like. In the case of ionizing Groups can be the solubilizing groups sulfon, carboxyl, Phosphonic groups and the like in the form of the free acids or in the form of an alkali (e.g. sodium or potassium) or ammonium salt. The ionizing groups can also quaternary ammonium or phosphonium or ternary sulfonium groups represent, in the form of salts with chlorine, iodine, methosulphate, tosylate or other anions,

According to the invention, substrate-reactive dyes of the general formula

D—

Y-N

Y /

CH ₂ CH ₂ CON

CH ₂ CH ₂ COI

_ _j η

909849/1527 '"" *

created, wherein D is a cfaromophorer or fluorophoric organic dye residue, Y is a covalent bond or a divalent bridging group, R is a hydrogen atom, an acyl group or an alkyl group with 1-4 carbon atoms, E ^{1 is} a hydrogen atom _{or a CH 2} OR group, in which R has the above meaning and η denotes the number 1 or 2.

The inventive method for the production of substrate-reactive Dyes is characterized in that at least one iminobispropionamide group in a chromophoric or fluorophoric organic dye or precursor is introduced, optionally completing the dye, and the iminobispropionamide group is alkoxymethylated or methylolated and optionally aeylated or the methylol group or groups obtained is or are alkylated.

• In particular, the method according to the invention provides a method .for the preparation of substrate-reactive dyes of the general formula;

CH ₂ CH ₂ CON

CH ₂ OR

Y-H

CH ₂ CH ₂ CON

R «

where D is a chromophoric or fluorophoric organic dye residue, Y is a covalent bond or a divalent J ₀ bridging group, R is a hydrogen atom, an acyl group ** - or an alkyl group with 1-4 carbon atoms, R ^{1 is} a hydrogen atom or the group CH ₅ OR, where R is the above

■

^ ₁ meaning is assigned, and η denotes the number 1 or 2, which consists in that

D '- (A) s with I B-F II

are implemented in which

a) D ^{1 is} a chromophoric or fluorophoric organic dye residue or precursor thereof, s and ρ are the numbers 1 or 2, Z is a 2-carbamylethyl or 2-cyanoethyl group or a cyanoethylatable hydrogen atom, one of the radicals A and B is an acylating, alkylating or arylating group and the other correspondingly denote an acylatable, alkylatable or arylatable group and wherein

1. if Z represents a 2-cyanoethyl radical, this too is hydrolyzed to a 2-carbamylethyl radical;

2. if Z is a hydrogen atom, this before or after the above reaction II by reaction with acrylonitrile is cyanoethylated and the 2-cyanoethyl radical obtained is hydrolyzed to a 2-carbamylethyl radical;

3. If necessary, the dye precursor group D ^{1 is} completed before or after the above reaction II;

being a dye of the general formula

Y-N

^ H ₂ CH ₂ CONH ₂

CH ₂ CH ₂ CONH ₂

III

is formed, where D, Y and η have the above meaning or

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b) D ¹ , s, ρ and Z of the above reaction II have the above meaning, one of the groups A and B represents the diazo-containing radical of a diazonium compound and the other is the radical of an azo coupling component, and where

1. if Z is not the 2-Carbaniyläthylrest, it is in these according to the above procedure. 1. or 2. of a) transferred before or after the above reaction II,

wherein a dye of the above general formula III is formed. The dye of the formula III resulting from the above reactions a) or b) is alkoxymethylated or methylolated and optionally then alkylated or acylated to form the corresponding dye of general formula I above.

The essential feature of the according to the invention ' The dyes that can be prepared consist in the fact that they contain at least one iminobispropionamide group. Regarding Dyes comparable to their other chromophoric or fluorophoric organic groups are from the German Auslegeschriften 1 079 756, 1 132 887 and 1 160 127 are known, but none of the known compounds contains an iminobispropionamide group. Surprisingly, it has been found that by introducing this group, dyes with higher Substrate reactivity can be obtained, thereby causing the dyes prepared according to the invention not only better to attach to the substrate, e.g. cotton, like this. that stronger colors can be obtained, but also adhere more firmly to the substrate than the constitutionally closest known dyes. It is straightforward it can be seen that a firm adhesion of the dye to the substrate leads to the washing of the dyed fabrics smaller amounts of dye are removed than when the bond between dye and substrate is less strong.

909849/1527 _{BAD oraQINA} L

Since the dyes obtainable according to the invention can be derived from any organic dye molecule, the radical D can be the radical of any dye e.g. from azo, anthraquinones (and other vat dyes), phthalocyanine, anthrone (e.g. anthrapyridone and anthrapyrimidones, indigo, xanthene, triaryl methanes Diarylmethane nitro, nitroso, azine, acridine, thiazine and oxazine dyes !!. Since according to the invention those dyes those in which the group D is derived from an azo, anthraquinone, anthrapyridone or phthalocyanine dye are preferred is derived, these are described in more detail.

The azo dye residues for the new dyes according to the invention are made from various aromatic diaz ^ components and clutch components derived. The components can be at least one methylolatable reactive Contain a bond or an immediate precursor for or the methylolatable reactive bond can be introduced into the dye after coupling.

Examples of diazotizable amines, the methylolatable Group which aur the formation of the diazo components can be used are;

3.3 ^L - (metanilylimino) bispropionamide; 3-Amino-4-methoxy-N, l ⁱ I-up "(2-carbaEiyläthyl) -benzol3ulfonamid; o-amino-ir,]! i-bis (2-carbamylethyl) -benzenesulfonamide; p-amino-N, N-bis- (2-carbainylethyl) -benzenesulfonamide; 4-chloro-3-nitro-ϊί, Έ- (2-carbamylethyl) -benzenesulfonamide; 3,3 '- (p-aminophenylimino) bis propionamide; m-amino-N, N-bis (2-carbamylethyl) benzamide;

Amines can be diazotized and used in the invention even if they do not contain the activating methylolatable bond. Such amines can be methylolatable with Coupling components are coupled. Optional

90 9.8 49/1527 BAD ORIGINAL

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The binding can also be attached when the coupler does not have the activated bond. Examples of amines which do not have a methylolatable activating bond and for the preparation of the diazo component « can are:

Aniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, o-, m- and p-chloroaniline, 2-l-nitro-4-chloroaniline, 2-amino-5-nitrotoluene, 4-aniino-3-nitrotoluene, 2 -Amino-4-nitrotoluene, 2-amino-5-chlorotoluene, 2-amin.o-4-chlorotoluene, 2 ~ amino-6-chlorotoluene, 2,5-dichloroaniline, 3,4-dichloroaniline, 3-amino-4 -chlorotoluene, o-, m- and p-anisidine, 3-liitro-4-ir.ethoxyaniline, 4-Ni fcro ~ 2 = -me bhoxyaniline, 2-liitro-4-ethoxyaniline, dianisidine, 1 ~ amino ~ 2, 5-diethoxy - 4- "benzoylaiainobenzene, 4-Alinino-1-benzoylamino-2, 5-dimethoxy-benzene, benzidine (including the monoacyl derivatives), tolidine, 4-chloro-2-methoxyaniline, 1,5-dinlethoxy 2-amino-4-chlorobenzene, 1-methoxy-2-benzoylamino-4-chloro-5-aminobenzene, 1-naphthylamine, 1 ~ aminoanthraquinone, i-amino-3-chloroanthraquinone, 3-amino-4-methoxybenzenesulfone diethylamide, 4- Methoxy-2-aminophenylethylsulfone, 4-benzoylamino-6-amino-m-xylidine, 4-kethoxy-4 ^l -aminodiphenylamine, 4-aminodiphenylamine, 4-chlorof-2-aminodiphenyl ether, 4,4'-dichloro-2-aininodiphenyl ether, o-aminodiphenylamine, 2,6,4'-trimethyl 1-3 • -nitro-4-aminoazobenzene, 5-methyl-4-methoxy-2-amino-2'-chloro-1-nitroanzobenzene, 4-phenyl-azo-1-naphthylamine, m - and p-aminoacetanilide, N-benzoyl-m- and p-phenylenediamine, sulfaniiamide, metanilamide, orthanilamide, m- and p-amino-iT-methylacetanilide, o-, m- and p-aminobenzamide, 4- and 5-aminosalicylainide , 2-aminophenol'-4-sulfonic acid, 6-amino-4-nitrophenol-2-sulfonic acid, 2-aminophenol-5-sulfonamide, 2-amino-2'-methyldiphenylether-4-sulfonic acid, 4-aminoazobenzene, 4-aminoazobenzene -4'-sulfonic acid, 4-aminoanzobenzene-3,4'-disulfonic acid, orthanilic acid, metanilic acid, sulfanilic acid, 6-methylmetanillic acid, 2-amino-5-chloro-4-methylbenzenesulfonic acid, 5-chlorothanilic acid, aniline-2,5-

^. ..- ^, .i ^ 909849/1527

BATH ORIGINAL

disulfonic acid, 4-chloro-5-methylorthani: iinsäura _f 4-methoxyorthanilic acid, 2,4-dimethylani lin-6-ßulfonic acid, 2-amino-4-trifluoromethylbenzenesulfonic acid, 3,4-dichloroaniline-6-sulfonic acid, 3,5-dichloroaniline -6-sulphonic acid, 3-methoxyaniline-6-sulphonic acid, 4-kethylaniline-2-sulphonic acid, dehydrothiotoluidinsulphon acids, 2-amino-naphtha in-4, 8-disulphonic acid, 2-aminonapbthalene-6-sulphonic acid, 2-aminonapbtbalin -6,8-disulfonic acid, 2-amino-1-napbtbol-4-sulf acid on, i-Aminonapbtbalin 4-, 5-, 6- and 8-su3fonsäuren, 2-Aminonapbtbalin-517-dieulfonsäure, 2-Ami nonapbtbalin -7-sulfonic acid, 2-aminonaphthbain-1-sulfonic acid, 'p-phenylenediamine-2-aminonapbtbalin-1,5-disulfonic acid, 3,3'-dichlorobenzidine, BenEidin-3 »3'-disulfonic acid; 2,2'-I) iobloro-3,3'-dimetboxy-4,4'-diaminodipbenyl, 4'-aminopyridine, 2-aminopyridine-N-oxide, 3-aminopyridine, 2-aminobenzothiaol _t 4-, 5- or 6 -Aminocbinoline.

The coupling components that are used with the above-mentioned diazo components for the preparation; of azo dyes ^ according to of the invention can be used, the Metbylolbaren bond or contain a precursor. But they can also be used with diazo compounds that have such bonds. Optionally, as indicated above, the methyIoIbaren banding to a existing azo dye can be attached to the components which was not methylolatable Had ties.

Examples of ethylolatable compounds that can be used as Coupling components can be used, - are:

3,3 '- (Pbenylimino) bispropionamide, 3,3' - ^ T6-Amino-2-naphthyl) -3ulfonylimino7-dipropionaiaid, 3,3 '- ^ S-hydroxy-1-naphthyl) -sulfonylimino7-dipropionamide, 3,3 '- / p- (5-hydroxy-3-metbyl-1-pyrazo} yl) -phenylsulfonylimino7-dipro ~ pionamid, 8-j y6-> m- ^ b "is- (2-carbamylethyl) -sulfamyl7-anilinoj-4-hydroxy-8-triazin-2-yl | -aminoj -i-naphtbol-3-, 6-

909849/1527 BAD OBlGINAt

disulfonic acid, U, N-bis- (2-carbamylethyl) ~ p- (5-hydroxy-5-metby1-1-pyrazolyl) -benzamide, N, W-bis- (2-carbamylethyl) -5-hydroxy-i- naphthamide, 6-amino-IT, iI-bis- (2-carbamylethyl) -2-naphthamide, 1-acetamido-8-naphthol-3,6-disulfonic acid; i-Benzamido-S-naphthol ^, 6-disulfonic acid, 3-acetamido-5-napthol-7-sulfonic acid, 2- or 3-benzamido-5-naphthol-7-sulfonic acid , 2-aminonapbtbalin-6,8-disulfonic acid and 2-aminonapbtbalin-6-sulfonic acid.

Examples of non-metabolizable compounds that are used as Coupling components that can be used are:

Aniline, o-toluidine, m-toluidine, 2,5-xylidine, o-anisidine, m-anisidine, ^ - metboxy-S-metbylaniline, 2,5-dimethoxyaniline, N-metbylaniline, N-metbyl-o-toluidine, N-metbyl-m-toluidine, N-ethyl-o-toluidine, N-metbyl-2-metboxy-5-metbylaniline, lί-ethyl-2-ffietboxy-5-metbylaniline, H-metbyl-m-anisidine, 1-amino-e-napbtbol-ö-sulfonic acid, 1-amino-8-napbtbol-3,6-disulfonic acid, 1-amino-8-napbtbol-4,6-disulfonic acid, i-Metbylamino-e-naphthobol-6-sulfonic acid, 2- or 3-amino-5-naphthobol-7-sulfonic acid, 2-methylamino-5-napbtbol-7-sulfonic acid, 1-amino-8-napbtbol-2,4-disulfonic acid, 1-amino-8-napbthol-4-sulfonic acid, 3-methyl-5-pyrazolone, 1-pbenyl-3-methyl-5-pyrazolone, 1- (4-sulfophenyl) -3-ethyl-5-pyrazolone, 1- (4-Cblorpbenyl) -3-metbyl-5-pyrazolone, 1-pbenyl-3-carbätboxy-5-pyrazolone, Acetoacetanilide, 4'-sulfo-acetoacetanilide, Bis-acetoacetbenzidide, bis-acetoacetbolidide, acetoacettolidide, m- and p ~ aminoacetanilide, m- and p-amino-N-metbylacetanilide, 1-Napbtbol-6-sulfonic acid, 3-hydroxy-2-naptatbamide, 3-carbamyl-2-napbtbol-1,6-disulfonic acid, K - ^ - Aminoätby ^ -N-ätbyl-m-toluidin, Beta-bydroxynapbtboesäure, Arylides of various napboic acids, e.g. 2-hydroxy-3-naphtbanilide, 2-hydroxynapbtbyltoluidine and like that. Many other coupling components and diazo components are known and can be used. In order to obtain the preferred azo dye residues, the

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Coupling and / or the diazo component is a solubilizing component Group included.

A particularly preferred class vO ^: n ""A2; öfarbatoffr-esten are the monoazo compounds which contain 1-3 sulfonic acid groups.

The various anthraquinones and other polychinoids Structures commonly known as vat dyes can be used. Vat dye residues with solubilizing groups, e.g., free sulfonic or carboxylic acid substituents, are preferred.

Examples of anthraquinone compounds which are used for the preparation of the dyes according to the invention can are:

1-Amino-4- (4'-aminoanilino) -anthraquinones, 3'-disulfonic acid, 1-methylamino-4- (4'-aminoanilino) -antbrachinone-2,3 '■ disulfonic acid, 1-amino-4- (4 '-aminoanilino) -anthraquinone-6,3'-disulfonic acid, 1-amino-4- (4'-aminoanilino) -anthraquinone-2,3', 5'-trisulfonic acid, 1-methylamino-4- (4'-aminoanilino ) anthraquinone-6-sulfonic acid, 1-methyl-amino-4- (4'-aminoanilino) -anthraquinone-6,3'-disulfonic acid, 1-cyclohexylamino-4- (4'-aminoanilino) -6-sulfonic acid, 1 -Methylami-110-4- (3'-aminoanilino) -anthraquinone-6-sulfonic acid, 1-amino-4- (3'-aminoanilino) -anthraquinone-2,5-disulfonic acid, 1-amino-4- (4 ' - ^ 4 "" - aminopheny lazo7-anilino) -anthraquinone-2,5,2 "-trisulfonic acid, 1-amino-4- (4 ^% - /% ⁿ -aminophenyl7-anilino) -anthraquinone-2,5,3" -trisulfonic acid, 1-amino-4- (4'-aminoanilino) -anthraquinone-3'-sulfonic acid, 1-amino-4- (3'-aminoanilino) -anthraquinone-4'-sulfonic acid, 1-amino-4- ( 4'-aminoanilino) anthraquinone-2-sulfonic acid, 1-amino-4- (3'-amino-4'-methylanilino) -anthraquinone-2-sulfonic acid, 1-amino-4 ~ (4'-amino-3 ' -methylanili no) -anthraquinone-2-sulfonic acid, 1-amino-4- (3'-amino-4 ', 6 ^l -dimethylanilino) -anthraquinone-

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- H-

2-sulfonic acid, 1-amino-4- (4'-aminoanilinoV-anthraquinone-3 '-sulfonic acid diethylamide, 1-amino ^ -bromantbrach Jjion-2-sulf onic acid, 1-amino-4-bromontbraebiri.on.-2,5-disulphonic acid 1-aminb-4-bromantbracbinon-2 »6-disulfona acid, .1-amino-4- ■ bromoanthraquinone-2, 7-disulfonic acid and 1-amino-2,4-dibromanthraquinone. -

Among these, the preferred class follows through de formula?

NH-E

wherein Y is a hydrogen atom or a sulfonic acid group and R is an aryl radical which can be substituted, in particular with solubilizing groups, such as sulfo- or carboxyl groups.

The class of anthrone dyes derives 3icb from the anthraquinone class by cyclization in the 1.9 position. These dyes represent a highly specialized class, which are characterized by their color shade range from orange to red and their generally good lightfastness. Many substituted anthrone dyes can be used as starting materials for the invention. These include, for example, the following: Pyrazolanthrones, such as 3,3'-Disulfon-5- (4 ^l -aminoanilino) -pyrazolanthrone and 2-Me'thy 1-4 *, 8-disulf o-5- (3'-aminoanilino) -pyrazolanthrones; Anthrapyrimidones such as 4,3'-disulfo-6- (4'-aminoanilino) anthrapyrimidines; Anthrapyrimidones, such as 3-methyl-4,4'-disulfo-6- (3 ^l -aminoanilino) -

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antbrapyrimidone and 3-ethyl-8,3'-disulfo-6- (4'-aminoanilino) anthrapyrimidone; and antbrapyridaz ones, such as the 2- (4'-sulf © phenyl) -6- (4 "-SuIfO ^" -aminoanilino) -anthrapyridazones.

A preferred class of antron dyes are the antbrapyridones, which are lightfast, bell-red dyes. represent. This preferred class can be represented by the following structural formula:

- Y

NHAr

where Y is hydrogen or the sulfonic acid group, R is an alkyl, aryl or acyl radical, R ^{1 is} a hydrogen atom or an alkyl radical and Ar is an alkyl radical which can be substituted, in particular with solubilizing groups such as sulfo or carboxyl groups.

The Pbthalocyanineruppe is a particularly stable and strongly colored chemical structure. Various amino-substituted phthalocyanines, including many those sulfonated or carboxylated or otherwise substituted with an acidic group can be used will. Amino groups can sit directly on the phthalocyanine rings or in a side chain, e.g. in the form an aminomethyl group. Such products can be made from Phthalocyanine itself by treatment with methylol

90984 9/1527

phthalimide and sulfuric acid as described in U.S. Patent No. 2,761,868. The sulfonation can take place at the same time under favorable conditions and up to 4-amino methyl groups can be used can be easily introduced as well as up to 4 sulfonic acid groups. Phtbalocyanine carboxylic acids can also be used in be aminometbylated in the same way. Similarly, ■ phthalocyanines substituted on the ring, such as those which 1 "to 4 chlorine atoms contain, sulfonated or be aminomethylated. The total number of substituents on a phthalocyanine molecule should not exceed 9. The phthalocyanines are either as metal-free phthalocyanines or in the form of their copper, cobalt, Nickel or other metal complexes are used. The copper phthalocyanine residues containing 2 or 3 sulfo groups, are preferred.

The dyes of the present invention differ from known dyes in that 1 or 2 hydrogens off atoms of a known paraffin molecule the following remainder are replaced:

OH ₂ OH ₂ OO ₁ TCH ₂ O,

Y-N

wherein R, R ¹ and Y have the above meaning.

The metabolizable bond, viz

CH ₂ CH ₂ CONH ₂
HN

^N CH ₂ CH ₂ CO NH ₂ ,

909849/1527

or the legacy bond

H-N

■ GH ₂ OH ₂ CN

CH ₂ CH ₂ CU

can be attached to any of the above-mentioned components by reacting iminobispropionamide or iminobispropionitrile with dye precursors or dyes, the residues have, such as an acyl (e.g. suIfo-, carboxy- or triazinyl) or an acyl halide (e.g. halosulfonyl, halo carbonyl or halotriazinyl) radical or have a reactive halogen, mercapto or phenolic hydroxyl group.

The dyes according to the invention are prepared by various alternative routes in which an iminobispropionitrile or iminobispropionamide function is linked to the paraffin portion or a part thereof. In the event that an iminobispropionitrile function is attached, the titrile radicals are then hydrolyzed to amido radicals. The final step consists in the '.Disposition of the amide functions with formaldehyde or a formaldehyde-releasing agent in order to introduce at least one ethylol group on the amido function. The first step in the overall production is the reaction of ^T : n iminobispropionitrile or iminobispropioamide with a dye or a dye precursor or a . Examples of such alkylating or acylating groups are: chlorosulfonyl, chlorocarbonyl,

909849/1 527

Carboxylic anhydride, halogenated methylaryl, activated Haloaryl (e.g. o- or p-nitrohalogenaryl), activated Vinyl (e.g. vinyl aryl sulfone), mono- and dihalo-s-triazinyl etc.

This reaction can be carried out under ordinary conditions such as an aqueous or non-aqueous one Medium in the presence of an acid binder, such as alkali carbonate, alkali hydroxide or a tertiary organic amine. It is not necessary that the acylating or alkylating group be complete Represents dye molecule. It can be provided by part of a dye residue e.g. by a coupling or diazonium component, those for the production of azo dyes or a mono- or dihalotriazine structure. 'suitable. is. The iminobispropionitrile or iminobispropionamide radical can optionally be incorporated into a dye or dye Vorlauf he introduced by direct cyanoethylation provided that the dye or dye forerun it contains an amino function that cyanoathylates. can be. Examples of such functional groups are the sulfamyl, carbamyl and amino groups.

If a bispropionitrile results from the above-mentioned reactions, it is used to convert the Cyano groups hydrolyzed to amido groups. The hydrolysis is carried out in an aqueous medium in the presence of an acid, such as sulfuric acid, and at room temperature, or carried out by treatment with alkaline hydrogen peroxide. If this is preferred, the hydrolysis step can be preceded by other steps that are necessary, to convert a coupling or diazo component into an azo dye «

The iminobispropionamide intermediates obtained in the hydrolysis reaction be easily in the finished

909 8 4 9/1527

BATH ORIGINAL

materials according to the invention converted, by reacting with at least 2 moles of formaldehyde and preferably with an excess at temperatures in the range of 20 - 65 ⁰ C, at a pH above the neutral point, for example, - 90 ⁰ C and preferably in the range of 20 pH 7.2 to about 10 treated until methylolation was complete. The methylol groups can be converted into alkoxymethyl groups by treatment with an alkanol in a strongly acidic medium.

With a suitable choice of solvents, the above synthetic steps can be equally successful can be used for the synthesis of dyes which do not contain any water-solubilizing groups. The received Dyes can be used on silk, nylon and wool by the usual dyeing processes and result in dyeings with superior color fastness.

The compounds obtainable according to the invention are, such as above, especially for the coloring of .polyr meren substances are suitable, which are characterized by a content of reactive hydrogen atoms. they show an extraordinarily high color yield, when properly applied, and can either alone or at the same time as textile auxiliaries to ensure both color and crease resistance to confer a level.

Among the polymeric materials that are particularly favorably treated with the dyes according to the invention, the cellulose derivatives such as rayon and cotton, super polyamides such as nylon, are natural proteinaceous Fabrics such as wool, silk, casein, zein and hair, and synthetic resins such as the phenolic resins.

909849Λ1527

The application process for the dyes according to the invention follows the usual techniques for use known methylated dyes. Her dye is in an aqueous medium with an acidic catalyst · is dissolved and the fabric or fiber is immersed in it. After a sufficient period of immersion the fabric or fiber is removed, dried 'and then to fix the dye on the substrate heated. Various suitable application techniques are illustrated in the following examples.

The following examples illustrate the invention Further.

Example 1:

SO ₅ Well

-SO ₂ N (CH ₂ CH ₂ C-NHCH ₂ Oh) ₂

■ SOjNa

A. m-Nitro-N, N-bis (2-cyanoethyl) -benzenesulfonamide

-SO ₂ N (CH ₂ CH ₂ CN),

909849/1527

10, Og (0.045 m) of m-nitrobenzenesulfonyl chloride, followed van 5.6 g (0.045 m) of 3,3'-iminodipropionitrile are added to 50 ml of pyridine stirred, the temperature being maintained at 15- 2O ⁰ C. The solution is then heated for 2 hours at 5O ⁰ C. It is then concentrated under reduced pressure until a precipitate begins to appear and is finally poured into 400 ml of a well-stirred ice-water mixture. The precipitate is filtered off, with 1.5. Liters of ice water and dried in vacuo at the temperature of the ambient dried to give 13.1 g (94% of theory) of m-nitro-N, N-bis- (2-cyanoethyl) benzenesulfonamide P 137 - 138 ⁰ C is obtained .

B. 3,3'-ZTm-nitrobenzenesulfonyl) -imino7-bispropionamide

Il

To 250 ml of stirred concentrated sulfuric acid at temperatures below 20 ⁰ C in portions 77.8 g (0.253 m) of m-nitro-N, N-bis- (2-cyanoätbyl) -benzenesulfonamide added. After completion of the addition, the solution is stirred for 5 hours at room temperature to .2 liters of well-stirred ice-water mixture poured, filtered and the Piltrat is adjusted by addition of concentrated ammonium hydroxide at 15 ⁰ C to pH 20. 8 The precipitate is filtered off, washed with 500 ml of water and air-dried, 75.5 g (87 $ of theory) 3,3'- ^ Tm-nitrobenzenesulfonyl) -imino7'-bispropionamide in the form of a light beige powder of P 199 - 200 ° C.

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C. 3 * 3 '-metanilyliminobisproOionamide

( λ -SO ₂ K (CH ₂ CH ₂ C-NH ₂

A well stirred mixture of 600 ml of water, 58.1 g (1.04 m) of iron powder and 12 ml of glacial acetic acid is heated to 70 ⁰ C, and then 131> 1 are partly g (0.38 m) of 3,3 '- ^ Cm-nitrobenzenesulfonyl) -imino7-bispropionamide added. The temperature at the end of the addition 9O ⁰ C and the mixture is then further 45 minutes at 90 - 95 ⁰ C stirred. The mixture is then ^{cooled to 75 °} C., and 250 ml of hot ethanol are added, followed by so much solid sodium carbonate that the soluble iron salts precipitate. Then activated charcoal is added and the warm mixture is filtered through diatomaceous earth, and the filtrate is cooled to 0-5 ° C. for one hour. The precipitate obtained is filtered off, / ater washed with 500 ml of ice-Y and dried in vacuo at 55 ⁰ C. Yield 106.6 g (89 % of theory) 3,3'-metanilyliminobispro-. pionamid in the form of very light tan crystals from P 182 to 183.5 ⁰ C

SO ₃ Na

-SO ₂ N (CH ₂ CH ₂ C-NH ₂ )

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1.98 g of cuprous chloride, 16.88 g (0.30 mol) of sodium bicarbonate, 29.58 g (0.056 mol) of 93.4 % sodium 1-amino-4-bromo-anthraquinone-2 are added to 200 ml of water sulfonate and 28.30 g (0.09 mol) of 3,3'-metanilyliminobispropionamide were added. The mixture is stirred slowly and heated ^{to 80 ° C. within 1 hour.} After 1 hour at 80 ^° C., 100 ml of water are added. Then 2 hours at 79 is - 81 ⁰ C stirred. After completion of the reaction, the product is filtered off hot and washed with 400 ml of water at 50 ⁰ C. The moist filter cake is reslurried in 2.5 liters of water at 87 ° C, 20 ml of ammonium hydroxide are added, and the mixture is heated to 95 ° C. To the resulting solution, 30 g of salt is added to precipitate the dye product. The product is isolated and washed with water. Then it is redissolved in 2.5 liters of water at 95 ^° C., and 20 ml of ammonium hydroxide are added. 30 g of salt are gradually added to the solution and the whole is stirred at room temperature and filtered. The moist cake is slurried again in acetone, sucked dry and dried ^{at 55 ° C. in vacuo.} Yield 21.40 g of a dark blue solid.

-SO ₅ Na

-SO ₂ N (CH ₂ CH ₂ C-NHCh ₂ OH) ₂

-SO ₃ Na

Sulfonation and methylolation

To 10 ml of cooled # 99.5 ml sulfuric acid 10 30 # fuming sulfuric acid is added, and .the mixture is cooled to 0 ⁰ C. Then be stirring

90984 9 / 1527-

2.0 g of the product from stage D were added over the course of 15 minutes. After stirring in an ice bath for 2 hours, the mixture is allowed to come to room temperature and stirred for a further 3 hours at room temperature. Then the reaction mixture is poured onto 100 g of ice, filtered and sucked dry. The moist cake is dissolved in 10 ml of water with the addition of 5N sodium hydroxide solution up to pH 9.5. To this end, 15 ml of 37% formaldehyde solution, which was previously buffered to pH 9.5, are added with stirring. The mixture is stirred for 6 hours at pH 9.5 at a temperature of 60 - 62 ⁰ C stirred and then poured into 500 ml of isopropanol. The product is filtered off, washed with acetone and dried in vacuo at room temperature. Yield 2.30 g of a dark blue product.

If, using the method described below, cotton is dyed in a 1.5 $ shade by padding with 20 # magnesium chloride, based on the weight of the dye (OWD) as an acid catalyst, at pH 4, a red-blue shade is obtained. The coloring is very moist, press-fast, wash-fast and sweat-fast. The fixation of the dye on the cotton is about $ 75.

' Method for staining blocks

A 1.5 # "by weight of fabric"("OWF") tint is obtained using 0.75 grams of dye per 50 ml of water. A 2 $ tint is obtained by using 1 g / 50 ml of "OWF" _. . *

The dye is pasted with water until it goes into solution. It is then made up to 100 ml and the pH is adjusted to 4-7, if necessary by

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Addition of an acid, usually hydrochloric acid. As a catalyst, one of the following is used

a. Magnesium chloride

b. Ammonium chloride
ο. Ammonium sulfate

d. Ammonium gluconate

e,! priethanolamine hydrochloride

added, the amount being 10 to 40 $> _r based on the weight of the solid dye, preferably 10 to 20 IO catalyst "OWD" (ie based on the weight of the dye).

The dye solution is placed on a 7 inch yard (17.8 cm) wide 80 square cotton padded under Application of a dip and a squeeze. The padded cotton is then dried.

The dry, padded cotton is then 5 minutes to 30 seconds at 135 thermally fixed to 190 ⁰ C, preferably from 1 1/2 minutes at 177 ⁰ C. Then it is soaped at the boil 5 minutes, rinsed and dried.

The amount of dye fixed on the fiber is then quantified by either of the following two methods certainly:

1. Comparison of the spectrophotometric reflection curve of dyed cotton before and after soaping.

2. Extraction of the dye from the tissue by dissolving the colored tissue in concentrated sweat

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acidic, dilute with ice water and measure the spectrophotometric transmission of the solution.

A comparison of the curve of the dyed cotton before and after soaping is given as the percentage fixation of the dye - expressed on the cotton.

Example 2

NaO, S- ( _v , YN C-OH

CH,

The cold aqueous diazonium solution obtained from 15.72 g (0.05 M) 3,3'-metanilyliminobispropionamide is dissolved in a solution of 12.72 g (0.05 M) 3-methyli-p-sulfophenylpyrazoline -5-one in 300 ml of water containing 20.8 g (0.2 M) sodium carbonate, stirred. The reaction mixture is stirred at room temperature for 2 hrs., The pH is adjusted with dilute hydrochloric acid to 6.9, then heated to 5O ⁰ C, with stirring pure salt is added to precipitate the dye, and the slurry in an ice water bath cooled to 5 ^{0 C.} The product is filtered, washed three times with 50 ml of 15% saline solution and then with 10 ml of v / ater and dried at 55 ⁰ C in vacuo. Yield 32.0 g of an orange dye of 80 # purity (85 # theoretical yield).

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A solution of 12.03 g of the above dye in 100 ml of water is adjusted to pH 9 * 5, - and then 32.43 g of 37 # aqueous formaldehyde are added, whose pH value is previously set to 9, 5. The mixture is ^{stirred at 65 °} C. for 6 hours, the pH value being kept at 9.5, then it is cooled and poured into 2.0 l of well-stirred isopropyl alcohol. The precipitate is filtered off, washed with 500 ml of isopropyl alcohol, followed by 700 ml of ethyl ether and dried in vacuo at room temperature, 12.24 g of a yellow dye being obtained.

By pad dyeing on cotton in 1 ×, 5 # shade under Using 20 # magnesium chloride OWD a light green yellow is obtained. The fixation at pH 6.1 is 90 #, at pH 4.0 95 #. Both colors are excellent Resistance to wet pressing, washing and perspiration.

Example 3

so

HO

-N = N

N-

- SO ₅ Well

CH,

The cold, aqueous diazonium solution, which consists of 15.72 g (0.05 M) o-amino-N, N-bis (2-carbamylethyl) -benzenesulfonamide is obtained is in. a solution of. 12.72 g (0.05 M) 3-methyl-1-p-sulfophenylpyrazolin-5-one in 300 ml of water,

90 9-8 49/1527

containing 20.8 g (0.2M) sodium carbonate was introduced. The solution is stirred for 45 minutes at room temperature, then the pH is adjusted with dilute hydrochloric acid to 6.5 and the solution filtered through diatomaceous earth. · The filtrate is heated to 5O ⁰ C, and then g stirring 162 salt is added in portions . The precipitate is filtered off and then washed twice with 100 ml 20 # sodium salt solution with 50 ml of 10 $ sodium chloride solution and dried at 55 ⁰ C in vacuo. Yield 43.3 g of an orange powder.

A solution of 12.03 g of the above dye in 150 ml ' Water is adjusted to pH 9 »5, and then 32.43 g of a 37 # aqueous formaldehyde solution of pH 9» 5 admitted. The reaction mixture is kept at pH 9.5 and 65 ° C. for 6 hours, then cooled to 25 ° C. by means of diatomaceous earth filtered, and the filtrate is poured into 3 liters of well-stirred isopropyl alcohol. The precipitate is filtered off, washed with isopropyl alcohol and ether and dried in vacuo at room temperature. Yield 6.80g of an orange powder.

Cotton is dyed with the product by padding it in a $ 2 tint. B _e i using 10% OWD ammonium chloride at pH 6.1 is the fixation of 83%. When using 20 i »OWD magnesium chloride at pH 4, the fixation is 86 ^. In both cases, a light, green-yellow hue is obtained on the cotton.

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Example 4

SO ₂ U / _{OH 2} CH ₂ C-NHCH

By slurrying 27.38 g (0.085 M) .3-Methy1-1- (2,5-dicblor-4-sulfophenyl) -pyrazolin-5-one in 600 ml of water, adjusting the pH to 7.0 and adding A coupling solution is prepared from 36.04 g (0.34 M) solid sodium carbonate. A cold diazonium solution obtained from 26.73 g (0.08-5 M) 3,3'-methanilyliminobispropionamide is added to this. The reaction mixture is stirred at room temperature for 2 hr., Heated to 50 ⁰ C, and then salt is added to precipitate the product which was filtered off, washed five times with 50 ml of 20 # sodium chloride solution and dried at 6O ⁰ C in an atmosphere furnace will. Yield 83.2 g of a yellow dye.

A solution of 75.27 g of the above dye in 200 ml of water is adjusted to pH 9.5, and then 120 g (1.48 M) 37% aqueous formaldehyde, the pH of which was previously adjusted to 9, 5 was set, added. The 'mixture is ^{stirred for 6 hours at 65 °} C., the pH being kept at 9.5, then cooled and poured into 3.0 1 of well-stirred isopropyl alcohol. The precipitate is filtered off and in vacuo at room temperature

909849/1527

dried to give 34.63 g of a yellow dye.

Block dyeing on cotton gives a light, greenish-yellow shade of 2% dyeing. 20 # OWD magnesium chloride at pH 4 - as an acid catalyst gives a color of excellent resistance to wet pressing, Wash and perspiration and good resistance to abrasion. The fixation was .83 ^.

Example 5

NaO, S-

When using 3-amino-4-methoxy-N, N-bis- (2-carbamylethyl) -benzenesulfonamide in the method of Example 2 (prepared from 3 ^ nitro-4-methoxyben2olsulfonyl chloride by the method of Examples 1A, 1B and 1C) , the result is a product with an actual dye content of 80 # and a total formaldehyde content of 4.5 ° · It dyes cotton light yellow with pad dyeing in 2 ^ tones using 10 # OWD ammonium chloride at pH 5.6 · The fixation is 88 $>, The coloring is very real to wet pressing, washing and perspiration.

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· <, 1544150 \

Example 6

ΟΗ, ΟΝΗ

-N = N-
-SO ^ Well

Il

SO ₂ N ^ h ₂ CH ₂ C-NH (CH ₂ OH) ₀

To a slurry of 15.97 g (0.05 M) of H-acid in 225 ml of water, enough 20 # strength aqueous sodium hydroxide solution is added until phenolphthalein indicator paper shows a positive reaction, and the solution obtained has enough 20% # Acetic acid added so that blue litmus paper indicates a positive reaction. The solution is ^{cooled to H 0} C in an ice-water bath, and then 9 ml of acetic anhydride are added all at once, the temperature rising to 17 ⁰ C taking place. The ice bath is removed, the solution is stirred for 1 hour and then so much solid sodium carbonate is added that the reaction against phenol-pbbalein indicator paper is positive. The solution is then ^{heated to 45 °} C. for half an hour, cooled, and the pH value is adjusted to 9.9 with sodium carbonate. In this solution of acetyl-H-acid an aqueous diazonium solution is then stirred in the cold, which was obtained from 15.72 g (0.05 M) 3,3 ^f -metanilyliminobispropionamide, prepared according to Example 1 C., and which The reaction mixture is stirred for 1/2 hour. The solution is adjusted to pH 6.5, stirred with activated charcoal for 15 minutes, filtered through diatomaceous earth, and the piltrate is poured into 3.0 l of well-stirred isopropyl alcohol. The precipitate is filtered off, washed with a mixture of 500 ml of isopropyl alcohol and 100 ml of water and dried ^{at 55 ° C. in vacuo.} Yield 4-6.7 g of a brownish red dye. His solution

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18.74 g of the above dye in 100 ml of water is adjusted to pH 9.5, and then 32.43 g of a 37 # aqueous formaldehyde solution of pH 9.5 are added. The reaction mixture is ^{stirred for 6 hours at 65 °} C., the pH being kept at 9-5, then filtered while warm and the filtrate in 3.0 l of well-stirred isopropyl alcohol. poured. The precipitate is filtered off, washed with 500 ml of isopropyl alcohol and then with 700 ml of ethyl ether and dried in vacuo at room temperature. Yield 19.01g dye.

When dyeing cotton in a 2 # shade using 20 $> OWD magnesium chloride and pH 6.5, a brownish-red shade is obtained which is very fast to wet pressing, washing and perspiration.

Example 7 pN = N- 0
M. 1-SO ₃ Na pil ρ we
I. NaO ₃ S -Ll

Il

Sufficient solid sodium carbonate is added to a solution of 18.66 g (0.05 M) acetyl H acid (pH 7.0) in 300 ml water to bring the pH to 9.9. A cold, aqueous diazonium solution, which was obtained from 15.72 g (0.05 M) o-amino-N, N-bis (2-carbamylethyl) -benzenesulfonamide, is then stirred into this solution, and the reaction mixture becomes half Hour stirred. The solution is adjusted to pH 7.4 with dilute hydrochloric acid, ^{heated to 50 °} C.,

S098A9 / 1 527

and 4-40 g of sodium chloride are under. Stirring added. The slurry is cooled to room temperature and the precipitate is filtered off, washed with 200 ml of 20 # brine and air dried. The near dye is placed in 500 ml of dimethylformamide, stirred for half an hour at 50 ° 0, filtered, and the filtrate is poured into 3 l of well-stirred isopropyl alcohol. The resulting precipitate is filtered off, washed with 500 ml of isopropyl alcohol and dried ^{at 55 ° C. in vacuo.} Yield 11.99 g of a dark red-brown powder.

A solution of 11.44 g of the above dye in 150 ml of water is adjusted to pH 9 »5, and then 32.43 g (0.4 M) of a 37 % solution. aqueous formaldehyde solution of pH 9.5 was added. The solution is stirred at 65 ⁰ C pH 9.5 for 6 h., Cooled to 25 ° C, filtered through diatomaceous earth and the Piltrat is poured into 3 1 well stirred isopropyl alcohol. The precipitate is filtered off, washed with 250 ml of isopropyl alcohol and dried in vacuo at room temperature. Yield 9.05 g of a dark red powder.

When pad dyeing the product on cotton in 2 # tint OWP using 10 # OWD ammonium chloride a coloration of brownish red-orange tint is obtained. The fixation is $ 86.

Example 8

0 CH ₃ CNH

ti

OH

SO ₅ Well

OCH

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1 54A350

If in Example 7 "17.20 g (0.05 M) of 3-amino-4-methoxy-N, N-bis (2-carbamylethyl) -benzenesulfonamide is used, a yield of 75.7 g of a red dye with 47 # real dye content is obtained. The methylolation a 30.42 g sample provides 26.36 g of one red dye a of 47 # dye content that is 2.49 # Contains formaldehyde and dyes cotton in light blue shades of red.

When puking cotton, a strong blue-red hue is obtained. The fixation is 92 # when 10 $> ammonium chloride is used as a catalyst at pH 4. The fixation is 90% when 20 i »magnesium chloride are used as catalyst at pH 6.0. The resistance to wet pressing, washing and perspiration is excellent.

Example 9

OH

It

SO ₂ IiZC ^- H ₂ CH ₂ C-NHCH ₂

SO ₅ Well

If you add 12.03 g of the dye obtained by coupling diazotized 3-amino-4-methoxy-N, N-bis (2-carbamylethyl) -benzenesulfonamide in an alkaline solution of 5-hydroxynaphthalene-1-sulfonic acid was obtained, methylolated by the usual method, 6.05 g of a dye are obtained, which gives a red tint on cotton.

The block dyeing of cotton in 2 % tint results in a brick-red color. The fixation is 80 # if 10 #

909849/1527

Ammonium chloride can be used as a catalyst at pH 4. The authenticity to moist pressing, washing and perspiration is excellent.

example 10 0 π CH ₅ C-NH
ι

OH

N = N

SO ₅ Well

SO ₂ N (CH ₂ CH ₂ CNHCh ₂ OH)

9.4 g (0.03 mol) of p-amino-N, N-bis (2-carbamylethyl) -benzenesulfonamide are dissolved in a mixture of 100 ml of water and 20 ml of concentrated hydrochloric acid. The solution is ^{cooled to 0 °} C. with ice, stirred, and then a solution of 2.31 g (0.033) sodium nitrite in 30 ml ^ water is added. Ee is stirred for half an hour, the solution being kept cold by the periodic addition of ice. Excess nitrous acid is destroyed with sulfamic acid, giving 225 ml of diazo solution *

9.58 g (0.03 M) Η-acid are dissolved in 100 ml of water with 5N sodium hydroxide. This solution is cooled with ice and 10 ml of acetic anhydride are added. The solution is stirred for half an hour and then 31.6 g (0.3 M) sodium carbonate is added. The diazonium compound obtained above is added rapidly with stirring. The coupling takes place immediately. The solution is stirred for half an hour, ^{heated to 40 °} C., and 100 g of salt are added. Then, the mixture is cooled to room temperature, filtered, washed with 15 $ 6-saline and in a vacuum oven at 6O ⁰ C and then at

90 9 8 49/1527

100 ° C dried. 21 g of dye are obtained in this way.

20 g of the above dye are mixed with 100 ml of water, the pH of the slurry is adjusted to 9.5 set, 33 g of 37 # formaldehyde solution are added * and the mixture is stirred for 6 hours at 65 ° 0, keeping the pH at 9.3 to 9.5. Then 2000 ml of isopropanol are added, the solution is filtered off and the pests are washed with 300 ml of isopropanol. The product is in a vacuum « oven dried at room temperature.

Example 11

A solution of 37.9 was added to a solution of 31.5 (0.11 M) sodium 4-aminodiphenylamine-2-sulfonate in 500 ml of water, which contained 16.4 g (0.2 M) of sodium acetate g (0.10 m) of 4-chloro-3-nitro-N, N- (2-carbamylethyl) -benzenesulfonamide in 75 ml of water and 100 ml of dioxane were added. The partial solution obtained is heated within three hours at 9O ⁰ C, held for one hour at 90 ⁰ C, cooled to 6O ⁰ C and filtered through diatomaceous earth. The filtrate is reheated to 6O ⁰ C and treated with sufficient sodium chloride that the product precipitates. The filtered product is washed with 200 ml of 10% salt solution and ^{dried at 55 °} C. in an atmosphere oven. Yield 43.6 g of a yellowish brown powder.

A solution of 12.58 g of the above powder in 150 ml of water is adjusted to pH 9.5 and 32.43 g of a 37 #

aqueous formaldehyde solution of pH 9.5 added. The solution is kept for 6 hours at pH 9.5 and 65 ^° C., then ^{cooled to 25 °} C., filtered through diatomaceous earth and the filtrate is poured into 3 liters of well-stirred isdpropyl alcohol "■ ··. ■■; · The precipitate is filtered off, washed with 500 ml of isopropyl alcohol and dried in vacuo at room temperature. Yield 10.61 g of a tan powder.

The product dyes cotton with a brownish-yellow tint of good fastness against wet pressing.

Example 12

SO ₂ N ^ h ₂ CH ₂ C-NH (CH ₂ OH) ₀ ,

1.4

To 70 ml of chlorosulfonic acid 11.5 g (0.02 m) of copper phthalocyanine are added with stirring and cooling so that the temperature does not exceed 30 ⁰ C., was added and the Eeaktionsmischung is then heated to 135 ° C and two hours at 135-137 ⁰ C, cooled, stirred at room temperature for 16 hours and poured into a well-stirred mixture of 165 ml of water, 94 g of sodium chloride and 150 g of ice.

909849/1527

The precipitate is filtered off and washed with 500 ml of ice-water washed. The moist sulfonyl chloride is with 100 g of ice * Slurried and 100 ml of water and adjusted the pH to 6.5. Then all at once a chilled mixture of 19.25 g (0.06 m) 3,3'-MetanUyliminofcispropionamid in 100 ml of acetone and -100 ml of water were added. The reaction

. mixture is stirred for 1 1/2 hours at room temperature and one hour at 43 ° C., the pH value increasing continuously

.6.5 is maintained, and then enough sodium chloride is added that the dye precipitates. The precipitate is filtered off, washed with 100 ml of saturated saline solution and dried in vacuo at room temperature. Yield 30.46 g of a green-blue dye. The crude dye is placed in 750 ml of water, the pH is adjusted to 7.5 and the solution at 50 ⁰ C is heated, filtered through diatomaceous earth, and the filtrate is poured into well-stirred 1 20.0 isopropyl alcohol. The precipitate is filtered off, washed with a mixture of 200 ml of water and 800 ml of isopropyl alcohol, followed by 250 ml of isopropyl alcohol, and dried ^{at 55 ° C. in vacuo.} Yield 19.37 g of the green-blue dye.

A solution of 18.26 g of the above dye in 100 ml water is adjusted to pH 9.5, and then 97.29 g of a 37 # aqueous formaldehyde solution of pH 9.5 are set to ^v. The reaction solution is stirred for 6 hours at 65 ° C., the pH being kept at 9.5, cooled and poured into 3.0 l of well-stirred isopropyl alcohol. The precipitate is filtered off, washed with 500 ml of isopropyl alcohol, followed by 400 ml of ethyl ether, and dried in vacuo at room temperature. Yield 18.91 g of a green-blue powder containing 5.06 # bound formaldehyde.

Block dyeing of the product in a 2 # shade on cotton gives a turquoise shade of excellent fastness to wet pressing. $ 90>

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Pixing is done by using 10 # ammonium sulfate OWD obtained as an acid catalyst at pH 5.7.

Example 13

SO ₅ Well

N ^ iB ₂ CH ₂ C-NHCH ₂ 0 ^ ₂

A solution of 7.85 g (0.021 m) of 4,4'-Diamino8tilben-2,2'-UiBuIfOnSaUTe in 75 ml water, 50 ml of acetone and 8 ml of 20? I-Katronlauge strength of 0- 5 ⁰ C is rapidly a A solution of 7.85 g (0.042 m) of cyanuric chloride in 70 ml of acetone was added. After half an hour the. pH adjusted to 6.5 with * NaOH, and then · we d _; ei, ne 'Aufsoblöm- /' ν · ;. mung of 3.38 g (0.042 m) 3.3 ^I -metanilyliminobispropionamide in 75 ml of water and 50 ml of acetone added. During the addition, the pH is hardened to 6-7 and the temperature below 10 ⁹ C. After one hour, the temperature is increased to 30 ^° C., a pH of 6.5 being constantly maintained. Then 4.37 g (0.047 m) of aniline are added and the reaction mixture becomes 2 1/2

Heated hours at 78 ° C to reflux, cooled to 25 ° C and the product filtered off, washed with 50 ml water and dried in an atmospheric oven at 55 ⁰ C. Yield 28.3 g of a yellow powder.

909849/1527

A solution of 26.8 g (0.02 m) of the above material in 150 ml of water of pH 9.5 is treated with 32.43 g (0.4 m) of a 37 # aqueous formaldehyde solution of pH 9.5 , and the mixture is heated with stirring for 6 hours at 65 ⁰ C, wherein the pH Ytert is constantly held at 9 ". 5 The. Solution is cooled to 25 ⁰ C, filtered through diatomaceous earth, and the filtrate is poured into well-stirred 3.5 1 of isopropyl alcohol. The precipitate is collected by filtration, washed with 1.5 1 of isopropyl alcohol followed by 300 ml of ither and dried in vacuo at room temperature. Yield 27.86 g of a product with a content of $ 3.18> formaldehyde (1.74 methyl groups) ♦

The compound has a high affinity for cotton even at room temperature and can be obtained from a detergent bath a non-ionic or anionic detergent or after the pad dyeing process. Under ultraviolet Light emits a blue fluorescence.

Example 14

NHO ₂ S-

909849/1527

ι 544

A slurry of 60.1 g (0.1 m) of the hydrochloride salt of JQkaliblaumonosulfonylchlorid in 1 l of ice and water is adjusted to pH 6.0 and with a solution of 28.6 g (0.1 m) 3.3 '~ ( p-amino, phenylimine) -bispropionamid-bydrocblorid in 100 ml of water at 0 - 5 ⁰ C was added. The mixture is slowly warmed to 45 ⁰ C, with a pH of 6.0 is maintained, held for two hours at 45 ° C, filtered through Diatömeenerde and the Piltrat is treated with sodium chloride at 25 ° C. The slurry is cooled to 25 ° C, filtered, and the residue is washed with 200 ml of 10 $ sodium chloride solution and dried at 55 ⁰ C. Yield 61.3 g of a blue powder.

A solution of 16.30 g of the above powder in 150 ml of water is adjusted to pH 7.5, and then 32.43 g of a 37 # aqueous formaldehyde solution of pH 7.5 are added. The solution is 24 hours at room temperatures - held (25 3O ⁰ C) and pH 7.5, then filtered through diatomaceous earth and the pH of the Piltrats is carefully adjusted to 6.5. The filtrate is then poured into 3 l of well-stirred isopropyl alcohol, and the precipitate is filtered off, washed with 500 ml of isopropyl alcohol and dried in vacuo at room temperature. Yield 14.3 g of a dark blue powder.

In the block dyeing of cotton, red-blue shades of good fastness to wet pressing are obtained.

Example 15

0 · ■ CH NH ₀

IJ

(HOCH ₂ -NHC-CH ₂ CH ₂ ) ₂ NO ₂ Sj ^ -N = N- (AfS -N =. N- [fVS0 ₂ N (CH ^ H ₂ GNHCH ₂ OiJ

S 0, Ha

NaO ₅ S

909849/1527

5 A 4350

11.0g (0.035 mol) of m-amino-NjN-bis ^ -carbamylethyl / benzenesulfonamide are concentrated under stirring to 50 ml of water, 20 ml Hydrochloric acid and 55 g of ice are added. A solution of 2.45 g (0.035 mol) of sodium nitrite in 15 ml of water is then added added.

The mixture is stirred for half an hour at 0 to 5 ° C, and excess nitrous acid is destroyed with sulfamic acid. The diazo solution is added to a cooled slurry of 5.58 g (0.0175 m)-acid in 150 ml of water, and 20 g of anhydrous sodium acetate are added in small portions to the stirred mixture over the course of 5 minutes. The mixture is then stirred at 5 to 7 ° C. for a further half an hour. The mixture is warmed to room temperature, the pH is adjusted to 8.0 with 20 # strength sodium hydroxide solution and the solution is saturated with salt. The dye precipitates as tar and solidifies quickly. The precipitate is filtered off, redissolved in 400 ml of water at 45 ° C., 120 g of salt are added and the mixture is cooled to room temperature. When the salt is added, the dye precipitates and solidifies. The solid is filtered off and ^{dried at 51 °} C., 15.8 g of product being obtained.

15 g (0.0148 mol) of the above product are dissolved in 50 ml of water dissolved and the pH adjusted to 9.5. For this purpose 50 g 37 # formaldehyde solution, the pH of which was previously adjusted to 9.5 had been admitted. The mixture is stirred, heated for 6 hours at 64-65 ° C., hot in 600 ml of isopropanol poured, filtered, washed with acetone and dried in vacuo at room temperature.

909849/1 527

Example 16

NaO ₃ S-

15443B0

A. m-Nitro-NN-bis (2-cyanoethyl) benzamide

-CN (CH ₂ CH ₂ CN) ₂

To a cooled solution of 61.60 g (0.5 m) of 3,3'-iminodipropionitrile and 39-55 g (0.5 m) of pyridine in 500 ml of dioxane are added at such a rate that the temperature is 17-19 ^° C is, 92.8 g (0.5 m) of m-nitrobenzoyl chloride in 100 ml of dioxane was added dropwise. After completion of the addition, the solution is stirred for one hour at room temperature and then for a further half hour at 5O ⁰ C. Then, activated carbon added, the hot solution is filtered through a diatomaceous earth, and the filtrate is in 2.5 1 gutgerührte ice-water mixture poured. The precipitate is filtered off, washed with 1.0 l of water and dried at 65 ° C. in an atmosphere oven. Yield 111.9 g (81.9 £ of theory) of m-nitro-N, N-bis (2-cyanoethyl) benzamide in the form of pale beige crystals with a melting point of 118-119.5 ° C.

909849/1527

B. m-nitro-N, N-bis (2-carbamyleth yl) -benzamide

(\ -0-N (OH ₂ CH ₂ OHH _{2 2}

NO ₂

To 500 ml of concentrated sulfuric acid at 0 - 5 ⁰ C are added with stirring 124.6 g (0.456 m) of m-nitro-N, N-bis (2-cyanoethyl) benzamide. After the addition is complete, the mixture is stirred for 5 hours at room temperature, poured into 2 l of well-stirred ice-water mixture and the dark solution is filtered through a diatomaceous earth filter. The filtrate is adjusted by adding concentrated ammonium hydroxide at 10-20 ⁰ C to pH 7, and the resulting precipitate is filtered off, the filter cake is washed with 3 1 of water, and dried in vacuo at 45 ⁰ C. Yield 111.5 g (78.6 $ of theory) of m-nitro-N, N-bis (2-carbamyläthyl) benzamide in the form of pale beige crystals, melting at 172 .5 - 173.5 ⁰ C.

G * mA.mino-N, N-bis ( 2-carbamylethyl) benzamide

NH ₂

A stirred mixture of 500 ml of water, 52 ₁ 5 g (0.94 m) of iron powder and 6 ml glacial acetic acid is heated to 75 ⁰ C, and then

9 £ 4 9 / ί Γ 2 7

BAD ORfGJNAL

104.8 g (0.34 m) ln-l · ίitro -]: I, iΓ-biB (2-yanoethyI) benzamide are added in parts. The temperature is allowed to rise to 90 ° O during the addition and the mixture gehalben at 90 ⁰ C -'95 minutes after completion of the addition, the mixture is cooled to 70 ° 0, sufficient solid sodium carbonate was added that the soluble Eiaensalao auafallen, and the heat mixture is filtered through diatomaceous earth. The filtrate is evaporated to dryness under reduced pressure at 40-45 ° C., and the residue is taken up in 300 ml of hot ethanol containing activated charcoal and diatomaceous earth, and the ethanol solution is filtered hot. The piltrate is poured into 2 liters of well-stirred dioxane, and ethyl ether is added to complete the precipitation. The precipitate is filtered off, washed with 1 liter of ethyl ether and dried in vacuo at room temperature. Yield 97.3 g of m-amino-N, N-bis (2 ~ carbamylätbyl) -benzamide pale beige in the form of crystals which decompose äumen at 109 ⁰ C under On sch. A umkristalliserter from isopropyl alcohol fraction decomposes at 162 ⁰ C and proves in the analysis as Sesq.ui ~ hydrate.

NaO ₅ S-

-N = N

Il

CN ^ H ₂ CH ₂ C-NHCH ₂ O ₁ Hj ₂ 0

A cold aqueous diazonium solution consisting of 13.92 g (0.05 m) m-Amino-li, N-bis (2-carbamylethyl) benzamide was obtained, wirä into a solution of 12.72 g (0.05 m) 3-methyl-1-p-sulfophenylpyrazolin-5-one in 300 ml of water containing 20.8 g (0.2 m) of sodium carbonate, stirred. The reaction mixture will

-. ,,. 909849/1527

- 46 - ■. .

Stirred for 3 S at room temperature, filtered off, the filtrate is heated to 50 ° C. and the pH is adjusted to 7.0, whereupon sodium chloride is added with stirring to precipitate the dye. The mixture v / ill to 2, ^r) ° G cooled, filtered, the filter cake is m.it 100 ml of 20 $ strength salt solution, followed by 100 ml of 10 $ sodium chloride solution, and dried in vacuo at 50 ⁰ C dried. Yield 40.4 g of an orange powder (yield 89 % of theory),

A solution of 32.31 g of the above powder in 150 ml of water is adjusted to pH 9.5 and then 60 g of 37 / ^ ™ ige aqueous formaldehyde solution, the pH of which is adjusted to 9 »5. , was suspended. The reaction mixture is stirred for 6 hours at 65 ° ö, the pH being kept at 9.5, cooled, with isopropyl alcohol to precipitate the dye diluted, and the isopropyl alcohol is then decanted off. The residue is sucked out with ether, filtered, the filter cake is washed with ether and dried in vacuo at room temperature. Yield 27.8g of a yellow dye.

In the block dyeing of cotton, a light green-yellow shade is obtained with excellent fastness to wet pressing, washing and acidic perspiration. Using 20 i »magnesium chloride OWD fixation 85 is fo at pH 4 and 80 i" at pH 6.5. The resistance to alkaline perspiration and the resistance to fear are good.

•. BATH ORIGINAL

909849/1527

Example 17

C ₂ H ₅ ο

<f ~ \ -N-CIigCH ₂ N (CHgCHgG-IiHGH ₂ OH),

A. 3,3 '-! / ^ - (N-ethyl-m-toluidinoJ-ethylT-inilno j -dipropionitril

M) -N-CH ₀ CHoN (CHoCH ₉ ON)

gCH ₂

CH,

89 g of N-ethyl-N- (2-aminoethyl) -m-toluidine are dissolved in 500 ml of t-butanol and 5 drops of 5N sodium hydroxide. 53 g of acrylonitrile are added dropwise to the stirred solution at normal temperatures in half an hour. The reaction mixture is then stirred for 6ü hours at normal temperature. The product is then isolated from the reaction mixture by vacuum distillation. In this way, one obtains

tril in analytically pure form with a bp 155-156 ⁰ G at 0.1 mm.

B. 3.3 ^l - | ^ '- (N-Ätbyl-m-toluiäino) -ätbyl7 «-iminofbis-propionami.d

C ₂ H ₅ O

«U

CK ₃

0 9 849/1527

BATH

28.4 g of 3,3 '- [^' - (N-ethyl-m-toluidino) -äthy37- ^imino T dipropionitrile are added in small portions with stirring at 30-4O ⁰ O within half an hour to 100 ml of concentrated sulfur · .Feic acid given. The reaction mixture is then stirred for a further 3 hours. The reaction mixture is then poured onto 1000 g of ice and made strongly alkaline by adding concentrated ammonium hydroxide. The product is suction filtered, washed with water and dried ^{at 50 0 O in an atmosphere oven.}

Are thus obtained 30.6 g of 3,3 ^l - | ^ - (N-ethyl-m-toluidino) -äthy37-iminof bispropionamid mp 78 - 79 ⁰ C.

/ ι \

-N = N - (^ ^ -N-OH ₂ CH ₂ N (CH ₂ CH ₂ O-NHOH ₂ Oh) ₂

22.7 g of 7-aminonaphthalene-1,3-disulfonic acid are diazotized, and the aqueous slurry of the diazotized salt is dissolved in a solution of 24 g of 3,3'-I ^ - (N-ethyl-m-toluidino) -ethyl / -imino (bispropionamide, which were prepared according to Example 17B and stirred in 20 parts by volume of concentrated hydrochloric acid in 300 ml. 62 parts of sodium acetate hydrate are then added all at once. After the coupling reaction has ended, the reaction mixture is stirred for half an hour. Then 1600 ml of ethanol are added and the whole mixture is stirred for another half an hour. Thereafter, the dye is filtered off, washed with ethanol and dried in an atmospheric oven at 5O ⁰ C. is obtained as 47.5 g of a reddish orange solid.

909849/1527

Purification and methylolation

47 »5 g of the above solid are leached with 300 g of water for half an hour. Then the dye is dissolved in 1000 ml of water with a sufficient amount of concentrated ammonium hydroxide to achieve the solution. 150 ml of glacial acetic acid are added to the clarified dye solution and the whole mixture is diluted to 4000 ml with ethanol. After stirring the dye is filtered off, washed with Ä'thanol and dried in an atmospheric oven at 50 ⁰ C.

20 g of the above dye become 100 ml of a 37 # Given formaldehyde solution, the pH of which was previously adjusted to 9.0. The reaction mixture is left at room temperature for 24 hours stirred, the pH being kept at 9.0 if necessary by adding 5N sodium hydroxide solution will. The reaction mixture is then poured into 2000 ml of acetone. The precipitated dye is filtered off with suction, washed with 300 ml of acetone and at normal temperature over " Calcium chloride dried in vacuo. This gives 21.7 g of analytically pure dye.

In the block dyeing of cellulose fibers, the product results an orange tint.

9098-49 / 1527

Example 18

-N = N-

-N-

ti

-CH ₂ CH ₂ C-NHOH ₂ OH

A. 5 «3 '- (phenylimino) bispropionamide

I!

CH ₂ CH ₂ C-NH ₂

CH ₀ CH ₉ C-NH ₍

To 200 ml of concentrated sulfuric acid, which is kept at ⁰ ° C., 22.0 g (0.094 m) of 3,3 * - (phenylimino) -dipropioni.trile are added with stirring and after the addition is complete, the solution is at room temperature for 5 hours stirred, poured onto ice and then concentrated ammonium hydroxide (approx. 700 ml) is slowly added at 10-15 ° C up to pH 9. The white precipitate is filtered, washed with water and dried in an atmospheric oven at 6O ⁰ C. This gives 16.8 g (76 $ of theory) 3,3 '- (phenylimono) bis-propionamide from P. 153,2-

SO ₃ Na

NaO ₅ S

-N = N-

0 11

-CH ₂ CH ₂ C-NHCH ₂ OH

9 0-98 A 9/152 7

42.7 g (0.1 mol) of 71% aminonaphthalene-1,3-disulfonic acid are added to 300 ml of water and 25 ml (0.5 mol) of hydrochloric acid. It is then cooled with ice to 1O ⁰ C and diazotized the whole with 7.0 g (0.1 mol) of NaNO ₂ in 25 ml of water, stirred for 1 hour and treated with sulfuric acid. The diazo solution is up-propionamide -phenylimino-to a solution of 24.4 g (0.104 mole) of 3,3 ^l added at 10 ⁰ C in 500 ml of water and 30 ml concentrated hydrochloric acid. To this end, 82 g (1.0 mol) of sodium acetate are added in small proportions. After the coupling has ended (about 10 minutes), the whole is filtered off and washed with 30% saline. The moist cake is slurried again in 1000 ml of water, 40 ml (0.2 M) of 5N sodium hydroxide solution are added and the whole is stirred for 1 hour. The product is filtered off and dried. It is then dissolved in 500 ml of water, 1250 ml of isopropanol are added, the mixture is heated to the boil, cooled, filtered off and the product is washed with isopropanol and dried. The yield of crude product is 73.2 g, 58.5 g recrystallized.

A solution of 100 ml of 37 # formaldehyde is adjusted to pH 9.0 with 5N sodium hydroxide solution. The above product is given for this purpose. A solution was obtained by stirring for 1 hour at 27-28 ⁰ C and then warmed to 45 ⁰ C. After cooling to 29-30 ° C. and stirring for a further 4 hours at pH 9.0, the whole is poured into 1500 ml of acetone. The product is isolated by decanting, 400 ml of isopropanol are added and the mixture is stirred for 1 hour. The slurry is filtered and the product washed with isopropanol and over dried in a vacuum oven. Yield 20.31g.

909849/15 27

The pad dyeing of cotton in 2 <? O toning OWP with 20 # magnesium chloride OWD results in a light orange shade with excellent wash fastness and wet press fastness.

Example 19

NaO, S-

OH ₂ O-NHCH ₂ OH J ^ ₂

A. 3,3 '- (N-p-nitrophenylimino) bispropionamide

/ = O (V) f ti \ _ CH C-NH
2 2 O ₉ E- ( CH ₉ C-NH = \ _ // > -N r ^ s ^, CH ₂ ^ CH ₂

To 53 ml of concentrated sulfuric acid slowly with stirring at 0 ⁰ C, 6.11 g (0.025 m) of 3,3 '- where (p-Nitrophenylimino) dipropionitrile and after completion of the addition the solution is stirred for 5 hours at room temperature to Pour ice and filter the solution through a diatomaceous earth filter. The piltrate is made by adding concentrated ammonium hydroxide with stirring

9 0 9849/1527

adjusted to pH 8 at 10-15 ° C. and the precipitate obtained is filtered off, washed with 100 ml of water and dried in vacuo at 60 ° C. This gives 6.64 g (95 $ of theory) of 3, 3 '- (p-Nitrophenylimino) - bisproionamid in the form of pale yellow crystals, melting at 209-210 ⁰ C.

B. 3 »3 ^> - (p-aminophenylimino) bispropionamide hydrochloride

. HCl

N- (CH ₂ CH ₂ C-IiH ₂ )

A well stirred mixture of 400 rnl of water, 27.9 g (0.5 m) of iron powder and 3 ml of glacial acetic acid is heated to 70 ⁰ C and then is added portionwise 50.2 g (0.18 ra) 3.3 ^L - ( p-Nitrophenylimino) bispropionamide was added. Wah end of the addition, the temperature increases and is at the end about 90 ⁰ C. The mixture is stirred at 90 - stirred 95 ° G half an hour after completion of the addition, cooled to 75 ° C and then sufficient sodium carbonate is added so that all of the dissolved iron salts removed. Activated charcoal is then added and the mixture is filtered hot through a diatomaceous earth filter. The filtrate is acidified with concentrated hydrochloric acid against Congo red indicator paper and cooled to 0 ° C. The precipitate obtained is filtered off and dried at 40 ° C. in vacuo. Yield 63.1 g (70.3 <fo the theory) 3i3 '- (p-aminophenylimino) -bispropionamide-hydro-

9098-49 / 1527

BATH ORIGINAL

Chloride in the form of pink tinted crystals, melting at 203-204 ⁰ C.

NaO, S-l

The "cold aqueous diazonium solution, which was obtained from 14.34 g (0.05 m) 3,3 '- (p-aminophenylimino) bispropionaide hydrochloride, prepared according to part B, is poured into a well-stirred solution at 15 ° C." which consists of 300 ml of water, 20.8 g (0.2 m) sodium carbonate and 11.51 g (0.05 m) sodium -3-hydroxynaphthalene-6-sulfonate The solution is allowed to come to room temperature and then on 50 ⁰ C is heated, after which sodium chloride is added to precipitate the dye. the precipitate is filtered off and washed with 400 ml of 20 $ sodium chloride solution. the wet cake is dissolved in 500 ml water at 6O ⁰ C, the solution is filtered through diatomaceous earth and the filtrate is poured into 3 liters of isopropyl alcohol, the precipitate is filtered off, washed with isopropyl alcohol and then with ethyl ether and dried in vacuo at 45 ° C. Yield 14.01 g.

A solution of 10.15 g of the above product in 150 ml Water is adjusted to pH 9.5 and then 30 g of 37% aqueous formaldehyde, the pH of which is previously adjusted 9.5 was adjusted, was added. The solution is stirred for 6 positions at 65 ° C., the pH being kept at 9.5

909843/1527

BATH ORIGINAL

and then in a mixture of 3 liters of isopropyl alcohol and poured 800 ml of ether. The mother liquor is decanted from the precipitate and this is in 55 ml Dissolved water for use on the paser.

By mixing 20 ml of the above dye solution with 1.5 nil $ 10 -iga? Magnesium chloride solution and replenishment A pad solution is made up to 50 ml with water. The solution is padded onto 8 square cotton Air dried and fixed at 177 ° 0 (350 ° F) for 1 1/2 minutes. The fixed dye is soaped at the boil and dried. An attractive red-brown color is obtained in this way. This dye shows excellent fastness (5) in the 3A cotton washing test, acidic and alkaline Sweat fastness and wet press fastness. The fixation of the dye is 95%, as is the sulfuric acid extraction and the spectrophotometric measurement of the dye solution results.

Example 20

-30, well

Il

909849/1527

154A350

The following substances are added to 150 ml of stirred water in the order given: 1.13 g (0.0045 m) of powdered cupric sulfate pentahydrate. 16.88 g (0.31 m) naftrium bicarbonate and 27.62 g (0.056 m) sodium 1-amino-4-bromoanthraquinone-2-sulfonate. Then, with slow stirring, a slurry of 22.62 g (0.079 m) 3.3 ^f - (p-aminophenylimino) bispropionamide hydrochloride, the pH of which has been previously adjusted to 5.5 with solid sodium bicarbonate, is added. The reaction mixture is stirred at room temperature for half an hour and the precipitate is filtered off and washed with 100 ml of 10 # saline solution. The moist cake is slurried in 1 l of water and the slurry is ^{heated to 40 °} C. with stirring, whereupon just enough 5N sodium hydroxide solution is added to effect dissolution. Then, activated carbon and diatomaceous earth are added, the mixture is heated to 5O ⁰ C and filtered through diatomaceous earth. The filtrate is heated to 45 ° C. and 5N hydrochloric acid is then slowly added dropwise until the dye has completely precipitated out. The precipitate is filtered off, washed twice with 100 ml of water each time and then with 200 ml of 10 # salt solution and dried at 45 ° C. in vacuo. Yield 14.71 g of a blue solid (42 # of theory).

A solution of 11.03 g of the blue solid in 150 ml Water is adjusted to pH 9.5 and then 3o g (0.37 m) 37 # aqueous formaldehyde was added, the pH of which was previously adjusted to 9.5. The solution is stirred for 6 hours at 65 ° C, the pH • being kept at 9i5 and then in a mixture of 3 Isopropyl alcohol and 1.6 1 ethyl ether poured. The precipitate is filtered off, washed with ethyl ether and im

9098A9 / 1527

" ⁵⁷ ". 15U350

Vacuum dried at room temperature. Yield 9.24 g of a blue dye.

A pad bath is prepared by mixing 0.75 g of the women’s dye with water, adding 1.5 ml of 10 $ ammonium sulfate solution, making up to 50 ml with water and allowing to stand. Then 7 ml of alcohol are added and made up to 80-square Cotton padded. The padded cotton is fixed 1 1/2 minutes at 177 ⁰ C (350 ⁰ F), soaped at the boil, rinsed and dried. The cotton is then dyed with a gray-blue tint, which has excellent fastness to wet pressing, washing and sweating. Fixation is 82 <fo.

Example 21

Il

45 ml of chlorosulfonic acid is added under stirring and cooling so that the Temperatur.3O does not exceed ⁰ C with 8.71 g (0.015 m) · copper phthalocyanine and the reaction mixture is heated to 14O ⁰ C and held for two hours at this temperature. Then it is cooled to room temperature, poured into a well-stirred mixture of 75 ml of water, 450 g of ice and 42 g of sodium chloride and the resulting precipitate is filtered off and washed with 100 ml of ice water. The moist sulfonyl chloride cake is then slurried in ice water, the pH value to 5.5

9 0 9 8 Λ 9/1 5 2 7

15U350

and then a slurry of 8.4 g (0.03 m) 3> 3 '- (p-aminophenylimino) bispropionamide in 40 ml of ice water of pH 5.5 were added. The reaction mixture is stirred at Ό -.5 ° C for one hour, the pH is kept at 6.5, filtered off and the cake is washed with 50 ml of water and in vacuo dried at 45 ° C. Yield 16.9 g of a solid.

A solution of 12.97 g of the above pesticide in 150 ml "■ Water is adjusted to pH 9> 5 and then 32.4 g 37% aqueous formaldehyde, the pH of which had previously been brought to 9.5, was added. The reaction mixture is heated to 65 ° O for 6 hours, the pH at 9 »5 is maintained, then filtered and the piltrate is poured into 3 l of well-stirred isopropyl alcohol. The "precipitation is filtered off, washed with 25Q-mV Ethylather and 'dried' in a vacuum at room temperature. "Yield 12.61 g of a green-blue dye.

The pad dyeing of cotton in a 1.5 $ OWP tint at pH 6.7 using 10 $ OWD ammonium sulfate gives a turquoise coloration with 96 $ fixation. With the same paraffin concentration at pH 6.6 and 2of OWD ammonium sulphate, a fixation of 95% is obtained.

909849/1527

Example 22

Il

-N (CH ₂ CH ₂ C-NHCH ₂ OH) ₂

Il

-N (CH ₂ CH ₂ C-NHCH ₂ OH)

A solution of 13.34 g (0.025 m) of the blue dye which is obtained from the condensation of bromaminic acid and m-Phenyldiaminsulfonsäure is at 0 - 5 ⁰ overall C. cools and then, with stirring, a solution of 4., 6] 1. \ -. g- (0.025 m) cyanuric chloride in 50 ml of acetone is added, the pH being kept at 5.5. The solution is kept at 0 - 5 ° C and a slurry of 15.77 g (0.05 "5 m) 3.3 ^f - (p-aminophenylimino) dipr.opionamide hydrochloride in 50 ml of water, which has a pH The temperature is then increased to 90-92 ^° C. within 1.5 hours and held for one hour, the pH being kept constant at 6.0. The solution is brought to room temperature cooled, filtered through diatomaceous earth and the piltrate is poured into 1.5 l of well-stirred isopropyl alcohol

9849/1527

" ⁶⁰ "^; . ·., 1J5U350 · ". ·. ·.

The precipitate is filtered off with 1.5 l of isopropyl alcohol washed and dried in an atmosphere oven at 55 ° C. Yield 24.8 g of a blue powder. A sample of this powder is made from a mixture of dimethylformamide and isopropyl alcohol recrystallized.

16.63 g of the above powder are dissolved in 150 ml of water, the pH is adjusted to 9.5 and then become

48.64 g of a 37% aqueous formaldehyde solution of

pH 9.5 added. The mixture is heated to 65 ° C. for 6 hours, the pH being adjusted if necessary by adding. 20 # NaOH solution constant. 9.5 is kept, cooled to ψ room temperature, filtered through dietary earth and the filtrate is poured into 3 l of well-stirred isopropyl alcohol. The precipitate obtained is filtered off, washed with 500 ml of isopropyl alcohol and dried in vacuo at room temperature. Yield 16.67 g of blue dye.

Example 23

3 g of the dye of B _e ispiel 12 are dissolved in 11 ml water and added to an emulsion that was obtained by homogenizing the following ingredients:

20 g of granulated sodium alginate, with 545 ml of water stirred into a paste;

10g sodium fatty acid amide sulfonate as surface-active Means and

455 g of a petroleum-based solvent with a sieve

9 0 9 8 Λ 9/1527

point between 16O ⁰ C and 198 ° C (321 - 388 ° F).

6 ml of 10% ammonium chloride solution are added to this. Then a 7 inch (17.8 cm) wide 80-square cotton is printed with it. The print is dried at 71 ° C. for 5 minutes. It is then acid-aged in an acetic acid-steam mixture for 2, 1/2 minutes. It is then ^{fixed at .177 0} O (350 ° F) for 1 1/2 minutes, followed by soaking for five minutes with boiling and drying. A brilliant turquoise print is obtained in this way.

Example 24 * "

HO

-N = N NaO S-

-N = N -SO ₅ Na

A slurry of 15.97 g (0.05 m)-acid in 00 ml of water is adjusted to pH 6.5 by adding 20% sodium hydroxide solution and the resulting solution is clarified with activated charcoal and diatomaceous earth , filtered and the filtrate is treated with 8.20 g (0.1 m) of anhydrous iatrium acetate. A cold aqueous diazonium solution, which was obtained from 15.72 g (0.05 m) of 3,3'-methanilyliminobispropionamide, is added all at once to this coupling component solution with stirring at room temperature. The pH of the mixture obtained becomes 1.7

909849/152

BATH

brought to 3.5 by adding solid anhydrous sodium acetate and then to 5.0 with 20 $ aqueous sodium hydroxide solution. The reaction mixture is then stirred for two hours, the pH value is adjusted to 5.0 with 20% aqueous sodium hydroxide solution, and then sufficient solid sodium carbonate is added that a pH value of 9.9 is obtained. Finally, a cold aqueous diazonium salt solution obtained from 6.91 g (0.05 M) p-nitroaniline is added alternately with solid sodium carbonate to maintain the pH at 8.0. The reaction mixture is stirred for two hours at pH 8.0 and then the pH was adjusted with 5N hydrochloric acid to 7.0 is stirred for several hours and W set. The product is filtered, washed twice with 250 ml of 20 $ ~ aqueous sodium chloride solution and then · partially at 55 ° E in "an atmospheric oven. The crude dye was dissolved in 500 ml of dimethylformamide at 6O ⁰ C, the solution is filtered and the filtrate is poured into 5 1 well-stirred isopropyl alcohol. the precipitate is filtered off, washed with 500 ml of isopropyl alcohol, followed by 500 ml acetone and dried at 6O ⁰ g. education · yield 26.42 g (63 $> of theory) of blue-black of a bronze gloss Dye.

A solution of 20.94 g (0.025 m) of the above dye in 200 ml of water is adjusted to pH 10.0 and then become 32.43 g (0.4 m) 37% aqueous formaldehyde solution were added. The mixture is stirred for 6 hours at 65 ° C., the pH value being kept at 9.5, then hot through Diatomaceous earth filtered and the filtrate is stirred well in 3 liters Poured isopropyl alcohol. The precipitate is filtered off, followed by 250 ml of isopropyl alcohol Washed 200 ml of ether and dried in vacuo at room temperature. Yield 17.24 g of a blue-black dye of $ 70 purity, the $ 8.27 bound formaldehyde (2.43 methylol groups) contains.

9098 4 9/15 27

'BAD ORIGINAL

For block dyeing on cotton in 2 # tint with 10 Ammonium chloride OWD as a catalyst gives a deep blue-black color with 75-80 # fixation.

Example 25

ON NH

-N = N

SO_Na

SO ₅ Well

SOjNa

> 0'h7;

Just enough 5N sodium hydroxide solution is added to a slurry of 15.97 g (0.05 m)-acid to effect solution and then the solution is treated with activated charcoal and diatomaceous earth, filtered and the filtrate is cooled to ^{0 ° C} and set to 5.5. Then, while stirring, a filtered solution of 9.22 g (0.05 m) of cyanuric acid chloride in 100 ml of acetone is added dropwise. The pH value is increased during the. Whole addition kept at 5.5 by adding 5N water, as required. The reaction mixture is stirred for 30 minutes at 0-5 ° C. and then a slurry of 15.72 g (0.05 m) of 3,3'-metanilyliminobispropionamide in 50 ml of water and ml of acetone is added all at once. The ice bath is removed and the terrace

909849/1527

^{Temperature increased to 6O 0} C within 2 1/2 hours, the pH being kept at 5.5. After stirring for 11/2 hours at 60 ° C., the solution is treated with activated charcoal and filtered hot through diatomaceous earth. The piltrate is poured into 3 liters of well-stirred isopropyl alcohol and the precipitate is filtered off and washed with 500 ml of isopropyl alcohol followed by 500 ml of acetone. The semi-dry ^1- triazinyl intermediate product obtained is placed in 300 ml of water, the pH is adjusted to 1.0 and then sufficient solid sodium carbonate is added that the pH is 9.9. A cold aqueous ™ diazonium solution, which was obtained from 8.66 g (0.05 m) of orthanilic acid, is added to the coupling component solution produced in this way, with stirring. The reaction mixture is stirred for several hours at room temperature and then heated to 60-65 ° C. The pH is adjusted to 7.0 to 7.5 with dilute hydrochloric acid and partially solid sodium chloride is added with stirring. The salted-out dye is filtered off, ml with the 250th 20 <? O aqueous brine and oven at 65 ⁰ C in an atmosphere .. getrocknet.- yield 39 _f 81 g of a red product (real basis) ..

A solution of 45 »59 g of the red as prepared above fc dye in 350 ml of water is adjusted to pH 9.5 and then 81.1 g (1.0 m) of a 37% aqueous formaldehyde solution of pH 9.5 are added. The mix will Stirred for 6 hours at 65 ° C., the pH being increased to 9 »5 is held, then filtered hot through diatomaceous earth and the filtrate is dissolved in 4 l of well-stirred isopropyl alcohol poured. The precipitate is filtered off, washed with 500 ml of isopropyl alcohol, followed by - 300 ml of ether and dried in vacuo at room temperature. Yield 32.0 g of a red dye, the 5.72 $ bound formaldehyde contains.

90984971527

A 2 f> dyeing on cotton with 10 fo ammonium chloride OWD as a catalyst gives a bright red with a blue shade with a fixation of 90 fo »

Example 26 ■.

CH ₃ OIiH

N = N

SO ₃ Na

OH ₂ SO ₂ H (OH ₂ OH ₂ O-HHOH ₂ Oh),

If one uses 0.05 m of the diazo, nium salt in the process of Example 2, which from 3.3 ^l - ^! '(- aminobenzyl) sulfonylimino7dipropionamid (prepared from 3-nitrobenzylsulfonyl chloride in a manner analogous to the amine of Example 1 C) is derived, a product is obtained which dyes cotton in a blue-red shade which has very good fastness to washing and perspiration.

Example 27 .

-N = N-

\ J

-CHpCHpN

C.

■ S0, Na

90 984 9/1527

If in the method of Example 9 .den- azo-color- ' ^{: is} used, the diazotized'3V3 ^l - ( ^: p- ·' ···· "aminophenethylimino) dipropionamide in an alkaline solution of 5- Hydroxynaphthalene-1-sulfonic acid is obtained, one arrives at a dye which gives orange-red dyeings of high wet fastness on cotton.The amine used as the diazonium component is converted into 3- (p-nitrophenyl) ethylamine by adding 2 moles of acrylonitrile and then Reduction of the nitro group produced.

Example 28

NaO ₅ S-

Il

CH ₂ CH ₂ CN (CH ₂ CH ₂ C-NH ₂ )

If in the process of Example 16 D 0.05 m of the diazonium salt is used, which is obtained from m-amino-N, N-bis (2-carbamylethyl) -hydrocinnamic acid amide ^ Prepared from β -. (3-nitrophenyl) propionyl chloride in a manner analogous to the amine is derived from Example 16 QjJ , the result is a dye which gives a yellow coloration on cotton with a somewhat less shade of green and which is just as fast to pretension, washing and sweat.

909849/1527

Example 29

NaO ₅ S

C-OH

Il

C-N = N-

A solution of 5.0 g of the dye prepared in Example 2 in 150 ml of methanol is heated to reflux with stirring and then enough concentrated hydrochloric acid is added dropwise that the pH is 6.0. The solution is heated for 15 minutes to reflux, then rapidly cooled to 30 ⁰ C and poured into 3 1 well-stirred isopropyl alcohol. The product is filtered off, washed with 500 ml of acetone and dried in vacuo at room temperature. Yield 5.9g of yellow dye. When used on cotton according to the usual methods, this product yields. drive bright yellow colors with superior washing and perspiration fastness.

Example 30

SO ₂ N (Ch ₂ CH ₂ C-NHCH ₂ OH).

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2.2 g (0.06 m) of sodium hydroxide and 2.9 g (0.03 m) of sodium carbonate (each in a minimal amount of water) are dissolved in a mixture of 500 ml of methanol and 500 ml of dioxane, followed by 14.5 g g (0.055 m) 3-hydroxy-2-naphthanilide added. The solution is cooled to 1O ⁰ C • and then a cold, aqueous diazonium solution is added of 15.7 g (0.05 · m) 3.3 ^L - bispropionamid (Metanilylimino) is derived. Alternating with the addition of diazonium, sodium carbonate is added, if necessary, in order to keep the pH at 8.0. After stirring for 1/2 hour, the precipitate is filtered off, washed with 1.0 l of water and dried in vacuo at room temperature. Yield 23.5 g (80 $> of theory) of an orange dye.

A solution of 16.1 g (0.027 ra) of the above dye in .200 ml of ethanol is treated with 50.1 g (0.062 m) of a 37 # aqueous formaldehyde solution of pH 9.5. The reaction mixture is stirred for 6 hours at 65 ⁰ C, the pH to 9.0 to 9.5 is maintained by addition of dilute aqueous sodium hydroxide solution, if necessary, then cooled to 3O ⁰ C and poured into 2.5 1 of water . The precipitate is filtered off, washed with 1.0 l of water and dried ^{at 25 ° C. in vacuo.} Yield 16.0 g (100 % of theory) of an orange dye with a content of 2.09 methylol groups.

If you have nylon, silk and wool or acrylonitrile-vinylpyrrolidone-mixed polymers dyes with this dye using the usual dyeing processes for these fibers, in this way, brilliant orange tints are obtained from superior ones Authenticity properties.

909849/1527

Example 31

SO _{x well}

SO ₉ N (CH ₉ CH ₀ OONHCH ₀ Oh) ₀

A mixture of 11.6 g (0.025 mol) of the azo dye, which was obtained by coupling diazotized amino-G-acid with m-toluidine, 11.55 g (0.025 mol) 3,3'- \ O & ^J ~ ( 4,6-dichloro-s-triazin-2-yl) metanilyl J7imino j bispropionamide and 100 ml of water are heated to 83 ° C. while stirring, the pH being maintained at 6.0. Once the test is negative on primary aromatic amino groups, the mixture to 25 ⁰ C is cooled, filtered and the Piltrat is poured into stirred ethanol. The precipitate is filtered off, washed with ethanol and dried at 6O ⁰ C. Yield. 20 g of an orange dye of 91 # purity ( $ 89> of theory). '.

A solution of 10.0 g of the above dye in 100 ml Water is adjusted to pH 9.5 and then 20.0 g of a 37 5 ^ aqueous formaldehyde solution are added, the pH of which had previously been adjusted to 9 »5. the

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Mixture is stirred for 6 hours at 65 ° C, whereby a pH of 9.5 is maintained, then cooled, filtered off and the filtrate is stirred in 3 l isopropyl alcohol poured. The precipitate is filtered off, washed with isopropyl alcohol and in a vacuum at room temperature dried, yield 7.5 g of an orange powder containing 1.71 methylol groups per Mole.

When dyeing or printing cotton in 2 <$> tint using 10 $> OWD NH. Cl gives a reddish yellow coloration of very good wet press, wash and abrasion fastness.

Example 32

W _e is nn in the above Example 31 0.025 mol of 2-N, N-bis (2-carbamyläthyl) amino-4,6-dichloro-s-triazine was used as triazine, one obtains a dye that 2.95 ^ δ Contains formaldehyde and produces similar colorations when dyeing or printing cotton.

SO ₃ Na

- OH

C ά.

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-.71 -

Example 33

N «N-

-N = N-.

-SO ₅ Na

O ₂ N (CH ₂ CH ₂ G ONHCH ₂ OS) _;

SO-Na
3

10.46 g (0.055 mol) of anilinomethanesulfonic acid (anilinomega salt) followed by 32.8 g of anhydrous sodium acetate are added to a cold aqueous diazonium solution derived from 15.72 g (0.05 mol) of 3,3'-metanilyliminobispropionamide, the mixture is stirred for 2 hours at 25 ° C, heated at 50 ^e C and salted out. After cooling to 25 ° C., the mixture is filtered off and the moist cake is dissolved in 700 ml of water which contains 6 ml of concentrated NH.OH and 10 ml of 5N NaOH. The solution "is clarified with activated carbon and then stirred for 24 hours at 25 ⁰ C. After heating to 80 ⁰ C, the mixture is cooled to 25 ° C and filtered to obtain g after drying 9.4 of a brown-orange Powders from P. 171 »5" ⁰ G receives.

A solution of 12.8 g (0.022 mol) of G-acid (dipotassium alc) and 200 ml of water is adjusted to pH 7.0, 10.6 g (0.1 mol) of Na ₂ CO ₅ are added and then with the cold one treated aqueous diazonium solution, which consists of 9.30 g

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(0.022 mol) of the above monoazo dye. After half an hour stirring, the solution is salted out and filtered at 55 ⁰ C and the cake dried at 6O ⁰ C. Yield 25.0 g of a light red powder.

A solution "of 3.5 g of the above dye in 100 ml of what ^{water is methylolated in the usual manner for 6 hours at 65 0} O and pH 6.5 and gives a yield of 3.34 g of a dye which is 2.23 $ contains bound formaldehyde.

When used on cotton with 10 fo OWD NH ₄ Cl, the above dye gives bright scarlet dyeings of high wet press and wash fastness.

Example 34

W _e nn one in the procedure of Example 33 in place of the aniline salt of m-Omega Toiuidin used, one obtains a · monoazo dye intermediate having a melting point 200-203 ° C (dec.). After completion of the subsequent steps, a dye of the formula below is obtained which contains 1.35 $ methylol groups and dyes the cotton in the presence of 10 $ OWD NH.C1 bright scarlet red with a little less shade of yellow than the dye of Example 36.

N = N-.

O ₂ N (CH ₂ CH ₂ CONHCH ₂ Oh),

SO-Na

909 84 9/1527

Example 35

N (OH ₂ OH ₂ CONHCh ₂ OH)

A solution of 21.34. g (0.04 mol) of the blue dye, which is obtained from the condensation of bromamic acid and m-phenylenediarainulfonic acid, is cooled to 0-5 ° C., the pH is adjusted to 4.5 and then a solution of 7, 38 g (0.04 mol) of cyanuric acid chloride in 75 ml of acetone were added, the pH value being kept at 5-3-5-5 with aqueous Na ₂ CO. The solution is kept at 0-5 ° C. and pH 5.5 for a further half an hour and then a cold solution of 22.64 g (0.088 mol) of 3,3'-iminodipropionamide sulfate in 50 ml of water at pH. 5.2 (adjusted with 50% NaOH) added. The mixture wird'dann for 40 minutes at 76 ° C and heated for half an hour at 77 - 79 ⁰ C held, with a pH of 5.3 - 5.5 is maintained. Then the solution is clarified, heated to 70 ° C and salted and delivered

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after cooling to 25 ° C, filtering, washing and drying at 6O ⁰ C 33 "4 g of a blue dye. The crude dye is purified from dimethylformamide / isopropanol and gives 25.8 g of a blue dye. Analysis shows that it contains a chlorine atom and an iminobispropionamide residue.

8 "75 g of purified dye is 9.5 methylolated 6 hours at 65 ⁰ C and pH in the usual manner and supply 7,10g of a blue dye, which contains 1.8 methylol groups.

A $ 2 stain of the above dye on cotton with a 10 # OWD NH.Cl catalyst gives reddish blue Dyeings of high wash and wet press fastness.

Example 36 *

O ₂ N (CH ₂ GH ₂ GONHCh ₂ OH)

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--75 -

15U350

If in Example 35 instead of 3,3'-propionamide sulfate 27.66 g (0.088 moles) of 3,3 * -metanilyliminobispropionamide used, the above dye containing 2.4 methylol groups is obtained. When dyeing of cotton with NIL Cl, it delivers brilliant blue Dyeings with a slightly greener shade than the above dye, with the same wash and wet press fastness.

Example 37

The dye obtained in Example 1 can also be prepared by following the procedure of Example 1 follows, but instead of 3 »3'-metanilyliminobispropionamide replaced in part D of Example 1 by m-aminobenzenesulfonamide and then with Gyanoäthylierung by reaction with Acrylonitrile, hydrolysis and methylolation continues.

Example 38

The dye prepared in Example 2 can also be obtained by the method of Example 2 if the diazo component m-aminobenzenesulfonamide used and after coupling with cyanoethylation by reaction with acrylonitrile, Hydrolysis and methylolation continues.

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Claims (1)

Claims 1. A process for the preparation of substrate-reactive dyes, characterized in that at least an iminobispropionamide group into a chromophoric fluorophoric organic dye or dye precursor is introduced, optionally the dye • is completed and the iminobispropionamide group is alkoxymethylated or methylolated, and optionally acylated the methylol group or groups obtained or is or are alkylated. 2. The method according to claim 1 for the preparation of substrate-reactive dyes of the general formula D- OHoCHpOON CH ₉ CH ₀ C 0N ^{ά 2} R ¹ wherein D is a chromophoric or fluorophoric organic dye residue, Y is a covalent bond or a divalent bridging group, R is a hydrogen atom, an acyl group or an alkyl group with 1 to 4 carbon atoms, R 'is a hydrogen atom or the group CH ₂ OR, in which R has the above meaning and η denote the number 1 or 2, characterized in that one. . ·. · ■; · ■ '"," V. \; ■ ·, ··' · '·.' · '. . · .. · - · · ■ 909849 / M527 Documents (Art. ? § I Paragraph 2 No. 1 Sentence 3 of the Amendment Lake. V. 4.9.1S67J D '- (A) _S with implements what a) D 'a chromophore or fluorophore organic Dye residue or precursor thereof, s and ρ the numbers 1 or 2, each Z a 2-carbamylethyl or 2-cyanoethyl group or a cyanoethylatable hydrogen atom, one of the groups A and B is an acylating, • alkylating or arylating group and the corresponding others denote an acylatable, alkylatable or or arylatable group, and where 1. if Z is a 2-cyanoethyl radical, this becomes one 2-Garbamyläthylrest is hydrolyzed; 2. if Z is a hydrogen atom, this before or after the above reaction II by reaction with acrylonitrile cyanoethylated and the 2-cyanoethyl radical obtained is hydrolyzed to a 2-carbamylethyl radical; and 3. if necessary, the dye precursor group D ^{1 is} completed before or after the above reaction II; being a dye of the general formula 909849/1527 D- Y-N CH ₂ GH ₂ CONH ₂ CH ₂ CH ₂ CONH ₂ III wherein D, X and η have the above meaning, or b) D ¹ , s, ρ and Z of the above reaction II have the above meaning, one of the radicals A and-B is the diazo-containing radical of a diazonium compound and the 'other'"is the radical of an azo coupling component, and where 1 . ΖΪ ,. if it is not a 2-carbamylethyl radical, before or after the above - "eaktioh II in this according to the procedure 1. or 2. is transferred from a) above, whereby a dye of the above general formula III is obtained, and the Dye of the formula III, which is obtained from the above process a) or b), alkoxymethylated or methylolated and is then optionally alkylated or acylated to form the corresponding dye of the above general Formula I. Method according to claim 2, characterized in that one of the groups A or B of the compounds which are reacted in the above reaction II, part a) Chlorosulfonyl, / chlorocarbonyl, carboxylic acid anhydride, Halomethylaryl-, o- or p-nitrohalogenaryl-, vinylarylsulfone- or mono- or dihalo-s-triazinyl radical is. 9Q98A9 / 152 7 - 7Q _ 1 54A35Ö 4. The method according to claim 2 or 3, characterized in that that the group Z in the compound reacted in reaction II represents a hydrogen atom, which part is a sulfamyl, carbamyl or amino group, and this group is cyanoethylated. 5 ". Method according to claim 2 or 3, characterized in that that 3 »3'-metanilyliminobispropionamide or its Siazonium derivative is used as the reagent in the above reaction II. 6. The method according to any one of claims 2 to 5, characterized in that the Iminobispröpionamidverbindungen the above formula III are methylolated by treatment with formaldehyde at a temperature between 20 and 90 ⁰ C and at a pH value above. 7 7. Reactive dyes of the general formula: -Y-N CH ₂ CH ₂ CON CH ₉ CH ₅ CON
^{2 2} CH ₂ OR ^ CH ₉ OR where D is an organic dye radical, Y is a covalent bond or a divalent bridging group, R is a hydrogen atom or an alkyl group having 1 to carbon atoms, R is a hydrogen atom or the group CH ₂ OR, in which R is as defined above, and m is the number 1 or 2 mean. 9098 4 9/15 27 15U350 8. Dye according to claim 7, in the formula Y of which is a sulfonyl, Denotes alkylenesulfonyl, alkylenoxy, alkylenethio, carbonyl, alkylenecarbonyl or alkylene group, wherein the alkylene groups contain 1 or 2 carbon atoms. 9. Dyestuff according to claim 7 or 8, in the formula D of which is the radical of one. Anthraquinone, phthalocyanine, azo or Anthrone dye means. 10. Color of the formula N C-OH I H - CH, 11. Dye of the formula CuPc 9 0 9 8 Λ 9/1527 .12. Formula dye? OH -N = N- ^S0 3 ^Na SO ₃ Na .0 It CH ₂ C-NHCH ₂ 13. Dye of the formula: CH, CNH NaO-S SO ₂ N ^ H ₂ CH ₂ C-NHCH ₂ OH / 2 14. Dye of the formula: 909849/1527