DE1644264A1 - Process for the production of water-soluble azo reactive dyes - Google Patents

Description

PATENT LAWYERS DR.-INQ. H. FINCKE DIPL.-ING. H. BOHR DIPL.-ING. S. STAEGER

Ftrarufi 8 MUNICH S, 31

MARCH 18. 1970

Tf 20502 - Dr.P / P ICX Oase D.13024

description

emr the

IMPKRIAL CHEMICAL IlfSUSTRISS IBJISED »

pertaining to: Manufacture τοη waesesOL

P. 1ο 1 '

■ ■ - 2 - ■ ■ "■ ■ -

the halo-s-triazine group with water and not with the Cellulose oil reacts, becomes a significant part of the The dye is not bound to the fibers.

As a result, the dye must be used in excess, and the dyed or printed matter must be boiling SeifenliJaungen to remove the bound dye be washed thoroughly, Burch the resulting loss of dye and additional treatments, the dyeing or printing process becomes more expensive, especially when deep shades of color should be achieved.

DI® present invention "shall look SICM in producing water-soluble halogen" s triasia "Re®letivfßrbstoffen ₉ in am® he neatly high MaQe be connected with the fibers and sine b <§ ± ä @ nm less Spftlbehmndliragen necessary!"

d®r ItflaiBag β lad vase exCLösli before Meaoaisofarfestoff®

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1 imä l ^r ! © because © © la

§ © ia ai © is? Ig @ 3? © e ®4gl = »allsjl © nr © 4i1ca, l AmE ¹ S part t

■ - 3 - ■. ■
Y represents a chlorine «or jfeomatosi · '-

Under a lower alkyl or universal radical is intended to be a such a radical with a maximum of 4 G atoms can be understood.

To ensure that the dyes are soluble in water, the nuclei of the residues represented by A and E should at least contain a suXfoeäuregruppe «They preferably contain at least two such groups each, also can these nuclei have other substituents, such as chlorine or bromine atoms or Methyl-, Methosy-, Ureide-, Carboaqr-, Sitro- or Carboniferous alcohol groups, contain »

The Fyrimldln- © der s-friazisifcern represented by T must have a chlorine or bromine atom in the Z, 4- or i-position. The pyrimidine nucleus should also have an electronegative substituent in the 5-3 position, such as a chlorine or bromine atom or an oyanogroup.

The new dyes can be made up by combining the following Starting materials together with the usual Eupplungs-. and generate eondensation methods

a) The diazonium compound of an aromatic amine Formula: A-

b) An amine of the benzene series coupling in the para position or a 5-pyrazolone, 5-aminopyrasolone or acetacetarylamide coupling component j one of the compounds a) and b) must be an amino or mono-substituted amino group or a group, e.g. a nitro or acetylamino group, after the coupling reaction into an amino group can uageeetst without destruction of the azo group contain;

c) Am cyanuric halide or a pyrimidine compound with Chlorine or bromine atoms in the 2-, 4- and 6-positions and an electronegati-yen substituent in the "5-position .;

16U264

d) An amine of the formula:

Th 2 - ^Y - ^z

R <JI

As examples of these compounds, the following can be mentioned:

<) Diazo compounds of the formula: A-NH ₂

Aniline and naphthylamine sulfoic acids and their derivatives with core substituents, such as, for example, orthanilic acid, aniline-2,5-disulfonic acid, 2-naphthylamine-4-8-di-sulfonic acid and 2-8-taphthylamine-3,6,8-trisulfonic acid, i -Naphthylamine-IjS-isulphonic acid, i-BTaphthylamine-3,6,8-trisulphoic acid , m-phenylenediamine-o-sulphoic acid, p-phenylenediamine-o-8ulphoic acid, 2,6-diaminonaphthalene-4,8-disulphoic acid.

b) coupling components

Anilines and -naphthylamines, which in the same ring as the amino group may contain niohtionic substituents, such as lower alkyl, lower alkoxy ·, acylamino and ureido groups, and N-lower alkyl derivatives of these compounds, such as z.ji. m-toluidine _f 2 «methoxy-5-methylaniline, o-anieidine, m-aminoacetanilide, m-arainophenylurea, 1-naphthylamine-6- or -7-sulfoic acid and N-methylaniline, 5-pyraeolones with a mono- or dicyclial aromatic Substituents in the 1-position and a methyl, carboxy or carbo-lower alkoxy group in the 3-position of the pyraeol nucleus, such as 1- (2'-methyl-5 '-eulfophenyl) -3-methyl-5-pyraBolone, 1- (3 ^f -amino-4 ^f sulfophenyl) -3-carboxy-5-pyrazolone, 1- (4 ^t -sulfophenyl) -3-methyl-5-pyrazolone, 1- (3 ^f -sulfophenyl) -3-methyl -5-pyraaolone, 1- (4'-sulfophenyl) -3-carboxy-5-pyrazolone, 1- (3'-sulfophenyl) -3-carboxy-5-pyrazolone, 1- (3'- or ^ '- aminophenylJ ^ -carboxy- or ^ -methyl-S-pyrazolone, 1- (4'-Ajnino ^l-3 -sulfophenyl) -3-methyl or carboxy-^ S-pyrazolone, 1- (4 ^l, 5 ^t -Disulfonaphth - -2'-yl) -3-raethyl- or -S-carboxy-S-pyrazolone, 1- (4 *, 8 · -Μ-

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eulfonaphth-2'-yl) -5-iaethyl-5 ^ pyrazolone; 5-Araincpyrazole, such as i-aryl-5-aminopyrazole such as i-phenyl ^ -methyl-S-aminopyrazel, 1- (3'-aminophenyl) -3-methyl-5-aminopyrazole and 1- (3 ^f -Jjaino- 4'-sulfophenyl) -3-methyl-5-hamopyrazole; and acetacetarylamides, such as. B. Aoetacetanllld, Acetacet-o-toluidid, Acetacet-m-xylidid, Acetacetanllid-3- or -4-sulfoic acid and Acetacet-3- or -4-arainoanilide.

c) cyanuric chloride, cyanuric bromide, 2.1 »> 5,6-tetrachloropyrimidine, ! T74 »6-! Eribromo-5-cyanopyrimidine and 2,4» 6-triehlor-5-cyanopyrimidine.

d) m- and p-Arainobenaoleulfon-ß-obloräthylamid, m- and p-Üinobenzolsulfon-ß-chlorpropylaraid, the corresponding ß-bromopropyl compounds and 3 * or 4-aminobenzene-sulfone-N- (ß, "f-dichloropropylamide) ·

The ax and way of connecting these starting materials with one another can differ »in» So can the diazonium compound for example, are first coupled with the coupling component to produce a monoazo compound of the formula: To generate [a - N * H - e] which contains an amino or monosubstituted amino group or a group which can be converted into such a group. In the latter case, the monoazo compound is used to form the condensation-enabling f Amino or monosubstituted amino group of a reduction or subjected to hydrolysis. To form the new dye, the monoazo compound obtained in this way can be condensed with the gjanur halide or the pyriraidine compound, whereupon the product is condensed with the amine d); or the monoazor bond can be obtained by condensation of the cyanuric halide or the pyrimidine compound with the area d) obtained compound to react. But one can also proceed in this way, since a group of the formula:

009837/1703

_R1

is introduced into the diazonium compound or coupling component before the coupling that a coupling component with an amino or monosubstituted amino group or a diazo component with a second imino or 'mono substituted amino group either with a condensation product of the cyanuric halide or the pyrimidine compound with the 1min d) is condensed or is first condensed with the cyanuric halide or the pyrimidine compound - ^ up the product is condensed with the amine d), whereby this such k dye is produced by coupling. In a further embodiment of the process, the yanuric halide or the pyrimidine compound is condensed with a coupling component which contains an amino or monosubstituted amino group or with a diazo component which contains a second amino or monosubstituted amino group, whereupon the product is coupled to get an intermediate of the formula:

-N-N- e] - Ϊ - halogen

to obtain which is condensed with the amine d) to form the new dye.

The new dyes can be used for dyeing or printing a wide variety of textiles. You are as Reactive dyes for cellulose particularly suitable with the they are reactive in the presence of acid-binding agents with a high degree of efficiency.

The invention is explained in more detail below with the aid of exemplary embodiments, purely by way of example, with all quantitative data being based on the (not.

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example 1

A neutral solution of Tim 15.25 parts of the irisodium salt of 2- (4 * -amino-2 »-ureidophenylazo) naphth * Ien-3» 6,8-trisulfonic acid in 250 parts of water slowly becomes a stirred suspension of 5.1 parts Cyanuric chloride in 25 parts of acetone and 100 parts of ice water at 0 to 5 ° C. A pH of 6.0 to 6.5 is maintained by adding 2N sodium carbonate solution at the same time. When the addition has taken place, the mixture is stirred for 15 minutes and then filtered to remove any insoluble substances, before a solution of 6.8 parts of 4-aminobeni5olaulfon-fl-chloroethylamide in acetone is added. The mixture is stirred for 7 hours at AQ ⁰ O , a pH of 6.8 to 7 being maintained by adding τοη 2N sodium carbonate solution, whereupon the mixture is filtered. 75 parts of potassium chloride are added to the pel and excretion of the dye, which is filtered off and washed with a solution of 60 parts of potassium chloride in 300 parts of water and then dried. In the case of colors τοη cotton with the dye, red-yellow shades result if the dyeing is carried out in the presence of an acid-binding agent.

Example 2

When using τοη 7.9 parts of 4-aminobenzenesulfon-ß, t-diohlorpropylamide instead of 6.8 parts of 4-aminobensolsulfon-ß-chloroethylamine according to Example 1, a dye of similar color and texture is obtained.

Example 3

When repeating τοη Example 1 instead of 5.1 parts Cyanuric chloride 5.8 part · 2,4,6-trichloro-5-oyanopyrimidine used. The suspension is stirred at 30 ° C. for several hours and then filtered. The filtrate is 6.8 parts of 4-aminobebesulfone-ß-chloroethylamide added, and this mixture is Stirred at 50 ° C. for 7 hours. After elimination by means of potassium chloride as in Example 1, a dye is obtained which is in similar in shade and texture to the dye of Example 1.

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If atatt the 15.25 parts of the trisodium salt of 2- (4'-Amino-2 '-ureidophenylazo) naphthalene-3 ₁ 6,8-trisulfonic acid according to Example 1 an equivalent amount of each of that in the 2nd column of the table below given diazo component and the dye obtained in the 3 * column given coupling component is condensed with cyanuric chloride and then with the compound given in the 4th column, dyes are obtained, the color shades of which are given in the 5th column of the table «

example

Tabel

2-naphthylamine-m-toluidine

3,6,8-trisulfo-

acid

·

"

Orthanilic acid

«-Phenylenediamine-o-sulfonic acid

N-methylaniline

p-aminobenzilsulfone yellow -ß-chloroethylamide

p-aminobenzenesulfone- ^n- β-chloropropylamide

4-N-methylanilnobenzene- " sulfone-ß-chloropropyl-

amide

m-ininobensoleulfone " -ß-chloroethylamide

1-Iaphthyl- · rotamine-6-sulfo yellow

acid

1- (4 "-amino- * yellow

3 * -sulfophenyl)

-3-hoethyl-5-

pyrasolon

1- (4 ^f -Sulfo- · ■ ■ · »

phenyl) -3-

carboxy-5-

pyrasolon

- (2 ^f , 5 '-Di- m-Jjainobenoleulf on- Green chlorine-4 ¹ - β, Υ-dichloropropyl yellow

sulfophenyl) amide

3-carboxy-5-

pyrazolone

8 3T / 1703

Table (continued)

Example 2 5 4 5

12 p-phenylenediamine- 1- (4'-SuIfO- m-aminobenzenesul- yellow o-sulfonic acid phenyl) -3- fon-ß, Y-dichloro-

methyl-5-propylamide pyrazolone

13 "" p-aminobenzenesul- "

fon-ß, f-dichloropropylamide

Example 14

A neutral aqueous solution of 26.9 parts of the monosodium salt of 1- (4'-Amines'-sulfophenyl) -3-diethyl-5-pyrazolone is added to a suspension of 18.5 parts of cyanuric chloride in 75 parts of acetone * and 150 parts of water dropwise added with stirring at O to 5 ⁰ C, and maintaining a pH value of 6 to 7 by simultaneous addition of 2N-lJatrlumcarbonatlöaung. After the reaction, a solution of 23.4 parts of 3-Aminobenzolsulfon-ß-chloräthylamid in acetone is added, and the temperature is at 40 - 45 ⁰ O accommodated, while a pH of 6 bie 7 is maintained by addition of 2N-Hatriuraoarbonatlöaung is * The mixture is kept at this temperature for several hours and then brought to 5-10 ⁰ O.

30 parts of concentrated hydrochloric acid are added to a neutral solution of 17 »4 parts of orthanilic acid in 400 parts of water, whereupon the suspension is cooled down ^{to 0 to 5 ° C.} Sine aqueous solution of 7 parts tfatrlumnltril wira dropwise over 15 Hinuten at 0 * 5 ⁰ C added. NaCN the addition, the Diazonlumsalzlösung the suspension of the coupling component (s paragraph 1.) Was added and the mixture is stirred at 5 - stirred 10 ⁰ O, while a pH value of 6 to 7 by addition of a 20jf-strength Natrlumcarbonatlösung is maintained. After continuous stirring for several hours, the product is precipitated by adding salt and then filtered off, washed with a 20% salt solution and removed

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«· 1 'j ° -
air dried at 40 ° C «When dyeing vqh. B & vaawcslle in the presence of an agent results in säurefbindenden exerts dye yellow tints.

Example 15

A suspension of 5.1 parts of cyanuric chloride in 25 parts of acetone and 100 parts of Eiswaeser at 0-5 ° "* L a solution of 6.8 parts of 3-aminobenzenesulfone-ß-ciilorätl ^ rlamid in acetone is added with stirring, with a pH 6 to 7 is maintained by adding a 2N sodium carbonate solution. The suspension is stirred for several hours . a neutral solution of 15 »25 parts of the TrimatrJhiaiealzes of 2- (4 '-amino-2 * -ureidophenylaso) naphthal & n-3 $ £, S-trisulf oeäure in 250 parts of water eye give, after which &±" mixture at 40 * 45 ⁰ O is stirred while a pH value of 6 to 7 is maintained by adding 2N sodium carbonate solution. After the reaction has taken place, the dye is isolated as in Example 1.

Patent claims:

0Ό9837 / 1703 _BAD

OBiGiNAL

Claims (3)

Claims 1. Process, sur production of water-soluble reactive dyes, characterized in that monoazo dyes the formula: R y R « whereby: A is the remainder of a diazo component of the benzene or Represents a row of caphthalene, S is the remainder of an amine coupling in the para position Benzene or caphthalene series or a 5-pyraeolone, Represents 5-aminopyrasol or aoetacetarylamid series, T represents a pyriaidin or s-trlazine nucleus which carries a reactive chlorine or bromine atom and via a nitrogen atom with an aromatic nucleus A or S is linked, R and R ¹ each represent a hydrogen atom or lower alkyl represent radical, Z is a lower ft; A-Alkylenradlkal, and T represents a chlorine or bromine atom, be caused by the fact that a compound of the formula: A - H - N - El - T - halogen where A, E and T have the above meanings, and where under Halogen is to be understood as a second chlorine or bromine atom attached to f, with a compound of the formula 0 (^ 9837/1703 16U264 where R, R ¹ , 7 and Z have the meanings given above, is caused to react. 2. Modification of the method according to claim 1, characterized in that a compound of the formula: [a-f-i-e] where A and E have the meanings given in claim 1, and where one of the radicals A and E is a nitrogen atom with an acylatable hydrogen atom, and a compound of the formula Halogen - T ¹ - N -f """! ^ An κ ν ι ι IJ ² I
R \ ^ _Rt where T ^{1 represents} “inen” in reactive chlorine or bromine atom-bearing pyrimidine or s-triazine kera, where halogen is a second chlorine or bromine atom attached to T *, and where R, R *, T and Z are those specified in claim 1 Have meanings, be made to react with one another. 3. Modification of the method according to claim 1, characterized in that the siazonium compound of a diazo component of the benzene * or ITaphthalene series with an amine of the benzene or naphthalene series coupling in para position or is coupled with a 5-pyrazolone, 5-aminopyrazole or acetacetarylamide coupling component, either the Dlasonian bond or the coupling component Group of the formula: - ϊ - Z 009837/1703 16U264 which is attached via a nitrogen atom, where T, R, R ¹ , Y and Z have the meanings given in claim 1. 4 «monoazo dyes of the formula: L J, whereby: A is the remainder of a diazo component of the benzene or Represents naphthaian series, E is the remainder of an amine coupling in the para position the benzene or naphthalene series or one 5-Pyrazolon-, 5-Aainopyraaol- or Aeetacetaryl- amide series represents, T represents a pyrialdine or s-triacine nucleus which carries a reactive β chlorine or bromine atom and via a stioketoff atom with an aromatic nucleus connected by A or B, R and R * each have a hydrogen atom or a lower alkyl represent radical, Z represents a lower alkylene radical, and T represents a chlorine or bromine atom. 009837/1703