DE3536718A1 - Monoazo compounds - Google Patents

Abstract

Compounds of the formula <IMAGE> where R1 is a branched C3- to C7-alkyl radical and R2 and R3 are independently of each other a C2- to C4-alkyl radical, and also mixtures of these compounds which contain at least two compounds of the above formula and differ in at least one of the substituents R1, R2 and R3, are very highly suitable in particular for use as dyes for dyeing and printing polyester materials in level blue shades.

Description

- it-

Dr. F. Zumstein Sr. - Dr. "JE * Asö £ nän! H. * .. *» .. Dipl.-Ing.F. Klingseisen - Qr. H.Zurn & teun jura / ··· "

PAT E N TA N WÄ LT E 3536718

APPROVED REPRESENTATIVES AT THE EUROPEAN PATENT OFFICE REPRESENTATIVES BEFORE THE EUROPEAN PATENT OFFICE

CIBA-GEIGY AG 1-15116 / -

Basel, Switzerland)

Monoazo compounds

The invention relates to new monoazo compounds, their mixtures with one another, processes for their preparation and their use as dyes for dyeing and printing substrates which can be dyed or printed with disperse dyes, in particular substrates Polyester materials.

The novel compounds according to the invention correspond to the formula

- / "Vn - ν - /" Vi / ²

in which mean:

Ri is a branched C3 to C7-alkyl radical and R ₂ and R3 independently of one another are a C ₂ to Cit-alkyl radical.

Ri represents a branched C3 to Cy-alkyl radical for example iso-propyl, iso-butyl, tert-butyl, 2-methyl-propyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl and 1-ethyl-pentyl radical. In the preferred compounds Ri denotes a branched C3 or Ct, alkyl radical, in particular den iso-propyl, 2-methylpropyl and tert-butyl radicals.

R ₂ and R3 in the meaning of a C2-Ci, -alkyl radical represent unbranched and branched alkyl radicals; it is, for example, the ethyl, n- and iso-propyl and n- and tert-butyl radical.

- b-

In preferred compounds, R2 and R3 denote the same alkyl radical; for example, it is a C3- or Cif-alkyl radical, but especially the ethyl radical.

Furthermore, those compounds are preferred whose number of alkyl carbon atoms in Rx, R2 and R3 together is at least 7 and at most 12 is.

The invention also relates to mixtures of compounds which contain at least two compounds of the formula I which are in at least one of the substituents Ri, R2 and R3 from one another differentiate. In the preferred mixtures, the individual components are present in approximately equal parts.

A particularly interesting mixture is that of the 2 compounds of the formulas

/ NO ₂

/ ~ \ / ~ \ y ^{C3ii7 (n)}

O ₂ If-f> -n = N - ζ ; - h;

CN NHCOR ₁

CN NHCORi

as well as those from the 3 compounds of the formulas

/ NO ₂

O ₂ NJ> -N - ν - ζ >-ν;

CN NHCORi / NO ₂
O ₂ N- <> -N - N - <> X and

/ O ₂

^{C3fi7 (n)}

o ₂ n- <; -n - ν -

^N CN NHCORi

where Ri is identical in each case and that given under formula (I) Has meaning and means, for example, isopropyl. Equally interesting mixtures are obtained if you combine the two The latter compounds are replaced by one in which R2 and R3 are each ethyl.

The compounds according to the invention and their mixtures can according to various processes known per se are produced; the compounds of the formula (I) are obtained, for example, by a diazo component of the formula

0 ₂ N- () -NH ₂ (IV),

Nlal

wherein Hal denotes a halogen atom, diazotized and on a coupling component the formula

• Ο-ζ ^(ΙΠ) ·

NiicORi

in which Ri, R ₂ and R3 have the meaning given in formula (I), and the coupling product of the formula

/ O ₂

O ₂ N- ^ y ~ Tü ■ N - ' y ~ \ _ (H)

THaI NHCOR ₁

with a metal cyanide in polar, optionally aqueous, organic solvents. Hai preferably means bromine.

As far as the mixtures according to the invention are concerned, these too can produced by different processes, e.g. in such a way that one can:

a) at least two compounds of the formula (I) are mixed with one another, or

b) at least two compounds of the formula (I) are fused with one another, or

c) a diazo component of the formula

JiO ₂
OzN-K ¹ V-NH ₂ (IV),

where Hai means a halogen atom, diazotized and on a mixture of at least 2 coupling components of the formula

(III), NHCORi

which differ from one another in at least one of the substituents Ri, R ₂ and Rj and in which Ri, R ₂ and R3 have the meaning given in formula (I), couples and reacts the mixture of the coupling product with a metal cyanide in polar, optionally hydrous organic solvents .

If you work according to process variant a), there is production of the mixture according to the invention in that the individual compounds of the formula (I) are dried with one another at room temperature or wet mixed. It is also advantageous to use this mixture

Dispersants, especially of an anionic or nonionic nature, and water, and grinds this mixture with the aid of grinding aids (e.g. glass balls) to a ready-to-use dispersion.

Anionic dispersants which are suitable for this purpose are, for example, condensation products of naphthalenesulfonic acids and Formaldehyde, especially dinaphthylmethane disulphonate or modified lignosulphonate.

Examples of known and particularly suitable nonionic dispersants are addition products of about 3 to 40 mol of ethylene oxide with alkylphenols, fatty alcohols or fatty amines.

If the mixture according to the invention is prepared using the variant b), the compounds are melted together to form a homogeneous melt and then cooled left and optionally with anionic or nonionic dispersant and water in the presence of grinding aids marry; even after this variant you get a ready-to-use one Dispersion.

The starting products of the formulas (III) and (IV) are known and can be prepared by known methods. So you get For example, the coupling components of the formula (III) such that, for example, the corresponding acylaminoanilines of the formula

• ^) -NH ₂ (V) NiiCORi

with alkyl halides of the formula
R ₂ -HaI or R ₃ -HaI

or alkyl sulfates of the formula

R ₂ -O-SO ₃ H or R ₃ -O-SO ₃ H,

or mixtures thereof when Rg Φ R ₃ , in the presence of acid acceptors, such as alkali metal carbonates, especially sodium carbonate, is reacted.

The coupling reaction of the coupling components of the formula (III) (individually or as a mixture) with the diazo component of the formula (IV) takes place in a known manner, the coupling products of the formula (II) or a mixture thereof being obtained. This coupling product or the mixture can be isolated. The halogen atom in the diazo component is then replaced by the cyano group; this is done by reacting the compound (II) or a mixture thereof with metal cyanides. This reaction, which is preferably carried out with copper cyanide, is preferably carried out in a polar, optionally water-containing solvent, such as dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone or pyridine-water mixtures at a temperature of about 40 to 150 ^° C., preferably 80 to 130 ^° C.

Another way of producing the coupling components of the Formula (III) consists in that you can get a compound of the formula

-

S ₃

NHCOCH3
to a compound of the formula

! ■ 2

(VI)

hydrolyzed and then with carboxylic acid halides of the formula

HaI-CO-R ₁
implements.

The new compounds of the formula (I) and mixtures thereof are used as dyes for dyeing and printing substrates, in particular textile materials which can be dyed with disperse dyes. Before using these compounds Advantageously, if this has not already happened during production, converted into dye preparations. To do this, they can be crushed, like this that their particle size is on average between 0.01 and 10 μτη. The comminution can take place in the presence of dispersants. For example, the dried dye mixture with a Ground dispersant or kneaded in paste form with a dispersant and then dried in vacuo or by atomization. With the preparations obtained in this way, after adding water, in a long liquor (liquor ratio greater than 1: 5) or dye, pad or print short liquor (liquor ratio 1: 1 to 1: 5).

The new compounds draw from aqueous suspension or dispersion excellent on moldings made from fully synthetic or semi-synthetic high molecular weight substances in a shade of blue. They are particularly suitable for dyeing, padding or printing fibers, threads or fleeces, woven or knitted fabrics made of linear, aromatic polyesters and cellulose-2 1/2-acetate and Cellulose triacetate. Synthetic polyamides, polyolefins, acrylonitrile polymerisation products and polyvinyl compounds can also be used to be colored and printed with them. Particularly valuable dyeings are obtained on linear, aromatic polyesters. These are in general polycondensation products from terephthalic acid and glycols, especially ethylene glycol, or polycondensation products from terephthalic acid and 1,4-bis (hydroxymethyl) -hexahydrobenzene.

Are dyed, the polyester fibers according to methods known per se in the presence of carriers at temperatures between about 80 and 125 ° C or in the absence of carriers under pressure at about 100 to 140 ⁰ C by the exhaust method. Further, one can these fibers with the aqueous dispersions of the compounds padding or printing, and the impregnation obtained fix at about 140 ° to 230 ⁰ C, for example with the aid of steam, contact heat or hot air. Cellulose 2 1/2 acetate is dyed preferably between about 65 to 85.degree. C. and cellulose triacetate at temperatures of up to 115.degree.

Usually the usual dispersants already mentioned are added, which are preferably anionic or nonionic and can also be used in a mixture with one another.

The usual thickening agents are used in padding and printing use, e.g. modified or unmodified natural products, e.g. alginates, British gum, gum arabic, Crystal gum, locust bean gum, tragacanth, carboxymethyl cellulose, hydroxyethyl cellulose, starch or synthetic products, for example polyacrylamides or polyvinyl alcohols.

The dyeings obtained have good coloristic properties; Particularly noteworthy is the property of the invention Compounds with any dyes, especially yellow dyes, mixed and applied to textile material, none to show "catalytic fading" (i.e. no negative influence on the lightfastness when mixed with other dyes) and further have good pH stability, especially in the exhaust process. The compounds of the formula (I) give level colorations very strong in color and show a very good build-up capacity.

The following examples further illustrate the invention without to limit them to that; Temperatures are given in degrees Celsius; Parts and percentages mean unless otherwise is indicated, parts by weight and percentages by weight.

Example 1 : 10.5 parts (0.036 mol) of 3-dibutylamino-isobutyryl-anilide, prepared by hydrolysing 3-dibutylaminoacetanilide with alcoholic aqueous hydrochloric acid and reacting the 3-dibutylaminoaniline obtained with isobutyryl chloride or from isobutyrylaminoaniline by reacting with excess butylbromide 300 parts of 50% strength aqueous acetic acid are dissolved and a diazonium salt solution is added dropwise over the course of 1/2 hour at 0-5 °, which is obtained by introducing 9.43 parts (0.036 mol) of 2,4-dinitro-6-bromoaniline in 38 parts IN nitrosylsulfuric acid was obtained at about 20 ° and then stirred for 2 hours at this temperature. The precipitated compound of the formula

/ O ₂
0 ₂ N- · ^ ^ -N - N - ^ VS

CH ₃

is suction filtered, washed with water and dried. 18.1 parts (89.3% of theory) of dark blue powder with a melting point are obtained 153 to 155 ° (sintering at 149 °).

16.9 parts (0.03 mol) thereof are dissolved in 63 parts of pyridine, with 2.85 parts of copper-I-cyanide and 36 parts of water are added and the mixture is stirred for 6.5 hours at 60-70 °, suction filtered at 50 °, at 50 ° Pyridine-water mixture, then washed with water and dried. The dye of the formula is obtained

(la), —f .- .. C, H ₉ (n) 0 ₂ N- () -N = N -ζ / - \

CH ₃

as a green-brown powder with a melting point of 190 to 199 ° (sintering at 186 °). Yield 10.0 parts (65.4% of theory)

The dyes of the formulas are obtained in an analogous manner:

(Ib) .- <, -ν C ₃ H ₇ (n) O ₂ Nf> -N - N -f> · <

NHCOC ^

^{# =} ', CH ₃ ^{Xc3H7 (n} >

'CH ₃

Melting point 204 to 260 ° melting point of the bromine precursor 145 to 150 °;

O ₂ N- ( > -N β Ν -ζ; · -ΝΤ

- \) ^{f =} _ΓΗ C, H ₉ (n)

^CN NHCOCH ₂ - ^

egg

Melting point 185 to 190 ° (sintering at 176 °) melting point of the bromine precursor 156 to 160 ° (sintering at 144 °);

JIO ₂

(Id), .- <, .-. C ₂ H ₅ ^ ^ .- N = N --ζ /

t s «rc

\. _M / .CH ₃ ^CN NHCOC |

CH ₃

Melting point 185 to 192 ° melting point of the bromine precursor 150 to 156 °;

(Ie), - <.-SC ₂ H ₅

o ₂ N -. () .- N = ν --ζ ; - \

"\ ν **" C ₂ H ₅

COCH (CH ₂ ) ₃ CH ₃ CH ₂ CH ₃

Melting point 173 to 174 ° (sintering at 170 °) melting point of the bromine precursor 69 to 82 °;

df) .—; .-ν C ₂ H ₅

o ₂ N- (; .- N - ν - ( y ~ \

' ~ C ₂ H ₅

CN

"CH ₃

Melting point 118 to 128 ° (sintering at 98 °) melting point of the bromine precursor 141 to 148 ° (sintering at 130 °);

/ NO ₂

O ₂ N- () - N = N - ( s' - \

C ₃ H ₇ (n)

COCH ₂ -ΪΗ CH ₃

Melting point 214 to 260 °. Melting point of the bromine precursor 135 to 180 °.

Example 2 : 5 parts of the dye (Ia) are mixed with 10 parts of a low-salt dispersant (dinaphthylmethanesulfonic acid type) and ground in a microsol mill in 85 parts of water with the aid of 300 parts of 0.5 mm diameter glass spheres. The dispersion obtained can be used for dyeing polyester materials.

In the same way, dispersions of the dyes (Ib), (Ic) and (Id) or mixtures thereof, e.g. equal parts of the dyes (la) and (Id), can be prepared and used.

Example 3 : The dye mixture containing the dyes of the formulas (Ia) and (Ib) in a ratio of approx. 50:50% by weight is obtained by adding equimolar amounts of the two coupling components of the formulas

y- _X C ₃ H ₇ Cn) ./-\_/

. . M. UUU. «.

; -; ^N C ₃ H ₇ (n)) - rw

/ CH ₃ / CH ₃

NHCOCH NHCOCH

CH ₃ CH ₃

with a diazotized diazo component of the formula

/ O ₂

couples and converts the mixture obtained with CuCN to the corresponding mixture of cyan derivatives. Diazotization, coupling and The bromine atom is exchanged for cyano under the conditions given in Example 1.

Example 4 ; A dye mixture containing the dyes of the formulas (la), (Ib) and

0 ₂ N- <> -N = N - ( > - <(lh)

CH ₃

is obtained by the mixed alkylation with equimolar Amounts of n-propyl and n-butyl bromide obtained isobutyrylaminoanilides coupled with diazotized dinitrobromaniline and the resulting mixture in a mixture with the corresponding cyano compounds convicted. The individual steps are carried out under the conditions specified in Example 1.

Example 5 : 4000 parts of polyester fabric (Diolen.) Are added to 100,000 parts of a dyebath adjusted to pH 4, the 192 parts of a dispersion according to Example 2 (corresponding to 9.6 parts of dye) and 50 parts each of a wetting agent (eg fatty acid -Methyltaurid) and a dispersant (eg based on Dinaphthylmethansulfonat), colored for one hour at 130 °. A strong blue coloration with very good lightfastness is obtained. The dye bath is completely drawn off.

Example 6 : If dyeings are carried out according to Example 5, but with the difference that the dyeings are buffered at pH 5, 6, 7 and 8, a slight change in shade is only noticed at pH 6.

Claims (12)

Claims 1. Monoazp ^ ßrbindungen of the formula where mean: Ri is a branched C3 to CyAlkylrest, and R2 and R3 independently of one another are a Cg to Οι, -alkyl radical. 2. monoazo compounds according to claim 1, characterized in that that Ri is a branched C3 or C ^ -alkyl radical. 3. Monoazo compounds according to claim 1, characterized in that R2 and R3 independently of one another are a C3 or Ci, -alkyl radical mean. 4. monoazo compounds according to claim 1, characterized in that the number of alkyl carbon atoms of Ri, R2 and R3 is at least 7 and is a maximum of 12. 5. monoazo compounds according to any one of claims 1, 2 or 4, wherein R2 and R3 each represent ethyl. 6. Mixture of compounds containing at least two in claim 1 defined monoazo compounds which differ from one another in at least one of the substituents Ri, R2 and R3. 7. A process for the preparation of compounds defined in claim 1, characterized in that one has a diazo component of the formula / O ₂ O ₂ N- wherein Hal denotes a halogen atom, diazotized and on a coupling component the formula NHCORi S, wherein Ri, R ₂ and R3 have the meaning given in claim 1, couples and the coupling product of the formula / NO ₂ . ν NiiCORi 0 _2N - / "\ - _N. Ν _ / ~ \ ϊ / is · »· jR.3 with a metal cyanide in polar, optionally water-containing organic solvents. 8. A process for the preparation of mixtures defined in claim 6, characterized in that one a) at least two different compounds of the formula given in claim 1 mixed with one another, or b) at least two different compounds of the formula given in claim 1 fused with one another, or c) a diazo component of the formula / NO ₂ wherein Hal represents a halogen atom, diazotized and on a mixture of at least 2 coupling components of the formula which is in at least one of the substituents Ri, R2 and R3 differ from each other and wherein Ri, R2 and R3 are those in claim 1 Have given meaning, couples and the mixture of the coupling product with a metal cyanide in polar, optionally aqueous organic solvents. 9. Use of the compounds defined in claim 1 or the im Mixtures defined in claim 6 as dyes for dyeing and printing of dyeable or printable with disperse dyes Substrates. 10. Use according to claim 9 for dyeing and printing Textile materials. 11. Use according to claim 10 for dyeing and printing polyester materials. 12. The materials dyed and printed according to claims 9 to 11. FO 7.1 RI / eg *