JPH0811785B2 - Monoazo compound - Google Patents

Description

The present invention relates to novel monoazo compounds, their mixtures, their preparation and the use thereof as dyes for dyeing or printing substrates, in particular polyester materials, which can be dyed or printed with disperse dyes. Regarding

The novel compounds of the present invention have the formula: (In the formula, R ₁ is a branched C ₃ -C ₇ alkyl group, and R ₂ and R ₃ are each independently a C ₂ -C ₄ alkyl group.).

Examples of R ₁ which is a branched C ₃ -C ₇ alkyl group include isopropyl, isobutyl, t-butyl, 2-methylpropyl, 2-methylhexyl, 3-methylhexyl, 2,2
-Dimethylpentyl and 1-ethylpentyl.
In preferred compounds, R ₁ is a branched C ₃ alkyl or C ₄ alkyl group, especially isopropyl, 2-methylpropyl and t-butyl.

R ₂ and R ₃ which are C ₂ -C ₄ alkyl include straight chain or branched chain alkyl groups, and examples of such groups include ethyl, n-propyl, isopropyl, n-butyl and There is t-butyl.

In preferred compounds, R ₂ and R ₃ are the same alkyl group. For example, a C ₃ alkyl or C ₄ alkyl group, especially ethyl.

More preferred compounds are alkyl groups R ₁ , R ₂ and R ₃
A compound having a total number of carbon atoms of at least 7 and not more than 12.

The invention also relates to at least one of the substituents R ₁ , R ₂ and R ₃ .
It also relates to mixtures comprising at least two different compounds of the formula I, such that the two differ in meaning. In the preferred mixture, each compound is present in approximately equal amounts.

Compounds of particular interest are those of formula and Containing two compounds of and The above three compounds are included.

(Wherein each of the substituents R ₁ represents the same and has the meaning defined in formula (I), for example isopropyl. Similarly, the last compound of each of the two mixtures is
By changing to a compound in which R ₂ and R ₃ are each ethyl, the mixture of interest is obtained.

The compound of the present invention and the mixture thereof can be produced by various methods known per se. That is, for example, the formula: (In the formula, Hal is a halogen atom.) The diazo component is diazotized, and the diazonium compound is represented by the formula: (Wherein R ₁ , R ₂ and R ₃ have the meanings defined in formula (I)) by coupling with a coupling component of the formula: Reacting the coupled product with a metal cyanide in a polar organic solvent with or without water gives a compound of formula (I). Hal is preferably bromine.

The mixture of the present invention can also be produced by various methods. For example: a) mixing at least two compounds of formula (I) or b) melting at least two compounds of formula (I) together, or c) formula (In the formula, Hal is halo.) The diazo component is diazotized, and the diazonium component is represented by the formula: (In the formula, R ₁ , R ₂ and R ₃ have the meanings defined in formula (I).) At least two types (the difference is the substituent R ₁ ,
At least one of the meanings of R ₂ and R ₃ is different. ) Coupling with a mixture of coupling ingredients from
By reacting the mixture of coupling products with a metal cyanide in a polar organic solvent with or without water.

If process a) is employed, the preparation of the mixtures according to the invention comprises mixing the individual compounds of formula (I) in the dry or wet state at room temperature. In particular, an anionic or nonionic dispersant and water are added to the mixture and the mixture is ground with the aid of grinding media (eg glass beads),
It is advantageous to have the dispersion ready for use. Examples of suitable anionic dispersants are the condensation products of naphthalene sulphonic acid and formaldehyde, in particular dinaphthylmethane disulphonic acid or modified lignin sulphonic acid.

Examples of known and particularly suitable nonionic dispersants are adducts of about 3 to 40 moles of ethylene oxide added to each mole of alkylphenols, aliphatic alcohols, and aliphatic amines.

If process b) above is employed for the production of the mixtures according to the invention, the compounds are melted together until a homogeneous melt is obtained, which is then allowed to cool, optionally with anionic or nonionic dispersion. It will be milled in the presence of milling media with the agent and water. This method also gives a dispersion ready for use.

The starting materials of formula (III) and (IV) are known and can be prepared by known methods. That is, for example, the expression Of the corresponding acyl amino aniline, and the alkyl halide of formula R ₂ -Hal or R ₃ -Hal, or alkyl sulfates of the formula R ₂ -O-SO ₃ H or R ₃ -O-SO ₃ H, or if R _{If 2} ≠ R ₃ , the mixture is reacted with an acid acceptor such as an alkali metal carbonate, especially sodium carbonate, to give a coupling component of formula (III).

The coupling reaction of the coupling component of formula (III) (individually or as a mixture) with the diazo component of formula (IV) is carried out in a known manner to give a coupling product of formula (II) or a mixture thereof. The coupling product or mixture can be isolated. The halogen atoms in the diazo component are subsequently replaced with cyano groups by reacting the compound of formula (II) or mixtures thereof with a metal cyanide. This reaction, which is preferably carried out with copper cyanide, is carried out in a polar organic solvent with or without water, such as dimethylsulfoxide, dimethylformamide or N-methylpyrrolidone or in a mixture of pyridine and water in the temperature range of about 40 to 150. ℃ preferably 80 ~ 130 ℃
And proceed appropriately.

The method for producing the coupling component of formula (III) is Hydrolyzing the compound of formula As a compound of formula (VI), comprising reacting the compound of formula (VI) with a carboxylic acid halide of formula Hal-CO.R ₁ .

The novel compounds of the formula (I) and their mixtures are used as dyes for dyeing and printing substrates which can be dyed with disperse dyes, in particular textile materials. If the compound has not been converted into a dye preparation during the manufacturing process, it is advantageous to convert it before use. For this purpose, the compounds can be ground to an average particle size of 0.01 to 10 μm. Grinding may be carried out in the presence of a dispersant. For example, a dry dye or dye mixture may be ground with a dispersant (grin
d) or knead as a paste with a dispersant (knea
d) followed by vacuum or spray drying. After adding water, the formulation thus obtained is either a high bath ratio liquid (substrate to dye ratio greater than 1: 5) or a low bath ratio liquid (substrate to dye ratio 1: 1 to 1: 1). 5) Can be used for dyeing, padding or printing.

This novel compound is prepared from an aqueous suspension or dispersion,
It is excellently exhausted on textile materials made of fully synthetic or semi-synthetic polymeric substances and gives a blue shade. This compound is particularly suitable for dyeing, padding or printing textiles, filaments, fleeces, woven or knitted fabrics made from linear aromatic polyesters, cellulose-21 / 2-acetate or cellulose triacetate. Synthetic polyamides, polyolefins, acrylonitrile polymers and polyvinyl compounds can also be dyed or printed with this novel compound. In particular, a highly valuable dyed product can be obtained when used for a chain aromatic polyester. Such polyesters are generally polycondensation products of terephthalic acid with glycols, especially ethylene glycol, or polycondensation products of terephthalic acid with 1,4-bis (hydroxymethyl) hexahydrobenzene.

The above polyesters can be prepared by a method known per se, for example, in the presence of a carrier in the temperature range of about 80 to 125 ° C.
Alternatively, without using a carrier, the temperature range is about 100 to 1 under pressure.
It can be dyed by the exhaust method at 40 ° C. These fibers can also be padded or printed with an aqueous dispersion of the compound and the impregnant obtained is fixed in the temperature range from about 140 to 230 ° C., for example using steam, contact heating or hot air. be able to. Cellulose-
21 / 2-acetate is suitable dyed in the temperature range from about 65 to 85 ° C, and cellulose triacetate is dyed at temperatures up to 115 ° C.

Usually, the above-mentioned conventional dispersants (preferably anionic or nonionic, which may be used as a mixture) are added thereto.

In the case of padding and printing, the customary pastes, i.e. modified or unmodified natural products such as alginic acid, dextrin, gum arabic, crystal gum, carob gum, tragacanth gum, carboxymethylcellulose, hydroxyethylcellulose, starch etc., or synthetic Thing such as polyacrylamide,
Polyvinyl alcohol or the like is used.

The dyeings obtained have excellent color properties, one of which is that, when mixed with other dyes, especially yellow dyes, when applied to textile materials, the compounds of the invention are catalytic It does not show fading and has excellent pH-stability, especially in exhaust dyeing. The compounds of formula (I) give level dyes, are very productive and have very good build-up properties.

The invention is further described by the following non-limiting examples. Parts and percentages are parts by weight and percentages by weight, respectively, unless otherwise stated.

Example 1: 3-dibutylaminoisobutyrylanilide (3
Produced by hydrolyzing dibutylaminoacetanilide with an aqueous alcoholic hydrochloric acid solution and reacting the resulting 3-dibutylaminoaniline with isobutyryl chloride or isobutyrylaminoaniline with excess butyl bromide. . ) 10.5 parts (0.036 mol) 5
It was dissolved in 300 parts of 0% acetic acid aqueous solution. To this, a diazonium salt solution (9.43 parts (0.036 mol) of 2,4-dinitro-6-bromoaniline) was added to 38 parts of 1N nitrosylsulfuric acid at about 20 ° C., followed by stirring at this temperature for 2 hours. ) To 0-5
It was added dropwise at 1.5 ° C. over 1.5 hours. formula The precipitate of the compound of (3) is suctioned off, washed with water and dried to a melting point of 153
This gave 18.1 parts (89.3% of theory) of a dark blue powder at ˜155 ° C. (sintered at 149 ° C.).

16.9 parts (0.03 mol) of the above powder was dissolved in 63 parts of pyridine. To this solution were added 2.85 parts of copper (I) cyanide and 36 parts of water. The reaction mixture was stirred at 60-70 ° C for 6.5 hours,
Suction at ℃, wash with a warm mixture of pyridine and water at 50 ℃, then wash with water and dry, Was obtained as a greenish brown powder with a melting point of 190-199 ° C. (sintering at 186 ° C.). Yield: 10.0 parts (65.4% of theory).

In a similar manner, a series of dyes of the following formula was obtained: Melting point 204-260 ° C, melting point of bromine precursor 145-150 ° C; Melting point 185 to 190 ° C (sintering at 176 ° C), melting point of bromine precursor 156 to 160 ° C (sintering at 144 ° C); Melting point 185 to 192 ° C, melting point of bromine precursor 150 to 156 ° C; Melting point 173-174 ° C (sintering at 170 ° C), melting point of bromine precursor 69-82 ° C; Melting point 118 to 128 ° C (sintering at 98 ° C), melting point of bromine precursor 141 to 148 ° C (sintering at 130 ° C); Melting point 214-260 ° C, melting point of bromine precursor 135-180 ° C.

Example 2: 5 parts of the dyestuff of the formula (1a) are mixed with 10 parts of a low salt content dispersant (dinaphthylmethanesulphonic acid type) and the mixture obtained is admixed with 85 parts of water and glass beads 300 with a diameter of 0.5 mm.
Parts were added and milled in a microsol mill. The resulting dispersion can be used for dyeing polyester materials.

In a similar manner, dyes of formula (1b), (1c) and (1d) or mixtures thereof, such as formula (1a) and formula (1
A dispersion of an equal mixture of dyes with d) can be prepared and used.

Example 3: Dyes of formula (1a) and (1b) in a weight ratio of about 50: 5.
A dye mixture with a proportion of 0 was obtained as follows. formula And the equimolar amounts of the two coupling components of The diazo component of 1 was coupled with the diazo compound, and the resulting mixture was reacted with CuCN to obtain a mixture of corresponding cyano derivatives. Diazotization, coupling and substitution of the bromine atom with cyano were carried out under the conditions given in Example 1.

Example 4: Formulas (1a), (1b) and Of a dye mixture containing the dye of 1-isobutyrylaniline with isobutyrylaminoanilide obtained by complex alkylation with an equimolar mixture of n-propylbromide and n-butylbromide, and diazobromoylaniline diazo. Prepared by coupling with a compound and converting the resulting mixture into a mixture of the corresponding cyano compounds. The individual steps were carried out according to the conditions given in Example 1.

Example 5: 4,000 parts of polyester fiber (Diolen) was immersed in 100,000 parts of a dye bath adjusted to pH 4 at 130 ° C. for 1 hour for dyeing. During this dyeing, 192 parts of the dispersion according to Example 2 (corresponding to 9.6 parts of dye) and 50 parts of wetting agent (for example methyl taurine of fatty acid) and dispersant (for example dinaphthyl methanesulfonate) are used. ) 50 parts included. A deep blue dyeing with very good fastness to light is obtained. The dyebath was completely exhausted.

Example 6: The procedure of Example 5 was repeated, buffering the dyebath to pH 5, pH 6, pH 7 and pH 8. A slight change in the color tone was observed above pH 6.

Continuation of the front page (56) References JP-A-56-143246 (JP, A) JP-A-49-87873 (JP, A) JP-A-54-152028 (JP, A) JP-B-41-4794 (JP , B1) European publication 39312 (EP, A1)

Claims (4)

[Claims] 1. A formula (In the formula, R ₂ and R ₃ are each independently a C ₂ -C ₄ alkyl group). 2. The monoazo compound according to claim 1, wherein R ₂ and R ₃ are each independently a C ₃ alkyl or C ₄ alkyl group. 3. The monoazo compound according to claim 1, wherein R ₂ and R ₃ are each ethyl. 4. A formula (Wherein Hal is a halogen atom) is diazotized, and the diazonium compound is represented by the formula (Wherein, R ₂ and R ₃ are each independently a C ₂ -C ₄ alkyl group), and a compound of the formula (Wherein Hal, R ₂ and R ₃ have the above meanings) The reaction product of the coupling product with a metal cyanide in a polar organic solvent containing or not containing water (In the formula, R ₂ and R ₃ have the above meanings) A process for producing a monoazo compound.