JPS5853667B2 - Monoazo dye and its manufacturing method - Google Patents

Description

[Detailed description of the invention] The present invention relates to monoazo dyes.

The dye according to the present invention has the following general formula I: It is a dye made of a compound.

In the above formula, R1 represents hydrogen, alkyl (ci~2), unsubstituted phenyl, or phenyl substituted with one substituent selected from chlorine, bromine and cyano,
R2 is alkyl (C1-2) or alkoxy (C1-2
), R3 represents hydrogen, alkyl (C1-2) or alkoxy (C1-2), and R4 represents alkyl (C1-2);
4) or allyl, R3 is alkyl (C1-2)
or represents β-alkoxy(C1-2)ethyl, al
kylene represents an alkylene chain having 2 to 4 carbon atoms (at least 2 carbon atoms in the chain).

For compounds of formula (1), R1 is preferably methyl or hydrogen, more preferably hydrogen.

Preferably R2 is methoxy or methyl, more preferably methyl.

Preferably R3 is hydrogen.

Preferably R4 is ethyl, propyl or allyl, more preferably ethyl.

Preferably R6 is methyl or ethyl, more preferably ethyl.

Preferably, alkylene is ethylene.

Among the compounds according to the present invention, R1 is hydrogen or methyl, R2 is methyl or methoxyethyl, R3 is hydrogen, the peak is ethyl, and R5 is methyl, ethyl, β-methoxyethyl. or β-ethoxyethyl, and the alkylene is as defined in formula I above, preferably ethylene.

More preferred compounds are those in which R1 is hydrogen or methyl;
R2 is methyl, R3 is hydrogen, R4 is ethyl, R5 is methyl or ethyl, alkyle
The most preferred compound is a compound in which ne is ethylene, and the most preferred compound is a compound in which R1 is hydrogen and R6 is ethyl.

According to the invention there is provided a process for producing dyes comprising compounds of formula I.

In this method, a diazonium salt of an amine represented by the following formula (1): [In the above formula, R1 represents the same thing as defined above] is converted into a diazonium salt of an amine represented by the following formula (2): [In the above formula, R2s R3] R42R5 and a lky 1ene are The same thing as in the above definition] is coupled with a compound represented by:

This process may be carried out in a conventional manner, for example in an acidic medium, buffered if necessary, in the pH range below 5.

It is suitable to use temperatures below 20°C, preferably between -5°C and +5°C.

Preferably, the buffer is an alkali metal salt of a low molecular weight alkanoic acid, such as acetic acid or propionic acid, with sodium acetate being a preferred buffer.

The resulting compounds are isolated and purified in conventional manner.

Compounds of formula (1) are known or can be obtained in conventional manner from available starting materials.

The compound of the formula (1) is obtained by condensing an equimolar amount of the glycol ether of the formula R5-0 CH2CH2-OH with phosgene, and converting the resulting reaction product into an equimolar amount of the following formula (2): [In the above formula, R2, R3 , R4, R5 and alkylene
e represents the same thing as defined above] It is produced by condensation with the compound shown below.

Such processes may be carried out in a manner customary for the type of reaction involved, for example in a water-free inert solvent such as pyridine.

The compounds of formula I are disperse dyes which can be used to dye synthetic or semi-synthetic, hydrophobic, polymeric organic materials, especially linear aromatic polyesters, cellulose-200 acetate,
It is useful for dyeing or printing substrates made of cellulose triacetate and synthetic polyamide materials, especially textile substrates.

The dyeing or printing of such substrates is carried out in the customary manner using customary amounts of dyestuffs and as described, for example, in French Patent No. 1,445,371.

The compounds of formula (2) are preferably used in the form of dye preparations which can be prepared in a conventional manner, such as by grinding with dispersants or fillers and drying using vacuum or spray drying methods.

The compounds of formula (1) have a good affinity for substrates which can be dyed with them, and their good affinity for cellulose acetate substrates is of particular interest.

Furthermore, the dyeings obtained have sufficient all-round fastness properties, such as sunlight, heat setting, pleating, water, seawater, washing, perspiration, dry cleaning, abrasion, overlays, dry cleaning, solvents such as solvents and lubricants, etc. Fastness to dyeing, ozone, flue gases and chlorine.

The dyeings are resistant to various permanent pressing processes and antifouling treatments.

Furthermore, these dyes have good decolorizing properties, resistance to reduction, and non-staining properties on wool and cotton.

The following examples are intended to explain the present invention in more detail, in which "parts" and "%" are expressed by weight.

Example 1 14.5 parts of 2-ano-5-nitrothiazole were added to 0
~5°CK Scratch and add portionwise to a mixture consisting of 107 parts of nitrosyl sulfuric acid (prepared by dissolving 7 parts of sodium nitrite in 100 parts of concentrated sulfuric acid), 85 parts of glacial acetic acid, and 15 parts of propionic acid. A mixture of 85 parts of glacial acetic acid and 15 parts of propionic acid was added to the resulting mixture at 0-5°C, and then stirred for 3 hours at 0-5°C. 29 in propionic acid
．． 5 parts of a solution of a compound of formula: were added in portions under stirring and the resulting coupling mixture was stirred at 0-5°C for 3 hours.

The reaction mixture was poured under stirring into a mixture of 600 parts of ice in 300 parts of water and the dye precipitated.

Separate this and wash with water until acid and salt are no longer contained.
Dry.

The dye obtained dyes synthetic fibers in a blue color with outstanding all-round fastness.

This staining corresponds to the following formula. Examples 2-26 Other dyes of formula I were prepared analogously to Example 1 above using appropriate starting materials.

These dyes are shown in the table below.

All these dyes have remarkable all-round fastness to polyester materials.

gave a blue stain. The maximum absorption wavelength λmax of the dye obtained in the above example is shown below.

These 2m2M values were determined by dissolving each dye in dimethylformamide and 2% phosphoric acid.

APPLICATION EXAMPLES 7 parts of the dye obtained according to Example 1 are ground for 48 hours in a ball mill with 4 parts of dinaphthylmethane disulfonic acid (sodium salt), 4 parts of sodium cetyl sulfate and 5 parts of anhydrous sodium sulfate, It was made into a fine powder.

Make a paste of 1 part of the dye preparation obtained with a small amount of water, and pass the resulting suspension through a sieve into 3 parts of 4000 parts of water.
of sodium lauryl sulfate.

With a bath ratio of 1:40, 100 parts of refined polyester fiber material were added to this bath at 40-50°C, followed by 20 parts of chlorinated benzene emulsified in water.

Gradually heat the bath to 100°C, and at 95-100°C for 1-2
The bright blue dyed material was washed, soaped, rinsed and dried for an hour.

A uniform dyeing was obtained and the coat showed good fastness to sunlight, washing, water, seawater, perspiration, sublimation, flue gas, heat setting, pleating and permanent pressing.

Claims (1)

[Scope of Claims] 1 The following general formula I: [In the above formula, Ro is substituted with hydrogen, alkyl (C1-2), unsubstituted phenyl, or one substituent selected from chlorine, bromine, and cyano. R2 represents alkyl (C1-2) or alkoxy (Ct~
2), R3 represents hydrogen, alkyl (C1-2) or alkoxy (C1-2), and R4 represents alkyl (C1-2);
1-4) or allyl, and R5 represents alkyl (C1-4) or allyl;
2) or β-alkoxy(C1-2)ethyl,
alkylene represents an alkylene chain having 2 to 4 carbon atoms (at least 2 carbon atoms in the chain)] A dye consisting of a compound represented by the following. 2. The dye according to claim 1, wherein in formula I, R1 is methyl or hydrogen. 3. The dye according to claim 2, wherein R1 in formula I is hydrogen. 4. A dye according to claim 1, 2 or 3, having the general formula Ii/l- and R2 being methyl or methoxy. 5. The dye according to claim 4, wherein R2 in general formula I is methyl. 6. The dye according to any one of claims 1 to 5, wherein in general formula I, R3 is hydrogen. 7. The dye according to any one of claims 1 to 6, wherein in the general formula (2), R4 is ethyl, propyl, or allyl. 8. The dye according to claim 7, wherein in general formula I, R4 is ethyl. 9. The dye according to any one of claims 1 to 8, wherein in the general formula (2), 'R5 is methyl or ethyl. 10. The dye according to claim 9, wherein R5 in formula I is ethyl. 11. The dye according to any one of claims 1 to 10, wherein alkylene in general formula (2) is ethylene. 12 For general formula I, R1 is hydrogen or methyl, and R
2 is methyl or methoxy, R3 is hydrogen, R
A dye according to claim 1, wherein 4 is ethyl. 13. The dye according to claim 12, wherein alkylene in general formula I is ethylene. 14 According to general formula I, R1 is hydrogen or methyl, and R
2 is methyl, R3 is hydrogen, R4 is ethyl, R5 is methyl or ethyl, alkylen
A dye according to claim 1, wherein e is ethylene. 15 General formula I according to claim 14, where R1 is hydrogen and R5 is ethyl
15. The dye according to claim 14, wherein R1 is methyl and R6 is ethyl. 17. The dye according to claim 14, wherein in general formula I, R1 is hydrogen and R5 is **methyl. 18. The dye according to claim 13, wherein R1 in formula I is hydrogen, R2 is methyl, R4 is n-propyl, and R6 is ethyl. 19. The dye according to claim 13, wherein in the general formula (2), R1 is methyl, R2 is methyl, R4 is n-propyl, and R5 is methyl. 20 The following general formula ■: [In the above formula, R1 represents hydrogen, alkyl (C1-2), unsubstituted phenyl, or phenyl substituted with one substituent selected from chlorine, bromine and cyano, R2 is alkyl (C1-2) or alkoxy (C1-2)
2), R3 represents hydrogen, alkyl (C1-2) or alkoxy (C1-2), and R4 represents alkyl (C1-2);
1-4) or allyl, and R6 represents alkyl (C1-4) or allyl;
2) or β-alkoxy(C1-2)ethyl,
alkylene represents an alkylene chain having 2 to 4 carbon atoms (at least 2 carbon atoms in the chain)
When producing a dye consisting of a compound represented by *, a diazonium salt of an amine represented by the following formula ■: [In the above formula, R1 represents the same thing as defined above] is converted into a diazonium salt of an amine represented by the following formula ■: [In the above formula ,
R2-R5 and alkylene are the same as defined above.] A method comprising coupling with a compound represented by: