JPS6020419B2 - Azo compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to azo compounds and their preparation and uses.

According to the present invention, a compound represented by the following general formula 1 is provided.

・In the above formula, R,' is -C ratio CH20 days or 1CQCOCH
3, R2' represents chlorine or bromine, RS represents hydrogen, chlorine or bromine, R6' and R7' each independently represent (C. to 4) alkyl, R and o are methyl, Represents ethyl, chloromethyl, bromomethyl, chloroethyl, bromoethyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methylpinyl, methoxy, ethoxy, methoxy or ethoxyshetoxy.

Preferably R8' and R7' are the same, most preferably both are ethyl.

Preferably R,o are methyl, ethyl, methoxyethyl or ethoxymethyl.

The present invention also provides a method for producing a compound of formula 1, which comprises the following formula 0: ] Coupling the diazonium compound obtained from the amine represented by the following formula m:m [in the above formula, R6', R7' and R, o represent the same as defined above]. Contains.

Diazotization and coupling reactions can be carried out according to known methods.

A compound in which R,' in formula D is -CQCOCH3 is, for example, a compound of C&COCH2-Hal [ratio 1 represents chlorine, bromine or iodine] as shown in the following formula W: W [in the above formula, R2' and R8 are the above-mentioned Same as the regulations, A
cyl represents acyl] and preferably 1:
It can be prepared by condensation and then saponification of the acylamino groups in a molar ratio of 1.

The condensation reaction is easily carried out in an inert solvent, such as water or dioxane.

A suitable reaction temperature is 20 to 100 qo, preferably 20 to 100 qo.
The temperature range is 85°C. Saponification can be carried out by known methods, preferably by acidification with a dilute mineral acid.
Compounds of formula 0' in which R,' are hydroxyethyl groups can be prepared by reacting the free acid of the compound of formula W with the corresponding alkylene oxide and then saponifying the acyl amide/group.

The reaction of the free acid of a compound of formula W with an alkylene oxide can be carried out analogously to known methods.

Saponification can be carried out as described above. formula m
The compounds represented by and W are known or can be produced from known starting materials by conventional methods.

The compounds of formula 1 are useful as disperse dyes and can be converted into dyeing preparations by known methods, for example by comminution in the presence of dispersants and/or fillers.

The dyeing preparations can be vacuum- or pulverized-dried and used for dyeing from long or short baths or for pad dyeing or printing. These dyes may be obtained in polymorphic, heat-labile forms and in such cases one of the methods described below may be used.
is advantageously transformed into a thermally stable form. 'a}
5 to 30 qC in water at a temperature of 20 to 100 qC, preferably 50 to 10 qC, in the presence or without the intervention of a surfactant or a water-insoluble or soluble organic solvent.
Key worship for 0 minutes (as a general rule, 15 to 45 minutes is sufficient).

[b' Same as {a) above. However, 10 in autoclave
At a temperature of 0 to 150°C, preferably 125 to 13°C.
'c} 50-140qo, preferably 100-140
At qo, vacuum drying or drying at normal pressure. [d' Recrystallization from organic solvent.

After the coupling is complete, the reaction mixture is heated to 50-100° C., preferably 60-90° C., adjusted to 4-7 to avoid saponification.

In exceptional cases, the dyestuff is ground in the presence of water and a dispersing agent, and then the dyestuff is ground for 5 minutes, taking care that no enlargement of the particles occurs.
It may be heated to 0-100°C, preferably 60-9000°C.

By carrying out the coupling reaction in the presence of surfactants or organic solvents, the formation of thermally unstable crystalline modifications is often avoided.

Even if any of the above-mentioned operations [a-'0] are carried out, the following advantages are particularly obtained.

(j) Improved dispersibility {In most cases, the production of sufficiently thermally stable dispersions at the dyeing temperature will result in thermally stable (i.e.
Only possible for heat-treated J pigments.

}. (ii) Improved build-up performance.

(ii) Increased solids content of the press cake (often important in the production of liquid dye formulations).

The dyes according to the invention can be used for dyeing or printing substrates made of or containing synthetic or semi-synthetic hydrophobic polymeric organic materials from aqueous suspensions.

Examples of such materials include linear, aromatic polyesters, cellulose 21/2 acetate, cellulose triacetate and, if the compound of formula 1 contains at least one hydroxyl group in R,', synthetic polyamides. There is. The substrate may be in the form of loose wool, yarn or cloth. Dyeing or printing can be carried out by known methods, for example the method described in French Patent No. 1,445,371. The dyeings obtained have outstanding light fastness, fastness to heat setting, sublimation and pleating, wet fastness, e.g. to washing, perspiration,
It has fastness to solvents, especially dry cleaning, multi-bath dyeing, ozone, Kando gas, chlorine and abrasion. Dyeing is done through various permanent press processes,
Antifouling and reduction (for dyeing mixtures containing wool)
shows remarkable resistance to These dyes do not stain wool and cotton. The following examples serve to further explain the invention.

In the examples, "parts" and "%" are expressed by weight. Example 1 'a1 Preparation of the diazo component 234 parts of 4-acetylamino-3-chlorobenzenesulfinic acid were added to a solution of 800 parts of water and 48 parts of sodium hydroxide.

Raise the temperature from 25°C to about 4°C and add 100% to this suspension.
of ethylene chlorohydrin was added over 20-30 minutes to obtain a brown solution. The reaction mixture was heated to reflux temperature (87°C)
I worshiped flies for three hours. The mixture was then allowed to cool to room temperature, and the crystalline precipitated product was filtered out and washed with a small amount of water. The furnace residue was boiled for 45 minutes at reflux temperature in a mixture of 80 parts water and 50 parts concentrated hydrochloric acid.

Five parts of decolorizing charcoal were added to the resulting solution, which was allowed to stand for a few more minutes and filtered. Volume 200 of clear furnace filtration solution with water
Adjusted to 0 guys. 'b) Preparation of dyes 200 g of the solution obtained as above was cooled to 0° C. by adding 10 g of ice and then 30 g with a solution of 6.9 parts of sodium nitrite in 50 g of water. Diazotization occurred within ~60 minutes.

Condensation was continued for an additional 30 minutes, 5 parts of aminosulfonic acid was added, and the resulting solution was filtered. The resulting diazonium salt solution was mixed with 20.6 parts of 3-acetylamine/-
It was added portionwise to a mixture consisting of 1-N,N-diethylaminobenzene, 5 parts glacial acetic acid, and 10 parts ice.
Sodium acetate was then added until the pH was 2.0-2.5 and heating continued for an additional 1-2 hours at 0-5° C. until the coupling was complete. The resulting dye was separated from the oven, washed with water, and then washed with 1000 parts of water in an autoclave and heated at 130° C. for 2 hours. After cooling to room temperature, the dye was separated in an oven and dried. The dye obtained above corresponds to the following formula and dyed synthetic fibers in bright red with extremely good fastness.

Example 2 6. $ 60 of powdered sodium nitrite
At ~70 qo, it was added to 10 parts of concentrated sulfuric acid.

Continue spraying at 60 pm for 1 minute, then apply this solution for 10 pm.
It was cooled down at midnight. At a temperature of 10 to 15 qo, 10 g of glacial acetic acid is added in portions, followed by 24.7 parts of the following formula:
After stirring for 2 hours, the resulting diazonium salt solution was heated to 20.
It was poured onto a mixture consisting of 6 parts of 3-acetylamino-1-N,N-jethylaminobenzene, 50 parts of glacial acetic acid, 30 parts of ice and 1 part of amidosulfonic acid.

The coupling was completed in acidic medium by adjusting the pH to 2.0-2.5 with sodium acetate. A dye was immediately formed and precipitated. This was filtered through an oven, washed until the acidity disappeared, and dried. A dyestuff of the following formula was obtained which dyed synthetic fibers in a bright red color of excellent fastness.

of the compound and 10 parts of glacial acetic acid were added.

A solution of 46.5 parts of this dye was suspended in 20 ml of dimethylformamide, 10.4 parts of Cu-cyanide or 12 parts of zinc methylsulfinate and 1 part of Cu-cyanide.
Together with bronze powder, it was heated to 13 psi for 180 minutes under the heat. This gave the corresponding 2-cyano or 2-methylsulfonyl substituted dyes. These dyes also dyed polyester fiber materials in red with good fastness.
Examples 3-23 In the examples shown in the table below, R,' is -CQCH20
It is day.

Table 1 Example 24 The following dye was obtained, which imparted a red color to polyester fibers.

R,': -CH2COCH3 R2': CI R3': CI R6': - Mr. C2 R7':-C2 melon R.

:1CHCICH3^maX:531mm Application example A 18 parts of the dye prepared as described in Example 1 were
．． 1 part sodium dinaphthylmethane disulfonate, 1 part
It was ground into a fine powder in a ball mill for 4 hours with 1.1 parts of sodium cetyl sulfate and 13.9 parts of anhydrous sodium sulfate.

1.5 parts of the dye preparation thus obtained were suspended in 300 parts of water containing 3 parts of a 30% solution of highly sulfonated castor oil and 2 parts of an emulsion of chlorinated benzene in water. . Add 20 to 25 q0 and 10 anchor parts of polyester fiber cloth to this bath, and increase the density to 95 to 10 in about 30 minutes.
It was heated to 0°C and dyed for 1 hour at this temperature. The dyed fabric was removed from the rack, washed with water, and treated with a 0.1% solution of alkylphenyl polyglycol ether at 70°C for 15 minutes.
Soaped for a minute, rinsed again, and dried. A red dyeing with excellent fastness properties was obtained. Application example B ta Dye 'all1 produced as described in Example 2
．． Commercially available ligene sulfonate of 7 days and 19.3 days was added to 1
10 by 00 evening's Kei rock beads and two-blade rope lasso machine.
Grinding was carried out for 2 to 8 hours at 2000 to 5000 times/min in ~15 liters of water.

The crushed pillow prey was diluted with approximately 30 g of water and filtered through a glass 0 vacuum filter GI into a 1000 pear-shaped flask. The dye and dispersant particles adhering to the quartzite beads were quantitatively washed into the pear-shaped flask with as little water as possible. The resulting dispersion was adjusted to pH 6-6 with 10% phosphoric acid.
．． 5 and then evaporated to dryness in a rotary evaporator at a maximum external temperature of 60°C. 100% purified polyester fiber material "Terylene" (registered trademark)
40~000 in a dispersion of the above dye preparation in water for 2 nights.
It was added at 50 qo and heated slowly.

Dyeing was carried out under pressure at 130° for about 60 minutes, and after washing, soaping, washing and drying, a red dyed product with excellent fastness was obtained. Application Example C An aqueous, finely dispersed suspension of the dyestuff of Example 15 (prepared as described in Example 1) consisting of 1 part, 2 parts sodium dinaphthylmethane disulphonate and 3 parts sodium alginate is mixed with water. 100 parts were mixed well.

A polyester cloth was padded with the badding liquid obtained above at 20°C, and squeezed to a liquid content of 70% for 60 minutes.
Air dry at ~100 qo, then heat dry air for 2
It was treated at 30qo for 60 seconds. The Futomi was then washed with water, soaped, washed again with water, and dried. A red dyeing with excellent fastness properties was obtained. Application example D Dyes obtained as described in Example 1 10.5 and 1
9.5 days' worth of commercially available sulfonic acid lignin, 100 days' worth of silica beads and a two-blade hawk azuma machine, in 10-15' water in a 200' beaker at 20-30°C, 2000°C.
Milled at ~250 blocks/min for 2-8 hours.

The grind was diluted with approximately 30' water and filtered through a glass suction filter GI into a 1000' pear-shaped flask. The dye and dispersant particles adhering to the silica beads were quantitatively washed into the pear-shaped flask with as little water as possible. The resulting dispersion was adjusted to pH 6-6.5 with 10% phosphoric acid and evaporated to dryness in a rotary evaporator at a maximum external temperature of 60°C. 3 parts Na in 400 eaves of water
A solution of 3P04.1 was adjusted to a strength of 9 with NaH2P04 and then 1 part of 25 mole ethylene oxide adduct of 1 mole oleyl alcohol was added.

To this solution was first added 1 part of the dye preparation obtained above and then 10 parts of nylon carpet (DuPon
t nylon 846) was added. The bath was heated to 98° C. for 30 minutes and dyed at 98° C. for 60 minutes, then the dyed fabric was removed from the rack, washed with flood water, then cold water and dried. A red dyeing with excellent fastness properties was obtained. Application Example E 20 parts of the dye of Example 20 (prepared as described in Example 1), 5
5 parts cellulose sulfite waste powder and 80 parts water were ground in a ball mill until the dye particles were less than 1 μm.

The resulting colloidal dispersion solution was mixed with 25 parts of 1-8-hydroxyethoxy 2-n-butoxychetane and 6% carboxymethylcellulose of 40 parts.

Claims (1)

[Claims] 1. A compound represented by general formula I. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the above formula, R_1' is -CH_2CH_2OH or -C
represents H_2COCH_3, R_2' represents chlorine or bromine, R^0_3 represents hydrogen, chlorine or bromine,
R_6' and R_7' are each independently (C_1 to
_4) Represents alkyl, and R_1_0 represents methyl, ethyl, chloromethyl, bromomethyl, chloroethyl, bromoethyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methylvinyl, methoxy, ethoxy, methoxyethoxy or ethoxyethoxy. 2. The compound according to claim 1, wherein R^6' and R^7' are the same. 3 R_1' is -CH_2CH_2OH and R_6
3. A compound according to claim 2, wherein ' and R_7' are each ethyl and R_1_0 is methyl, ethylmethoxymethyl or ethoxymethyl. 4 General formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the above formula, R_1' is -CH_2CH_2OH or -
CH_2COCH_3, R_2' represents chlorine or bromine, R^0_3 represents hydrogen, chlorine or bromine, and R_6' and R_7' each independently represent (C_1
~_4) represents alkyl, R_1_0 represents methyl, ethyl, chloromethyl, bromomethyl, chloroethyl, bromoethyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methylvinyl, methoxy, ethoxy, methoxyethoxy or ethoxyethoxy]; In producing the compound shown below, the following II:▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the above formula, R_1'
, R_2' and R^0_3 represent the same thing as defined above] The diazonium compound obtained from the amine shown by the following formula III: ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ [In the above formula, R_6', R_7' and R_1_0 represent the same thing as defined above]. 5 General formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the above formula, R_1' is -CH_2CH_2OH or -
CH_2COCH_3, R_2' represents chlorine or bromine, R^0_3 represents hydrogen, chlorine or bromine, and R_6' and R_7' each independently represent (C_1
~_4) represents alkyl, R_1_0 represents methyl, ethyl, chloromethyl, bromomethyl, chloroethyl, bromoethyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methylvinyl, methoxy, ethoxy, methoxyethoxy or ethoxyethoxy]; A process for dyeing or printing a substrate made of or containing a synthetic or semi-synthetic hydrophobic organic polymeric material, comprising using the indicated compound as a dyeing or printing agent.