DE1469689A1 - New, reactive dyes, their uses and intermediate products for their manufacture - Google Patents

Description

X / Gd 13 213

P U 69 689.0

Lawyer file no. 13 213

) AUG 8, 1968

UGINE KUHLMANN, Paris I6e / France.

"New reactive dyes, their uses and intermediates for their manufacture."

Maurice Vallette Inventor: Paul Kienzle

Andre Simonnet.

The present invention has been found to be resistant to wet treatments and solvents Color shades on fibers, which contain mobile hydrogen atoms, with the general dyes Formula:

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New underground

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(D

wherein A represents the radical of an anthraquinone, azo «, or phthalocyanine dye molecule containing at least one acid group, one of the X represents a chlorine atom, the other X represents hydrogen atoms, Y represents a bond -NR-CO-," NR-SO ₂ - or -NN - represents, wherein R represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, Z represents a hydrogen atom or a group -NO ₂ or -SO, H and η represents 1 or 2.

The dyes of radical A can be metallizable or contain metals and metals such as copper, chromium, cobalt, Contains nickel, manganese and iron.

Among fibers containing mobile hydrogen atoms are for example the polyhydroxylated fibers such as cellulose, keratin fibers such as wool and silk, fibers on the basis of polyamides, such as those based on the. . Market known under the names "Nylon" and "Rilsan" are to be understood as polyurethane fibers.

The dyes according to the invention can be prepared are, for example, through the action of an acid chloride of the general formula:

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ci-w »

Kk

X X

in which W * represents a group “SO ₂ ” * ^or “00”, X and Z have the same meanings as above on organic dyes A (NHR) _n , where A, R and η have the same meanings as above.

The dyes according to the invention can also be prepared if one starts with amines of the general formula:

(III)

in which X and Z have the same meanings as before. With a view to this manufacture, the Amines of the formula III various classical reactions of the dye diffraction industry, such as the following, subject to: diazotization and domes with usual domes " treatment components, which can themselves be dyes, condensation en with halides of carboxylic or sulfonic acids, which contain chromophoric groups, condensing with halides of carboxylic acids, which are phenolic

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Contain OH group that is suitable for coupling with the Cause diazo derivatives and later coupling with this

The dyes according to the invention are very stable at ordinary temperature, which enables them to be dried without damaging their alkaline, neutral or weakly acidic solutions, see below. They can be applied to the fibers by dyeing, padding or printing. For this purpose, solutions or aqueous suspensions of these dyes, if necessary thickened, with the possible addition of solvents, hydrotropes, wetting agents, dispersants, stabilizers, acid-absorbing agents or other auxiliary products, are applied to the fibers by conventional methods, which are in various forms such as thread, Tissue, wool or full hair, bobbins, felts or even films can be present. The material is subsequently dried, then in the range between 80 and 20O ⁰ C, subjected to a thermal treatment at temperatures. During the course of this treatment, the dye fixes on the fiber. The chemical bond between the dye and the fiber is shown by the fact that dimethylformamide does not extract the dye from the dyed fabric when heated «

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The following examples, in which parts are parts by weight, unless otherwise stated, explain the invention without restricting the scope of the invention β

Example ^

53 _f l parts of 1-amino «» 3 ¹ «amino» 2 ¹ , 4 *, 6 »-trlmethylphenyl * 4-amino-anthraquinone-2,5 * -disulphonic acid are dissolved in 1000 parts of water about 8 parts of a sodium hydroxide solution at 38 ⁰ Bl. are added subsequently slowly at 15 to 20 ⁰ C, 25 parts of 5 '' 0hlorsulfonyl-2-ohlor-pyridin _f dissolved in 150 parts Aoeton to, being carried out at the pH of the solution 7 to 8, maintained by the progressive addition of a 1Ox sodium carbonate solution.

The reaction has practically ended after 24 hours. The |

dye formed is precipitated by adding sodium chloride and Salasfture, filtered, washed with a Natriumohio ridlö solution and dried under vacuum at 40 to 50 ⁰ C dried · The obtained dye is a blue powder, easily soluble in Lasser. It is formed by N. ^ "• Chler (5") pyridylsulfonyl-3 ^l -amino «» 5 ^f -sulfo-2 ^l , 4 *, 6 ·· trimethyl-phenyl7 «1 ^ -dlamino-a-eulfo- anthraquinone in the state of disodium al »es. _Λ

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Is padded cotton fabric with a solution containing per liter 20 parts of the above dye, 120 parts of a Hatrium-hydroxide solution at 38 ⁰ Bl and 100 parts of urea includes · The impregnated fabric is dried, heated 5 minutes at 140 to 150 ⁰ C, with Rinsed with water and boiled in a soap bath for 30 minutes. The result is a blue shade with good fastness properties, especially when it comes to washing «

5 * chlorosulfonyl «» 2 «» chloropyridine «can, starting from 2-chloropyridine by transformation into N-methyl «» 2-pyridon-5 «» sulfone « acid (German patent specification 597 432), then conversion of this acid into 5-chlorosulfonyl "2-chloro" pyridine, according to the Information from Haegli, Kündig, Brandenburger (HeIv.Chim.Acta (1938) page 1750).

Example 2

48.9 parts of 1 »amino-3'-amino ~ 4-phenylan & no-anthraohinone-2,4 ¹ -disulfonic acid are dissolved in 1000 parts of water and the solution is made slightly alkaline by adding sodium carbonate. It is then added over the course of 2 hours at 10 to 15 ^° C. with stirring, adding 30 parts of 3-chlorosulfonyl-2-chloro-5-nitro-pyridine, dissolved in 150 parts of acetone.

The pH of the reaction medium is kept at 7 to 8 progressive addition of a 10bigen sodium carbonate «·

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solution at. After 24 hours of stirring at 20 to 25 ° C., the reaction is practically complete. The reaction product is precipitated by the addition of sais and hydrochloric acid, filtered, washed with a concentrated solution of sodium chloride and, at 40 to 5O ⁰ C under vacuum.

The dye obtained is a dark blue powder, easily soluble in water; it is given by N ₄ - ^ S "-CJr ^ or-f" -nitro (3 ") -pyridylsulphonyl-3'-amino-4'-sulpho-pheny ^ 7-1,4-diamino» 2-sulpho-anthraquinone formed in the state of the disodium salt.

A cotton fabric is padded in a bath which contains 20 parts of the above dye, 20 parts of sodium carbonate and 100 parts of urea per liter. The impregnated fabric is dried, ^{exposed to heat for 5 minutes at 95 to 10O 0} O, rinsed with water and boiled for 30 minutes in a soap bath. A blue color shade with good fastness properties, especially against washing, is obtained.

The dye dyes wool in a lightly acetic acid bath in a greenish-blue shade with good natural properties.

3-chlorosulfonyl "5-nitro" 2-chloropyridine can be produced

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starting from 2-aminopyridine by reforming the same in 2-hydroxy * 5-nitro-pyridine according to the information from Phillipe (Jeumal Chemical Soc. 1941 pages 12-13) and CaIdwell-Kornfeld (Journal Amer.Chem.Soe.64 (1942) page 1696). 2 "Hydroxy" 5-nitro-pyridine is subsequently converted into 2-hydroxy-5 "nitro-pyridine-3-eulfonic acid, a new product, reshaped in the following manner t

One mieoht 100 parts of 2-Hydrexy "5" nitro-pyridine with 300 parts by volume Ohlorsulfonsäure. The temperature increases to approximately 75 to 80 ^° C. The temperature is then raised progressively to 145 ^° C. and this temperature is maintained for 6 1/2 hours. The release of hydrochloric acid, which is released as the temperature rises, is then very weak. The mass is then poured over a mixture of 1500 parts of ice and 1000 parts of water, left to rest overnight, filtered to remove 1.6 parts of insolubles and washed thoroughly. This gives 33-50 parts by volume ·

To the resulting solution of 2 «hydroxy-3-sulfo-5-nitropyridine, 510 parts of calcium carbonate are added, brought to the boil, filtered and the calcium sulfate formed is washed with 510 parts by volume of water.

The potassium salt solution of 2-hydroxy-5-nitro-pyridine-3-sulphonic acid is then added to 140 parts of sodium carbonate,

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Calcium carbonate is precipitated. You wash it. The filtrate is concentrated to the beginning of the precipitation (585 parts by volume). The mixture is left at 30 ⁰ C to cool down, dried in air and trooknet the obtained crystals (100.3 parts) · These include essentially the starting product and sodium chloride ·.

The mother liquors are concentrated with stirring in order to reduce the volume by half. the released crystals separate out. They are collected by filtration, air dried, and im Heat oven dried. separated from sodium chloride.

The chloride of 2 »chlorine" 5-nitro "pyridin" 3-sulfonic acid, also a new product is manufactured in the following manner t

In an apparatus equipped with a reflux condenser, 100 parts of phosphorus pentachloride, 50 parts by volume of phosphorus bxychloride and 71 parts of the sodium salt of 2-hydroxy-5-nitro-pyrldine-3-sulfonic acid are added, as previously described.

The mixture is heated under reflux for 5 hours, then cooled, the mass is poured over a mixture of 1000 parts of ice and

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100 parts of sodium chloride. Sulfochloride is obtained in the form of an adhesive mass which is dried under vacuum, then distilled at 204 ^° C. with 24 mm of mercury.After cooling, sulfochloride is obtained in the form of colorless crystals, melting point 81 ^° C.

The product can be recrystallized in petroleum ether obtained in the form of crystalline, rectangular, transparent and practically colorless rods; Melting point 83 ° C. The analysis is as follows:

calculated for 23.40 ψ O 0.78 i> η 10.90 i » ν 12.45 1 » p 27.60 1 » Cl

found

23.52> 0.93 ° /> 10.85 ⁰ A 12.55 Jt 27.49 lh

Example 3

In 600 parts of water were dissolved 48.3 parts disodium salt of 1,8 "^{'dihydroxy-4-f} -amino ^ -benzolnaphthalin Oiö-disulfonic acid. The solution is cooled to 10 to 15 ⁰ C and added in

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Over the course of 2 hours, with stirring, 30 parts of 3-chloro-8ulfonyl-2-chloro-5-nitro-pyridine. 150 parts in solution

·

Acetone sui is added on the same side as fiatrlum carbonate in 1Obiger solution to maintain the pH of the reaction medium at 7 to 8 su. It is stirred for 24 hours at 20 to 25 ⁰ C ₁ then precipitates by salting out the ^? ^t -Chlor «5 '~ nitro-4-pyridylsulfonylamino * benso ^ 7 · ^ I aso 2 ^ · / Τ, β-dihydroxy · L ^, ö-dieulfo-naphthalene /, in the state of disodium salt, from ·

The dye is filtered and dried under vacuum at 40 to 50 ⁰ C, Ir produces on cotton, according to the specified in Example 2, a dark red Färb · tint having good fastness properties, particularly to washing,

If instead of the 48.3 parts of the preceding dye it, 46.6 parts ^ 2 *, 5 ^f -dichlor "4 ^f -eulfo" 1-phenyl3-methyl "5-oxo-pyraeol - ^ asoy- ^ X -amino-beneo ^, used in the state of the Sodium Alsee, you get the corresponding N, - (2-chloro-5-nitro »3-pyridylsulfonyl) derivative,

Applied according to the same procedure, this dye produces a golden yellow tint on cotton the same authenticity.

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Example 4

A cotton fabric is printed with a printing paste which comprises 20 parts of anthraquinone dye from Example 2, 200 parts of urea, 300 parts of water, 360 parts of sodium alginate in a 5% solution and 120 parts of sodium carbonate in a solution. The fabric is dried at low temperature, steamed for 5 minutes at 10O ⁰ C, rinsed and treated for 30 minutes to sum cooking with soap. The result is a blue tint that is very resistant to damp loads.

Example 5

57.8 parts of copper phthalocyanine and 300 parts by volume of chlorosulfonic acid are mixed with stirring at ordinary temperature. After the mixture is homogeneous, heated to 130 to 135 ⁰ C and stirred for 6 hours at 130 to 135 ° C. It is then cooled to 80 to 85 ⁰ C and slowly added 125 parts by volume of thionyl chloride are added. The mixture is heated for 2 hours at 80 to 85 ⁰ C, cooled to ordinary temperature, then pouring the mass on a mixture of 100 parts of sodium chloride and 3500 parts gestossenee ice, "Man the dispersion is filtered, then washed with Eiewaeser the TetrasulfoChlorid thus obtained of the copper phthalocyanine. It is reabsorbed in a small amount of ice water. When the slurry is homogeneous, the pH is adjusted to 7 to 7.5 by the fractional addition of a

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Sodium hydroxide solution. One adds while stirring a solution of 42 parts of 2,4-amino-benzene-sodium sulfonate in 500 parts of water and then also adds 30 parts of sodium carbonate.

The temperature is increased progressively in the course of 24 hours to 7ü ° C, the pH is adjusted to 4 by adding

Hydrochloric acid and falls the oulfamide by adding JUsodium chloride. The precipitate is filtered with a 12.55% sodium chloride solution and washed under Vacuum dried at ordinary temperature.

30 parts of the blue powder thus obtained are suspended in 1000 parts of water and the pH is adjusted to 7 by adding a dilute sodium carbonate solution. A solution of 10 parts of 3-chlorosulfonyl 2 is then added over a period of about 2 hours with stirring -chlor-5-nitro-pyridine in 50 parts by volume of acetone. At the same time, a 10% sodium carbonate solution is introduced in order to keep the pH at about 7; after 24 hours of stirring at normal temperature, the dye is carried out Addition of salt precipitated, filtered, dried in the air and dried under vacuum at 40 to 50 ^° C. It is obtained in the form of a blue powder which is soluble in water. The dye can be represented by the formula:

ÖWAV -14-

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(SO, H) ^m - PCu -

NO.

, NH-SO

in which PCu represents copper phthalocyanine and m4n equals 4. He dyes cotton in a turkish blue shade, resistant to washing,

Example 6

5 parts of the chloride of 2-chloro-5-nitro-pyridine-3-sulfonic acid, as described in Example 2, are suspended in 50 parts of water. Sodium carbonate are added with stirring at 25 to 3O ⁰ C until complete solution.

The 2 "chlorine" 5-nitro-pyridine-3-sodium sulfonate solution obtained is reduced by the Bechamp process: 10 parts of iron powder are added and it is made slightly acidic by adding acetic acid and heated at 90 to 95 ^° C. for about 30 minutes .

When the reduction is complete, sodium carbonate is added slightly alkaline, clarifies to separate the Elsenschmamm and washes the cake with water. The solution of the sodium salt of 2-chloro »5-aminopyridine-3-3ulfonic acid,

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ORIGINAL INSPECTED

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a new product is acidified by adding hydrochloric acid, then diazitized by reacting with sodium nitrite in a slightly alkaline medium with the disodium salt of 1-hydroxy · 8 «amino-naphthalene * 3» 6-disulphonic acid coupled ·

The ^ 2-ChIOr-O-SuIfο-pyridine / - ^ 5 azo 2ξ) »^! 5,6-disulf ο · 8 ~ amino-1-hydroxy-naphthalene / is isolated in the state of the trisodium salt by salting out, filtered and dried under vacuum at 40 to 50 ^{° C.} It is a dark red powder which is very soluble in water. Applied to cotton according to the method of Example 1, it produces a red shade with good fastness properties, especially to washing.

Example 7

Production of 3- and 5-chloroulfonyl * »2-chloro-pyridines, (Mixture).

116 parts of chlorosulfonic acid are charged into an apparatus equipped with stirrer and heating means, and 94 parts of 2 »aminopyridine ^{are added, without exceeding TO 0 C.} The temperature is raised progressively to 170 ^° C. and this is maintained until the release of hydrochloric acid has ended. The 2 "amino" pyridine * 3 and 5 sulfonic acids are obtained in a mixture with an almost theoretical yield. The finely ground product appears in the form of a white, slightly graying powder.

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In an apparatus equipped with a stirrer, 174 parts of the mixture in powder form are dissolved in 1 230 parts by volume of 20% salic acid. It is cooled to 5 to 1O ⁰ C, then a solution of 102.5 parts of dry sodium nitrite in 266 parts of water. The mixture is stirred for a quarter of an hour, then left to rest for one night at room temperature. It is then concentrated to a volume of 390 parts in order to separate out the greater part of the sodium chloride formed. It is separated by filtration. The filtrate is then concentrated to dryness. This gives a mixture of 2-Hydrexypyridin "" 3- and 5-sulfonic acids with a low content of sodium chloride, Schneispunkt at 210 to 220 ⁰ C.

175 parts of the aforementioned acid mixture, 417 parts of phosphorus pentachloride and 23 parts by volume of phosphorus oxychloride are introduced into a reaction vessel with stirring. The mixture is refluxed for 5 hours, then the contents are distilled under reduced pressure between 10 and 4- ^ mercury. After retirement of the oxychloride and excess pentachloride, the mixture of 3- and 5-formed Chlor8ulfonyl-2-chloro-pyridines proceeds at 150 ⁰ C in the mold through a yellow oil which solidifies after a certain rest period.

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BATH ORIGINAL 8098 13/1363

Analysis: Found Calculated for C ^ H.f 31 _O N 0 _o S C. £ 28.56 28.30 9 * C. C. H 1.59 9 * 1.415? * Cl 32.39 * 33.49 5 * N 6.54 % 6.60 5 * S. 15.03 9 * 15.09 5 * at s Ό i e 1 8

Preparation of 3,5-dichlorosulfonyl-2 «chloro ·· pyridine.

175 parts of 2-hydroxypyridine 3 · and 5-sulfonic acids, prepared as in Example 7, and 119 parts of chlorosulfonic acid are introduced into a reaction vessel. The temperature is brought progressively to 200 ⁰ C, and "she maintains 2 hours. Cool the mass to 40 ⁰ C., and 780 parts Phoaphorpentachlorid and 62.5 parts by volume of phosphorus' oxychloride to.

The mixture is heated under reflux for 3 hours with stirring, Destil "the mass then profiled under reduced pressure" wipe 15 and 22 to mercury _c Naoh departure of the oxychlorides, then dee excess pentachloride, the mass BWisehen 208 and 215 ⁰ C is transferred to a yellow oil which solidifies after a certain period of rest and drops off ^{at 69 to 70 0,}

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Analysis: C. Found , 24 * Calculated .33 * H 20th , 80 * 19th , 65 f> Cl 0 , 29 i s 0 , 23 t N 35 , 71 34 »? L ^ S. 4th , 16 4th , 61? T 19th B e 20th : ρ i e 1!

15 parts of 1-amino-4 ^l «methylamino« 4-phenylaminoanthraquinone, 2 »« »disulfonic acid (obtained by condensation of 1« »amino« 2-sulfO "» 4 «bromo« anthraquinone with acetyl «^« »methylamino- aniline, sulfonation then deacetylation) in 240 parts of water and 3 parts of sodium carbonate.A solution of 8 parts of the mixture of 3- and 5-chlorosulfonyl-2-chloropyridines in 20 is gradually added with stirring between 20 and 25 ° C Add acetone, maintaining the pH at 7 to 7.5 by simultaneously adding a 10% sodium carbonate solution. After about 8 hours, no more sodium carbonate is added. The reaction product is then separated off by adding sodium chloride. filtered, dried in air and dried at 40 to 5O ⁰ C under vacuum to give a dark blue water-soluble blue powder. This dye is a mixture of N "2" (~ chloro and 6-chloro-3 ^B ""Pyridylsulfonyl) N * methyl" 4 ^r -amino "" 4-anilino * "1 -aminoanthraquinone-2 _f 2'-disulfonate en of sodium »

ORIQWAL

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Example 10
9 parts of ^ S-methyl - ^ - amino-benzoj / ·· <1 azo disulfo-i-hydroxy-8-amino-naphthalene / in the state of the disodium salt are dissolved in 200 parts of water. A solution of 6 parts of the mixture of 3- and S-chlorosulfonyl ^ -chloropyridines in 15 parts of aoetone is slowly added, the whole being the pH of 7 to 7.5, by simultaneous addition of a 1Obigen sodium carbonate solution and the temperature at 20 to 25 ⁰ C maintains. After having 5 stabilizes the pH to 7 to 7 *, precipitating the reaction product by addition of Hatrium chloride, filtration, air dried and dried at 40 to 45 ⁰ C under vacuum, The resulting dye ordered from a mixture of ^ l "(2 ^f chlorine * 3 ^l " pyrldylsulfonyl) "N" methyl-4-amino-benaoj7 · ^ I azo 2) - ^ 3,6-disulfo "1-hydroxy-8-amino-naphthalene / and its isomer 6 * -chlorine in the state of the sodium disulfonate. This mixture dyes cotton in a bluish-red shade, which is very resistant to washing.

Example 11

Replacing in Example 10, the azo dye used by ^ fl-liethyl "4-amino * benioj7 ~ - ^ azo 1 / • ^ _3> 6 * disulfo * 2-hydroxy-naphthalene / in the state of the disodium salt, one obtains a reactive dye that dyes cotton in orange-red.

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Example 12

15 parts of 1-amino-4 ^l methylamino-4-phenylaminoanthraquinone-2.2 ^f- disulfonic acid are dissolved in 240 parts of a 1% sodium carbonate solution, then a solution of 9.6 is added at 20 to 25 ^° C. with thorough stirring 2 parts of chlorine-3,5-dichloro-sulfonyl-pyridine in 30 parts of acetone. The pH value is maintained at 7 to 7.5 by the progressive addition of a 100% sodium carbonate solution. After the pH value is finally at 7 to 7, 5 is stable, the dye is precipitated by adding sodium chloride, filtered, dried in air and dried under vacuum at 40 to 50 ^° G. A blue powder is obtained which is easily soluble in water. Eb essentially comprises a mixture of N- (6 "-Qior ~ and 2 ^w -chloro-5 ⁿ -sulfo-3 ⁿ -pyridylsulfonyl) -N-methyl-4 ^f amino-2'-sulfo« »4 '" phenylamino-2-sulfo-1 -amino ~ anthraquinones in the state of trisodium salts.This mixture produces a blue color tint on cotton with very good fastness properties, especially compared to boiling with sodium carbonate and the like nd washing with chlorine.

The washing test with chlorine is carried out as follows: 1 part of dyed cotton fabric is for 45 minutes at 83 C held in 50 parts of an aqueous solution, which per liter 5 g of soap, 2 g of sodium carbonate and 0.1 g of active

3
vas contains chlorine (6.3 cm Javel water with 16 g / liter active chlorine). The fabric is rinsed, a minute-e

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treated at 27 C with dilute acetic acid, dried and ironed while hot. One compares the shades of and after the exam,

Example 13 Preparation of 2-chloro «3-nitro ^ ~ chloroformylpyridine.

18.4 parts of 100% sulfuric acid are introduced into a device which is provided with a stirrer and has means for external cooling or heating, then gradually 1 part of 2-hydroxypyridine-5-carboxylic acid at 15 to 20 ⁹ g . When the solution is complete, 0.74 parts of nitric acid with a density of 1.49 are gradually added, while maintaining room temperature. The mixture is stirred for another two hours at 20 to 25 ⁰ C, the temperature takes 75 to ⁰ G and maintains this 18 to 20 hours. Cool the mass to 20 ⁰ C and poured over 30 parts gestoasenes ice. The mixture is stirred for three hours, filtered under vacuum, washed with two parts of ice water and then dried.

The resulting 2 'hydroxy-3-nitropyridine-5-oarbonsäure melts at 274-276 ⁰ C. It is identical with the melt at 277 ° C product, which after Räth and Prange (' β Liebig Annalen 467, pages 3 to 9) was obtained starting from 2 · Αΐη1ηο · 3-nitropyridine »carboxylic acid ·

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In a device equipped with a stirrer and means for removing oases, heating and cooling 1 part of the previously obtained 2 "hydroxy" 3-nitropyridine-5-carboxylic acid, 0.56 Parts by volume of phosphorus oxychloride and 2.95 parts of phosphorus pentachloride. It develops a pretty lively one Reaction with strong release of hydrochloric acid, liquefaction

ο the mass and the temperature of the ash rise to 105 C. If the release of hydrochloric acid slows down, the mixture is heated under reflux. After one hour the reaction mass becomes cloudy. The reflux is maintained for 15 hours; the release of hydrochloric acid is then very weak. Cool the Maase to 20 to 25 ⁰ C, then via a suitable device in to work under reduced pressure destinations, where they were fractionated at 20 to 22 mm of mercury. The phosphorus oxychloride is removed, then intermediate fractions: 2-chloro »3-nitro-5-chloroformylpyridine, passes over at 170 to 175 ° C. and condenses to give a mobile, pale yellow liquid of the following analytical composition.

found 31.9 "/» 12.2

calculated for C ₆ H ₂ Cl ₂ N ₂ O ₃ 32.1 ⁰ A 12.7

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ORIGINAL INSPECTED

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Example 14

15 parts of 1-amino-4 ^l -methylamino--4-phenylamino-anthraquinone-2 _f 2 ^f -disulfonic acid are dissolved in 240 parts of a sodium carbonate solution, then a solution of 9 parts of 2 is added ^{at 10 to 15 0 with stirring} "Chlorine" 3-nitro-5-chloroformylpyridine in 30 parts of acetone. The pH is maintained at 7 to 7.5 by the gradual addition of a 10% sodium carbonate solution. When the pH is finally stable at 7 to 7.5, the dye is precipitated by adding sodium chloride. The sodium "N *" (2 "-chloro-3" -nitro "5 ^ll * pyridoyl)" 4 ^f -methylamino-4-anilino-1 -amino anthraquinone-2,2 ^l "disulfonate obtained is filtered, centrifuged and under vacuum at 40 to 50 ⁰ C'getrocknet. A blue powder which is readily soluble in water is obtained.

This dye can be applied by the following methods will :

a) A cotton fabric is padded with a solution of 2 parts of the designated dye, 20 parts of urea, 2 parts of sodium carbonate, 0.2 part of wetting agent and 100 parts of water. After drying between 50 and 80 ^° C., the fabric is treated with dry heat ^{at 150 ° C. for 5 minutes.} After rinsing and soaping, a lively blue shade is obtained with very good fastness properties to moisture.

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b) A dyebath is made with 0.150 parts of the dye prepared above and 150 parts of lasser. The mixture is heated to 40 ⁰ C, 5 parts of bleached cotton leads and lasts 5 minutes 40 ⁰ C. During 30 minutes the temperature is raised to 80 ⁰ C and are waeeerfreies sodium sulfate to 15 parts by little. 3.5 parts thereafter are added to 10 # Lge sodium carbonate solution and the temperature is maintained for one hour at 80 ⁰ C. The cotton is then washed, treated with soap and rinsed again. A vivid blue shade is obtained with very good fastness properties to damp exposure.

c) is padded with a Bauntwollgewebe a solution of 2 parts of the dye prepared above, 1 part of anhydrous sodium sulfate, 0.6 part of 35 Natriumhydroxidlauge ⁰ Bl and 100 parts of water. The fabric is rolled up and stored at room temperature and constant humidity. After 6 to 12 hours, the 'fabric is rinsed with cold water, then with warm water, treated with soap for 15 minutes until boiling and rinsed again. The same shade of color is obtained as in the processes of a and b.

Example 15

15 parts of 4-phenylamino-1,3'-diaminoanthraquinone-2,4'-disulfonic acid are introduced into 330 parts of water a. You give them

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amount of sodium carbonate necessary for neutralization, then a solution of 9 parts of 2 "chlorine" 3-nitro-5-chloroformylpyridine in 30 parts of acetone at 10 to 15 ° C with stirring . When the pH is stable final 7 to 7.5, causes to the precipitation of disulfonated, little soluble dye by addition of sodium chloride, then dried under vacuum at 40 to 5O ⁰ C.

The dry, powdered dye is sulfonated as follows: 1 part of the disulfonated dye is added to 8 parts of 1005% sulfuric acid at a temperature of 10 to 15 ° C. with stirring. When the solution is complete, 8 parts of 20% oleum are added. Stirring is continued at 10 to 15 ° C. until a sample is readily soluble in water. It is then poured over the whole sulfonation überschüssigea ice, salted out by adding sodium chloride, filtered and washed the precipitate to neutrality with a 2Q? 6igen sodium chloride solution, then dried at 40 to 50 ^Q C under vacuum. The sodium (2 "~ chlorine" 3 "" nitro-5 ^ll -pyridoyl) "3 ^l " airdno "4-anilino" 1-aminoanthraquinone-2,4 ¹ , 6 * -trisulfonate is very soluble in water and can can be used according to procedures a and ο of example. This dye yields on cotton

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a reddish-blue shade with very good fastness properties against damp loads.

Example 16

Is introduced 57.6 parts of copper phthalocyanine in 270 parts of chlorosulfonic acid, where the temperature is maintained between 20 and 5O ⁰ C, heated over one hour to "HO ⁰ C and this temperature retains 3 hours. After cooling to room temperature, poured the reaction mixture is poured into 2000 parts of crushed ice, the precipitate is ^{centrifuged at 0} ° C. and washed with 3% hydrochloric acid. The precipitate is mixed with 500 parts of ice water and the pH is adjusted to 5 by adding a 3% aqueous sodium hydroxide solution . Add 15 parts of 1-amino-4 ~ to acetylaminobenzene and heated to 50 ⁰ C, with the pH adjusted to 5.0 to 5.5) by adding a dilute sodium hydroxide solution is maintained. After 3 hours, making the solution easily alkaline and heated during one hour to 8O ⁰ C ₈ are then added 200 parts by volume aqueous solution of hydrochloric acid # 30 to keep the mixture at 70 to 80 ⁰ C until the acetyl group is removed and. filter the precipitated, aminated Compound and wash it a little with hydrochloric acid. The filter cake is dissolved in 300 parts of warm water and the pH is brought to 6 by adding a 30 # strength aqueous sodium hydroxide solution. Man

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are little by little at 10 to 15 ⁰ C a solution of 29.5 parts of 2-chloro-3-nitro »5 to chlorforaylpyridin in 80 parts of acetone. An aqueous solution of 10 sodium carbonate is introduced at the same time in order to keep the pH in the region of 7. When the condensation has ended, the dye is precipitated with the aid of sodium chloride. The dye is filtered, washed with a neutral sodium chloride solution, dried under vacuum and pounded. A blue powder is obtained which dyes cotton in a turquoise-blue shade with good fastness properties to moisture.

Example 17

Dissolve 20 parts of 4 ^t »Amino-2 ^t -iaethylphenyl-2-azonaphthalene-4,8-disulfonic acid in 300 ropes water, adding a sodium hydroxide to maintain a neutral pH's. At 10 to 15 ° C., then a solution of 14 parts of 2 performs "chloro" 3-nitrochler-5-formylpyridine a λ in 42 parts of acetone and the pH at about 7 by gleicheei term "addition of a sodium carbonate solution 1Obigen. If you can no longer detect any free amino group, the dye is precipitated by adding sodium chloride. It is isolated by filtration and placed under vacuum at 40 ° C dried. It corresponds to sodium «(2 ' ^l «' Ghlor <»3 '' * nitro« 5 "-

»· Pyridoyl) -4 * -amino-2 ¹ -methyl» 2 »phenylazonaphthalene-4,8 disulfonate. It dyes cotton in a yellow shade that is color-fast to damp loads.

- 28 -809813/1363

Claims (2)

Claim: New colorants of the general formula wherein A represents the residue of an azo ·, anthraquinone or phthalocyanine dye molecule containing at least one acid group, one of the X represents a chlorine atom, the other X represents hydrogen atoms, Υ a bond -NR-CO-, -NR-SO ₂ - or -NN - where R is a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, Z is a hydrogen atom or a group -NO "or -SO-H and η is 1 or 2. 809813/1363 New documents (Art. 7 S 1 Para. 2 no. 1 sentence 3 of the amendment. v. 4.9. »67;