BE357880A - - Google Patents

Description

       

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  * Process for the preparation of azcic dyestuffs "It has been found that a wide class of valuable azo dyestuffs, heretofore unknown, is arrived at when selecting for the constitution of azo dyestuffs starting material such that at least one of the compounds entering into /

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 the constitution represents a heterocyclic body of the general formula:
 EMI2.1
 (A.R1.

   H2 (hey
In this formula, A should be understood to mean "nitro" groups or their reduction phases such as "azoxy" or "azo" groups or particularly the "amino" group or also their acidylation products.
 EMI2.2
 such as - NHCO-NH-, -NH-Co-c6R4 -NH2 etc; R1 denotes a carbocyclic chain, R2 a heterocyclic chain assembled to the carbocyclic chain R1 by the carbon-carbon bond; by x and y it is necessary to understand the numbers and ± 1 or 2 designates finally a halogen atom or a residue intervening in the place of the halogen atom and connected to the hetero chain by a nitrogen atom, of oxygen or sulfur.



   As types of the extremely large number of similar starting materials for constituting the compounds for the azo dyestuffs, only a few may be mentioned: -
 EMI2.3
 

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 (see Berichte der deutschen chem.Ges. 12, 1127, (1879)
 EMI3.1
 by decomposition with 1,4-phenylenediaminosulfonic acid; we can also react with acid @
 EMI3.2
 -oaa7, yuobeol - 3-sulfonic and then saponify; yellowish gray powder which may be diazotized; the diazotization is easily separable by means of salt.
 EMI3.3
 
 EMI3.4
 



  (consisting of 7-nitro-4-methyl-2-ehlorequinoline and i-atn.ienaphthaline-3,6-disulfonic acid, yellowish gray powder easy to separate by means of salt; s' mates with 1 molecule of diazo compounds).
 EMI3.5
 



  (is obtained from molecular amounts of 7-
 EMI3.6
 nitro-9-eh.orghenanthridine (see Journ.Amer.Chem.Soc. 1927, page 2618) and 1,4-phenylenediaminesul- .fonic acid; yellowish-gray powder. In the state of salt

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 alkaline, the compound is well soluble in hot water;

   it can be indirectly diazotized, its diazo combination is hardly soluble in water. @
 EMI4.1
 (by condensation of molecular quantities of the acid
 EMI4.2
 1 aminr.t --- 8-oxynaphthaline-3.6-disu2fonique and 6-nitro-4-chlorequinazoline, one obtains, according to the French patent application No. 23 880 of February 2, 1928, example
 EMI4.3
 3, 6-nitrcx-4- 8 --oxy-, 6 --disulfoE-1 -naphthyla-aminoquinazoline; the latter is reduced by means of glucose in an alkaline sodium hydroxide solution, to 50, to give the azoxy compound; yellow powder properties. gray, soluble in water with yellow coloring; mates with two molecules of diazo compounds).
 EMI4.4
 
 EMI4.5
 



  (from 2- (4-nitrophenyl) -4-methyl-6-chlorine-pyrimidine (see Rappaport, dissertation, Berne 1900) @ by means of -reduction of iron in the presence of cooking salt; as of hydrochloric salt colorless crystalline powder.

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 EMI5.1
 



  (can be obtained from 2- (4'-nitrophenyl) - 4.6-dichlorepyrimidine (see Pinner, Berichte der deut- shen chem. Ges. 1908, 41, 3517) by decomposition with
 EMI5.2
 average of 1 molecule of 1-amin-8- * xynaphthalene-3,6-disulfonic acid in aqueous solution in the presence of sodium acetate at elevated temperature further processing inU, aniline medium; when the transformation is finished, it is made alkaline by means of sodium carbonate and the excess of aniline is expelled by means of steam, then the separation is carried out by means of salt;

   a yellowish gray powder, easily soluble in hot water, the alkaline solution is not fluorescent.
 EMI5.3
 

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  (can be made as 6 by transformation with 2 molecules of 2-amino-5-oxynaphthaline-7-sulphonic acid, at elevated temperature, under pressure.



  After purification, yellowish gray powder soluble in hot water without fluorescence; 1 molecule couples to 2 molecules of diazo compounds).



   7.)
 EMI6.1
 
 EMI6.2
 (from 2- (3'-nitrophéoyl) -6- chlorepyrimidine + 4-carbonic acid chloride (see Pinner Die Im ± dD, a.therlt, Berlin 1892) by transformation using 1 molecule of acid 1-amino-8-oxnaphthalin-3. 6 ... d, pi in water, in the presence of sodium acetate at 70, and subsequent transformation of the intermediate body formed containing chlorine by means of 1 molecule of 4-methyl-thio-phenol, in the presence of sodium bicarbonate, with long cooking with stirring; gray-yellow powder which can be salted; aqueous solutions do not show fluorescence.

   The amino compound

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 obtainable by reduction is a gray powder
 EMI7.1
 diazotization of the diazo compound does not couple slowly when poured into sodium carbonate to form a hardly soluble red coloring matter, precipitating *
 EMI7.2
 
 EMI7.3
 (2. C - dichloro-4- (3'-nitrophrrl) rimi-dine (see Berichte der deutschen Chem.Gesellschaft, 32 1533 year 1899) is first transformed by means of an aqueous solution of the salt sodium of 5-amino-2- acid
 EMI7.4
 1 oxybenzoic, at 50 - 6. The intermediate compound obtained is made of aniline at 100.

   Treatment as in 6; powder of a grayish yellow hardly soluble in the sea; dissolves in hot water when adding sodium hydroxide solution.)

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 EMI8.1
 
 EMI8.2
 (2-. nitrophénrl - (3'-uitrophéL) -6hZorepyrimidine is converted to ', 115-120, in the presence of sodium a4tate, by means of 2 # amino # 5oxys & phthaline # 7-sul - fonique. Grayish yellow powder easily salted in a gelatinous mass. the sodium salt is soluble in hot water ;. the solution has no fluorescence)
 EMI8.3
 (from 6-nitro-4-chlorequinazoline and acid
 EMI8.4
 14-.amino phenyl) - 5-pgrazalane-3 - carbonic s 40 in the presence of acid-combining agents.

   Yellowish powder, soluble in much hot soda solution, well soluble in caustic soda lye. Reacts with nitrous acid to form a

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 yellowish nitrous compound see French patent application No. 23 880 of February 2, 1928 10.)
 EMI9.1
 (see French patent application No. 23 880 of February 2, 1928.)
 EMI9.2
 (formed according to French patent application No. 24157 of March 29, 1928, condensation of 2 molecules of 5-amino-2-oxybenzoic acid or 1,4-phenylenediaminesulfonic acid by means of 1 molecule of 6-nitro-2, 4-dichlorequinazoline, in aqueous medium, first at 40, then at 85).

   

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 EMI10.1
 



  (constituted according to the French patent application No. 24157
 EMI10.2
 of March 29, example 2,). S03H ..



  3.) ÙN "1 ¯ -NE S0'H '-CM, 2 / <::> - 003H (7-nitro-2.3-dichlor-quinoxaline (small, weakly yellow needles with a melting point of 152, see dissertation Dörbecker, Marburg, 1899} is transformed at 90 - 100, in aqueous solution, in the presence of sodium acetate, by means of 1 molecule
 EMI10.3
 2-amino acid - $ - axrnaphthaline-3..6-d.isulfonig, ue, the compound obtained is reduced by means of iron and acetic acid and the amino compound forming, - a grayish-white powder whose compound diazo gives

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 in alkaline sodium hydroxide solution a red coloring matter,

   is converted to 40-50 using 1 molecule of 3-nitrabenzoyl chloride. Compose it! nitrobenzoyl precipitated most often in a viscous form is finally reduced by means of iron and acetic acid. Properties: gray powder which easily precipitates in the jelly state on cooling of the hot, diazotizable aqueous solution ; the diazo compound gradually mates in alkaline sodium hydroxide solution to give a hardly soluble bluish-red coloring matter.



  13 a. )
 EMI11.1
 
 EMI11.2
 (7-nitro-2.µ-dichiorequinoxaline, is heated to 60 with 1 molecule of sodium methoxide in methyl alcohol. The nitro compound obtained can be reduced by means of tin and dihydrochloric acid. Composa amino hydrochloric acid is a greyish white crystalline powder which is very poorly soluble in organic solvents.) 13 b. )
 EMI11.3
 

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 EMI12.1
 (7-nitro-2.µ-ichlorequinaxaline is condensed as in 23 with 1 molecule of 2-.amina-oaynaphGalin-7-sulfonic acid. Condensed as in 6 with dl-aniline.

   Yellowish gray powder, soluble in water with a yellow coloration, can be easily salted.)
 EMI12.2
 
 EMI12.3
 (2.4-di- (-nitraphenyl-6-ehlare.l, .. 5 triazin (see Pinner, tv4'-cit.) is condensed to 1000. with an aqueous solution of l- acid. amino-8-oxynaphthahine-3a6-âisulfoniq, r, e ,, in the presence of sodium acetate.



  Yellow gray powder, which can be salted; its alkaline solutions are not fluorescent. Condensation is carried out in exactly the same way with
 EMI12.4
 2-ammo-5-oxynaphthaline -? - sulfonic acid, as well as

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 condensation with lucid 1.4-phenylenediaminesulfonic acid ,. The compound obtained from the latter is soluble in hot water, indirectly diazotized; its diazo compound is yellow and very poorly soluble.)
The process is carried out in such a way that during the diazotization and coupling reaction at least one heterocyclic compound of the general formula mentioned above is employed.



     However, it is also possible to take a heterocyclic compound of the general formula above in which A represents the nitro group and B a mobile halogen atom, and condense it with compounds which bear a nitrogen atom, of oxygen or. ' sulfur, hydrogen atoms capable of easily reacting at least one of these compounds containing the azo group; following this process, compounds are obtained as by
 EMI13.1
 example NO 2 15 ..) cxNú 1 S05H NC SOB C BE 1 W-N = N- cE5 SQ) Ir

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 (obtained by converting 2-nitrc-9-chloreacridine with the aminoazoic body obtainable from diazotized 2-aminonaphthaline-4.8-disulfonic acid, by coupling with 3-aminotoluol).



  16.)
 EMI14.1
 (obtained by transformation of the azo coloring matter formed from 4-diazotoluol-3-sulphonic acid and acetacetyl-4-amino-anilide, using 6-nitre-2.4-dichlor-quinazcline, in water at 40, further transformation of the intermediate body containing chlorine by means of 5-sulfo-3-aminobenzoic acid, at 85 C.



  Yellow powder, soluble in water with an intense yellow coloring; the nitro group can be reduced by means of sodium hydrosulfide at room temperature).



  17.)
 EMI14.2
 

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 (in a manner 'analogous to 16, from moderate quantities
 EMI15.1
 leculars of 4 "'wamino-4obenzol-3-carbonig acid, 6-nitro-2.4-'dïch-loréquinazolïne and dimthylamine. During the last transformation, one works advantageously with dimëthy lamin. excess, in a closed container, to 80.)
In the new azo dyestuffs obtained by the method outlined, the nitro groups can be further modified by reduction to azoxy groups. azo or amino and in the latter case by diazotization and coupling or also by acidylization or further condensation with heterocyclic compounds having mobile halogen atoms.



   Depending on the choice of constituents, coloring materials are thus obtained which are used as acid coloring materials for wool, as mordanting coloring materials, as direct coloring materials for cotton, as cotton coloring materials which can be treated on fiber, etc.,
The following examples explain the process without limiting it.



    Example 1 :: -
The aqueous solution of the diazo compound from
 EMI15.2
 of 217 parts by weight of 6-chlorine-4-methyl-2- (4'-aminophenyl) -pyrimidine (formula 5 above} is poured in

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 to 0 in an alkaline soda solution of 254
 EMI16.1
 parts by weight of 1- (2 "-sulfophenyl) -j-methyl-5-pyrazolone. After the rapid coupling has ended, the mixture is separated into salt and worked in the usual manner. The new coloring matter dyes the wool in an acid bath in very uniform yellow tones and at the same time very resistant to crushing and light.



   A monoazo dyestuff which dyes wool in a pure greenish yellow tone in an acid bath in a light and washing resistant manner is obtained by combining the diazo compound of
 EMI16.2
 Bz-amino-3-metho: J!: Y-2-chlorinequinoxaline (formula 1301. above), in alkaline solution, with 1- (2'-chlorine- 5 "-sulfopherri-3-ethyl - 5 -pyrazQlane.



   If the reduced condensation product of 1 molecule of 6-nitro-4-chlorine-quinazoline and 1 molecule of 2-amino-5-oxynaphthalene-7-sulfonic acid (formula 10 above) is used as a diazotization component and if the diazo compound, in the presence of sodium acetate, is coupled with the monosulfonic acid of aceto-2-acetyl anisidide, an orange is obtained which faintly draws to yellow which passes well on cotton in the bath of soda and Glauber's salt and which, developed on the fiber by means of 4-nitrodiazo-

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 benzol, turns into an intense light orange-red with very good resistance to washing and over-dyeing.



   Example 2: -
The aminodisazoic compound, diazotized in the manner. ordinary, from 605 parts by weight of acid
 EMI17.1
 l-, Aminobenzol-2.5-disulfonic acid + 1-aminonaphthaline + l-amino-2-ethoxynaphthalene -? - sulfonic acid is stirred with a little ice to form a fine paste and is combined at + 5 to a solution of 501 parts in weight of the condensation product reduced by 1 acid molecule
 EMI17.2
 2 * -amina-µ-axynqphthaline-7-aulfonic acid and 1 molecule of 2-chlorine-4 ... 6-di t nitrcghényl) -L .., 5-triazine (see formula 14 above} in a a little water and a lot of pyridine After the mating is completed quickly, it is diluted with water and separated into salt.

   The coloring matter purified by a single redissolution dyes the cotton in shades of blue tending to green; by tetrazotage on the fiber and development 'by means of
 EMI17.3
 2 molecules of 3-methyl-I-pherrl-5- pyra.zoT, one, we obtain a beautiful green very resistant to washing, over-dyeing and light.

   A development green having the same properties is obtained by the replacement of the reduced condensation product, indicated above, employed as a coupling component, by the reduced condensation product, of constitution

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 analogue, derived from 1 molecule of 2-amino acid
 EMI18.1
 5-axynaphthalene -'- sulfonïg, ue and 1 molecule of 6- chlorine-4- (µ'nitrophenyl) -2- (4Lnitrophenyl) ± pyrimain (see formula 8a above).

   In such cases it is also possible to proceed in such a way that the corresponding non-reduced condensation products are coupled to diazo or diazoazo compounds and that in the coloring matters thus formed the nitro groups are reduced, for example by means of sodium sulphide, sodium sulphide hydrate etc ... preferably at low temperature.



   In addition, also very strong green, grayish, green and olive developing colorants are obtained when the compound is coupled.
 EMI18.2
 pose diazo oicue from psi ': exemplified' -dè acidEt '1-aminobénZ.µ-àisulfoniquà, from' lak;: ÙrJn1ihtaJ.ine and l-aminonaphthaline-7-sulfoHic acid with reduced condensation product, indicated to formula 10 below
 EMI18.3
 l .. û ...: ', "'" (f "" "1 <; :: ..

    .. above from 6-nitra-4-chlâxeqûiriâzôline and 2-aminQ-5-oxyaphthaline-j-sn2ftinfqû, and which is dinitrogenated on the fiber; the coloring material thus obtained dyeing the plant fibers directly blue,
 EMI18.4
 and that is developed by means of c'ïe 3 = methyl-lpéyl-5-pyrazolone, acetic arylides,: & t ir'n1ande or. -. ,, ", '.,.'! -:,". c7 "". r. sulfazones. The product of Formula 10, already used

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 EMI19.1
 ,. <above, can also be used for achieving remarkable burgundy development tones:
 EMI19.2
 for example di- (2 .'-meth3rl-.4'-aninazolenzol-4-sulfonic acid and it is then coupled in alkaline sodium hydroxide solution with the above compound of quinazoline.



  In this way, an amino-disazo coloring matter is obtained, which dyes the cotton in a beautiful wine red.



  The diazotized tincture, developed with beta-naphthol, has a similar but more intensive tone; is very resistant to washing, over dyeing and light.



   Solid chromium-plating dyestuffs for wool are obtained when coupling with the condensation product from 1 molecule of 5nitro-4-chlorequinazoline and 1 molecule of 1-amino-8- diacid.
 EMI19.3
 ornaphthaline-.6-diulfan3.g, a compound of ortho-oxy- or ortho-carboxy-di, aaoiques; the chrome dye of the monoazo dyestuff from 4,6-dinitro-2-diazophenol and the mentioned compound is, for example, a beautiful greenish black with good resistance to crushing and to light.



   In addition, solid di- reotic dyestuffs ranging from blue to blueish green, passing well on vegetable fibers, are obtained when the condensation product of 1 molecule of a

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 EMI20.1
 peri..aminonaphtholsulfonic acid, for example 1-amino-8-oxynaphthaline-µ.6-disulfonic acid and 1 molecule of 2-chlorine-4.6-di .. (- nitrQphenyl-1,3 .-- tri-azine or its equivalents as final constituents (see formula 14 above}. A dyestuff of this kind is, for example, the secondary disazo dyestuff from diazotized 1-amino-8-oxynaphta- acid.
 EMI20.2
 Iine-3.6-âisu.fon3que + 3-amino-4-orésoiéthyiiqae ether, further diazotized and coupled to the condensation product just mentioned.

   A noticeably more greenish blue, having apart from that similar properties, is constituted by the disazoic secondary coloring matter.
 EMI20.3
 from 4-ammoaeetanilide-5-xulfonic acid, 1-amino-2-ethoxynaphthaline-6-sulfonyl acid and 1-molecule condensation product of 1-amino8-oçynaphthaline-3.6-disulfon3 acid. and 1 molecule of 6-chl.ore-4-3t n.traphén, rl - 2-C4.nitropherl pyrfidine (see formula 8a above). Similar secondary disazo dyestuffs are also suitable. perfect for uniform dyeing of viscose of different origin.



   The capacity of passing these dyestuffs over cotton is further increased by long stirring at about 4Q - 50 with insufficient sodium sulfide to reduce nitro groups to.

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 amino phases, or also by treatment carried out as usual with an alkaline solution of glucose.



   In addition, interesting azo dyestuffs are obtained which are derived from di- (nitro-
 EMI21.1
 phenyl) -triaZine..l: 3.5, when impregnating (scarf) for example on the plant fiber 2% of the reduced compound indicated in formula 14 above, originating from molecular quantities of 2-chlorine-4.6-di- (-nitrophenyl) -triazine-
 EMI21.2
 1.3. 5, and 2-amino-5-oxynaphthaline-7-sulfonic acid, which then pass the fibers thus treated in an acidulated nitrite bath which produces a tetrazotage and which finally makes the coupling with 2-Naphthol-sodium or 2,3-oxynaphthol-aid arylides or 4-oxynaphthylaryl-ketones or the like. This gives brilliant red tones, resistant to washing, and very good resistance to friction.



   Finally, the preparation of a direct dye from this group dyeing cotton in light pink tones very resistant to light will be indicated: In the product. of condensation of formula 14 come from
 EMI21.3
 Using 1,4-phenylenediaminesulfonic acid and 2-chlorine-4-6-di- (-nitrophenyl) -triazme-1.3.5, the two nitro groups are reduced in the usual way.

   The triamino compound obtained is acetylated with a little more than 2 mol-

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 Acetic acid anhydride capsules in aqueous solution, yielding a compound having the following formula:
 EMI22.1
 (gray powder soluble in alkali, diazotized; poorly soluble diazo compound) 533 parts by weight of this compound are indirectly diazotized; the Congo acidic medium is first of all coupled with 239 parts by weight of 2-amino-8-oxynaphthaline-6-sulfonic acid; by adding more sodium acetate the formation of the coloring matter is completed.



  The coloring matter is converted in the usual manner into an alkaline salt. A slightly lighter yellowish pink still occurs when 2-methyl-amino-naphthalene-7-sulfonic acid is used as the coupling component.
Example 3: -
532 parts by weight of the condensation product of 2 molecules of 5-amino-2-oxybenzoic acid and 1 molecule of 6-nitro-2,4-dichlor-quinazoline (see formula 11 above) are indirectly dinitrogenated and mates in the usual manner in the presence of sodium acetate '

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 with 173 parts by weight of 1-aminonaphthalene-6-sulfonic acid; after termination of the coupling, it is indirectly further dinitrogenated, the diazoazo compound is isolated with salt and filtered.

   The slurry is returned to ice temperature and it is coupled to 0 again using an aqueous solution of 173 parts by weight of 1-aminonaphthaline-6-sulfonic acid, while a little by little is added of sodium acetate solution. The isolated aminodiazo dyestuff thus obtained is further diazotized at 0 - +5 and coupled to 315 parts by weight of 2-phenyl- acid.
 EMI23.1
 amino-5-oxynaphthaline-'7-sulonic acid, and by flowing the diazo-disazo compound advantageously by stirring well under the surface of the alkaline sodium hydroxide solution of the coupling components at 0.

   The pure trisazo dyestuff passes over the cotton in blue tones: the dye with the addition of copper in the usual way is a blue which is very resistant to washing and to light.



   If the quinazoline derivative employed here as the starting constituent is replaced by the pyrimidine derivative of similar constitution, which is obtained by reducing the condensation product by 1 molecule
 EMI23.2
 of 5-amino-2-oxybenzoS.que acid with 1 molecule of 2.6-dichlor-4- (3'-nitrophenyl) -pyrimidine, and exchange of

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 second atom of chlorine against aniline (see formate 8 above), a blue coloring matter is obtained, the dye of which, with the addition of copper, possesses similar valuable properties on the plant fibers.



   A copper trisazoque, blue and solid coloring material is further obtained when the reduced reduced condensation product from 1 is coupled.
 EMI24.1
 molecule of 3-amino-2-oxyben2oic acid and 1 molecule of 6-nitro-4-chlorine-quinazoline (see formula 10 above) successively to 2 molecules of 1- aminonaphthaline-7-sulfonic acid , which further dinitrogenates and which finally combines in an alkaline sodium or ammoniacal medium with 1 molecule of the condensation product of 1 molecule of 2-4-dichlorequinazoline, 1 molecule
 EMI24.2
 2-amino-5-oxynaphthaline -? - sulfonic acid and 1 molecule of 5-amino-2-oxybenzoic acid (preparation according to French patent application 23,704 of December 21, 1927.



   For the preparation of valuable direct dyestuffs, the quinazoline and pyrimidine derivatives employed in this example can also be employed.



  If, for example, the mixed condensation product indicated in formula 11 above is dinitrogenated; derived from molecular amounts of 6-nitro-2.4-dichlor-quinazo-
 EMI24.3
 line, 1,4-phenylenediaminesulfonic acid and djael

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 5-amino-2-oxybenzoic and if one couples the precipitated di-azo compound, hardly soluble, in a weakly acidic medium in Congo, with 2-methylamino-naphthaline-6-carbonic acid, if one then reduces with the aid of sodium sulphide or ammonium sulphide, the nitro group of the azo dyestuff and if the aminoazic body thus obtained is finally phosgene, a coloring matter is obtained which dyes the cotton in the bath soda ash and Glauber's salt,

   in very beautiful deep pink tones resistant to light; by subsequent copper plating, a slightly darker pink is obtained with good resistance to washing.



   Useful polyazole dyestuffs are obtained when the reduced condensation product of 1 molecule of 6-nitro-2-4dichlorequinanzoline or similarly constituted nitro- compound is hexitrogenated with 2 exchangeable halogen atoms attached to it. a hetero chain, and 2 molecules of 1,4-phenylenediamine-sulfonic acid (see for example formula 11 above) or of 1,3-phenylenediamine-4-sulfonic acid and that the compounds are coupled; hexazoic, gelatinous, most often precipitated in a brownish form, with 3 molecules of 1,3-phenylene diamine. Similar coloring materials dye cotton brown.

   By development with p-nitro-diazobenzol, dark tones of a

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 black brown which are very resistant to washing and perfectly fading.



   Example 4: -
The diazo compound made in the usual manner using 469 parts by weight of the aminoazic body
 EMI26.1
 from 1 "amino-8-oxynaphthaline-r.6-ü-sulfonic acid and 3-amino-4-oresolmethyl ether is coupled to -10 to -5 advantageously in the presence of pyridine, with 475 parts. by weight of the reduced condensate from 1 molecule of 2- (4'-nitro
 EMI26.2
 phenyl) -4-6-diehlarepyrimidine, 1 molecule of 1-mîne-8-oxynaphthaline-3.6-disulfonic acid and. of 1 molecule of aniline (formula 6 above). After the coloring matter has quickly formed, the blue solution is diluted with hot water, separated into salt and filtered.

   For this coupling, it is also possible to operate in such a way that the diazo compound of 1-amino-8-oxynaphthaline-3.6-disulfonic acid is acetylated on the hydroxyl with acetic acid anhydride, for example in the presence of chalk, or
 EMI26.3
 that aminonaphthoisulfonic acid is toluolsulfonated in an alkaline solution of caustic soda, which is then dinitrogenated and which is coupled in a known manner to
 EMI26.4
 3-amine-4-cresolmethyl ether, which is still indirectly cold diazotized and which is finally combined

 <Desc / Clms Page number 27>

 to the derivative mentioned above of pyrimidine in the presence of pyridine, sodium carbonate and ammonia.



   By indirect diazotization of the aminoazoic compounds obtained (preferably diluted, temperature 20-30) and coupling, in alkaline sodium hydroxide solution, at 218 per-
 EMI27.1
 Ties by weight of 1- (r-carhvxyphenyl-3tethyl - pyrazolone one arrives, - in the case of 1 + 1-amino-8-oxynaphthaline-3.6-disulfonic acid esterified on the hydroxyl one dissociates all d ' first the acidyl residue by heating with soda or a caustic soda lye -, to a trisazoic coloring matter of a pure green. This material passes on the cotton, dyed according to one of the usual methods, in beautiful green tones of solidity remarkable in the light.The product is also ideal for dyeing half-wool.



   Instead of the above-mentioned condensation product, for example also the corresponding product from 1 molecule of 2- (4'-nitrophé) can be used.
 EMI27.2
 nyl-4.6-dichlctrepyrimidine and 1 molecule of l-amino-8-oxynaphthaline-µ.6-disulfonic acid in which the second chlorine atom of the hetero chain is replaced by hydroxyl, which can be done for example by cooking intermediate body containing chlorine with a little more than the calculated amount of sodium hydroxide solution;

   the new compound has the formula: -

 <Desc / Clms Page number 28>

 
 EMI28.1
 There is thus obtained with the aid of the diazaazo compound
 EMI28.2
 from 1-amino-8-uxynaphthaline-3.6-diaulfoniqge and µ-amin0-4-cfôsolmethfliquej-ether and using the above-mentioned pyrazolone as a final product, a green which dyes cotton in a shade more blue than the coloring matter described above * The fastness properties are the same.

   In place of the 1-amino-8-oxynaphthalene-3.6-disulfonic acid employed as a starting material in this coloring material, it is possible to use
 EMI28.3
 also 1-amino-8-oxynaphthaline-4.7-disulfo; ic, and in place of 3-amino-4-cresomethyl ether, the corresponding ethyl or oxethyl ether or their sulfuric acid esters; in case of use of the latter
 EMI28.4
 and replacing 1- (2'-carboxyphenyl) -3-methyl-5-pyrazolone with aceto-anilide-4-carbonic acid as a final component, a light bluish green is obtained.



   Green developing colorants are obtained by combining the diazoazo compound from 1-amino-8-oxynaphthalene-6-sulfonic acid and '
 EMI28.5
 of ether 3-amino-4-ereesoliciual with the benefits of condensation employed in the preceding example and which one develops on
1

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 EMI29.1
 the fiber by means of 1-phenyl-µ-methyl-5-pyrazolone; the obtained blue eminodisazoic dyestuffs. It goes without saying that unreduced condensation products originating from molecular amounts can also be used in such coloring materials.
 EMI29.2
 2- (.f -ti.trrtpï3enyl j ..6-dick.orepyrimidine, tacids, .- 1-amino-8-oxmaphthaline-sultonics and amines or phenols or thiophenols;

   one must then, in the obtained nitrodisazoic coloring matter, reduce the nitro group by means of sodium sulfide, sodium sulfhydrate, etc ...



   Dyestuffs of the type indicated in the above example can moreover also be constituted by the fact that, for example, the reduced condensate corresponding to formula 6 above is dinitrogenated and obtained. 'mates, advantageously in the presence of
 EMI29.3
 sodium acetate, 1- (2'-sulfophenyl) -3 "& ethyl-5-pyrazolone, aceto-2-anisidea-sulfonic acid or methyl-aetolaulfonic acid and equivalent compounds and which are then coupled the coloring matter obtained from disazo compounds, for example those of acid
 EMI29.4
 1-Amino-8- (aeidyl) -oxy-naphthalme-J.6-isisulfonate and 3-.amino-4-oresolethyl ether or 1.-anaphtha7.ixe
The trisazo dye formed by one of the above processes:

  3-amino-2-oxy- acid
 EMI29.5
 be..o1que z 1-emino-naphthalene 4- le? reduced condensation product of formula 6 above + 1- (5'-carboxy- 4t.OXY-3f-SUlfQPhenYl} -, - métb1'-pypaZolonr dyes the

 <Desc / Clms Page number 30>

 cotton in bluish green in the bath of solder carbonate and Glauber's salt; by subsequent copper plating, a green resistant to washing and remarkably fast to light is obtained.

   In addition, developing dyestuffs of other tones can also be established with the aid of condensation products of 2- (4'-nitroché-
 EMI30.1
 nyl) - .. 6-diehloropyrimidine by reducing for example the condensation product indicated in formula 6 a above originating from 1 molecule of the mentioned nitrophenyl dichlor-pyrimidine and from 2 molecules of acid
 EMI30.2
 2-amino-µ-oxynaphthaline-7-sulfonic acid, which is then coupled to 2 molecules of 3-diazoph6nyl-oxaminic acid in an alkaline sodium hydroxide medium, and which is finally eliminated the remainder of oxalic acid by saponification. The coloring matter obtained, hexitrogenated on the fiber and developed with beta-naphthol or arylides of 2,3-oxynphthoic acid, gives red tones which are very resistant to light and to washing.



   Example 5.)
469 parts by weight of the still diazotized aminoazo compound, used in Example 4, from 1-amino acid
 EMI30.3
 no-8-oxynaphthalene-3.6-disulfonic acid and 3-amino-1-cresolmethyl ether are coupled to -5 to -100, advantageously in the presence of pyridine, to 598 parts by weight of the reduced condensation product from
 EMI30.4
 1 molecule of 6-ohlorus-2- (31-nitrophenyl) -pyrimidine-4-carbonic acid chloride, 1 molecule of 1- amino-8-oxynaphthaline-3.6-disulfonic acid and 1 lplecule

 <Desc / Clms Page number 31>

 
 EMI31.1
 1-metbyl-4-mercapto-benzom (see formula 7 above -d4SSUS); it is also possible to use variants let us indicate in an example. with 1-8mino-8-oxynap% talin-µ.6 - 0-acydilated disulfonic acid.

   The resulting intense blue coloring matter is separated in the usual manner.



  It passes on cotton in blue tones and is transformed by development, for example by means of 1-phenyl-3-methyl-5-pyrazolone, into a green of good resistance to washing, well caustic and remarkable resistance to light. In this series, it is also possible to achieve solid direct greens for the vegetable fibers when, for dyestuffs of the type described in this example, the last coupling is carried out not on the fiber but in the substance. .

   A similar coloring matter arises, for example, from the aminoazoic body obtained from 3-chlorine-2-amino- acid.
 EMI31.2
 1-methyl-benzol-58ulfonic acid and 1-amino-2-6thoxy -naphthaline-6-sulfon: only by further diazotization and coupling in the presence of pyridine with the reduced oonden sation product of formula 7, further diazotization and
 EMI31.3
 final mating with 1- (3t-carboxyphenyl) -3-methyl-5-pyrazolone.



   Example 6.)
381 parts by weight of the saponified condensate product Indicated in formula 1 above is indirectly dinitrogenated from 1 molecule of 6-nitro-2-chiore
 EMI31.4
 benzo-thiazol and k-oxalylamino-1.> aminobenzol-3-sulfonic acid. The diazo compound precipitates in a

 <Desc / Clms Page number 32>

 hardly soluble;

   it is coupled in the presence of sodium carbonate or magnesia with 138 parts by weight of salicylic acid at 0. One precipitates hot in acidic solution in congo, one filters, one reduces the coloring matter again pulping in the manner usual with sodium hydrosulphide, the aminoazo dyestuff is separated, dissolved again in alkaline medium, indirectly further dinitrogenated and finally coupled in the usual manner to 234
 EMI32.1
 parts by weight of 1- (g'-oxy-µt-earboxyphenyl) -µ-methyl -5-pyrazolone. The processing is done as usual.



   The new coloring matter passes over the cotton in intense yellow tones which are transformed by subsequent copper plating and a dark yellow with good resistance to washing and fading. A copper yellow having similar properties is obtained by the use of the thiazol derivative used in this example.

   A very intense yellowish-red color, resistant to washing, is obtained on cotton when one molecule of the sparingly soluble diazo compound of the reduced condensation product from 1 molecule of 6-nitro-2-chlorine benzothiazol is coupled, and from 1 molecule of 2-amino-5-oxynaphthaline-7-sulfonic acid (see formula 1 above) to molecule of 5.5'-dioxy-2.2'-dinaph- acid
 EMI32.2
 tyl-ure-7.7'-disulfonic acid, which the isolated coloring matter is applied to the cotton in the usual manner and which is finally treated with 4-nitro-diazobenzol.

 <Desc / Clms Page number 33>

 



   Example 7.)
644 parts by weight of the condensation product from the aminoazo compound obtained from the acid
 EMI33.1
 2naphthylamine - .. 8-disulfonic acid and 3-aminotoluol with Ù-nitro-9-chloro-aeridine (according to formula 15 -% - above), are dissolved in as little water as possible and are reduced. partially in the presence of magnesia at 50 per 357 parts by weight of crystallized sodium sulfide. The aminoazic body obtained is, after indirectly diazotized purification and coupled in an alkaline sodium hydroxide medium to 492 parts by weight of the reduced condensation product produced according to French patent application 23,880 of February 2, 1928, originating from 1 molecule of 6-
 EMI33.2
 n: ktro-4-ohlorequi, 'nazoline and 1 molecule of 2- am3no-oxynaphtas3: rte-l .'- dâ.aulfonic acid.

   The eco-friendly material thus formed gives on the cotton, in the diazotized state, developed with sodium beta-naphthol, an intense reddish orange resistant to washing and overdyeing.



   When in-the condensation product, indicated in formula 17 above, from 1 molecule of
 EMI33.3
 6-nitro-2 ...- dich.orquiraaaline, 1 molecule of diacid .-- am.no -.'- axya.zobenzP3.-3 <t-cxabonique and 1 molecule of dimethylamine, the nitro- group is reduced preferably by means of sodium hydrosulfide in aqueous alcohol suspension, which is further dinitrogenated indirectly in large dilution and which is finally coupled in medium
 EMI33.4
 alkaline sodium hydroxide with I- (5'-carboxy - ?. 1 .'- oxy-3'-sulfophnyl-3-y .-- pyrazolo, e 'one obtains a material

 <Desc / Clms Page number 34>

 disazo dye dyeing cotton in intense yellow,

   the dye of which having undergone the subsequent copper plating ('\ .on .. stutues a yellow very resistant to light and to washing. In addition, coloring matters of light development are obtained when in the transformation product
 EMI34.1
 with the medium of 6-nitno-g-ehione-quinazolme, of the aminoazoic compound which is obtained by coupling 2-diazonaphthalin-6.8-àisulfonique acid. with 1.4-dimethyl-3-aminobenzol, the nitro group is reduced, after purification of the reduction product, it is still indirectly dinitrogenated and it is finally coupled in an alkaline medium with
 EMI34.2
 sodium hydroxide has 1- (3t-amincphenyl) -3-methyl-3-p-yrazolone The azo coloring matter thus formed has the
 EMI34.3
 
Its dye, diazotized on the fiber and developed by means of beta-naphthol,

   is a beautiful solid orange, The deve-
 EMI34.4
 development with 3-methyl-1-P16UY1-5-p7razolone produces a beautiful yellow;
Example 8.)
The diazole compound of 93 parts by weight of aniline is prepared in the usual manner and this is coupled at 0 to an alkaline solution at the bottom of 936 parts by weight of the azoxyquinazoline derivative of the formula

 <Desc / Clms Page number 35>

 4. The coloring matter, separated in the usual way and processed in the usual way, passes over the cotton in light bluish pink tones of good fade resistance.



   If one couples, in alkaline sodium hydroxide solution, 1 molecule of the diazo compound of pseudo-cumidine with 1 molecule of the condensation product indicated in formula '13 b above originating from 1 molecule of 6-nitro-2.3- dichlorequinoxaline, 1 molecule of 2-amino-5-oxynaphthalin-7-sulphonic acid and 1 molecule of aniline, and if we then reduce, in the red nitrogen coloring matter thus obtained, the nitro group by For example, by means of sodium sulphide, a coloring matter is obtained which dyes cotton in janunish red tones; by diazotization and coupling to the fiber with betanaphthol the dye becomes darker and is resistant to washing.



   Example 9.)
The diazo compound prepared in the usual manner from 520 parts by weight of the coloring matter
 EMI35.1
 aminoazoic acid from diazotized 4.5-dichlor-1-aminobenzo1- 2-sulfonic acid and 1-amino-2-ethoxynaphthalin-6-sulfonic acid is combined 5 - 10 to a solution prepared by means of 567 parts by weight of the reduced condensation product from 1 molecule of 6-nitro-
 EMI35.2
 4-ohlorequînazolîne and 1 molecule of 1 - (.'- esti.nobenzo,.) - amino-8-oxynaphthhal-.6-disulfonic acid, 3000 parts by volume of water,

     60 parts by volume of water

 <Desc / Clms Page number 36>

   20% ammonia and 1500 parts by volume of pyridine Disazo coloring matter is formed instantly; it is separated into salt and treated in the usual way it goes well on cotton in green tones. If we dinitrate the tincture in the usual way and develop it
 EMI36.1
 by means of methylphenylpyrazolone a very pure yellowish green is obtained which is resistant to over dyeing and very resistant to washing and fading. An analogous coloring material is obtained by the use of the isomeric compound.
 EMI36.2
 



   A 3-methyl-1-phenyl-5-pyrazolone developing green which is even more yellowish and also clear is formed when the disazo compound used in this example is replaced by that obtained by subsequent diazotization.
 EMI36.3
 from 4-amino-1-methylbenzol-3-sulfonic acid and 1-ammo-2-ethoxynaphthalin-6-sulfonic acid, and additionally used as the coupling component the following compound containing two residues quinazoline:

   
 EMI36.4
 is obtained by a new condensation by means of
 EMI36.5
 6-nitro-4-ehlore-quinazoline from the condensation product

 <Desc / Clms Page number 37>

 reduced, obtained according to the process of the French patent application 23 880-of February 2, 1928 example 3, coming from
 EMI37.1
 1-amino-8-oxy-naphthalene-µ.6-disulfonic acid and 6-nitro-4-eb.lore-quinazoline and by further reduction with iron and acetic acid; properties: yellow powder well soluble in water as a neutral sodium salt; diazotizes, reddish-brown diazo compound.



   Similar green developing dyestuffs are also obtained by introducing, instead of the mentioned quinazoline derivatives, correspondingly constitutive derivatives of quinoxaline. A similar compound is indexed to formula 13 above.



   Example 10.



   The diazo compound from 241 parts by weight
 EMI37.2
 5-Riichlor-amino-benol-2-sulfon.que acid is coupled in an alkaline sodium hydroxide solution at 362 parts by weight of the reduced condensation product of formula 9
 EMI37.3
 above, from 6-nitro-4-chlorequ1nazoline and 1-3-aminçz-phënrl) - pyrazolone-3carbonic acid. The yellow aminoazoic body, quickly formed completely, is isolated by means of salt. It is put back into a paste with water, a little sodium hydroxide solution is added for better dissolution and it is indirectly dinitrogenated.



  When, after long stirring, the whole is completely diluted, the diazoazo compound is isolated with salt and filtered. In the meantime, the aminoazo compound of 168 parts by weight of 5-nit ro-2-amino- was prepared by coupling in an acid medium in a known manner.

 <Desc / Clms Page number 38>

   anisol and 319 parts by weight of 1-amino-8-oxy-naphthalin-3.6-disulfonic acid. In its solution made strongly alkaline with sodium hydroxide, the diazoazo compound indicated above is poured at 0, with good stirring. Mating takes place immediately with green coloring of the solution. When after long stirring the formation of the coloring matter is complete, it is heated and the salt separation is produced.

   The new trisazo colourant passes over cotton in green tones that resist well to light.



   Example 11
 EMI38.1
 21.3 parts by weight of finely powdered 2 -.- diahlor-6-nitro-quinazoline are introduced into a well-stirred aqueous solution of 278 parts by weight of the salt of
 EMI38.2
 4-Amino-49-oxurazobenzol-3 '-carbonic acid sodium at a t7'1vjoe.1 "11: u .., e of 400. The em11 \ oazoic compound can soon no longer be detected. an aqueous solution was prepared of a further amount of 278 parts
 EMI38.3
 by weight of 4-amino-41-oxyazobenzol-3t-carbonlque acid (sodium salt).

   In the solution heated to 85 and well stirred, the solution, prepared according to the above data, is made to arrive in drops from the intermediate body, still containing 1 atom of mobile chlorine and coming from
 EMI38.4
 of 1 molecule of 6-nitro-2, h-diahlorequinazoline and of 1 molecule of 4-an.no - oxyazobenzol-3-carbouic acid with good stirring, the temperature being kept constantly at 80-85. The second molecule of the amino-azo body thus condenses quite rapidly; as soon as we do

 <Desc / Clms Page number 39>

 can detect more than traces of the amino-azo compound, it is separated into salt and filtered.

   We thus obtain the condensation product of 2 molecules of acid
 EMI39.1
 4-amino = 4, '- oxyazobenzol-µ'-aarboniqUe and 1 molecule of 6-nitro-2.4-dia,% loreqninazoline produced in which ;. "f / ':'" 1: By reduction with 40-50 sodium sulfide, the nitro group can be converted to an amino group.



  By treating the aqueous solution of the bisodium salt of the aminodisazoic compound thus obtained, with approximately 40 phosgene, in the presence of agents which combine with acids, the urea having the formulation is obtained.
 EMI39.2
 
This product passes over cotton in more intense yellow tones which turn green with subsequent copper plating. The copper dye is very resistant to light and washing.



   Interesting dyestuffs of similar constitution are further obtained by rendering the product.

 <Desc / Clms Page number 40>

 condensate of 1 molecule of 6-nitro-2.4-di- o
 EMI40.1
 cblQ'requina.za lil1.e of 1 molecule of 1 - aminc - $ - oxynaphthaline -,. 6-disulfonic acid and 1 molecule of 2.6-â.ch2are --- smina - 4- acid rayyazabenaal -! - carbariic, 1 product in which the nitro group is converted by partial reduction with ammonium sulfide, at a moderately elevated temperature, into an amino group,

   and that this product is coupled to the diazotized aminoazo body further from 1-amino-8-axynaphthaline- acid.
 EMI40.2
 3.6-diaulfonic acid and 3--ami.na --- areolzdët # lic ether and that in the trisazo dye thus obtained the free amino group is acetylated or benzoylated. The coloring matter having the formula: -
 EMI40.3
 goes for example on cotton in deep yellowish green tones very resistant to light.

   We arrive at the
 EMI40.4
 same coloring matter by benzcil.sation of the partially reduced condensation product from 1
 EMI40.5
 nitro2 fi molecule ... dzcl22ore quinazoline, 1 molecule

 <Desc / Clms Page number 41>

 
 EMI41.1
 1-amino-8-oxynaphthaline-µ, 6-disulfonic acid, 1 molecule of 2.6-diehlore-4-amîno-4? -ôxyazo-benzol-3'-carbonic acid and by subsequent coupling with the compound diazoazoic mentioned above.



   Summary :-
Process for the preparation of azo dyestuffs, characterized in that the starting materials are chosen such that at least one of the compounds entering into the constitution has a heterocyclic product of the general formula: - (A.R1 ) x R2 (B) y in which A represents nitro groups or their reduction phases such as azo, azoxy or amino groups or the acidylation products of the latter R represents a carbocyclic chain and R2 a chain
 EMI41.2
 heterocyclic, R1 being linked to R2 by the carbon bond

** ATTENTION ** end of DESC field can contain start of CLMS **.


    

Claims (1)

bone-carbon, k and y represent the numbers 1 or 2 and B a halogen atom or any residue which takes the place of the halogen atom and which is linked to the heterocyclic chain R2 by an atom nitrogen, oxygen or sulfur 1.) - in the sense that during the diazotization and coupling reactions at least one heterocyclic product of the general formula above is used, <Desc / Clms Page number 42> #) .- or else in the sense that one takes a heterocyclic product of the above formula in which A represents nitro groups and B a mobile halogen atom, and that it condenses with constituents which lead to . a nitrogen, oxygen or sulfur atom hydrogen atoms capable of easily reacting constituents of which at least one contains the azo group, while in the azo bodies formed the nitro groups can be transformed by reduction into azoxy, azo or amino groups and - in the latter case - to be further transformed by diazotization as well as by coupling or also acidylation or further condensation with heterocyclic compounds having mobile halogen atoms.