US3048584A - Hydrophilic optical wmtening agents - Google Patents

Hydrophilic optical wmtening agents Download PDF

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US3048584A
US3048584A US3048584DA US3048584A US 3048584 A US3048584 A US 3048584A US 3048584D A US3048584D A US 3048584DA US 3048584 A US3048584 A US 3048584A
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems

Definitions

  • Optical whitening agents have in recent years found extensive use in the treatment of textiles particularly during washing and are designed to counteract the yellow or off-white colour which white textiles, particularly cellulosic textiles, may possess, especially after repeated washing. Such optical whitening agents also tend to improve coloured textiles as they impart a general brightness to them. They are also widely used to impart whiteness to other cellulosic material, particularly paper.
  • Optical Whitening agents in general absorb light in the ultra-violet range of the spectrum and emit in the visible spectrum, usually in the bluish-green to bluishviolet. Thus, the fluorescence of such compounds in white material tends to counteract any yellowing as, for example, that resulting upon repeated washing of a white cotton or linen textile.
  • the compounds used as optical whitening agents must be substantive to the material being treated, and must be substantially stable when dyed on the material being treated.
  • optical whitening agents which give a shade of fluorescence which is complementary to that of the aged fibre, so that the colours will cancel out each other. Since, in general, the most common off-White shade of textiles resulting from ageing or repeated washing is yellow, the most desirable optical whitening agent is one that fluoresces blue.
  • optical whitening agent should not be destroyed or removed by bleaching agents; that is, it should be bleach-fast.
  • fluorescent optical whitening agents are generally incorporated into soaps and synthetic detergents, which are marketed for household use and articles washed therewith are often subjected to bleaching with various bleaching agents, for example sodium hypochlorite. It is therefore desirable that the optical whitening agents already on the fibre or in the treating solution should be affected as little as possible by the action of any bleaching agent which may be present.
  • X is a member of the group consisting of a hydrogen atom, a halogen atom and a lower alkoxy group and A is a group selected from the group consisting of:
  • R is a member selected from the group consisting of a hydrogen atom and a lower alkyl group and alkali-metal salts of these compounds, e.g. sodium salts can be used with advantage as optical whitening agents in that they possess favourable properties from the point of view of the above-mentioned desiderata for the ideal optical whitening agents.
  • the invention comprises such compounds, together with their alkali-metal, in particular sodium salts.
  • the compounds of the present invention show a good affinity for cellulosic material and exhibit a blue fluorescence, giving to the fibre a particularly pleasant hue. They show in general good resistance to bleaching agents and have good build-up qualities; that is-due to wellbalanced substantivityon repeated treatments with a bath of the same concentration, the whiteness of the fabric being treated continually increases up to a maximum, which maximum does not in general cause unpleasant visible colour or hue, as is often the case.
  • those compounds in which the group A is ment of paper and photographic paper where high whiteness is necessary.
  • composition having optical whitening propert-ies comprising a compound of the formula:
  • the invention also includes cellulosic materials when treated with the above compositions, in particular cotton or linen textiles, and protein and polyamide materials when treated with a composition containing a compound in which the group A is Specific preferred new compounds according to the invention are those set below together with their alkali metal salts.
  • a particularly preferred compound is 2-(4"-styryl-3"- sulpho phenyl) (indazolo-4':5-4:5 -1 :2z3-triazole.
  • the intermediate compound may if desired be isolated before being coupled.
  • Example 1.2 (4" Styryl 3 Sulpho Phenyl) (Indaz0l04 :5 4 :5 -1 :2 :3 -Triaz0le) (Indaz0l04 :5 4 :5 -1 :2 :3 -Triaz0le)
  • a solution of 16.32 parts of the sodium salt of 4- amino-stilbene-Z-sulphonic acid (91% pure) and 3.45 parts of sodium nitrite in 150 parts of water is indirectly diazotized at 810 C. with 20 parts of concentrated HCl.
  • the diazo compound is isolated by filtration, suspended in Water and mixed with a solution of 6.7 parts of S-aminoindazole in aqueous hydrochloric acid to effect coupling.
  • the pH of the mixture is controlled .to 7-8 by addition of sodium acetate during coupling.
  • the mixture is made alkaline by addition of sodium carbonate, and the sodium salt of the o-amino-azo dyestufi is salted out.
  • the o-amino-azo dyestutf is dissolved in pyridine and refluxed for 3 hours with g. of copper sulphate and ml. of dilute ammonia, with ml. of water.
  • the product is precipitated by addition of hydrochloric acid.
  • the crude product obtained is dissolved in dilute sodium carbonate solution, boiled with sodium hydrosulphite and activated charcoal, screened and crystallized, giving a very pale yellow product having A max. 352 m n.
  • This compound gives a vivid blue flourescence, and when a piece of cotton, nylon or wool is washed in a detergent solution containing a small amount of this compound, .the material acquires a much whiter appearance than before treatment.
  • Example 2.-2 (4" Styryl 3" Sulpho Phenyl) (Indazol0-6 7-4 :5) -1 :2 :3-Triaz0le
  • a solution of 16.32 parts of sodium salt of 4-aminostilbene-Z-sulphonic acid (91% pure) and 3.45 parts of sodium nitrite in 150 parts of water is indirectly diazotized at 8l0 C. with 20 parts of concentrated HCl.
  • the diazo compound is isolated, suspended in aqueous alcohol, and mixed with a solution of 6.7 parts of 6-aminoindazole in acidified aqueous alcohol to effect coupling of the components.
  • the acidity of the mixture is controlled by addition of sodium acetate during coupling.
  • the o-amino-diazo dyestuff obtained is filtered off at 2530 C.
  • the o-amino-azo dyestuff is dissolved in aqueous alcohol and sodium hydroxide and is oxidized by addition of an excess of sodium hydroxide and is oxidized by addition of an excess of sodium hypochlorite solution added dropwise at -75 C.
  • the desired product obtained is salted out.
  • the compound is slurried with aqueous alcohol, made alkaline and treated With sodium hydrosulphite for a few hours at 70 C. to remove the last trace of coloured impurities. Finally, the compound is recrystallized from aqueous alcohol. It has a x max. Of 353 I'D/L.
  • the compound so obtained is a greyish powder which in dilute solution gives vivid blue fluorescence and when a piece of cotton is washed in a detergent solution containing a small amount of this compound the material acquires a much whiter appearance than before treatment.
  • a solution of 17.21 parts of the sodium salt of 4-amino- 4'-methoxy stilbene-Z-sulphonic acid (95% pure) and 3.45 parts of sodium nitrite in parts of water is indirectly diazotized at 8-10 C. with 20 parts of concentrated HCl.
  • the diazo compound is isolated, suspended in water and mixed wih a solution of 6.7 parts of 6-amino indazole in dilute hydrochloric acid to effect the coupling of the components.
  • the acidity of the mixture is controlled by addition of sodium acetate during coupling.
  • the o-amino azo dyestulf is dissolved in pyridine and refluxed for 3 hours with 30 parts of copper sulphate and 35 mls. of ammonia, with 60 mls. of water. On completion of the oxidation the product is precipitated by the addition of hydrochloric acid.
  • the crude product obtained is dissolved in aqueous alcohol, made alkaline and treated with sodium hydrosulphite to remove the last trace of coloured impurities.
  • the triazole crystallizes from the solution on cooling. It has A max.
  • the mixture is basified by addition of sodium carbonate and the sodium salt of the o-arnino azo dyestufi is salted out.
  • the o-amino-azo dyestufi is dissovlved in water and refluxed for 3 hours with 30 parts of copper sulphate and 35 parts of ammonia, with 60 parts of water.
  • the product is precipitated by addition of hydrochloric acid.
  • the crude product obtained is dissolved in dilute alcoholic sodium carbonate solution boiled with sodium hydrosulphite and activated charcoal, screened and crystallized, giving a pale yellow solid, having A max.
  • the pH of the mixture is controlled to 7-8 by addition of sodium acetate during coupling.
  • the mixture is basified by addition of sodium carbonate and the sodium salt of the o-amino azo dyestuff is filtered at 25-30 C.
  • the o-amino azo dyestufi is dissolved in pyridine and refluxed for 3 hours with 30 parts of copper sulphate and 35 parts of ammonia, with 60 parts of water. After the oxidation the product is precipitated by addition of hydrochloric acid.
  • the crude triazole is recrystallized from 40% aqueous pyridine. It has A max. 353 mu.
  • a solution of 16.5 parts of the sodium salt of 4-amino stilbene-Z-sulphonic acid (90% pure) and 3.45 parts of sodium nitrite in 150 parts of water is indirectly diazotized at 8-10 C. with 20 parts of concentrated hydrochloric acid.
  • the diazo compound is isolated by filtration, suspended in water and mixed with a solution of 8.05 parts of 1,3-dimethyl-6-amino indazole in dilute acetic acid to effect the coupling of the components.
  • the pH of the mixture is controlled during coupling at 7-8 by the addition of sodium acetate solution.
  • the o-amino-azo dyestufl is filtered off at 25-30 C.
  • the o-amino-azo dyestufi is dissolved in pyridine and refluxed for 3 hours with 30 parts of copper sulphate and 35 parts of ammonia, with 60 parts of water. After the oxidation the product is precipitated with hydrochloric acid. The crude product is recrystallized from 25% aqueous pyridine. It has A max. 355 mp.
  • a solution of 18.62 parts of the sodium salt of 4-chloro- 4-amino s-tilbene-Z-sulphonic acid (89% pure) and 3.45 parts of sodium nitrite in parts of water is indirectly diazotized at 8-l0 C. with 20 parts of concentrated HCl.
  • the diazo compound is isolated by filtration, suspended in water and mixed with a solution of 6.65 parts of 6- amino indazole in dilute acid to effect the coupling of the components.
  • the pH of the mixture is controlled at 7-8 during the coupling by the addition of sodium acetate.
  • the o-amino azo dyestutf is filtered off at 25-30 C.
  • the dyestuff is dissolved in pyridine and refluxed for 3 hours with 30 par-ts of copper sulphate and 35 parts of ammonia, with 60 parts of water. After oxidation the product is precipitated by the addition of hydrochloric acid. The crude product is recrystallized from aqueous alcohol. It has A max.
  • Example 9.2(4"-(2"'-Chl0r0styryl)-3"-Sulph0 Phenyl) (Indazol0-6':7'-4 :5 )-1 :2 :3-Triaz0le This is prepared as in Example 8, replacing 4-chloro-4- amino stilbene-Z-sulphonic acid by 2-chloro-4-amino-stilbene-Z-sulphonic acid. It has A max.
  • Example 10.2 (4"-(4"-Chlorostyryl) -3"-Sulpho Phenyl) (Indazolo-I' :5-4:5)-1 :2 :3-Triaz0le This is prepared as in Example 8, replacing 6-amino indazole by S-amino-indazole. 'It has A max. 355 mp.
  • optical whitening agents Some examples of the use of the compounds according to the invention as optical whitening agents are as follows:
  • the material thus obtained shows a much brighter and whiter appearance than Without this after-treatment.
  • a good eifect can also be obtained by washing the wool in a soap bath containing 0.05 gram per litre of the above whitener.
  • Example (c) A piece of aged white poplin (slightly yellowish) is washed in a detergent solution containing 0.05 gram per litre of the compound mentioned in Example No. 2. After rising and drying the material shows a brilliant white appearance.

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Description

FEESE United States Patent 3,048,584 HYDROPHILIC OPTICAL WHITENING AGENTS OF THE STILBYL TRIAZOLE TYPE Dennis Arthur William Adams, Leeds, and Asim Kumar Sarkar, Adel, England, assignors to Hickson & Welch Limited, Castleford, England, a British company No Drawing. Filed Apr. 15, 1960, Ser. No. 22,410 Claims priority, application Great Britain Sept. 18, 1956 9 Claims. (Cl. 260240) This invention is concerned with improvements in or relating to optical whitening agents and is particularly concerned with certain new compounds for use as optical whitening agents. This application is a continuation-inpart of our application Serial No. 683,702, filed September 13, 1957, now abandoned.
Optical whitening agents have in recent years found extensive use in the treatment of textiles particularly during washing and are designed to counteract the yellow or off-white colour which white textiles, particularly cellulosic textiles, may possess, especially after repeated washing. Such optical whitening agents also tend to improve coloured textiles as they impart a general brightness to them. They are also widely used to impart whiteness to other cellulosic material, particularly paper.
Optical Whitening agents in general absorb light in the ultra-violet range of the spectrum and emit in the visible spectrum, usually in the bluish-green to bluishviolet. Thus, the fluorescence of such compounds in white material tends to counteract any yellowing as, for example, that resulting upon repeated washing of a white cotton or linen textile. The compounds used as optical whitening agents must be substantive to the material being treated, and must be substantially stable when dyed on the material being treated.
In general best results are obtained with optical whitening agents which give a shade of fluorescence which is complementary to that of the aged fibre, so that the colours will cancel out each other. Since, in general, the most common off-White shade of textiles resulting from ageing or repeated washing is yellow, the most desirable optical whitening agent is one that fluoresces blue.
It is also of importance that the optical whitening agent should not be destroyed or removed by bleaching agents; that is, it should be bleach-fast. Thus, fluorescent optical whitening agents are generally incorporated into soaps and synthetic detergents, which are marketed for household use and articles washed therewith are often subjected to bleaching with various bleaching agents, for example sodium hypochlorite. It is therefore desirable that the optical whitening agents already on the fibre or in the treating solution should be affected as little as possible by the action of any bleaching agent which may be present.
It is an object of the present invention to provide optical whitening agents having improved properties in the foregoing respects.
We have now found that certain new compounds represented by the general formula:
N X O H I in which X is a member of the group consisting of a hydrogen atom, a halogen atom and a lower alkoxy group and A is a group selected from the group consisting of:
CROSS REYEYZENCE station-1 auuw:
3,048,584 Patented Aug. 7, 1962 in which R is a member selected from the group consisting of a hydrogen atom and a lower alkyl group and alkali-metal salts of these compounds, e.g. sodium salts can be used with advantage as optical whitening agents in that they possess favourable properties from the point of view of the above-mentioned desiderata for the ideal optical whitening agents.
Accordingly the invention comprises such compounds, together with their alkali-metal, in particular sodium salts.
The compounds of the present invention show a good affinity for cellulosic material and exhibit a blue fluorescence, giving to the fibre a particularly pleasant hue. They show in general good resistance to bleaching agents and have good build-up qualities; that is-due to wellbalanced substantivityon repeated treatments with a bath of the same concentration, the whiteness of the fabric being treated continually increases up to a maximum, which maximum does not in general cause unpleasant visible colour or hue, as is often the case. In addition, those compounds in which the group A is ment of paper and photographic paper where high whiteness is necessary.
According to a feature of the invention therefore there is provided a composition having optical whitening propert-ies comprising a compound of the formula:
(in which X and A have the above-stated meanings) and alkali-metal salts thereof. The invention also includes cellulosic materials when treated with the above compositions, in particular cotton or linen textiles, and protein and polyamide materials when treated with a composition containing a compound in which the group A is Specific preferred new compounds according to the invention are those set below together with their alkali metal salts.
2 (4" styryl 3 sulpho phenyl) (indazolo 6':7'- 4:5)-1:2:3-tn'azole.
2 (4" styryl 3" sulpho phenyl) (indazolo 4:5'- 4:5)-l:2:3-triazole.
2 (4" (4" methoxy styryl) 3" sulpho phenyl) (indazolo-6:7'-4: -1 :2: 3-triazole.
2 (4 (4"' methoxy styryl) 3" sulpho phenyl) (indazolo-4 5-4 5 -1 :2: S-triazole.
2 (4" styryl 3" sulpho phenyl)(1' methyl indazolo-6:7-4:5)-l :2: 3-triazole.
2 (4" styryl 3" sulpho phenyl) (3 methylindazolo-6':7'-4:5 -1 :2 3-triazole.
2 (4" styryl 3" sulpho phenyl) (1,3' dimethylindazolo-6 7'-4: 5 -1 2: 3-triazole.
2(4" (4' chloro styryl) 3" sulpho phenyl) (indazole-6' 7-4: 5 -l 2: 3-triazole.
2(4" (2" chlorostyryl) 3" sulpho phenyl) (indazole-6' 7'-4:5 -1 :2: 3-triazole.
2(4" (4 chlorostyryl) 3" (indazolo-4:5-4: 5 -1 :2: 3-triazole.
2(4" (2" chlorostyryl) 3" sulpho phenyl) (indazolo-4 5 -4: 5 -1 :2 3-triazole.
A particularly preferred compound is 2-(4"-styryl-3"- sulpho phenyl) (indazolo-4':5-4:5 -1 :2z3-triazole.
In the above compounds the nomenclature adopted is based on the numbering shown in the following formulae:
- sulpho phenyl) 3 III 2m The new compounds according to the invention can conveniently be prepared by oxidizing an o-amino azo dye of Formula II given below, and according to a feature of the invention therefore we provide a process for the preparation of the compounds of the general Formula I above by oxidizing an o-amino azo dye of the general formula x -ca=cn- (where X has the above-stated meaning), and coupling the resultant diazotized compound with a compound of the formula H N--A, where A has the above-stated meaning. The intermediate compound may if desired be isolated before being coupled.
In order that the invention may be more fully understood the following examples are given by way of illustration only:
Example 1.2 (4" Styryl 3 Sulpho Phenyl) (Indaz0l04 :5 4 :5 -1 :2 :3 -Triaz0le A solution of 16.32 parts of the sodium salt of 4- amino-stilbene-Z-sulphonic acid (91% pure) and 3.45 parts of sodium nitrite in 150 parts of water is indirectly diazotized at 810 C. with 20 parts of concentrated HCl. The diazo compound is isolated by filtration, suspended in Water and mixed with a solution of 6.7 parts of S-aminoindazole in aqueous hydrochloric acid to effect coupling. The pH of the mixture is controlled .to 7-8 by addition of sodium acetate during coupling. When the coupling is complete, the mixture is made alkaline by addition of sodium carbonate, and the sodium salt of the o-amino-azo dyestufi is salted out. The o-amino-azo dyestutf is dissolved in pyridine and refluxed for 3 hours with g. of copper sulphate and ml. of dilute ammonia, with ml. of water. On completion of the oxidation the product is precipitated by addition of hydrochloric acid. The crude product obtained is dissolved in dilute sodium carbonate solution, boiled with sodium hydrosulphite and activated charcoal, screened and crystallized, giving a very pale yellow product having A max. 352 m n.
This compound gives a vivid blue flourescence, and when a piece of cotton, nylon or wool is washed in a detergent solution containing a small amount of this compound, .the material acquires a much whiter appearance than before treatment.
Example 2.-2 (4" Styryl 3" Sulpho Phenyl) (Indazol0-6 7-4 :5) -1 :2 :3-Triaz0le A solution of 16.32 parts of sodium salt of 4-aminostilbene-Z-sulphonic acid (91% pure) and 3.45 parts of sodium nitrite in 150 parts of water is indirectly diazotized at 8l0 C. with 20 parts of concentrated HCl. The diazo compound is isolated, suspended in aqueous alcohol, and mixed with a solution of 6.7 parts of 6-aminoindazole in acidified aqueous alcohol to effect coupling of the components. The acidity of the mixture is controlled by addition of sodium acetate during coupling. When the coupling is complete the o-amino-diazo dyestuff obtained is filtered off at 2530 C. The o-amino-azo dyestuff is dissolved in aqueous alcohol and sodium hydroxide and is oxidized by addition of an excess of sodium hydroxide and is oxidized by addition of an excess of sodium hypochlorite solution added dropwise at -75 C. On completion of the oxidation which is shown by the change of colour from red to orange the desired product obtained is salted out. The compound is slurried with aqueous alcohol, made alkaline and treated With sodium hydrosulphite for a few hours at 70 C. to remove the last trace of coloured impurities. Finally, the compound is recrystallized from aqueous alcohol. It has a x max. Of 353 I'D/L.
The compound so obtained is a greyish powder which in dilute solution gives vivid blue fluorescence and when a piece of cotton is washed in a detergent solution containing a small amount of this compound the material acquires a much whiter appearance than before treatment.
A solution of 17.21 parts of the sodium salt of 4-amino- 4'-methoxy stilbene-Z-sulphonic acid (95% pure) and 3.45 parts of sodium nitrite in parts of water is indirectly diazotized at 8-10 C. with 20 parts of concentrated HCl. The diazo compound is isolated, suspended in water and mixed wih a solution of 6.7 parts of 6-amino indazole in dilute hydrochloric acid to effect the coupling of the components. The acidity of the mixture is controlled by addition of sodium acetate during coupling.
5 When the coupling is complete the o-amino azo dyestuif is filtered off at 25-30 C.
The o-amino azo dyestulf is dissolved in pyridine and refluxed for 3 hours with 30 parts of copper sulphate and 35 mls. of ammonia, with 60 mls. of water. On completion of the oxidation the product is precipitated by the addition of hydrochloric acid. The crude product obtained is dissolved in aqueous alcohol, made alkaline and treated with sodium hydrosulphite to remove the last trace of coloured impurities. The triazole crystallizes from the solution on cooling. It has A max. 362 m A solution of 17.21 parts of the sodium salt of 4-amino- 4'-methoxy stilbene-Z-sulphonic acid (95% pure) and 3.45 parts of sodium nitrite in 150 parts of Water is indirectly diazotized at 8-l0 C. with 20 parts of concentrated HCl. The diazo compound is isolated by filtration, slurried in water and mixed with a solution of 6.7 parts of 5-amino indazole in aqueous hydrochloric acid to effect the coupling of the components. The pH of the mixture is controlled to 7-8 by addition of sodium acetate during coupling. When coupling is complete, the mixture is basified by addition of sodium carbonate and the sodium salt of the o-arnino azo dyestufi is salted out. The o-amino-azo dyestufi is dissovlved in water and refluxed for 3 hours with 30 parts of copper sulphate and 35 parts of ammonia, with 60 parts of water. After the oxidation the product is precipitated by addition of hydrochloric acid. The crude product obtained is dissolved in dilute alcoholic sodium carbonate solution boiled with sodium hydrosulphite and activated charcoal, screened and crystallized, giving a pale yellow solid, having A max. 363 m Example 5.2-(4"-Styryl-3"-Sulph0 Phenyl) (1 Methyl Indazl0-6 7'4 -1 :2 z3-Triaz0le A solution of 16.5 parts of sodium salt of 4-amino stil bene-Z-sulphonic acid (90% pure) and 3.45 parts of sodium nitrite in 150 parts of water is indirectly diazotized at 8-10 -C. with 20 parts of concentrated HCl. The diazo compound is isolated by filtration, suspended in water and mixed with a solution of 7.35 parts of l-methyl- 6-amino indazole in dilute acid to etiect the coupling of the components. The pH of the mixture is controlled to 7-8 by addition of sodium acetate during coupling. When coupling is complete the mixture is basified by addition of sodium carbonate and the sodium salt of the o-amino azo dyestuff is filtered at 25-30 C. The o-amino azo dyestufi is dissolved in pyridine and refluxed for 3 hours with 30 parts of copper sulphate and 35 parts of ammonia, with 60 parts of water. After the oxidation the product is precipitated by addition of hydrochloric acid. The crude triazole is recrystallized from 40% aqueous pyridine. It has A max. 353 mu.
This is prepared exactly as in Example 5, replacing 1-methy1-6-amino indazole by 3-methyl-6-amino indazole. It has A max. 355 m Example 7.2-(4-Styryl-3"-Sulpho Phenyl) (1,3- Dimethyl-Indazol0-6' 7'-4 :5 -1 :2 :3-Triazole A solution of 16.5 parts of the sodium salt of 4-amino stilbene-Z-sulphonic acid (90% pure) and 3.45 parts of sodium nitrite in 150 parts of water is indirectly diazotized at 8-10 C. with 20 parts of concentrated hydrochloric acid. The diazo compound is isolated by filtration, suspended in water and mixed with a solution of 8.05 parts of 1,3-dimethyl-6-amino indazole in dilute acetic acid to effect the coupling of the components. The pH of the mixture is controlled during coupling at 7-8 by the addition of sodium acetate solution. When coupling is complete the o-amino-azo dyestufl is filtered off at 25-30 C.
The o-amino-azo dyestufi is dissolved in pyridine and refluxed for 3 hours with 30 parts of copper sulphate and 35 parts of ammonia, with 60 parts of water. After the oxidation the product is precipitated with hydrochloric acid. The crude product is recrystallized from 25% aqueous pyridine. It has A max. 355 mp.
A solution of 18.62 parts of the sodium salt of 4-chloro- 4-amino s-tilbene-Z-sulphonic acid (89% pure) and 3.45 parts of sodium nitrite in parts of water is indirectly diazotized at 8-l0 C. with 20 parts of concentrated HCl. The diazo compound is isolated by filtration, suspended in water and mixed with a solution of 6.65 parts of 6- amino indazole in dilute acid to effect the coupling of the components. The pH of the mixture is controlled at 7-8 during the coupling by the addition of sodium acetate. When coupling is complete the o-amino azo dyestutf is filtered off at 25-30 C. The dyestuff is dissolved in pyridine and refluxed for 3 hours with 30 par-ts of copper sulphate and 35 parts of ammonia, with 60 parts of water. After oxidation the product is precipitated by the addition of hydrochloric acid. The crude product is recrystallized from aqueous alcohol. It has A max. 354 m Example 9.2(4"-(2"'-Chl0r0styryl)-3"-Sulph0 Phenyl) (Indazol0-6':7'-4 :5 )-1 :2 :3-Triaz0le This is prepared as in Example 8, replacing 4-chloro-4- amino stilbene-Z-sulphonic acid by 2-chloro-4-amino-stilbene-Z-sulphonic acid. It has A max. 352 m Example 10.2 (4"-(4"-Chlorostyryl) -3"-Sulpho Phenyl) (Indazolo-I' :5-4:5)-1 :2 :3-Triaz0le This is prepared as in Example 8, replacing 6-amino indazole by S-amino-indazole. 'It has A max. 355 mp.
This is prepared as in Example 8, replacing 4-chloro- 4-amino stilbene-2-sulphonic acid by 2'-chloro-4-ann'nostilbene-Z-sulphonic acid and 6-amino-indazole by 5- amino-indazole. It has A max. 351 me.
Some examples of the use of the compounds according to the invention as optical whitening agents are as follows:
Example (a).White wool is boiled for 30 minutes in a bath containing 0.05 gm. of the compound obtained in Example No. 1, and 2 grams of formic acid per litre. The material thus obtained shows a much brighter and whiter appearance than Without this after-treatment. A good eifect can also be obtained by washing the wool in a soap bath containing 0.05 gram per litre of the above whitener.
Example (b).-Yellowish-white paper (due to ageing) is treated with a solution containing 0.05 gram per litre of the compound mentioned in Example No. 1. After rinsing and drying the paper shows a much whiter appearance.
Example (c).A piece of aged white poplin (slightly yellowish) is washed in a detergent solution containing 0.05 gram per litre of the compound mentioned in Example No. 2. After rising and drying the material shows a brilliant white appearance.
It will be appreciated that although only compounds in which the groups R are hydrogen and methyl groups and in wihch the groups X are hydrogen, methoxy or chloro have been exemplified in the foregoing examples, the nature of these groups is not restricted thereby. Thus, for example, it will be clear to those skilled in the art that the groups R can be other lower alkyl groups. Similarly the groups X can for example be any lower alkoxy groups and need not necessarily be a methoxy group. Other variations will be apparent to those skilled in the art.
We claim: I 1. A compound selected from compounds of the formula:
X CH=CH N A G N X S0 11 the group consisting of l I @012 -NR and in which R is a member selected from the group consisting of a hydrogen atom and a lower alkyl group; and alkali-metal salts thereof.
2. 2-(4"-styryl-3"-sulpho phenyl) (indazo1o-4:5-4:5)- 1:2 3-triazole.
3. 2-(4"-styryl-3-sulpho phenyl) (indazo1o-6':7-4: 5 1 :2: 3-triazole.
4. 2-(4 (4"' methoxy styryl) 3" sulpho phenyl) (indazolo-6':7'-4: 5 )-1 :2: 3 tr iazole.
5. 2-(4-styryl-3"-sulpho phenyl) (1'-methy1 indazolo- 6:7'-4:5)-1:2:3-triaz0le.
6. 2-(4"-styryl-3"-sulpho phenyl) (3-rnethyl-indazolo- 6':7-4: 5)-1 :2: 3-t1'iazole.
7. 2-(4-styryl-3"-sulpho phenyl) (1':3-dimethy1-indazolo-6' 7-4 5 -1 2:3-triaZo1e.
8. 2 (4"-(4"'-chloro styryl)-3"-sulpho phenyl) (inda- 2010-6 7-4:5 -1 :2: 3-triazole.
9. 2(4"-(2' chlorostyryl)-3" -su1pho phenyl) (indazolo-6':7-4:5)-122:3-triazole.
Zweidler et a1. Mar. 5, 1957 Adams et a1 Mar. 15, 1960

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3447943A (en) * 1964-09-02 1969-06-03 Ici Ltd Process for the whitening of polymeric materials
US20030182745A1 (en) * 2002-03-28 2003-10-02 Hartman Frederick R. Power toothbrush

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2784184A (en) * 1957-03-05 - methyl -
US2928830A (en) * 1956-10-02 1960-03-15 Hickson & Welch Ltd Pyrazolo-triazole optical brighteners

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2784184A (en) * 1957-03-05 - methyl -
US2928830A (en) * 1956-10-02 1960-03-15 Hickson & Welch Ltd Pyrazolo-triazole optical brighteners

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3447943A (en) * 1964-09-02 1969-06-03 Ici Ltd Process for the whitening of polymeric materials
US20030182745A1 (en) * 2002-03-28 2003-10-02 Hartman Frederick R. Power toothbrush

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