DE1250444B - - Google Patents

Description

^ JTSCHES -J ^^ lk PATENT OFFICE

German class: 12 ρ-10/05

Circulee

DESIGN FONT - U50444

File number: G 44093 IVd / 12 ρ 1250 444 Filing date: 7Jul M965

Opening day: - 2iTSepternber 1967

The invention relates to a process for the production of cyclic brighteners with improved durability against active chlorine.

It is known that fiber material made of cellulose or synthetic polyamide can be optically lightened can, if this material is treated with a liquor, in particular washing liquor, which as optical brightener 2- (stilbyl-4 ") - (naphtho-1 ', 2': 4.5) -1,2,3-triazole-2" sulfonic acid contains.

However, since this brightener is gradually destroyed by active chlorine in aqueous solution, a liquor containing this brightener cannot be used for the simultaneous (ie one-bath) optical brightening and chemical bleaching of fiber material, which is a disadvantage since the single-bath chemical bleaching and optical brightening nowadays is becoming more and more important. In addition, the stilbyl-triazolesulfonic acid mentioned gives this material an undesirable greenish tinge at higher concentrations, such as those which accumulate on the fiber material during repeated washing with liquors containing these brighteners. This is very disadvantageous
For the optical brightening of textiles which have been treated with sizes ("anticreases") which improve the crease resistance, relatively large amounts of brightener are required.

It has now been found that, with regard to the deficiencies mentioned, improved optical brighteners the stilbene series is obtained if the diazonium compound of the 4-ami is used in a manner known per se

Process for the production of optical brighteners
the stilbene series

Applicant:

JR Geigy AG, Basel (Switzerland)
Representative:

Dr. F. Zumstein, Dr. E. Assmann,
Dr. R. Koenigsberger

and Dipl.-Phys. R. Holzbauer, patent attorneys,
Munich 2, Bräuhausstr. 4th

Named as inventor:

Dr. Reinhard Zweidler,

Dr. Rudolf Keller, Riehen;

Dr. Max Keller, Basel (Switzerland)

'riontätt—— ■ ——
Switzerland of July 9, 1964 (9043) J ^>

no-2 ', 4'- or -3', 4'-dichlorostilbene-2-sulfonic acid with - aminonaphthalene or 2 - aminonaphthalene-1-sulfonic acid couples and the o-aminoazo dye obtained by methods known per se a compound of formula I.

Xi X ₂

oxidized. In this formula, of Xi and X> one X denotes a hydrogen atom and the other X a chlorine atom.

For lightening from an aqueous bath, the sulfonic acid of the formula I is used in particular in the form of its salts with monovalent cations, preferably as alkali or ammonium salt, used.

The 4-amino-2 ', 4'- or -3', 4'-dichloro-stilbene-2-sulfonic acid used as starting material is obtained for example by condensation of 2,4- or 3,4-dichlorobenzaldehyde with 4-nitro-toluene-2-sulfonic acid phenyl ester, Saponification of the sulfonic acid phenyl ester group and reduction of the 4-nitro-2 ', 4'- or -3 ', 4'-dichloro-stilbene-2-sulfonic acid by known methods.

The coupling of the diazotized 4-amino-2 ', 4'- or -3', 4'-dichloro-stilbene-2-sulfonic acid with 2-amino- ■ naphthalene or 2-aminonaphthalene-1-sulfonic acid is carried out by known methods, advantageously in aqueous pyridine solution, the oxidation of the o-aminoazo dye to the naphthotriazole compound of the formula I z. B. with air in the presence of copper (II) salts, namely copper sulfate, as a catalyst.

The new compounds of the formula I are surprising in aqueous solutions containing active chlorine good resistance. This is especially true for the

709 648/341

2- (3 "', 4"' - dichloro-stilbyl-4 ") - (naphtho-1 ', 2': 4,5) -l, 2,3-triazol-2" -sulfonic acid, which is why this compound is preferred.

The fiber material treated with a brightener obtainable according to the invention is pleasing slightly purple-tinged white appearance. The new brighteners of the formula I also have the further advantage that they increase the whiteness of the textile material treated with them with each further Increase laundry. This "white structure" means a further and unforeseeable advance.

The new brighteners of the formula I can also be used to brighten detergents.

The good lightening properties of the compounds of the formula, the manifold Meeting needs are very surprising for the following reasons.

The commercially available brightener of the formula II

ΛΥ- CH = CH N - N

HO ₃ S ^N π Y I

shows a considerable loss in washing liquors with a higher content of active chlorine (0.5 to 0.6 g / l) the whiteness effect. The known compounds obtained from the above compound II by introducing of 1 or 2 chlorine atoms in the benzene ring A are now not shown compared to the chlorine-substituted compound, especially on nylon fabrics that have been washed in chlorine-free washing liquors which contain the appropriate brighteners in quantities that can be used on cotton achieved an equal degree of brightening, a significant decrease in fluorescence. This is for that structurally closest related chlorinated compound, the 2- (2 "', 6"' - dichloro-stilbyl-4 ") - (naphthol ', 2' : 4,5) -l, 2,3-triazol-2 "-sulfonic acid III, can be seen from the fluorescence values given in the table below, which were obtained with a fluorometer from Type 240 (manufacturer: Schildknecht A. G., Zurich) were obtained.

It is therefore very surprising that the 3,4-dichloro- and 2,4-dichloro-substituted compounds I a and I b, the properties of which are also listed in ^{Table 1} below, which can be obtained according to the invention, show fluorescence effects on nylon which are the same Range like those of the corresponding unsubstituted compound II are or even exceed them and are considerably higher than those which are achieved under the same conditions with the multiple amount of the structurally most closely related 2,6-dichloro compound III.

Ver
binding substitution
in ring A
of formula II Used
Amount (mg) in
Liters of chlorine-free
Washing liquor Fluorescence on
white nylon
after ten
Washes. II no 3.50 97 III 2,6-dichloro 14.25 73 Yes 3,4-dichloro 2.85 103 Ib 2,4-dichloro 4.05 92

60 Cotton is washed with wash liquors containing about 3.5 mg / 1 brightener and about 0.6 g / 1 active Contain chlorine, the compounds I a and I b give values which are 36 and 30% higher, respectively than the fluorescence value obtained under the same conditions with 2,6-dichloroisomer III, while the fluorescence value of this compound is more than 18% lower than that in RingA unsubstituted analog II.

Furthermore, compared to the o-monochloro derivative there is a higher maximum brightening and compared to the greenish-tinged lightening p-monochlorine derivative achieved a more pleasing, whiter appearance.

In addition, the compounds of the formula I give commercial detergents, in particular non-soap heavy detergents, a white and attractive appearance, which is surprising is because the 2,6-dichloro compound III causes a significant discoloration in the same washing powders.

The following examples illustrate the invention. Parts mean if nothing else is noted, parts by weight.

example 1

34.4 g of 4-amino-3 ', 4'-dichloro-stilbene-2-sulfonic acid. are dissolved neutrally with sodium hydroxide solution in 800 ml of water. To the solution, 7.0 g of sodium nitrite was added and the mixture is added dropwise to ⁰ C in a solution of 9.2 g of hydrochloric acid in 100 ml water with good stirring at a temperature of 8 to IO. The mixture is then stirred at 8 to 10 ° C for a further 30 minutes, then the excess nitrite is removed with a little sulfamic acid and the resulting diazo suspension is converted to a solution of 14.5 g of 2-naphthylamine at a temperature of -5 to + 2 ° C run into 900 g of technical grade pyridine. After the coupling has ended, the mixture is made alkaline to phenolphthalein with sodium hydroxide solution and separated into two layers by adding 180 g of sodium chloride. The upper pyridine layer containing the o-aminoazo dye is then treated with a solution of 2.5 g of crystallized copper sulfate in 100 g of water and 10 g of monoethanolamine (this copper sulfate solution is hereinafter referred to as the "copper catalyst"). At a temperature of 95 to 97 ° C., a vigorous stream of air is now introduced into the reaction mixture, which is kept under rapid stirring, until the red o-aminoazo color. substance is completely oxidized to the naphthotriazole compound. The copper salts are then precipitated by adding a little excess sodium sulfide and the copper sulfide is separated off by clarifying the boiling solution by filtration.The aqueous pyridinic solution of the triazole is now brought to the boil by direct introduction of steam, 5 g of sodium hydrosulfite are added and the pyridine is then distilled off using steam . Once the crude triazole compound to the greatest

Claims (1)

1 Part of the precipitate is eliminated, the steam distillation is interrupted, the mixture is cooled down a little, the crystal mass is suction filtered and washed out thoroughly with warm water. The crude product is further purified by addition of a little sodium hydroxide in an aqueous, about 70 ^(dissolved) / pc alcohol technical pyridine under gentle reflux and filtered. The precipitated product is filtered off, slurried with a little sodium hydroxide solution and water and distilled again with steam to remove the excess pyridine. After the pyridine has been completely removed, the mixture is cooled somewhat, the precipitate is filtered off while warm and washed on the suction filter with warm water. The product thus obtained is stirred in 96 ° / pc alcohol for 30 minutes at reflux temperature, cooled, suction filtered, in the filter with a little alcohol and then washed thoroughly in vacuo at a temperature of 120-125 ⁰ C dried. The purified naphthotriazole compound must have any content of coloring impurities being checked. 200 mg of the product should be dissolved in 10 g of dimethylformamide in the UV-free Daylight result in a colorless solution. If the solution has a yellow tinge, the above must be followed Cleaning measures are repeated. The sodium salt of 2- (3 '", 4"' - dichloro-stilbyl-4 ") - (naphtho-1 ', 2': 4.5) -1,2,3-triazole-2'-sulfonic acid is obtained as a pale green-yellowish powder with a melting point above 300 ° C. This compound is a valuable lightening agent for cellulose fibers, polyamide fibers, soap powder, Detergents, etc. With good washfastness and lightfastness, it is also distinguished by an excellent one Chlorine and chlorite resistance on the substrates, in the liquors and in powder form Mixing off. Is used in place of the 34.4 g of 4-amino-3 ', 4'-dichloro-stilbene-2-sulfonic acid equal amounts of 4-amino-2 ', 4'-dichloro-stilbene-2-sulfonic acid are obtained, with otherwise the same procedure, 2- (2 "', 4"' - dichloro-stilbyl-4 ") - (naphtho-1 ', 2': 4,5) -l, 2,3-triazol-2" -sulfonic acid, which is also a valuable brightener. Example 2 A solution of the sodium salt of 34.4 g of 4-amino-3 ', 4'-dichloro-stilbene-2-sulfonic acid and 7.0 g of sodium nitrite in 800 ml of water is at a temperature of 8 to 10 ° C by running into a Solution of 9.2 g of hydrochloric acid in 100 ml of water indirectly diazotized. The suspension of the diazo compound is then at a temperature of 5 to 10 ° C within 2 to 4 hours of a solution of 22.7 g of 2-amino-naphthalene-1-sulfonic acid in a mixture of 900 g of technical pyridine and 50 g Water added. After finishing the Diazo-444 reaction, the mixture is stirred for a short time. Then make an approximately 30% aqueous solution from 14.4 g of sodium hydroxide to the clearly phenolphthalein-alkaline reaction and then 200 g Sodium chloride added. After standing for a short time, the two resulting layers are separated, and after adding the copper catalyst described in Example 1, the pyridinic dye solution oxidized with air to the naphthotriazole compound. The removal of the copper salts and the Purification of the crude product is carried out as described in Example 1. The sodium salt is obtained der2- (3 "', 4"' - dichloro-stilbyl-4 ") - (naphtho-r, 2 ': 4,5) -l, 2,3-triazole-2" -sulfonic acid. The product is identical to the compound described in Example 1. Example 3 Cl A solution of the sodium salt of 34.4 g of 4-amino-2 ', 4'-dichloro-stilbene-2-sulfonic acid and 6.9 parts of sodium nitrite in 500 ml of water is at a temperature of 8 to IO ⁰ C by running into a Solution of 9.2 g of hydrochloric acid in 100 ml of water indirectly diazotized. This suspension of the diazo compound is then allowed to run in at a temperature of 5 to 10 ° C. in a solution of 22.7 g of 2-amino-naphthalene-1-sulfonic acid in a mixture of 600 g of technical pyridine and 100 ml of water over the course of 4 hours . After the diazo reaction has disappeared, stirring is continued for a short time, then a 30% strength aqueous solution of 14.5 g of sodium hydroxide is added until the reaction is clearly alkaline to phenolphthalein, and 140 g of sodium chloride are then added. After standing for a short time, the two layers are separated and the pyridinic dye solution is then oxidized to the triazole compound with air after the copper catalyst described in Example 1 has been added. After the work-up and purification described in Example 1, the sodium salt of 2- (2 "', 4'" - dichloro-stilbyl-4 ") - (naphtho-1 ', 2': 4.5) -l, 2 is obtained , 3-triazole-2 "-sulfonic acid as a pale yellowish powder with a melting point above 300 ° C This compound is a valuable lightening agent for cellulose fibers, polyamide fibers, soap powder and detergents. With good wash and lightfastness, it is also characterized by excellent Chlorine and chlorite resistance on the substrates, in the liquors and in powder form Mixing off. Claim: Process for the production of optical floaters of the stilbene series, thereby marked e t that in a known manner the diazonium compound of 4-amino-2 ', 4'- or -3 ', 4'-dichloro-stilbene-2-sulfonic acid with 2-aminonaphthalene or 2-aminonaphthalene-1-sulfone- 7 8 acid couples and the resulting o-aminoazo dye to a compound of formula I. Cl-V V-CH = CH- / ' V -N-N HO ₃ SN Xi X ₂ VAy in which of Xi and X ₂ one X is a hydrogen atom and the other X is a chlorine atom, ox> diert. 709 648/341 9. 67 © Bundcsdrui.-keri.-i Berlin