DE1695057A1 - Process for the preparation of substituted stilbene sulfonic acids - Google Patents

Description

The present invention relates to new and useful ones Stilbene triazole compounds and, in particular, di ~ substituted oxybenzotriazolyi-stilbene sulfonic acid compounds, • Which as optical brighteners and as a means of increasing the degree of whiteness are useful.

It is known that textiles tend to take on a yellowish color as they age, which through - Not the usual methods of bleaching or washing can be removed. The previously used procedures of the "blueing" of. white materials with blue pigments or with volatile blue dyes, in practice The modern laundries are becoming more and more obsolete and due to the use of fluorescent optical Bleaches or brighteners largely replaced which one

■ the soap or the surface-active agent added in the washing bath. These optical brighteners are generally used in

■ Easily used form as intimate admixtures with soap

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or to the surface-active agent in the form of bars, Flakes, put on the market in powder form, etc. The fluorescent optical brighteners do their job Puncture thanks to the fact that they are able, in a characteristic way, to absorb ultraviolet rays and then their energy in light energy that is within of the visible spectrum is to convert. This converted and emitted light energy tends to be anything To neutralize the degree of yellowness of the material, thereby increasing its 'visible' / degree of ice.

As the predominant textile material in normal laundry practice Made of cotton, the brighteners are that in the Laundries used in conjunction with the usual surfactants, generally by the presence characterized by ionic or water-soluble groups, the preferably consist of JuIfonsäuregruppen to the necessary To ensure affinity to the cotton material. Such compounds can sometimes be compared to other synthetic ones Textile fibers, for example those made from polyamide or from acetate rayon, be effective. While such ionic So brighteners in many cases and especially opposite Cotton are useful, they point towards Uylon or acetate rayon basically only limited usability.

It has now been found a new class of Benzotriazolylstilbensulfonsäure compounds, which have both the aesthetic and from the economic point excellent Aufhellereigenschaften which two substituted oxy groups in a specific position in the molecule and ^v containing at least one SuIfonsäuregruppe which compounds and further in the presence of Chlorine-containing bleaches

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are stable.

Certain of these di-substituted oxybenzotriazole whitening agents have a unique whitening power on cotton when not ionic detergent baths in the presence of hypochlorite.

For example, it is from compound H H

(A)

"N-JO ₃ Well

only half the amount necessary to achieve the same lightening effect with cotton when using commercially available cotton ionic detergents, in the presence of sodium hypochlorite, as when using the very strong used commercial product of the formula:

The new connections are therefore of the greatest advantage with ™

Uses in the presence of non-ionic detergents and hypochlorite bleach where the need for good Brightener is particularly large. In these types of application, no brightener of the prior art has a brightening effect which is comparable to that of the above-mentioned compound (A) is comparable.

The compounds produced according to the invention are therefore in particular can be used in conventional iJasch operations of Textile materials, especially cotton, as they are very

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are effective when used in conjunction with detergents The new brighteners are also stable in the presence of chlorine-containing bleaches.

The novel compounds according to the invention correspond to general formula:

in which R-, and R ^ independently of one another lower alkyl groups and preferably those having 1 to 4 carbon atoms, lower carboxyalkyl groups, and preferably those Carboxymethyl group, R-, and R2 can also be used together the methylene group mean j ra and η mean the fourth 0 or 1, the sum of m and η is 1 or 2. M is hydrogen or a salt-forming cation, preferably an alkali metal (sodium, potassium or lithium), the ammonium group or substituted ammonium such as an amine.

Preferred compounds include those which have a Sulfone group, preferably on the benzene ring of the stilbene residue have, which is more distant from the triazole ring. Accordingly, they have the most to. preferring compounds the the following lOrmel:

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-5- BAD ORlGiHAL

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in which the symbols -R- ,, Rp and M have the meaning given above. ^N i ■

Some specific connections are given below:

SO ₃ ha

CH SO ₃ Na

CH

CH = s CH 'SO ₃ Na

^X N ^ N

OCH ₂ COOHa

OC ₄ H ₉ OCH ₂ CH ₂ COONa

: CCo

OCH ₂ COONa OCH ₂ COONa

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CH β CH

.N ^ N

OCU ₃ OCH ₃

SO ₃ Na

CH »CH-O ₃ Na SO ₃ Na

GH · CH .—- fi ^

SO ₃ Na

'N --- v ^ i ^ -OCHgCOONa

SO ₃ Na

CE

.N- ^ JJ-OCH ₂ CH ₂ COONa

CH a CH if ^x > N ^

SO ₃ Na

Ν-

, _f whom. - ^> - <izecss

StS ₃ Na

CH

OCH ₃ OCH ₂ COONa

gh ■ αι.

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The compounds of the present invention are distinguished by their excellent paser-attachment, especially at Cellulose fibers and similar hydrophilic fibers, the compounds also have an aesthetically pleasing ion, very excellent whiteness, and very high resistance to bleach -like chlorine and excellent lightfastness property.properties..

While these compounds according to the present invention a particular advantage when used in detergents stones, when applied to textile materials, while deserve the washing operation, these compounds can also be incorporated into organic materials. So can these compounds are added, for example, to spinning solutions of cellulose acetate, they can be used for impregnation of paper, they can also be worked into paper by adding them to the mixer Pulp or incorporated at any desired time before the paper dries; the new connections can furthermore generally also waxes, rubber-like bodies or resins for the purpose of achieving a Incorporate whiteness effects *

The compounds of the present invention are generally produced by using a diazotized sulfostilbene coupled with the selected substituted dioxyaniline compound and then the resulting azoamino compound to the corresponding triazole is oxidized.

The method of oxidation can depend on the choice of oxidizing agent in the individual case. If for example ammoniacal copper sulfate (you can also use

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other organic bases, e.g. use pyridine) than oxy-. used dating agent, you can remove the resulting by-products of this reaction simply by that the pH value of the solution is adjusted, i.e. the reduction products of the oxidizing agent are thereby made soluble, that the solution is acidified more strongly, so that the by-products are removed with the filtrate during the filtration. on the other hand you can remove the by-products with the filtrate by that the reaction medium is made alkaline with ammonia before filtration (pH 11).

! If you drive preferably metal-containing oxidizing agents, such as Copper sulfate, iron (III) chloride or iron (III) ammonium sulfate you can also use hydrogen peroxide, XtInO., Use CaOCl, sodium perborate or oxygen.

The following examples serve to further illustrate the subject matter of the invention. All parts are parts by weight if nothing else is said.

Example It - ■

Production of: ·

^oai 3

BQtfBä

24s. 4'-Amino-2-stilbenesulfonic acid (o, O87 mole), 5oo ml. Of water and 8.6 cc of NaOH (4o% w / v) were mixed at 40 ⁰ C to give a pH of 6.5 was established. Then 17.4 ecm NaNOg (58 # aqueous solution) were slowly added. This mixture was poured into one within an hour

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at a temperature of 5 to 10 ⁰ C mixture of 240 ecm water, 1.4 ecm MaETOp (38 % 1 ge aqueous solution) and 27 ml. HOl, an ice bath being used. After then was 2 hours at a temperature of 5 to 1O ⁰ C for, the excess of nitrite with sulphamic acid 7ml (10 #ige aqueous solution) was destroyed. 14.7 g of 3,4-dimethoxyaniline distilled in vacuo were dissolved in 100 ml. Acetic acid and slowly added at 5 to 10 ⁰ O, then stirred for 1 hour and finally adjusted to pale congo blue by adding 48 g of sodium acetate Stirring had continued overnight, was adjusted to Congo-neutral by adding sodium acetate, then filtered off, washed with 500 ml of 3% HCl, then with 500 ml of water and finally with 200 ml of isopropanol, after which 72 g of reaction product were obtained received.

36 g of this product, 200 ml of picoline, 100 ml of water and 20 inl of concentrated aramonium hydroxide were mixed and heated to 95.degree. C., a solution being formed. 27.25 g of OuSO..5HgO in 50 ml of water were added to this. The mixture was stirred for 2.5 hours at 95 ⁰ C, cooled to 85 ⁰ O in 75 ml and. Sodium sulfide (2o% weight / volume) treated. The material was filtered off at 95 ⁰ C and washed with a 3% ± gen Pieolinlösung in water. The pH was adjusted to 9 by adding a 20% sodium carbonate solution; then carried steam distillation, cooling to 75 ⁰ C, filtering off, washing with loo ml of warm water and schliesslieh drying in air at 80 ⁰ O. The final product had a K _max = 133 at

- example 2; ^v
In order to achieve the excellent brightening effect of the according to Example 1

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- To explain the connection made in the sheet, it was made in a customary manner Washing operation using surfactants compared to other brighteners, all of which are equivalent K-value concentrations at the maximum absorption points these connections had. A K value of 80 was chosen as a point of comparison since each of the compounds tested had a K value t at the maximum absorption of over 80. This provided a meaningful comparison on a weight basis. The general procedure for testing the Connection is described below:

50 mg of the brightener compound was dissolved in 10 ml of dimethylformamide and then one liter of water was poured over it. An exact aliquot was then taken to achieve the desired concentration of brightener on a percentage basis at a K-80 concentration. To eineia measuring Washing bath containing 1 g of "All" (= non-ionic ethylene oxide-phenol condensate) in 5oo ml of water at 49 ⁰ C, the selected quantity of brightener and Io ml 'Uatriumhypochlorit-Iösung, o, 2 % of released chlorine was added. After 1 rainütigem standing, a 5 g "pattern of cotton cloth · was immersed in the bath and stirred in the measuring-machine, containing the surface-active medium and the Baumwolltueh, 2o minutes at 49 ⁰ C; then the cloth was taken out, with clear water rinsed and dried.

Using the same procedure, using the compound prepared according to Example 1 at a brightener concentration of 0.0064 %, based on the weight of the 5 g cotton cloth sample, it was found that the finished washed and dried cloth had a brightness value of 76.

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Following the same procedure but with

this time with a concentration of o, oo96 %, based on

the weight of the fiber (K = 80) worked and the cotton cloth pattern with a compound of the formula

was treated, the result was a brightness value of 66. It is hereby shown that the use of the last-mentioned brightener in the one and a half times the amount to a considerable extent leads to a lower brightness value than the use of the brightener which was produced according to Example 1,

Example J>:

Example 2 was repeated with the modification that instead of "ALI" as a detergent so-called "ALPIÖITQIi" was used, which from a biodegradable non-ionic reaction ons product of A'thylenoxvd and a aliphatic alcohol.

Here too, using the two brighteners mentioned in Example 2 with the same K value of 80, the result was that the brightener produced according to Example 1, which was used in a concentration of 0.032 % _s based on the weight of the paser, caused a brightness value of 68, while the commercially available suIfostilbylnaphthotriazole specified in Example 2 only led to a brightness value of 59 at a concentration of ο, οο64% (based on the weight of the pasers). From this it is clear that when using half the amount of brightener according to Example 1, a significant amount is obtained in comparison with a commercially available brightener

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higher degree of brightness achieved.

Example 4t

Example 3 was repeated, with the modification that the compound prepared according to Example 1 was used this time in a "concentration of 0.04 %, based on the fiber weight." The K-Vert was again 8o; the cloth sample had a brightness value of 65 at the end of the treatment.

Instead of the commercially available brightener described in Example 3, a compound of the formula was used in a low concentration, ie in an amount of 0.064 %

^ S —CH «CK— f

SO ₃ ha

used, the cloth pattern had one after the treatment Brightness value of 65 *

Example 5;

Example 2 was repeated again, using a compound prepared according to Example 1, which was used in the concentration given in Example 2. Instead of the commercially available brightener from Example 2, 0.0064 %, based on the weight of the fiber, of a compound of the formula

-13-

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used, which is well known in the art. Instead of the "ALL" of Example 2, this time "TEDS" (= anionic alkyl aryl sulfonate) used. The cloth pattern, which with the compound that was produced according to Example 1 had a brightness value after the treatment of 87, whereas the cloth sample washed with the compound just mentioned only had a brightness value of 32.

Example 6:
Production of:

This compound was prepared according to the procedure described in Example 1, with the modification that 16 g of 3-methoxy-4-ethoxyaniline were used instead of 3,4-dimethoxyaniline. After applying the latter compound to cotton in accordance with the procedure of Example 1, practically the same results were obtained.

Example 7: 'f

Production of;

CH - · CH

This compound was made following the procedure of the example 1, with the modification that this time, instead of 4'-amino-2-stilbene sulfonic acid, 4-amino-2-stilbene sulfonic acid and instead of 3,4-dimethoxyaniline 19 g of 3,4-methylenedioxy-

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aniline were used,! multiple application of the / mentioned ■ Compounds following the procedure of Example 1 gave practically the same results. The manufactured Connection had a K "■ 138.8 at 358m / 4.

Example 8; Production of:

OCII ₂ COONa OCH ₂ COOHa

This compound was prepared according to the procedure of Example 1, with the modification that instead of A -'- amino-2-otilbene sulfonic acid, 4-amino-2-stilbene sulfonic acid and instead of 3,4-dimethoxyaniline 21 g 1,2- (4 -Aminophenylen-) ■ bisoxyacetic acid were used. Using the compound prepared according to this example by following the procedure of Example 1, excellent results were obtained. This connection had a KL _3x = 76 at 355 m u ,.

Example 9; Production of:

CH = »CH

OCH ₂ COOKa ' ^0CH 3

SO ₃ Na

It was initially the intermediate compound of the formula H, N— r ^^ OCH ₂ COOH

produced by equimolar amounts of, 2-metlioxy-5-

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nitrophenol and chloroacetic acid were reacted with one another, with subsequent reduction. The brightener was then after the procedure of Example 1, with the modification, that 3 »4-dimethoxyaniline by 14.9 S 3-amino-6-methoxyphenoxyacetic acid has been replaced »When using the connection established according to this example after In the procedure of Example 1, practically the same results were obtained.

Example lo; Production of:

CH <= CH- / M-K

This compound was made according to that described in Example 1 Procedure established, with the modification that instead of 4 · -amino-2 "-stibenesulfonic acid 4-amino-2 -stibenesulfonic acid was used. Subject allowing the compound prepared to act on cotton according to the method of the example 1 excellent results were obtained.

Example 11t production from

CH β CH

.OCH ₃ OCH ₃

SO ₃ Na

SO·

This compound was also made according to the procedure of

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Example 1 produced, with the modification that instead of 4 ^l -amino-2-3tilbehsulphonic acid, 3o.8 g of 4-amino-2,2'-stilbene disulphonic acid were used. Using the compound prepared according to this example by following the procedure of Example 1, excellent results were obtained.

Example 12; . ·

Example 6 was repeated, with the modification that this time 4-amino-2-stilbene sulfonic acid was used ^{instead of 4 l -ATnino-2-stilbene sulfonic acid.} After exposure to cotton in accordance with the procedure described in Example 1, excellent results were obtained.

example 13:

Example 11 was repeated with the modification that instead of 3,4-diethoxyaniline this time 3-methoxy-4-ethoxyaniline was used. After exposure to cotton in accordance with the procedure of Example 1, this was obtained excellent results.

Example I4i ₌

The previous example was repeated with the Modification that an equivalent amount by weight of 3 »4-methylenoxyaniline was used. Good results were obtained after allowing it to act on cotton according to the procedure of example 1.

Example 15 a

The previous example was repeated with the Modification that an equivalent weight of 1,2- (4-amiaophenylene) «bisoxyacetic acid -Established & t, ifea received

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after allowing it to act on cotton according to the procedure Example 1 gives good results. ■

Example 16?

The procedure of Example 9 was repeated, with the modification that this time, instead of stilbene sulfonic acid, _{an equivalent amount of 4-amino-2 1} 2 ^{l -ätilbenedisulfonic acid.} was used. After allowing the cotton to act in accordance with the procedure in Example -1, good results were obtained.

While some of the examples described above, in particular the Use of the compounds prepared according to the invention for Explain the lightening of cotton material, applies in general, these compounds are generally used to lighten cellulose materials and cellulosic derivative materials, as well as from other textile products can be used.

The compounds prepared according to the invention can be also apply to other organic substrates for the purpose of improving their degree of whiteness,

The amount of brightener used is not critical and can be varied within wide limits. It was found that even such a small amount as o _f ool% effective. Provides results, the upper limit is determined only by practical considerations of compatibility and price * It has been found that in general no more than 5 percent by weight, based on the weight of the organic material _t, is necessary even under the most unfavorable conditions.

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If the manufactured according to the present invention Products used together with detergents is it is advantageous to use the brighteners in amounts of about 0.1 to about 2 percent by weight, based on the detergent, to be used.

/ Claims:

BADORiGINAL 209813/1765

Claims (2)

Claims 1.) Process for the preparation of substituted stilbene sulfonic acids by coupling a diazotized sulfostilbene with dioxyaniline and subsequent oxidation the resulting Äzoainino connection to the corresponding Triazole, characterized in that as substituted Stilbene sulfonic acids those of the formula CH «CH— are used, in which R ^ and Rg lower alkyl Sd he lower carboxyalkyl groups, or taken together the methylene group, m and η represent the value O or 1, the sum of m and η is 1 or 2 and M is hydrogen or a salt-forming cation. 2.) Use of a compound of the formula: - CH «CH- as an optical brightener, preferably for cellulose materials, where in the aforementioned formula R 1 and Ro are lower alkyl or lower carboxyalkyl groups or R 1 and R 1 taken together are the methylene group, m and η are the value O or 1, the sum of m and η is 1 or 2 and M is hydrogen or a salt-forming cation. 209813/1765