DE1568725A1 - Colorless compound suitable for filtering sunlight and processes for its preparation - Google Patents

Description

Colorless compound suitable for filtering sunlight and processes for its preparation

The present invention relates to a colorless compound suitable for filtering sunlight, which thereby is characterized as having the formula

R 'H

(Ar) ₁ - 0 s N - ^ - N— (Ar)

corresponds, in which in the form of the free acid (Ar) ₁ and (Ar) _? Benzene rings, Y and Z are salt-forming groups, R is an aliphatic radical and η and m are integers from 1 to 3 and the compound has an absorption maximum in the range from 2900 Å to approximately 3500 liters. The invention further relates to the production of new and more suitable for filtering sunlight und.Kompositionen substances containing these substances and a process for protecting the human skin against _o-burning, tanning and degradative effects of sunlight °. In particular, the inventive

oo sen compounds incorporated into cosmetic compositions, which are extremely suitable for protecting the skin against sunlight. They are generally sunlight - developed "filtered substances that give very satisfactory ~> Sohutz against the burning rays but

the tanning rays _2 «

ÜjUbmv Uf) t © rläflÖII (Art. / N ι, v ^ ", _ ,, j, ι _" ^ ^ cictf AnuerunfllflU.y, 4, '- - ><*

let through. The most deleteriously scorching wavelengths of sunlight are in the range of approximately 2900 to 5100 A. The action of these wavelengths on human skin causes the severe burns, redness, blistering and edema that are characteristic of many burns. This is undesirable from an aesthetic point of view and at the same time poses a serious threat to human health. In order to overcome the effect of the burning rays of sunlight, various compounds have been used which cancel out the burning rays. The public assumes, and generally accepts, that tanning is a desirable phenomenon and has something to do with good health. The public has been educated to accept the numerous commercially available products that screen out the scorching rays and transmit the tanning rays. For the past few years, it has generally been assumed that tanning, although useful in protecting the skin from continued exposure to sunlight, is associated with a general degradation of the skin from chemical radiation, albeit in the greatest number of people are not hard attacked by tanning rays acting, there are a large number that are even sensitive to the tanning action rays of the sun, so that the radiation in this

009816 / 176t

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Wavelength causes great health risks for them. Therefore there is for those who want protection against both burning and tanning of the sun's rays and for those- those who don't want to be tanned have a real need for one in a broad spectrum, sunlight filtering agent, which gives the skin adequate protection, is sufficiently stable under the conditions of use and its effects for several hours, can be easily applied to the skin and cannot be easily removed, for example by simply washing with water. This latter property must be guaranteed because it is undesirable, for example, a material that can be easily removed while bathing to use.

It is a particular advantage of the present invention that through them connections can be established which have outstanding filter properties for sun rays with wavelengths from 2900 A to 3500 A; the range of wavelengths from 3200 A to 3500 A encloses the range of sunlight, which has a tanning effect.

Connections have now been found that have outstanding filter properties have for the burning and tanning rays of the sun and especially the rays with wavelengths

BATHROOM OFIIGlHAL

0098 16/1761

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in the ultraviolet range from 2900 1 to about 3500 A. The compounds have excellent K values as well as unexpected ones light resistance and stability to ultraviolet rays.

The K value is a measure of the effectiveness of the compound in filtering out specific wavelengths of light. iSine connection with a K-value of 1 reduces the transmitted light in a concentration of 0.1 ^ and a rail thickness of 1 cm to 10 ^ of the incident light. For example, a compound with a K = 10 at a given wavelength in a concentration of 0.1% reduces the transmitted radiation to 10 "A of the incident radiation with a layer thickness of only 1 mm.

The compounds of the present invention have the following general formula:

H *
NN

in which (Ar) ₁ and (Ar) _{2 represent} benzene rings;

Y and Z are salts or salt-forming groups, in particular sulfonic acid or carboxylic acid groups; η = 1 to 3;

009816/1761

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m = 1 to 3 and

R is an aliphatic radical, preferably a low molecular weight alkyl radical with 1 to 6 carbon atoms.

The compounds of the present invention that can preferably be prepared have the following general formula:

R.
(Ar) ₁ - G = N - N - (Ar) ₉

ι ι

(SOvM) Z

^ ti m

in the (Ar) -, and (Ar) «benzene rings, Z are the radicals -S0, M or -GOOM,
η and m have the value 1 to 3,

R is a low molecular weight alkyl radical with 1 to 6 carbon atoms and

M is hydrogen or a salt-forming cation, advantageously an alkali metal such as sodium, potassium, lithium or ammonium or amine. Suitable R radicals are alkyl, alkenyl, cycloalkyl, cycloalkenyl, haloalkyl,. (e.g. chloroethyl, bromopropyl, fluoroarayl, iodopentyl), haloalkenyl, cyanoalkyl, hydroxyalkyl, carbalkoxyalfcyl, alkoxyalkyl or hydroxyalkoxyalkyl radicals, as well as the cyano, hydroxy, alkoxy, carbalkoxy, Hydroxy-alkoxy derivatives of the alkenyl radicals.

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In addition to the salt or salt-forming group, the benzene ring can contain other substituents that are not chromophore. These substituents can be the following radicals: hydroxyl, halogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, cyano, alkylsulfonyl (for example —SO ₂ CU,), arboxamido or sulfonamides ».

Ghrotnophore groups, such as nitro, azo, Azoxy or other groups should be avoided.

If an oxy radical (for example a hydroxy, alkoxy or alkenoxy radical) is auxochrora or bathochromic, there should not be more than one such radical, because the absorption maximum of compounds with 2 or more oxyrenes is too close in most cases , if not entirely in the visible region of the spectrum, thereby tending to reduce the effectiveness of these compounds as sunlight filters. It is also advantageous if the invention according to related and prepared compounds contain no amino radicals, in particular those directly bonded to the benzene ring, because these compounds generally have lower light stability, although their absorption properties can be satisfactory.

The general procedure for making the compounds

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the invention includes the condensation of a sulfo or Carboxybenzene aldehyde, if necessary in the form of its sodium salt, with a sulfo- or carboxyphenyl (R-substituted) hydrazine. The condensation can take place in an aqueous medium, especially if the starting materials are soluble in water, or carried out in any selected solvent medium will. The process product can be carried out in the customary manner Distillation, extraction, crystallization or .Precipitation can be isolated. In general, this results in one to two hours Heating the starting materials with the aldehyde, which is present in the form of the sodium salt, under reflux, high yields.

Of the suitable aldehydes that are used as starting materials for Preparation of the compounds according to the invention used can be named:

2-sulfobenzaldehyde (o-formylbenzenesulfonic acid), 4-chloro-2-sulfo-benzaldehyde, 5-chloro-2-sulfo-benzaldehyde, 6-chloro-2-sulfo-benzaldehyde, 4-hydroxy-2-sulfobenzaldehyde, 3-sulfo-benzaldehyde, 4-bromo-3 -sulfobenzaldehyd, 4-0hlor-3-sulfοbenzaldehyd, 4-fluoro-3-sulfobenzaldehyde, 4-iodo-3-sulfobenzaldehyde, 4-hydroxy-3 _r sulfobenzaldehyä, 2,6-dichloro-3-sulfobenzaldehyde, 4-sulfobenzaldehyde, 2 -0chloro-4-sulfobenzaldehyde, 2-methyl-4-sulfobenzaldehyde, 2-ethyl-4-sulfobenzaldehyde, 2-n-butyl-4-sulfobenzaldehyde, 2-methylsulfonyl-4-sulfobenzaldehyde, 2-carboxamido-4-sulfobenzaldehyde, 2 -Methoxy-4-sulfobenzaldehyde, 2-ethoxy-4-bulfobenzaldehyde, 2-n-hexoxy-4-sulfobenzaldehyde,

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2-hydroxyethyl-4-sulfobenzaldehyde, 2-ethoxyethyl-4-sulfobenzaldehyde, 2-carboethoxyethyl-4-sulfobenzaldehyde, 2-cyano-4-sulfobenzaldehyde, 2-cyanoethyl-4-sulfobenzaldehyde, 3-kydroxy-4-sulfobenzaldehyde, 3-methoxy-4-sulfobenzaldehyde, 3-hydroxy-6-sulfobenzaldehyde, 2-hydroxy-5-sulfobenzaldehyde, 3-methy1-2-sulfobenzaldehyde, 3-methyl-6-sulfobenzaldehyde, 4-chloro-3-methyl-6-sulfobenzaldehyde, 4-methoxy-3-sulfobenzaldehyde, 4-isopropoxy-3-sulfobenzaldehyde, 4-0arbethoxy-3-sulfobenzaldehyde, 4-ßrom-3-ethyl-6-sulfobenzaldehyde, 4-ethoxy-3-isobutyl-6-sulfobenzaldehyde, 4-0yan-3-methyl-6-sulfobenzaldehyde, 2,4-dieulfobenzaldehyde, 5-chloro-2,4-disulfobenzaldehyde, 6-chloro-2,4-disulfobenzaldehyde, 6-ethoxy-2,4-disulfobenzaldehyde, 5-cyano-2,4-disulfobenzaldehyde, 5-Ghloräthy1-2,4-d isulfobenzaldehyde, 3-Methy1-2,4-d isulfο benzaldehyde, 2,5-disulfobenzaldehyde, 2,6-disulfobenzaldehyde, 6-hydroxy-3-methyl-5-sulfobenzaldehyde, 3,5-di-sulfobenzaldehyde, 2-hydroxy-3,5-disulfobenzaldehyde, 2-methoxy-3,5-disulfubenzaldehyde, 2,4,6-trisulfobenzaldehyde, 2-formylbenzoic acid, 3-iOrmylbenzoic acid, 4-formylbenzoic acid, 2-chloro-3-forraylbenzoic acid, 2,6-dichloro-3-formylbenzoic acid, 2,4,6-trichloro-3-formylbenzoic acid, 2-chloro-4-formylbenzoic acid, 2,5-dichloro-4-formylbenzoic acid, 2,3,6-trichloro-4-forray1benzoic acid, 4-formyl-o-tcquylic acid, 4-isopropoxy-3-formylbenzoic acid, 4-cyano-3-forray! Benzoic acid, 4-chloro-3-iOrmylbenzoic acid, 4-Carbethoxy-3-formylbenzoic acid, 4-fluoro-3-formylbenzoic acid, 4-propenyl-3-formylbenzoic acid, 4-methylisulfonyl-3-iormylbenzoic acid.

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Examples of suitable pheny! Hydrazines are:

l-methyl-l- (p-sulfophenyl) hydrazine, 1-ethyl-l- (p-sulfophenyl) hydrazine, l-isopropyl-l- (p-sulfophenyl) hydrazine, 1-n-hexyl-l- (p-sulfophenyl) hydrazine, l-methyl-l- (3-sulfo-4-methylphenyl) hydrazine, l-ethyl-l- (3-sulfo-4-methylphenyl) hydrazine, 1-methyll- (2-methyl-3-sulfophenyl) hydrazine, l-ethyl-l- (2-methyl-3-sulfophenyl) hydrazine, l-methyl-l- (2-methyl-5-sulfophenyl) -hy d razine, 1-n-propy1-1- (2-methy1-5-sulfopheny1) -hyd razine, l-ethyl-l- (3-sulfo-4-ethylphenyl) hydrazine, l-methyl-l- (2-sulfo-4-chlorophenyl) hydrazine, l-methyl-l- (2-sulfo-4-methylphenyl) hydrazine, 1-n-Propy1-1- (2-sulfo-4-methylphenyl) hydrazine, 1-Is ο buty1-1- (2-sulfo-4-cyanopheny1) -hydrazine, 1-Methy1-1- (2,6-disulfo-4-methylphenyl) -hydrazine, 1-Μθ thy 1-1- (2-sulf o-4-methylsulfonylphenyl) hydrazine, 1-Methy1-1- (2-sulfo-4-carboxanide opheny 1) hydrazine, 1-methyl-l- (2-sulf ο-4-Ν, ϊϊ -dime thy lcarboxamidopheny1) hydrazine, l-methyl-l- (2-sulfo-4-carboethoxyphenyl) hydrazine, l-ethyl- (2-sulf o-4-m.ethy isulfony! phenyl) hydrazine, 1-methyl- (2-chloro-4-sulfophenyl) hydrazine, l-methyl- (3-chloro-4-sulfophenyl) hydrazine, l-methyl- (2-cyano-4-sulfophenyl) -hydrazine, l-ethyl- (3-cyano-4-sulphenyl) -hydrazine, l-isoamyl- (3-ethyl-4-sulfophenyl) -hydrazine, 1-n-hexyl- (3-carbomathoxy-4-sulfophenyl) hydrazine, l-isohexyl- (2-fluoro-4-sulfophenyl) -hydrazine, 1-allyl- (2-chloro-4-sulfophenyl) -hydrazine, l-chloroethyl-l- (2-sulfophenyl) hydrazine, l-chloroethyl-l-l- (4-sulfophenyl) hydrazine, 1-gyanpropy1-1- (4-sulfophenyl) hydrazine, l-hydroxyethyl-l- (4-sulfopheny 1) -hy draz in, 1-Chloräthy 1-1- (2-0hlor- »4-sulfophenyl) -hydrazine, l-Garboäthoxyäthyl-l- (2- "brQ®-4" -Bulfopheayl) -hydrazine,

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l-cyclohexyl-l - ^ - sulfophenylJ-nydrazine, l-cyclohexyl-l- (4-sulfophenyl) hydrazine, l-cyclohexyl-l- (2-chloro-4-sulfophenyl) hydrazine, l-cyclopentyl-l- (2-methyl-4-sulfophenyl) hydrazine, l-methoxyethyl-l- (2-chloro-4-sulfophenyl) hydrazine, 1-cyanoethyl (2-cyano-4-sulfophenyl) hydrazine, l-Gyanäthyl-l- (2-fluoro-4-sulfopheny1) -hydrazine, 1-cyanoethyl-1- (2-methylsulfony1-4-sulfophenyl) hydrazine, l-allyl-l- (2-ethyl-4-sulfophenyl) hydrazine, l-methyl-l- (4-carboxyphenyl) hydrazine, 1-methyl-l- (3-carboxyphenyl) hydrazine, I-Μθthyl-l- (2-carboxyphenyl) hydrazine, l-ethyl-l- (4-carboxyphenyl) hydrazine, l-isopropyl-l- (4-carboxyphenyl) hydrazine, l-isohexyl-l- (4-carboxyphenyl) hydrazine, l-ethyl-l- (3-carboxyphenyl) hydrazine, l-ethyl-l- (2-carboxyphenyl) hydrazine, l-methyl-l- (2-chloro-6-carboxyphenyl) hydrazine, 1-methyll- (2-bromo-6-carboxyphenyl) hydrazine, l-Me1; hyl-l- (3-bromo-6-carboxyphenyl) hydrazine, l-methyl-l- (3-chloro-6-carboxyphenyl) hydrazine, l-ethyl-l-O-chloro-ö-carboxyphenylJ-hydrazine, 1-ethyl- (3-bromo-6-carboxyphenyl) hydrazine, l-methyl-l- (4-chloro-6-carboxyphenyl) hydrazine, 1-methy1-1- (5-chloro-O-CaTbOXyphenyl) hydrazine, l-methyl-l-CS-bromo-ö-carboxyphenylJ-hydrazine, 1-ethyl- (4-bromo-6-carboxyphenyl) hydrazine, l-ethyl-l- (5-bromo-6-carboxyphenyl) hydrazine, l-n-propyl-l- (5-bromo-6-carboxyphenyl) hydrazine, l-ethyl-l- (5-chloro-6-carboxyphenyl) hydrazine, l-methyl-l- (2-methyl-6-oarboxyphenyl) hydrazine, l-methyl-l- (3-methyl-6-carboxyphenyl) hydrazine, l-methyl-l- (4-methyl-6-arboxyphenyl) hydrazine, 1-ethyl -. (4-methy 1-6-carboxyphenyl) hydrazine, l-methyl-l- (5-t-methyl-6-oarboxyphenyl) hydrazine, l-ethyl-l- (5-methyl-6-oarboxyphenyl) -

009816/1761

hydrazine, 1-methyl-1 - ^ - chloro-S-carboxyphenyl) hydrazine, 1-methyl 1-1- (4-chloro-3-carboxyphenyl) hydrazine, 1-methyl 1-1- (5-chloro-3 ~ carboxyphenyl) hydrazine, l-methyl-l- (6-chloro-3-carboxy phenyl) hydrazine, 1-methylene 1-1- (2-broin-3-carboxy phenyl) hydrazine, l- Methyl l- (4-bromo-3-carboxyphenyl) -hyärazine, 1-methy1-1- (5-bromo-3-carboxyphenyl) -hydrazine, 1-methy1-1- (6-bromo-3-carboxyphenyl) - hydrazine, l-methyl-l- (4-methyl-3 ~ carboxyphenyl) hydrazine, l-methyl-l- (5-methy1-3-carboxyphenyl) hydrazine, l-methyl-l- (6-methyl-3 . auOa -o ,, - ¹ - l) hydrazine, 1-methyl 1-1- (2-chloro-4-carboxyphenyl) hydrazine, l-methyl-l- (3-chloro-4-carboxyphenyl) -hydrazine , l-iViethyl-l- (2-bromo-4-carboxyphenyl) hydrazine, l-methyl-l- (3-bromo-4-carboxyphenyl) hydrazine, l-Μθthyl-l- (2-met] iyl- 4-carboxyphenyl) hydrazine, l-methyl-l- (3-methyl-4-carboxyphenyl) hydrazine.

One of the methods for preparing the hydrazine components is to nitrosate N-alkylaniline, to the corresponding one Reduce hydrazine with · zinc in acetic acid and finally to sulfonate with oleum. Alternatively, the N-alkylanilines can first be sulfonated and then nitrosated and be reduced. When the N-alkylanilines are in the para position contain a substituent such as halogen or an alkyl, cyano, sulfonyl, carbalkoxy or similar radical, the sulfonation takes place in the ortho position. If those Substituents are in the ortho or meta position, finds the

BATH ORIGINAL 0098 16/1761 _ ₁₂ _

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Sulfonation takes place in the para position. The general reaction and the specific connections, as well as the conditions, can be found in HeIv. Ghim. Acta 29, 1965-82 (1942) will.

The Garboxyphenylhydrazine can in the same way by Nitrosating and reducing the corresponding Garboxyaniline getting produced.

In the following examples, which serve to illustrate the present invention, the parts are parts by weight, unless otherwise stated.

Example 1;

The following ingredients were placed in a three-liter flask equipped with a stirrer, thermometer, reflux condenser and heating mantle:
42.3 g of l-methyl-l- (p-sulfophenyl) hydrazine (molecular weight ¹⁸⁸ » ^K rnax ^{= 6} 9» ² ^ '253 «^ -),

52.5 g of 2-Natriurasalz Sulfobenzaldehyds (88.2 i «pure;

Molecular weight 186),
1200 ml. Ethanol and

30.6 g of sodium acetate crystals.

The mixture was refluxed,

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Stirred to cool and then cooled to 1O ⁰ G in an ISO bath. The crystals obtained were filtered off and the filter cake was washed with 240 ml of cold ethanol. The pressed filter cake was then suspended in 750 ml of water, a teaspoon full of activated carbon (decolorizing carbon) was added and the mixture was filtered. Isopropanol was then added to the filtrate at room temperature until the formation of crystals was observed. The mass obtained was then ^{cooled to 10 °} C., filtered and ^{dried at 40 °} C. in a vacuum oven. 77 g of l-methyl-l- (p-sulfophenyl) -2-sulfophenylhydrazone-l-sodium salt were obtained, with a K _max equal to 70 at 360 m

Example 2t

Example 1 was repeated with the modification that instead of the sodium salt of 2-sulfobenzaldehyde, the same amount by weight (ie 46.3 g of 100% product) of 3-sulfobenzalahyd were used. The product was 1-methyl-1- (p-sulfophenyl) -2-sulfophylhydrasone sodium salt _{or the like}

Example 3;

Example 1 was repeated with the changing measure, that an equivalent amount, based on 100% product, 2,4-Msulfobengaldehyd-lfai; riuaisalg instead of the sulfobensaldehyde of the example 1 wrwisclot was a »Daa ariialtens product was

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I-methyl-1- (2,4 ~ d isulfopheny1) -2-aulfophenylhydrazone sodium salt.

Example 4;

Example 2 was repeated with the modifying measure, that instead of the p-sulfonated hydrazine equimolar Amounts of the o-sulfonated product were used. That The product obtained was the sodium salt of 1-methyl-1- (o-sulfophenyl) -2-sulfophenyl hydrazone.

Examples 6 to k5:

In the following examples, example 1 was carried out with the amending measure that instead of the 2-SUj., "Benzaldehyds die fol ^ onden. Benzaldehydes in equivalents Quantities applied:

6. 4-chloro-2-sulfobenzald ehyd

7. 4-Hydroxy-2-sulfobenzaldehyde

8. 4-Bromo-3-8ulfobenzaldehyde

9. 2,6-dichloro-3-sulfobenzaldehyde

10. 2-methyl-4-sulfobenzaldehyde

11. 2-MethyIsulfonyl-4-sulfobenzaldehyde

12. 2-Carboxamido-4-sulfobenzaldehyde

13. 2-Ethoxy-4-sulfobenzaldehyde

14. 2-cyano-4- sulfobenzaldehyde

BATH

009816/1761 " ¹⁵ ~

Biatt I ₅ -

15 .. 2-cyanoethyl-4-sulfobenzaldehyde

16. 3-Bydroxy-4-sulf © benzaldehyde

17. 3-methyl-6-sulfobenzaldehyde

18. 5-chloro-2,4-disulfobenzaldehyde

19. 3-chloro-2,4-d isulfobenzald ehyd

20. 2-chloro-3-formylbenzoic acid

21. 4-iormyl = O-toluic acid

22. 4-0arbathoxy-3-forminyibenzoic acid

23. 4-propenyl-3-formylbenzoic acid

24. 4-MethyIsulfonyl-3-formybenzoic acid

25. 3 -]? Ormylbenzoic acid.

Examples 26 to 35?

In the following examples, Example 1 was modified with the Repeated measure that the following hydrazines were used in equivalent amounts instead of the sulfohydrazine:

26. l-ethyl-l- (p-sulfophenyl) hydrazine

27. l-n-hexyl-l- (p-sulfophenyl) hydrazine

28. l-methyl-l- (3-sulfo-4-methylphenyl) hydrazine

29. l-n-Propyl-1- (2-ynethyl-5-sulfophenyl) -liyärazine

30. l-Μθ thy l-l- (2,6-d isulf o-4-methylphenyl) hydrazine

31. l-Hydroxyethyl-1- (4-sulfophenyl) hydrazine

32. l-Cyclohexyl-l- (2-chloro-4-sulfophenyl) hydrazine

33. l-methyl-l- (4-carboxyphenyl) hydrazine

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34. 1- Ethyl-1- (3-carboxyphenyl) hydrazine

35. l-methyl-l - ^ - chloro-o-carboxyphenylJ-hydrazine.

Example A;

The product of Example 1 was converted into a neutral detergent composition incorporated in the form of a stick, the main component of which is a coconut oil acid ester of sodium isethionate contained. The amount of product of Example 1 used was 0.2 percent by weight, based on the total weight of the detergent stick. The rod was then separated while bathing used by five individuals. The five people were then exposed to the afternoon summer sun for two hours. One A group of five people of the same size used similar eggs Detergents stick, but not a product of the example contained. These individuals were exposed to the summer sun just like the first group. Every person in the second group showed reddening of the skin after exposure to the sun, while none of the first group showed any visible evidence for sunburn showed. The tests carried out not only show the excellent sunlight filtering properties of the compound of Example 1, but also its excellent substantivity for human skin, which in the Bathing was treated with the detergent piece.

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Example B;

The procedure of Example A was repeated with the modification that instead of a detergent bar, a conventional bar of soap (pH approximately 10) containing 0.3 ^Q β> of the product of Example 1 was used. Results comparable to Example A were obtained.

Example C:

The product of Example 1 was prepared as a 10 percent by weight solution in water. In this solution a Sample cellulosic textile material immersed beforehand with dyed a dark red cotton dye. After removing and drying the sample, it was put together with a similarly colored sample, but not treated with the product of Example 1, into a fadeometer given. After four hours of exposure, the untreated one showed Sample a sharp drop in the. Coloring, while the treated goods showed no change in color.

/ Claims «

009816/1761

Claims (4)

Claims '. Colorless compound of the formula R.
H (Ar) ₁ - 0 a N — N— (Ar), , 1, 2 in the form of the free acid (Ar) ₁ and (Ar) ₂ benzene rings, Y and Z salt-forming groups, R an aliphatic radical and η and m integers from 1 to 3 and the compound ei »absorption maximum in the range of 2900 X has up to about 3500 liters. 2. Method of making sunlight filtering Substances of the formula η f «Ν R. (Ar) _L "- G I. Z (Ar). m γ in which (Ar) ·, and (Ar) «are ßenzene rings with free acid residues, Y and Z are salt-forming groups; R is an aliphatic radical and η and m are integers from 1 to 3, the compounds having an absorption maximum in the range from 2900 A to approximately 3500 A, characterized in that a sulfobenzene 009816/1761 - patent claims - or a carboxybenzene aldehyde with a sulfophenyl or garboxyphenyl (R-substituted) hydrazine is condensed. 3. The method according to claim 2, characterized in that the condensation is carried out in an aqueous medium will. 4. The method according to claims 2 or 3, characterized in that the condensation of the aldehyde in Form of the sodium salt is applied. ORJGIMAL INSPECTED 0 0 9 8 16/1761