DE2156556A1 - Nucleotide and amino acid adducts - for protection of products against actinic light eg in cosmetics - Google Patents

Abstract

Cpds. of formula (I) : Nucleoside-(PO3)n.Men+1.Asm (where Me is H, alkali metal, NH4 or amine-cation; As is opt. substd. aminocarboxylic- or aminosulphonic acid or a salt; n is 1,2 or 3; m is 1-(n+1)). Pref. natural nucleotides are used, e.g. adenine, guanine, cytosine, uracil or thymine. Amino acids are pref. basic and different from one another and may contain carboxylic as well as sulpho gps. Water is prefd. solvent for both reactants which are dissolved separately and mixed. Cpds. (I) have UV-light absorbing activity and may be used as stabilisers for protecting from actinic light, as buffering agents or protecting agents for skin-care against actinic light in cosmetics. Examples of (I) include uridine-51-monophosphoric acid-(p-Na-aminobenzoate)2.

Description

New organic molecular compounds from nucleotides and amino acids The invention relates to new organic, stoichiometric addition compounds Nucleotides and aminocarboxylic acids or aminosulfonic acids. Such connections are has not yet been described. The new connections have among other things ultraviolet absorbing effect and are therefore used as stabilizers for products suitable that protected against the damaging effects of ultraviolet rays Need to become. The new compounds are also used as buffering, skin-nourishing and agents protecting against actinic radiation can be used in cosmetic preparations.

The compounds according to the invention are stoichiometric addition compounds of one molecule of a nucleotide and 1 to 4 molecules of an amino acid. The nucleotide can be any of the known nucleotides. nucleotides are the phosphoric acid esters of N-glycosides of purines and pyrimides, such as z.ß. of adenine, guanine, cytosine, uracil or thymine. Below is z.ß. the formula for the adenosine l-diphosphoric acid Na salt is given: The nucleotides occur in nature as the mono-, di- or triphosphoric acid esters and are also obtained synthetically.

Examples of further nucleotides are: adenosine-5'-monophosphoric acid, Adenosine-2'-diophosphoric acid, cytidine-3'-triphosphoric acid, uridine-3'-diphosphoric acid, Guanosine-2-monophosphoric acid, uridine-5'-monophosphoric acid-Na salt and others

5 it has now been found that such nucleotides are stoichiometric compounds form with amino acids. Depending on whether it is the mono-, the di- or the triphosphoric acid compounds acts, or their sodium or other alkali salts, have the new compounds the following general formula: nucleoside # (PO3) n # Men + 1 # ASm where: Nucleoside: N-glycoside made from a gurine or pyrimidine compound and a sugar, such as e.g., ribose; Nucleoside # (PO3) n # Men + 1 # nucleotide; Me: hydrogen, alkali metal, Ammonium or amine nation; AS: aminocarboxylic or aminosulfonic acid or its alkali metal, Ammonium or amine salt or acid amide; n: a number from 1 to 5; m: a number from 1 to (n + 1).

The amino acids contained in the new compounds can be aliphatic, aromatic, naphthenic or heterocyclic aminocarboxylic acids or aminosulfonic acids which can also be arbitrary, e.g.

be substituted by OH groups, and carboxy groups and sulfo groups can contain at the same time. It can also be the salts of the amino acids, e.g. to be those of the alkali metals, etc. Basic amino acids are preferred, in particular can the in a molecular compound according to the present invention contained amino acids may be different from each other. Examples of amino acids, which can be contained in the molecular compounds according to the invention are: o-dminobenzoic acid, p-aminobenzoic acid, aminosalicylic acid, sulfanilic acid, 5-amino-3-sulfosalicylic acid, Aminophenol sulfonic acid, 1-amino-2-hydroxyhaphthalene sulfate, Na-aminoisophthalate, histidine, Arginine, cystine, hminonaphthoesulfonic acid, etc.

The new compounds can be obtained on various goats.

In general, one assumes separate solutions of the nucleotide and the amino acid. The preferred solvent for the nucleotide is water used. Water is also preferably used for the amino acid, however has z.ß. acetone also proved to be very suitable.

The solutions are put together. If a precipitate forms, this is filtered off, suspended in water and again by adding alkali brought into solution. The new addition connection can be derived from the joint solution according to known methods, such as concentration to dryness, application of vacuum, freeze-drying etc. can be obtained.

In the following examples, the preparation of some of the inventive Compounds explained: Example 1 Preparation of uridine-p-aminobenzoic acid 1 mol Uridine - monophosphoric acid is dissolved in 10 parts of water.

Separately, 2 moles of p-aminobenzoic acid in 90 parts of anhydrous become Dissolved acetone. The p-aminobenzoic acid is slowly added to the solution Given solution of uridine phosphoric acid.

A precipitate formed, which was filtered off and dried at 40.degree until it runs out of acetoin. Then the filter cake in Suspended iiasser, and MaOII is added until the precipitate dissolves. The solution of uridine 5'-monophosphoric acid (p-Na-aminobenzoate) 2 is in vacuo evaporated. A white, crystalline compound is obtained.

Example 2 Preparation of adenosine-tryptophan: 1 mol of adenosine-5s-monophosphoric acid is dissolved in 5 parts of water. Regardless, there are 2 moles of tryptophan in 5 parts Dissolved in water. Then the amino acid solution is divided into 9 parts of a methanol / acetone mixture (2: 1) given. The nucleotide solution is slowly added to this mixture with stirring given, whereby a precipitate forms. This is filtered off and dried at 60.degree. Then the precipitate is suspended in water. The suspension will be just as much a added, as is necessary to the free carboxyl groups of the tryptophan neutralize. The precipitate dissolves in the process. The solution is in vacuo evaporated; a white, crystalline powder will be obtained, consisting of adenosine 5'-monophosphoric acid (sodium tryptophanate) 2 consists.

Table 1 shows further molecular compounds according to the invention and their properties are listed. The table also shows the good absorption behavior of the new connections.

When used, e.g. in cosmetic preparations, the new compounds in any:; otherwise in these preparations one will work, as is customary in this industry. The use of the new connections will be special thereby facilitated that they have good water solubility and e.g. the corresponding purines and pyrimidines increased by a factor of 10 to 100 Have solubility.

The new compounds can especially be used together with other, commercially available Skin care and protection products are processed.

In the following example, the production of Compounds described on a different from Example 1 and Example 2 ege.

Example 3 Preparation of guanine-5'-diphosphoric acid-mono-Na- (3-amino-2-K-naphthosnate) - (5-di-ammonium-5-amino-3-sulfosalioylate).

4.63 g (u, oi ol) guanosine-5'-di-phosphoric acid-mono-Na-salt in 100 ml dist. Dissolved in water. 2.25 g (0.01 mole) 3-amino-K-2-naphthoenate and 2.67 g (0.01 mol) of 5-amino-3-sulfo-salicylic acid diammonium salt are combined in 200 ml dist. Dissolved water and added to the solution of guanine-5'-di-phosphoric acid mono-Na salt given.

After vigorous stirring of the solution, it becomes dry in vacuo thawed. The resulting crystal mass can be recrystallized from water-propanol and represents the desired molecular compound. The yield is 100%.

Table 1 Molecular Compound Molecular Formula M.G. N (%) pH UV spectrum Extinction quotient calculated c = (c = 0.005; d = 1; water) 0.005 mol. Ext. E250 / E280 / E290 / coefficient E260 E260 E260 uridine 5'-monophos-31H37N6O13P 732.63 11.45 11.43 6.5 # max = 223mµ # = 27800 + 4% 0.77 0.69 1.51 phosphoric acid- (tryptophan) 2 adenosine-5'-monophos- C24H26N7O11 665.34 14.75 14.89 6.5 # max = 265mµ # = 253000 + 4% 0.89 0.70 0.4 phosphoric acid (Na-p-amino- PNa2 benzoate) 2 Na-uridine-5-monophosphor- C16H18N3O11 505.21 8.30 8.13 6.95 # max = 206mµ # = 173500 + 4% 0.79 0.71 0.32 acid (Na-p-aminoben- PNa2 zoat) uridine-5'-monophosphorus- C15H20N8O11 676.47 16.55 16.85 7.0 # max = 210mµ # = 156000 + 4% 0.75 0.42 0.09 acid (Na-histidine) 2 PNa2 adenosine-5'-monophos- C32H36N9O11 799.68 15.8 15.07 7.0 # max = 220mµ # = 320000 + 4% 0.76 0.67 0.33 phosphoric acid- (na-trypto- PNa2 phan) 2 uridine-5-monophosphorus- C31H25N6O13 766.59 10.8 10.53 7.25 # max = 222mµ # = 329200 + 4% 0.71 0.76 0.30 acid (na-tryptophan) 2 PNa2 adenosine-5'-monophos- C22H26N7O15 769.23 12.72 12.65 6.35 # max = 214mµ # = 332000 + 4% 0.62 0.45 0.46 phosphoric acid (o-Na-amino PNa2S2 phenolsulfonate) 2 cytidine-5'-monophosphorus C21H26N5O16 745.57 9.39 9.04 6.60 # max = 215mµ # = 298000 + 4% 1.41 1.07 0.69 acid (Na-o-aminophenolsulfonet) 2 PS2 Na2 Adenosine-5'-mopophos- C22H26N7O13 737.62 13.3 13.5 6.50 # max = 208mµ # = 263300 + 4% 1.06 0.21 0.11 phosphoric acid (Na @@@ fanilat) # S2P Na2 Table 1 (continued) Molecular compound Molecular formula M.G. N (%) pH UV spectrum extinction quotient calc. c = (c = 0.005; d = 1; water) 0.005 molecular ext. E250 / E280 / E290 / coeff. E260 E260 E260 Cytidine 5'-monophos- C27H34N5O14 729.39 9.65 9.50 6.65 # mex # 224mµ # = 189000 # 4% 0.75 1.15 0.40 phosphoric acid- (Na-tyrosine) 2 PNa2 uridine-5'-monophos- C27H51N4O15 728.35 7.43 7.80 7.05 # max = 224mµ # = 164500 # 4% 0.64 0.62 0 phosphoric acid (Na tyrosine) 2 PNa2 cytidine 5'-monophosphorus C31H36N7O12 775.65 12.70 12.70 7.0 # max = 223mµ # = 295500 + 4% 0.71 1.11 0.42 acid (Na-tryptophan) 2 PNa2 adenosine-5'-monophosphoric acid- (p-aminobenzoic-C24H28N7O11P 621.34 15.73 16.16 6.2 # max = 265mµ # = 236000 + 4% 0.82 0.89 0.57 acid) 2 Na-cytidine-5'-monophosphorus-C16H19N4O12 504.25 11.10 11.30 7.35 # max = 206mµ # = 161000 + 4% 0.66 1.00 0.51 acid (Na-p-aminobenzoe- P Na2 acid guanosine-5'-monophos- C24H24N7O20 917.59 10.68 10.01 7.05 # max = 215mµ # = 358000 + 4% 1.3 0.44 0.14 phosphoric acid (5-aminosul- PS2Na4 foselicylate) 2 guanosine-5'-monophos- C30H30N7O14 853.73 11.48 11.18 6.85 # max = 210mµ # = 333000 + 4% 1.86 0.47 0.31 phosphoric acid (5-aminonaph- PS2Na2 thalin-1-sulfate) 2 guanosine-5'-monophos- C30H30N7O16 885.71 11.07 10.57 6.85 # max = 215mµ # = 346000 + 4% 1.37 0.53 0.41 phosphoric acid (1-amino-2-PS2Na2 hydroxy-naphthalene sulfate) 2

Claims (6)

Claims: Organic molecular compounds of the general formula Nucleoside # (PO3) n # Men + 1 # ASm, in which Me is a hydrogen, alkali metal, ammonium and / or amine cation, AS an optionally substituted aminocarboxylic or aminosulfonic acid or a salt thereof, n is an integer from 1 to 3 and m is an integer from Is 1 to (n + 1). 2. Compounds according to claim 1, characterized in that the Amino acids are basic amino acids. 3. Compounds according to claim 1 or 2, characterized in that the nucleoside * (PO3) nMen + 1 is a natural nucleotide. 4. Compounds according to any one of claims 1 to 3, characterized in that that they contain different amino acids in the molecule. 5. Compounds according to any one of claims 1 to 4, characterized in that that the amino acids contain both carboxyl groups and sulfo groups. 6. Compounds according to any one of claims 1 to 5, characterized in that that the amino acid salt is the alkali, ammonium or amine salt or an acid amide.