FR2760746A1 - New acyl:amino acid derivatives used in cosmetics, hygiene compositions, agriculture and therapeutic compositions - Google Patents

Abstract

Acylamino acid derivatives (I) produced by acylation of a mixture of amino acids or peptides (obtained by partial or total hydrolysis of proteins from the seeds of Chenopodium quinoa, with a 1-30C acyl radical. The products are then optionally salified using mineral bases such as soda or potash, organic bases such as amines or biological bases such as choline or lysine, or by metal oligoelements, such as alkaline earth metals or aluminium. The following compositions are also claimed: (i) cosmetic compositions comprising (I); (ii) body detergent compositions comprising (I) characterised in that the acylating agent is C12 lauric chain; (iii) antimicrobial and antifungal compositions comprising (I) characterised in that the acylating agent is octanoyl or undecylenoyl; (iv) antiperspirant compositions comprising (I) where the salification is with mono- or dibasic aluminium; (v) hygiene compositions comprising (I) characterised in that the acylating agent contains 3-11C; (vi) medica ments for treatment of cutaneous inflammation comprising (I) characterised in that the acylating agent contains 8-22C; and (vii) agricultural compositions for stimulating the vegetable development and protection comprising (I) salified with oligoelements characterised in that the acylating agent contains 8-22C.

Description

- 1

NEW ACYLAMINOACIDS

  The acylation of a fatty chain on amino acids or on short or medium chain peptides obtained by hydrolysis of animal or vegetable proteins has been the subject of numerous patents relating both to their preparation and to their destination of use, and in particular in the cosmetic, pharmaceutical fields

and agriculture.

  The study of the acylation technique can be illustrated by the publications Chemical Abstract Volume 101,1984,59982d and Volume 102,

  1985, 115009b, as well as by numerous patents.

  The object of the present invention is to produce new weakly odorous and poorly colored acylamino acid structures obtained from partial or total hydrolysates of proteins.

  contained in the seeds of CHENOPODIUM QUINOA (CHENOPODIACEAE).

  The total hydrolysis of these polypeptide structures leads to the release of the amino acids which compose them, with two particularly dominant amino acids, glutamic acid whose average content is between 20 and 25% and aspartic acid which

represents between 12 and 15%.

  The 7 amino acids listed below represent approximately 50% in total

polypeptide chains.

  These are: glycine between 8 and 10%, arginine and lysine between 6 and 8% each, alanine, serine and leucine between 5 and 7% each,

proline between 4 and 6%.

  The 7 amino acids listed below represent a total of between 15

  and 20% of the polypeptide chains.

  These are: threonine between 3.8 and 4.5%, valine between 3 and 4%, histidine and isoleucine between 2 and 3% each,

isoleucine between 2 and 3%.

  methionine between 1.8 and 2.5% phenylalanine between 1 and 1.5% tyrosine between 0.6 and 1% From the hydrolysis method used, we could note the absence or

  traces of cystine and tryptophan.

  It is interesting to note that the composition of the total seed protein hydrolyzate of CHENOPODIUM QUINOA is close to

  that of the total soy protein hydrolyzate (GLYCINE MAX).

  The small volume occupied by CHENOPODIUM QUINOA seeds allows

  to carry out partial or total hydrolysis directly.

  For this, three parts (by weight) of seeds are immersed in a solution containing three parts of 33% hydrochloric acid and one

part of water.

  The whole is heated to a temperature sufficient to obtain reflux, until a solution having a reaction is obtained.

  negative biuretic (approximately 5 hours of reflux heating).

  -2- The hydrolyzate obtained is neutralized with a 30% sodium hydroxide solution up to approximately pH 5, then treated with an activated carbon for discoloration. In order to be able to determine the quantity of chloride or anhydride of fatty or organic acids necessary for the acylation, the

  titration of the hydrolyzate by formalin titration.

  In the case of the use of fatty chains from 5 carbons, the acylation is carried out by pouring the acylating agent into the hydrolyzate, at temperatures between 15 and 50 ° C., depending on the nature of

  the acylating agent, and maintaining the pH of the medium between 10 and 11.

  When all of the acylation reagent is introduced, the temperature of the reaction medium is brought to 70 ° C. for one hour in the case of the use of fatty acid chlorides. The medium is then cooled to reach a temperature below 30 ° C. , then treated with hydrochloric acid at 33% to arrive at a pH close to 1.11 then forms a white, voluminous matte, comprising

about 70% water.

  Washed on filter to remove hydrochloric acid, this matte will be dehydrated under vacuum, at a temperature below 50 C to avoid

the appearance of a coloration.

  Liposoluble acylamino acids are obtained, which, depending on the nature of the fatty chain used, will be pasty or may be reduced to powder. When the acyl chain used contains from 1 to 4 carbon atoms (acetyl, propionyl, butyryl), and after having brought the pH of the medium to 1 1.5 then eliminated the hydrochloric acid resulting from the reaction and the water by distillation under vacuum, the water-soluble acylamino acid obtained can be extracted with an appropriate solvent such as ethanol by

example.

  The acylamino acids produced according to the invention are mixtures of acylated amino acids having the following structure:

R1-NH-CO-R2

  in which R1 represents the structure of the amino acid where the amine function is fixed, and R2 represents a radical of fatty acids

  from C5 to C30 or an organic acid from Cl to C4.

  A mixture of acylamino acids is thus obtained, easily revealed by thin layer chromatography, and corresponding precisely to the

  composition of CHENOPODIUM QUINOA seed hydrolyzate.

  EXAMPLES OF PREPARATION OF ACYLAMINOACIDS ACCORDING TO THE INVENTION:

  EXAMPLE No. 1 - Hvdrolvse of the spores of CHENOPODIUM OUINOA: In a reactor containing 300 ml of 33% hydrochloric acid and

  ml of water, 300 g of seeds of CHENOPODIUM QUINOA are introduced.

  The temperature is brought to the boil (around 100 C) for

about 5 hours.

  After cooling, the hydrolyzate obtained is obtained with a sodium hydroxide solution at pH 5, and filtered to remove the remaining hydrocarbon elements from the seeds. With activated carbon, the hydrolyzate is decoloured, ie at room temperature, i.e. -3-

hot around 80 C.

  The titer of the hydrolyzate is determined by formalin titration, which makes it possible to calculate the quantity of acylating agent to be used relative to the content of NH 2 functions of the amino acids released by the hydrolysis. FXAMPLE No 2 - Acquisition of Dalmitovl chloride: At room temperature, to 200 ml of hydrolyzate obtained according to Example 1 is added with stirring 400 ml of water and soda, to bring the pH to 10.5. The palmitoyl chloride is poured in dropwise while maintaining the pH between 10.5 and 11 with sodium hydroxide. The temperature of the medium rises to 40 C. When all of the palmitoyl chloride has been

  introduced, the temperature of the medium is brought to 70 ° C. for one hour.

  After cooling, a hydrochloric acid solution is added to reach pH 1. The mixture of acylamino acids decanted under the

  form of a whitish matte which will be washed in cold water.

  Dehydrated under vacuum at a temperature below 50 C to avoid

  colorings, a melting product is obtained around 60 - 65 C.

  EXAMPLE N 3 - Acvlation with caprvlovl chloride: Under the same conditions as in Example 2, to 200 ml of hydrolyzate obtained according to Example 1, capryloyl chloride is added according to the same procedure. After acylation and heating at 70 ° C. for one hour, the medium is cooled and the derivative obtained is released with hydrochloric acid. The product obtained is liquid and

reddish brown color.

  After decantation and successive washing with water to remove

  the hydrochloric acid remaining, it is dried under vacuum.

  The invention also relates to various compositions prepared with the acylamino acids of the invention, which can be used in the cosmetic, hygienic, therapeutic and

Agriculture.

  These new acylamino acids can be used as such, that is to say in their acylated form, or in the form of their respective salts with alkaline metals or organic bases, such as the various amines, ammonia or amino alcohols , or bases

  organic like choline, lysine.

  Alkaline earth metals can also be used, just like metals like iron, manganese, cobalt, copper, and

general trace elements.

  The choice of agent used for salt formation will depend

  the use for which the compound obtained is intended.

  For example, for the production of antimicrobial, antifungal and antiviral compositions, acylating agents at C8 will be used

or Cll.

  For the production of detergent compositions, salification with a mineral, organic or biological base of lacylamino acid, the acyl fraction of which corresponds to the lauric chain, is preferred. The product thus obtained is mainly intended for personal hygiene and is characterized, at the content of 20%, by a foaming power and an exceptional characteristic softness. As a mineral base, it is possible to use soda or potash, as organic base monoethanolamine or triethanolamine, and as a biological base choline, lysine or ammonia. Antiperspirant compositions active on hyperhydrosis can be produced with mono and dibasic aluminum salts and

acylating agents in C8 or Cll.

  The presence of serine in a fairly large amount (5 to 7%) gives the acylamino acids thus produced anti-dehydrating and anti-toxic characteristics which are particularly advantageous in the cosmetic field, in particular when the acyl fraction used is the palmitoyl chain (A. KAPLAN: "Hydrogene bonding properties of N- Palmitoyl_Serine "- Journal of Colloid and interface

  1s Science, 1967 (25), 63-70); MAC FARLANE: Adv Lipid Res. 1964 (2), 96-

  ). In the field of hygiene, it will be possible to graft acyl chains comprising from 3 to 11 carbon atoms, and the salified forms will be usable. In agriculture, the C8 & C22 acylamino acids, salified with trace elements (including copper in particular), can be used as agents for protecting or stimulating plant growth. In pharmacies, anti-inflammatory compositions in C8 to C22 can be produced to fight against microbial inflammations,

fungal or viral skin.

  Various compositions produced according to the invention can be cited by way of nonlimiting examples: 1) - Cosmetic product of shampoo TV: Lauroyl Chenopodium Quinoa amino acids (20% M.A.). 25.0 Octanoyl Chenopodium Quinoa amino acids ............. 0.5 Sodium chloride ........................ .......... 4.0 Demineralized water ................................... qs 100 2o) - Cosmetic product of cream tv: DEA-cetylphosphate ...................

  ............. 3.5 Stearic acid ................................ ... DTD: .. 1.5 Isopropyl palmitate .............................. 5.0 Cetyl alcohol. ................................... 1.0 Palmitoyl Chenopodium Quinoa amino acids ........ .... 5.0 Glycerin ...... DTD: .................................. ... 7.0 Octanoyl Chenopodium Quinoa amino acids ............. 0.5 Lanolin ....................... .... DTD: ................. 3.5 Gel of carboxyvinyl acids .................. DTD : .... 4.0 Demineralized water ................................... qs 100 3) - Soap for the toilet: soap base on copra ................ DTD: .............. 94.0 Lauroyl Chenopodium Quinoa amino acids .. ....... 4.0 Palmitoyl Chenopodium Quinoa amino acids ........ 1.0 Octanoyl Chenopodium Quinoa amino acids ............. 1.0 4) - Antisentiaue composition against acne: Octanoyl Chenopodium Quinoa amino acids ....... .DTD: ..... 5.0 Polyethoxylated castor oil ................... ..... 25, 0 Cleared water made ................................... qs 100) - Composition Dour fight against hvDerhvdrose: Octanoyl Chenopodium Quinoa amino acids ............. 3.0 Palmitoyl Chenopodium Quinoa amino acids ............ 1.0 Ethanol & 35% v / v ...... ................ DTD: ............ 96.0 6) - AntiDissoirante composition: Undécylenoyl Chenopodium Quinoa amino acids ....... .. 5.0 (salified with aluminum dibasic form) Glycerol palmitostearate ............................ 7.0 Polyoxyethylene glycol stearate ................... 4.0 Propylene glycol ........................... .......... 12.0 Demineralized water ................................... qs 100 7) - Vegetable rotator: Octanoyl Chenopodium Quinoa amino acids ......... 3.0 (salified with copper) Palmitoyl Chenopodium Quinoa amino acids ........ 1.0 Solution of ammonia & 30% ..................... DTD: ... 6.0 Demineralized water ............... .................... qs 100 6 - .. DTD:

Claims (9)

  1 - Acylamino acids resulting from acylation by an acyl radical containing from 1 to 30 carbon atoms, from a mixture of amino acids or peptides obtained by partial or total hydrolysis of the proteins contained in the seeds of CHENOPODIUM QUINOA (CHENOPODIACEAE).   2 - Acylamino acids according to claim 1, characterized in that they are salified with mineral bases such as sodium hydroxide or potassium hydroxide, organic bases such as amines or bases   organic like choline or lysine.   3 - Acylamino acids according to claim l, characterized in that they are salified with metals known as trace elements, with   alkaline earth or by aluminum.   4 - Cosmetic compositions characterized in that they   contain acylamino acids according to one of claims 1 to 3.   5 - Detergent compositions for body use containing acylamino acids according to claim 1, characterized in that   the acylating agent is the lauric chain C12.   6 - antiperspirant compositions containing acylamino acids according to claim 3, where salification is carried out with aluminum   in monobasic or dibasic form.   7 - Antimicrobial and antifungal compositions containing acylamino acids according to claim 1, characterized in that   the acylating agent is the octanoyl or undecylenoyl chain.   8 - Hygienic compositions containing acylamino acids according to claim 1, characterized in that the acylating agent comprises of 3 to 11 carbon atoms.   9 - Medicinal compositions for the treatment of skin inflammations, containing acylamino acids according to claim 1, characterized in that the acylating agent comprises of 8 to 22 carbon atoms.     - Compositions for agriculture containing acylamino acids salified with trace elements according to claim 3, intended for stimulating the development of plants and their protection, characterized in that the acylating agent comprises from 8 to 22 atoms of carbon.