FR2503144A1 - Compsns. contg. N-butyryl alpha-aminoacid(s) - for cosmetic, hygienic, therapeutic or agricultural use - Google Patents
Compsns. contg. N-butyryl alpha-aminoacid(s) - for cosmetic, hygienic, therapeutic or agricultural use Download PDFInfo
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- FR2503144A1 FR2503144A1 FR8106593A FR8106593A FR2503144A1 FR 2503144 A1 FR2503144 A1 FR 2503144A1 FR 8106593 A FR8106593 A FR 8106593A FR 8106593 A FR8106593 A FR 8106593A FR 2503144 A1 FR2503144 A1 FR 2503144A1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/46—N-acyl derivatives
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/185—Acids; Anhydrides, halides or salts thereof, e.g. sulfur acids, imidic, hydrazonic or hydroximic acids
- A61K31/19—Carboxylic acids, e.g. valproic acid
- A61K31/195—Carboxylic acids, e.g. valproic acid having an amino group
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
- A61K8/447—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof containing sulfur
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
- A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
- A61K8/65—Collagen; Gelatin; Keratin; Derivatives or degradation products thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q15/00—Anti-perspirants or body deodorants
Abstract
Description
L'invention concerne de nouveaux dérivés d'acides aminés autres les acides aminés soufrés,ainsi que la proline,hydroxyproline et hydroxylysine qui ont fait l'objet également < i' autres brevets d'invention; caractérisés en ce que leurs fonctions acylables sor essentiellement combinées à la chaine Wutyrique;cette chaine éte le premier représentant de la série des acides gras.The invention relates to novel amino acid derivatives other than sulfur-containing amino acids, as well as proline, hydroxyproline and hydroxylysine, which have also been the subject of other invention patents; characterized in that their acylable functions are essentially combined with the Wutyric chain; this chain is the first representative of the fatty acid series.
Dans le cadre de la présente invention,on entend par acides aminés ,les constituants fondamentaux des protéines, conformément aux structures décrites dans la littérature scientifique et par la nomenclature biochimique,caractérisés par une fonction amine acide en position alpha. In the context of the present invention, by amino acids is meant the fundamental constituents of proteins, in accordance with the structures described in the scientific literature and by biochemical nomenclature, characterized by an acidic amine function in the alpha position.
Comparativement aux autres lipoaminoacides comportant des chaines grasses à plus de 5 atomes de carbone,les lipoaminoacide à chaine butyrique réalisés par la présente invention,conduisent aux avantages suivants:
I-En raison de la structure lipidoprotidique,de la nature de la chaine acyle hydrosoluble et soluble dans de nombreux solvant les butyrylaminoacides sont hydrophiles et lipophiles.Leur hydro solubilité varie en fonction de la nature de l'acide aminé,il en est de mème pour leur liposolubilité.Compared with other lipoamino acids comprising fatty chains with more than 5 carbon atoms, the lipoamino acid with butyric chain produced by the present invention, lead to the following advantages:
I-Due to the lipid-protein structure, the nature of the water-soluble acyl chain and soluble in many solvents, butyrylamino acids are hydrophilic and lipophilic. Their hydro-solubility varies according to the nature of the amino acid, it is the same. for their fat solubility.
Contrairement aux acides aminés qui sont pratiquement insolubles dans l'éthanolrtous les dérivés butyryes y sont très solubles.Ils sont également solubles dans les solvants polaires et apolaires:acétone,méthanol acétate d' éthyle,benzène chloroforme ether éthylique etc... Unlike amino acids which are practically insoluble in ethanol, all butyry derivatives are very soluble there. They are also soluble in polar and nonpolar solvents: acetone, methanol ethyl acetate, benzene chloroform ethyl ether etc ...
Comme pour les structures lipoaminoacides comportant des chaines grasses à plus de 5 atomes de carbone,les b'ftyrylaminoac sont très solubles dans les mélanges de solvants polaires et apc laires:chloroforme/méthanol par exemple. Ils sont insolubles dan l'éther de pétrole,l'hexane et, dans certains cas dans l'éther i propylique. As for the lipoamino acid structures comprising fatty chains with more than 5 carbon atoms, the b'ftyrylaminoacs are very soluble in mixtures of polar and apc solvents: chloroform / methanol for example. They are insoluble in petroleum ether, hexane and, in some cases in propyl ether.
2-Du fait de l'existence dans la structure de ce type de lip aminoacides,d'une chaine butyryle courte,le pouvoir- acidifiznt d carboxyle en position alpha,de l'acide aminé,est doué d'un poten tiel acidifiant très nettement superieur. 2-Due to the existence in the structure of this type of lip amino acids, of a short butyryl chain, the acidifying capacity of the carboxyl in alpha position, of the amino acid, is endowed with a very acidifying potential. significantly higher.
3-Le pouvoir de pénétration tissulaire est sensiblement plus élevé en raison de la nature de la structure lipidoprotidique et de son caractère d'hydrosolubilité. 3-The tissue penetration power is significantly higher due to the nature of the lipid-protein structure and its water-solubility character.
4-De pouvoir conduire a des résultats d'efficacité nettement plus rapides,pour des teneurs sensiblement moins levées. 4-To be able to lead to significantly faster efficiency results, for significantly less raised contents.
Dans la présente invention,on classera les butyrylaminoacide en deux catégories:
a) ceux obtenus à partir d'acides aminés,utilisés individuellement,conduisant ainsi à des butyrylaminoacides.In the present invention, the butyrylamino acids will be classified into two categories:
a) those obtained from amino acids, used individually, thus leading to butyrylamino acids.
b) ceux obtenus à partir de mélanges d'acides aminés issus d'hydrolysats totaux de protéines animales ou vegétales,conduisant ainsi à des butyrylpolyaminoacides. b) those obtained from mixtures of amino acids derived from total hydrolysates of animal or vegetable proteins, thus leading to butyrylpolyamino acids.
Dans les deux cas,on aur & recours comme agent d'acylation, à l'anhydride butyrique qui permet l'acylation complète des acides aminés,donnant ainsi un butyrylaminoacide et de l'acide butyrique selon la réaction:
anhydride butyrique Butyryl amino acide
+ CH3-CH2-CH2-COOH
acde gutyBicue
Comme exemples non limitatifs de préparations de butyrylmonoaminoacides, citons:
Exemple I
Butyrylglycocolle ta Butyrylglycine
30 grs de glycocolle sont introduits dans un réacteur (4/IOe de mol) placé dans un bain marie.On ajoute 40 ml d'une solution de soude à sous agitation.Lorsque la solution est limpidewon coule goutte à goutte 65 grs d'anhydride butyrique, en maintenant le pE entre IO et I0,5 à la fin de l'acylation.In both cases, recourse will be had, as acylating agent, to butyric anhydride which allows complete acylation of the amino acids, thus giving a butyrylamino acid and butyric acid according to the reaction:
butyric anhydride Butyryl amino acid
+ CH3-CH2-CH2-COOH
acde gutyBicue
As nonlimiting examples of butyrylmonoamino acid preparations, let us quote:
Example I
Butyrylglycocolle ta Butyrylglycine
30 g of glycocolle are introduced into a reactor (4/10 mol) placed in a water bath. 40 ml of a soda solution are added with stirring. When the solution is limpide, 65 g of anhydride drip butyric, keeping the pE between IO and I0.5 at the end of the acylation.
La température du milieu réactionnel s'élève entre 450 et 500.The temperature of the reaction medium rises between 450 and 500.
On porte la température à 700 durant 30 minutes. Après refroidisse~ ment,on libère le butyrylglycocolle de son sel sodique par addition d'acide chlorhydrique de D=I,19,jusqu1à pH 2.The temperature is brought to 700 for 30 minutes. After cooling ~ ment, the butyrylglycocolle is released from its sodium salt by addition of hydrochloric acid of D = I, 19, up to pH 2.
On obtient une huile surmageante qui sera décantée et transférée dans un ballon comportant un dispositif de distillation sous vide,qui sera chauffé à l'aide d'un bain d'huile. Par distillation sous un vide de IO mm,on élimine l'eau et l'acide chlorhydrique ayant été entrainé .Après refroidissement du ballon, le contenu est traité par de l'éther de pétrole.Le butyrylglyco- colle cristallise. On filtre;on effectue trois fois de suite le traitement à l'ether de pétrole qui élimine l'acide butyrique. An over-oil is obtained which will be decanted and transferred to a flask comprising a vacuum distillation device, which will be heated using an oil bath. By distillation under a vacuum of 10 mm, the water is removed and the hydrochloric acid which has been entrained. After cooling the flask, the contents are treated with petroleum ether. The butyrylglyco-glue crystallizes. It is filtered and the petroleum ether treatment which removes butyric acid is carried out three times in succession.
Poids obtenu 51 grs
Rendement par rapport à
la théorie 88 > ó
Analyse: P.x.:I45-Azote théorique: 9,6, Azote trouvé: 9,4- Indj d'acide théorique:386,Indice d'acide trouvé: 382
Exemple 2 Butyrylphénylalanine
33 grs de phénylalanine sont introduits dans le réacte contenant 40 ml de solution de soude caustique à 3Oc%.On ajoute 20 ml d'eau.0n coule goutte à goutte 36 grs d'anhydride butyriq on opère ensuite comme pour l'exemple precédent.Weight obtained 51 grs
Performance versus
theory 88> ó
Analysis: Px: I45-Theoretical nitrogen: 9.6, Nitrogen found: 9.4- Theoretical acid index: 386, The acid index found: 382
Example 2 Butyrylphenylalanine
33 grs of phenylalanine are introduced into the reaction vessel containing 40 ml of caustic soda solution at 3Oc%. 20 ml of water are added. 36 g of butyriq anhydride are added dropwise, the procedure is then carried out as for the previous example.
Poids obtenu 42 grs
Rendement par rapport à
la théorie 90 < k
Analyse: P.M. : 235- Azote théorique: 5,9%, Azote trouvé: 5,7%
Indice d'acide théorique: 238, Indice d'acide trouvé: 235.Weight obtained 42 grs
Performance versus
theory 90 <k
Analysis: MW: 235- Theoretical nitrogen: 5.9%, Nitrogen found: 5.7%
Theoretical acid number: 238, Found acid number: 235.
Exemple 3
Butyrylthréonine
36 grs de thréonine (3/IOe de mol) sont introduits dan le réacteur contenant 50 ml de solution de soude caustique à 3C et 25 ml d'eau On coule,sous bonne agitation,5I grs d'anhydrid butyrique;le reste des opérations s'effectue de la mème façon q pour l'exemple I.Example 3
Butyrylthreonine
36 grs of threonine (3/10 mol) are introduced into the reactor containing 50 ml of caustic soda solution at 3C and 25 ml of water 5I grs of butyric anhydrid are poured in, with good stirring; the rest of the operations is carried out in the same way q for example I.
Poids obtenu 57 grs
Rendement par rapport à
la théorie 99%
Analyse: P.M. : I89- Azote théorique: 7,4, Azote trouvé: 7,2
Indice d'acide théorique: 296, Indice d'acide trouvé: 293.Weight obtained 57 grs
Performance versus
theory 99%
Analysis: PM: I89- Theoretical nitrogen: 7.4, Nitrogen found: 7.2
Theoretical acid number: 296, Found acid number: 293.
Exemple 4
Acide butyrylaspartique
53 grs (4/IOe de mol) d'acide aspartique sont introduit dans le réacteur contenant 60 ml de solution de soude à 309. On coulercomme indiqué en I, l'anhydride butyrique: 64 grs. On pro cède par la suite,comme dans l'exemple I,jusqu'au stade de la distillation de l'eau. Dans ce cas;on doit éliminer l'acide but rique restant par distillation sous vide,à la température du ba d'huile portée à I3C/I400,sous un vide de IOmm,
Après élimination complète de l'acide butyrique,on pèse le ballon réfroidi,celui ci ayant été préalablement taré. On aj te la mème quantité d'eau distillée que celle du dérivé butyryl anhydre présent dans le ballon.0n décolore à l'aide de noir,par chauffage,en complétant la quantité d'eau évaporée. On filtre, on obtient ainsi une solution à 50% d'acide butyrylaspartique.Example 4
Butyrylaspartic acid
53 grs (4 / IOe of mol) of aspartic acid are introduced into the reactor containing 60 ml of sodium hydroxide solution at 309. We pour as indicated in I, butyric anhydride: 64 grs. One proceeds thereafter, as in Example I, to the stage of distillation of water. In this case; the remaining butic acid must be removed by vacuum distillation, at the temperature of the oil bath brought to I3C / I400, under a vacuum of 10 mm,
After complete elimination of the butyric acid, the cooled flask is weighed, the latter having been tared beforehand. The same amount of distilled water is added as that of the anhydrous butyryl derivative present in the flask. It is discolored using black, by heating, completing the amount of water evaporated. Filtered, thus obtaining a 50% solution of butyrylaspartic acid.
Poids obtenu 75 grs
Rendement par rapport à
la théorie 94%
Après éliminition de l'acide butyrique,on obtient une masse visqueuse,en partie cristalline,dificile a faire cristalliser en totalité et hygrosconique,ce sui nécés ite,la nise en solution.Le poids indioué et les nalyr:es portent sur la substance anhydre.Weight obtained 75 grs
Performance versus
theory 94%
After elimination of the butyric acid, one obtains a viscous mass, partly crystalline, difficult to make crystallize in whole and hygrosconique, this sui nécés ite, nise it in solution. .
Analyse: P.M. 203- Azote théorique: 6,9, Azote trouvé: 6,7
Indice d'acide théorique 55I, Indice d'acide trouvé: 547
Exemple 5
Butyrylvaline
58 grs de valine (I/2 mol) sont introduits dans le réacteur contenant 80 ml de solution de soude caustique à 30%. On coule goutte à goutte 85 grs d'anhydride butyrique;en fin d'acylation on maintient le pH entre IO et I0,5.On opère ensuite comte pour l'exemple I. Les cristaux de butyrylvaline étant très peu solubles dans l'eau froide,on élimine 11 acide butyrique par lavage à l'eau glacée.Analysis: PM 203- Theoretical nitrogen: 6.9, Nitrogen found: 6.7
Theoretical acid index 55I, Acid index found: 547
Example 5
Butyrylvaline
58 grs of valine (I / 2 mol) are introduced into the reactor containing 80 ml of 30% caustic soda solution. 85 g of butyric anhydride are poured in drop by drop; the pH is maintained between 10 and 10.5 at the end of acylation. The procedure is then counted for example I. The butyrylvaline crystals being very slightly soluble in water cold, 11 butyric acid is removed by washing with ice water.
Poids obtenu 85grs
Rendement par rapport à
la théorie 92%
Analyse: P.M.: I87- Azote théorique: 7,4 , Azote trouvé: 7,3
Indice d'acide théorique: 297, Indice d'acide trouvé: 294
Exemple 6 Butyrylleucine
65 grs de leucine (I/2 mol) sont introduits dans le réacteur contenant 60 ml de solution de soude caustique à 30%;on coule 85 grs d'anhydride butyrique;on procède ensuite comme dans l'exemple 5,1a butyrylleucine étant également très peu soluble dans l'eau glacée.Weight obtained 85grs
Performance versus
theory 92%
Analysis: PM: I87- Theoretical nitrogen: 7.4, Nitrogen found: 7.3
Theoretical acid number: 297, Found acid number: 294
Example 6 Butyrylleucine
65 grs of leucine (I / 2 mol) are introduced into the reactor containing 60 ml of 30% caustic soda solution; 85 grs of butyric anhydride are poured in; then the procedure is as in Example 5.1a butyrylleucine also being very slightly soluble in ice water.
Poids Obtenu 89 grs
Rendement par rapport à
la théorie 92%
Analyse: P.X. :20I - Azote théorique: 7%, Azote trouvé: 6,85
Indice d'acide théorique: 280, Indice d'acide trouvé: 277.Weight Obtained 89 grs
Performance versus
theory 92%
Analysis: PX: 20I - Theoretical nitrogen: 7%, Nitrogen found: 6.85
Theoretical acid number: 280, Found acid number: 277.
Exemple 7
Butyryllysine
60 grs de lysine à 5; (2/ICe de mol) sont introduits dans le réacteur contenant 20 ml de soude à 30%.On coule 64 grs d' anhydride butyrioue,en maintenant le pH entre IC et IC,5 à 1' ide de la solution de soude.La suite des opérations s'effectue comme pour l'exemple I
Poids obtenu 5I grs 2503144
Rendement par rapport 85%
à la théorie
Analyse: P.M. 286- Azote théorique 9,7 , trouvé: 9,5- Indice d'acide théorique: I95, trouvé:I93
Comme exemples non limitatifs de butyryipolyaminoacides citons:
Exemple 8
Acide butyrylcollagénique
On hydrolyse durant 8 heures 200 grs de gélatine dans ml d'une solution d'acide chlorhydrique de D=I,I9,à 50%.On véri que la réaction biurétique est négative. On neutralise à pE 6,5/ on traite par un noir décolorant et on filtre.Example 7
Butyryllysine
60 grs of lysine to 5; (2 / mol ICe) are introduced into the reactor containing 20 ml of 30% sodium hydroxide. 64 g of butyrious anhydride are poured in, maintaining the pH between IC and IC, 5 with the idea of the sodium hydroxide solution. The rest of the operations are carried out as for example I
Weight obtained 5I grs 2503144
Efficiency vs 85%
to theory
Analysis: PM 286- Theoretical nitrogen 9.7, found: 9.5- Theoretical acid number: I95, found: I93
As nonlimiting examples of butyryipolyamino acids, let us quote:
Example 8
Butyrylcollagenic acid
Hydrolysis is carried out for 8 hours 200 g of gelatin in ml of a hydrochloric acid solution of D = I, I9, at 50%. It is verified that the biuretic reaction is negative. Neutralized at pE 6.5 / treated with a bleaching black and filtered.
On calcule la quantité d'anhydride butyrique a utilise en fonction du dosage de l'azote obtenu par formol-titration,en considérant un poids moléculaire moyen de IIO,pour les acides a nés issus de l'hydrolysat.D1autre part,on détermine la teneur e extrait sec que l'on traite par le méthanol pour éliminer le; c rure de sodium; après filtration et évaporation du méthanol,on o tient le poids d'acides aminés contenu dans l'hydrolysat,sur le on effectue un autre dosage par formol-titratio
200 ml d'hydrolysat,comportant approximativement 50 gr d'acides aminés, sont introduits dans le réacteur.On ajoute envi I5 grs de soude anhydre.0n coule 80 grs d'anhydride butyrique;, e maintenant en fin d'acylation le pH entre IO et I0 5. Comme pou l'exemple I,on acidifie après avoir chauffé 30 minutes à 700. We calculate the amount of butyric anhydride used according to the nitrogen dosage obtained by formalin-titration, considering an average molecular weight of IOI, for the born acids from the hydrolyzate. On the other hand, we determine the content of dry extract which is treated with methanol to remove the; sodium cure; after filtration and evaporation of the methanol, the weight of amino acids contained in the hydrolyzate is maintained, on which another assay is carried out with formalin-titratio
200 ml of hydrolyzate, comprising approximately 50 gr of amino acids, are introduced into the reactor. About 15 gr of anhydrous soda are added. 80 gr of butyric anhydride are poured in; now, at the end of acylation, the pH between IO and I0 5. As for example I, acidification after heating 30 minutes to 700.
Après refroidissement,avant acidification, on ajoutera viron 50 grs de chlorure de sodium pour provoquer une bonne sép tion des butyrylaminoacides et réduire les pertes par solubilis tion. After cooling, before acidification, about 50 grs of sodium chloride will be added to cause good separation of the butyrylamino acids and reduce losses by solubilization.
La partie surnageante est introduite dans un ballon a tiller et on procède comme pour l'exemple 4 relatif à l'acide; butyrylaspartique. The supernatant is introduced into a spinning flask and the procedure is as for Example 4 relating to the acid; butyrylaspartique.
Poids obtenu (sur l'anhydre) 74 grs
Rendement par rapport à
la théorie 92%
Analyse:Tenant compte d'un P.X. moyen de IIO pour les acides aminés:azote théorique 8%, azote trouvé 8,2%- Indice d'acide théorique 327, indice d'acide trouvé: 335
Exemple 9
Acide butyrylkératinique:
On hydrolyse durant I5 heures,200 grs de corne,dans les mèmes conditions que l'exemple précédent.Par prélèvement on véz que la réaction biurétique est négative.On neutralise et décolore comme indiqué dans l'exemple 8.Weight obtained (on anhydrous) 74 grs
Performance versus
theory 92%
Analysis: Taking into account an average PX of IOI for amino acids: theoretical nitrogen 8%, nitrogen found 8.2% - theoretical acid index 327, acid index found: 335
Example 9
Butyrylkeratinic acid:
200 grs of horn are hydrolyzed for 15 hours, under the same conditions as the previous example. By sampling, the biuretic reaction is negative. We neutralize and discolour as indicated in example 8.
On détermine l'azote acylable par rapport à la cystine,par formol-titration. The acylable nitrogen is determined relative to the cystine, by formalin-titration.
300 ml d'hydrolysat de kératine sont introduits dans le ré c- teur;on ajoute 20 grs de soude caustique anhydre et on coule 80 grs d'anhydride butyricue,on procède ensuite comme pour l'exemple 8. On obtient une solution à 50% de butyrylaminoacides de kératine qui devra cpmporter 3 à 5% de propylèneglycol pour faciliter la solubilisation des butyrylvaline,leucine et isoleucine. 300 ml of keratin hydrolyzate are introduced into the reactor, 20 g of anhydrous caustic soda are added and 80 g of butyric anhydride are poured in, then proceed as for Example 8. A 50% solution is obtained % of keratin butyrylamino acids which should include 3-5% propylene glycol to facilitate the solubilization of butyrylvalin, leucine and isoleucine.
Poids obyenu en anhydre 87 grs
Rendement par rapport à
la théorie 96%
Analyse:Considérant un poids moléculaire moyen des acides aminés de 120,soit exprimé en Butyryl,de I9I,ce qui conduit à un azote théorique de 7,4. Azote trouvé: 8,2,chiffre superieur du à la présence de dibasiques.Indice d'acide trouvé: 287 (indice d' acide de la butyrylcystine: 294)
Exemple IO
Acide butyrylcaséinique
On effectue l'hydrolyse de 200 grs de Caséine,dans les mêmes conditions que celles des exemples 8 et 9,l'azote acylable est calculé par formol-titration, considérant que I ml de NaoK I N correspond à O gr I2 d'un acide aminé de poids moléculaire moyen de 120. Weight obtained in anhydrous 87 grs
Performance versus
theory 96%
Analysis: Considering an average molecular weight of amino acids of 120, ie expressed in Butyryl, of I9I, which leads to a theoretical nitrogen of 7.4. Nitrogen found: 8.2, higher figure due to the presence of dibasic agents. Acid index found: 287 (butyrylcystine acid index: 294)
IO example
Butyrylcaseinic acid
The hydrolysis of 200 g of casein is carried out, under the same conditions as those of examples 8 and 9, the acylable nitrogen is calculated by formol-titration, considering that I ml of NaoK IN corresponds to O gr I2 of an acid amine with an average molecular weight of 120.
On verse dans le réacteur 300 ml d'hydrolysat,correspon- dant approximativement à 41 grs d'acides aminés de P.r. moyen de I20.On introduit ensuite I5 grs de soude caustique anhydre et, goutte à goutte 60 grs d'anhydride butyrique.0n procède ensuite selon les exemples 8 et 9
Poids obtenu sur l'anhydre 63 grs
Rendement par rapport à
la théorie 95%
Analyse: Azote théorique 7,3, Azote trouvé: 8,2- Indice d'acide théorique 253, Indice d'acide trouvé: 260
A titre de produits industriels nouvezux,l'inventior s' étend à toutes compositions destinées à ètre utilisées chez lthomme,l'animal ou le végétal,carectérisées en ce qu'elles comportent comme principes actifs des butyrylaminoccides,issus de la combinaison de la chaine butyrique avec les acides aminés autres que les acides aminés soufrés,la proline,l'hydroxyproline et l'hydroxylysine,décrits dans d'autres brevets. 300 ml of hydrolyzate are poured into the reactor, corresponding to approximately 41 g of amino acids of average Pr of I20. We then introduce I5 gr of anhydrous caustic soda and, drop by drop 60 gr of butyric anhydride. then proceed according to examples 8 and 9
Weight obtained on anhydrous 63 grs
Performance versus
theory 95%
Analysis: Theoretical nitrogen 7.3, Nitrogen found: 8.2- Theoretical acid number 253, The acid number found: 260
As new industrial products, the invention extends to all compositions intended to be used in humans, animals or plants, characterized in that they contain as active principles butyrylaminoccides, derived from the combination of the chain butyric with amino acids other than sulfur amino acids, proline, hydroxyproline and hydroxylysine, described in other patents.
L'invention s'étend également à toutes covpositions destinéee à ètre utilisées chez l'homme,l'animal ou le végétal,caractérisf en ce que la chaine butyrique est combinée aux fonctions acylab des acides aminés,obtenus en mélange,par hydrolyse totale de n'i porte quelle protéine animale ou végétale. The invention also extends to all covpositions intended to be used in humans, animals or plants, characterized in that the butyric chain is combined with the acylab functions of the amino acids, obtained as a mixture, by total hydrolysis of i carry what animal or vegetable protein.
L'invention s'étend enfin,à toutes compositions comportant cc principes actifs ,les butyrylaminoacides issus des acides aminés pris individuellement,hormis les acides aminés soufrés,la prolir l'hydroxyproline et l'hydroxylysine ayant fait l'objet de brevet ou de mélanges d'acides aminés issus d'hydrolysats totaux de prc téines,dont les carboxyles rendus libres et actifs,sont salifié par des bases minérales, organiques ou biologiques ou encore par des métaux classés comme oligo-éléments. Finally, the invention extends to all compositions comprising cc active ingredients, butyrylamino acids derived from amino acids taken individually, apart from sulfur-containing amino acids, the proliferating hydroxyproline and hydroxylysine which have been the subject of patents or mixtures amino acids from total protein hydrolysates, including the free and active carboxyls, are salified by mineral, organic or biological bases or by metals classified as trace elements.
Dans le cadre de la présente invention,on entend,à titre d'exemples:
Par Bases minérales:potasse,soude,ammoniaque,chaux,magnésie
Par bases organiques: triéthanolamine ,diéthylamine ,morpholinr
etc..In the context of the present invention, the following are understood as examples:
By mineral bases: potash, soda, ammonia, lime, magnesia
By organic bases: triethanolamine, diethylamine, morpholinr
etc.
Par bases biologiques: arginine,lysine, ornithine,choline, g;ua
nidinet bétaine etc..By biological bases: arginine, lysine, ornithine, choline, g; ua
nidinet betaine etc ..
Par métaux: cuivre,cobalt,fer,manganèse,aluminium,zinc etc.. By metals: copper, cobalt, iron, manganese, aluminum, zinc etc.
A titre d'exemples non limitatifs de compositions comportant les dérivés butyryls,faisant l'objet de la présente invention, citons
I- Dans le domaine cosmétique et hygiénique
a) Crème acidifiante:
Butyrylglycocolle 2
Stéarine 5
alcool gras oxyéthyléné 5 Palmitate d'isopropyle IO
Glycérol IO
Conservateurparfum qs
Eau qs ICO
b) Crème de soin:
Acide butyrylcollagé
nique 2
excipient comme a)
c) Acide butyrylcaséinique I
Acide butyrylkératinique I
Excipient comme a)
d) Crème contre la transpiration:: Butyrylcollagénate d' alu-
minium 2
excipient comme a)
e) Pàte dentifrice
butyrylcoîl agénate de
calcium 3
Kaolin I7
Phosphate tricalcicue I7
Glycérol 10
Sorbitol IO
laurylsulfate ether 2
Conservateur,parfum qs
Eau qs 100 2- Dans le domaine thérapeutique: Ccmpositions dermatologiques:
a) acide butyrylcollagénique à
50% 5
Stéarate de glycérol IO Perhydrosqual ène IO
Glycérol 10
Conservateur qs
Eau as I00
b) Butyrylcollagénate de zinc 3
excipient comme a) 3- Dans le domaine agricole:
a) Traitement des semences et des racines: :
I) Acide butyrylkératinique à
50% 4
Bentonite 96
2) Butyrylcollagénate de Cuivre 2
Kaolin 98
3) Butyrylkératinate de cuivre 2
Eau 98
b) Traitement des feuilles:
I) Butyrylcollagénate de cuivre 2
Eau 98
2) Butyrylkératinate de zinc 2
Eau 98 By way of nonlimiting examples of compositions comprising the butyryl derivatives which are the subject of the present invention, let us cite
I- In the cosmetic and hygienic field
a) Acidifying cream:
Butyrylglycocolle 2
Stearin 5
oxyethylenated fatty alcohol 5 Isopropyl palmitate IO
Glycerol IO
Preservative perfume qs
Water qs ICO
b) Care cream:
Butyryl bonded acid
pic 2
excipient as a)
c) Butyrylcaseinic acid I
Butyrylkeratinic acid I
Excipient as a)
d) Cream against perspiration :: Aluminum butyrylcollagenate
minium 2
excipient as a)
e) Toothpaste
butyrylcoîl agenate
calcium 3
Kaolin I7
Tricalcium phosphate I7
Glycerol 10
Sorbitol IO
lauryl sulfate ether 2
Preservative, perfume qs
Water qs 100 2- In the therapeutic field: Dermatological compositions:
a) butyrylcollagenic acid to
50% 5
Glycerol stearate IO Perhydrosqual ene IO
Glycerol 10
Conservative qs
Water as I00
b) Zinc butyrylcollagenate 3
excipient as a) 3- In the agricultural field:
a) Seed and root treatment::
I) Butyrylkeratinic acid to
50% 4
Bentonite 96
2) Copper Butyryl Collagenate 2
Kaolin 98
3) Copper butyrylkeratinate 2
Water 98
b) Treatment of leaves:
I) Copper butyrylcollagenate 2
Water 98
2) Zinc butyrylkeratinate 2
Water 98
Claims (4)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8106593A FR2503144A1 (en) | 1981-04-02 | 1981-04-02 | Compsns. contg. N-butyryl alpha-aminoacid(s) - for cosmetic, hygienic, therapeutic or agricultural use |
| GB8208378A GB2097256B (en) | 1981-04-02 | 1982-03-23 | Compositions containing n-butyryl alphaaminoacids |
| DE3212448A DE3212448C2 (en) | 1981-04-02 | 1982-04-02 | Agents containing N-acylates of α-amino acids |
| US07/940,184 US4859653A (en) | 1981-04-02 | 1986-12-09 | Use of compositions of matter containing N-acylates of alpha aminoacids for the treatment of skin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8106593A FR2503144A1 (en) | 1981-04-02 | 1981-04-02 | Compsns. contg. N-butyryl alpha-aminoacid(s) - for cosmetic, hygienic, therapeutic or agricultural use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR2503144A1 true FR2503144A1 (en) | 1982-10-08 |
| FR2503144B1 FR2503144B1 (en) | 1984-09-14 |
Family
ID=9256907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR8106593A Granted FR2503144A1 (en) | 1981-04-02 | 1981-04-02 | Compsns. contg. N-butyryl alpha-aminoacid(s) - for cosmetic, hygienic, therapeutic or agricultural use |
Country Status (1)
| Country | Link |
|---|---|
| FR (1) | FR2503144A1 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2587173A1 (en) * | 1985-09-17 | 1987-03-20 | Mil Edmond De | PROCESS FOR INCREASING FLORAL FERTILITY OF PLANTS |
| FR2636238A1 (en) * | 1988-09-14 | 1990-03-16 | Morelle Jean | NEW ANTISUDORAL COMPOSITIONS |
| FR2669629A1 (en) * | 1990-11-22 | 1992-05-29 | Morelle Jean | New inhibitors of proteolytic and decarboxylase enzymes |
| FR2675015A1 (en) * | 1991-04-12 | 1992-10-16 | Astruc Jean | Compositions intended for protection and for elimination of human parasites, in particular Pediculus capitis and corporis, containing acetylpolyamino acids, extracts of Ginkgo biloba and Propolis |
| EP0601911A1 (en) * | 1992-12-09 | 1994-06-15 | Laboratoires Phytocos | Acylamino acids obtained by acylation of protein hydrolipates and antimicrobial, antiparasitic or cosmetic compositions containing them |
| WO1994026694A1 (en) * | 1993-05-17 | 1994-11-24 | Givaudan Lavirotte | Method for the preparation of n-acylated aminoacids |
| FR2705673A1 (en) * | 1993-05-25 | 1994-12-02 | Givaudan Lavirotte | Compositions comprising amino acid derivatives, methods for their preparation and uses thereof |
| FR2747309A1 (en) * | 1996-04-16 | 1997-10-17 | Morelle Jean | Compositions for treating burns and wounds with antimicrobial, anti-free radical and regenerating activity |
| FR2751177A1 (en) * | 1996-07-17 | 1998-01-23 | Morelle Jean | Compositions free from proteins and peptides |
| FR2771632A1 (en) * | 1997-12-01 | 1999-06-04 | Seppic Sa | Cosmetic compositions containing N-acyl amino acid and 1,2-diol |
| CN108029863A (en) * | 2018-01-19 | 2018-05-15 | 广州英赛特生物技术有限公司 | The application of butyryl glycine and its derivative in animal feed additive is prepared |
Citations (3)
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|---|---|---|---|---|
| GB644915A (en) * | 1946-07-13 | 1950-10-18 | Merck & Co Inc | Lower alkyl esters of n-acylamino aliphatic carboxylic acids |
| FR1518665A (en) * | 1966-10-13 | 1968-03-29 | New biological compositions intended for the care of human skin | |
| DE2559285A1 (en) * | 1975-01-02 | 1976-07-08 | Searle & Co | PROCESS FOR THE PREPARATION OF L-PHENYLALANINE ALKYLESTERS FROM THE CORRESPONDING DL-PHENYLALANINE ALKYLESTERS |
-
1981
- 1981-04-02 FR FR8106593A patent/FR2503144A1/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB644915A (en) * | 1946-07-13 | 1950-10-18 | Merck & Co Inc | Lower alkyl esters of n-acylamino aliphatic carboxylic acids |
| FR1518665A (en) * | 1966-10-13 | 1968-03-29 | New biological compositions intended for the care of human skin | |
| DE2559285A1 (en) * | 1975-01-02 | 1976-07-08 | Searle & Co | PROCESS FOR THE PREPARATION OF L-PHENYLALANINE ALKYLESTERS FROM THE CORRESPONDING DL-PHENYLALANINE ALKYLESTERS |
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| Title |
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| CA1959 * |
| CA1962 * |
| CA1964 * |
| CA1965 * |
| CA1980 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2587173A1 (en) * | 1985-09-17 | 1987-03-20 | Mil Edmond De | PROCESS FOR INCREASING FLORAL FERTILITY OF PLANTS |
| EP0218501A1 (en) * | 1985-09-17 | 1987-04-15 | Edmond De Mil | Process for causing the promotion of floral germination of plants |
| FR2636238A1 (en) * | 1988-09-14 | 1990-03-16 | Morelle Jean | NEW ANTISUDORAL COMPOSITIONS |
| DE3930638A1 (en) * | 1988-09-14 | 1990-04-12 | Jean Morelle | CONNECTIONS AGAINST EXCESSIVE SWEATING |
| FR2669629A1 (en) * | 1990-11-22 | 1992-05-29 | Morelle Jean | New inhibitors of proteolytic and decarboxylase enzymes |
| FR2675015A1 (en) * | 1991-04-12 | 1992-10-16 | Astruc Jean | Compositions intended for protection and for elimination of human parasites, in particular Pediculus capitis and corporis, containing acetylpolyamino acids, extracts of Ginkgo biloba and Propolis |
| EP0601911A1 (en) * | 1992-12-09 | 1994-06-15 | Laboratoires Phytocos | Acylamino acids obtained by acylation of protein hydrolipates and antimicrobial, antiparasitic or cosmetic compositions containing them |
| WO1994026694A1 (en) * | 1993-05-17 | 1994-11-24 | Givaudan Lavirotte | Method for the preparation of n-acylated aminoacids |
| FR2705341A1 (en) * | 1993-05-17 | 1994-11-25 | Givauban Lavirotte | Process for the preparation of N-acylated amino acid mixtures, N-acylated amino acid mixtures, and their uses |
| FR2705673A1 (en) * | 1993-05-25 | 1994-12-02 | Givaudan Lavirotte | Compositions comprising amino acid derivatives, methods for their preparation and uses thereof |
| WO1994027561A1 (en) * | 1993-05-25 | 1994-12-08 | Givaudan-Lavirotte | Compositions comprising amino acid derivatives, their methods of preparation and use |
| FR2747309A1 (en) * | 1996-04-16 | 1997-10-17 | Morelle Jean | Compositions for treating burns and wounds with antimicrobial, anti-free radical and regenerating activity |
| FR2751177A1 (en) * | 1996-07-17 | 1998-01-23 | Morelle Jean | Compositions free from proteins and peptides |
| FR2771632A1 (en) * | 1997-12-01 | 1999-06-04 | Seppic Sa | Cosmetic compositions containing N-acyl amino acid and 1,2-diol |
| CN108029863A (en) * | 2018-01-19 | 2018-05-15 | 广州英赛特生物技术有限公司 | The application of butyryl glycine and its derivative in animal feed additive is prepared |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2503144B1 (en) | 1984-09-14 |
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