LU83912A1 - APPLICATION OF BETA AMINO ENONES AS U.V.-A. RADIATION FILTERING AGENTS - Google Patents

Description

1283/81 LU 295 2.4546

"" ‘—Ji« RAND-DUCHÉ OF LUXEMBOURG

tN ° ...... Q o d! L

from 2 9.-4 year Vier ...... 1982 ... ÿèÊÈ Minister gÖsGjg of the Economy and the Middle Classes

Title issued ......................................... Intellectual Property Service

- LUXEMBOURG

Invention Patent Application I. Request ..The ..... public limited company called: L'OREAL, 14 rue Royale, 75008 ..... Paris .. * <d - ..Era.ri.ce * ..... rap.r.ë.s..eaté..e ..... by .... Moii.sieur Charles M un ç hen, c ojis..e. it.............

... patent s ... to ..... Luxe.fflb..Qurg. * .. en ...... gu al i té ..... de mandataire? ...... ................ (2) deposit (s) this v..lng.trne.uf ..... January ..... 19QQ. .gua..tr.e ..... v..in.gt.-d.eux ...................... (3) to. ..1.5..0.0 hours, at the Ministry of the Economy and the Middle Classes, in Luxembourg: 1. this request for obtaining a patent for invention concerning: "Application ...... d. .es ..... beta ..... friend no ..... ënones ..... like ..... agents ..... filtering ..... the (4) .. ........ ra d ù.'tùçm.s ...... U .... y .. * .- A ................ .................................................. .................................................. .................................................. ....................................

2. the delegation of power, dated. f.d RIS. »..... Er.a.n.CÊ ........... the 2.7 ...... j.an.V..î.e.r ...... 1.982 ..

3. description in language .... frÂ.n.Ç.al $ .. e ............................ ..... of the invention in two copies; 4. .................... drawing boards, in two copies; 5. receipt of taxes paid to the Luxembourg Registration Office, ie 2.9 ..... jmylar ...... 1.98.2 ................. .................................................. .................................................. .................................................. ............................................

declares (s) assuming responsibility for this declaration, that the inventor (s) is (are): ....................-.... ...... I ........................................... .................................................. .................................................. .................................................. ................................. (5) claims (s) priority for the above patent application one (s) request (s) from (6) .......................... n ./ “........ ............................................. filed in (7) ............................................... .................................................. ................

on ........................... zl.2 ................... .................................................. .................................................. .................................................. .................................................. ... (8) * on behalf of .....................- / -................ .................................................. .................................................. .................................................. ................................... (9) elect (elect) for him / her and, if appointed, for its representative, in Luxembourg ....................................

... XI &., ...... bo.ul. £ v.ä.rd ..,. Erince-.HßRr.i ................. .................................................. .................................................. .................................. (ίο) seeks (s) the grant of a patent for invention for the object described and represented in the annœp ^ above ^ ^^^ - ^ with deferment of this delivery to .d.î.X .. “.. b..Ult ............ ...............month. (11) II. Deposit Minutes

The aforementioned patent application has been filed with the Ministry of Economy and Middle Classes, Intellectual Property Service in Luxembourg, on: fj C I K 29 -January 1982 ®Pr. the Minister for the Economy and the Middle Classes, p., _ "t 3. t / 5 Vé

1283/81 - GS / MB

295

Public limited company called: L'OREAL

Application of beta amino enones as agents filtering CLV.-A. radiations

Invention of (j.

# 11 "<

Application to beta amino enones as U.V.-A. radiation screening agents

The invention relates to U.V.-A radiation absorbing agents and their use in various industries.

It is known that the absorbed light energy can cause a chemical transformation in the system which absorbs it.

Ultraviolet rays, which are short-wavelength radiation, are responsible for photochemical action on many organic products such as plastics, oils, dyes, etc.

These photochemical actions can consist in oxidation, polymerization, hydrolysis and in general cause the degradation or the modification of the molecule and can result in a change of structure or "aging" of the products having absorbed these radiations, such as cosmetic products, paints, plastics; the rancidity of oils, in particular vegetable oils such as walnut oil, sunflower oil; polymerization of unsaturated compounds such as linseed oil and the like.

It is also known that the UV rays of sunlight exert an action on human skin. This is how the UV-B rays whose wavelength is between 280. and 320 nm cause erythemas or even burns. However, UV-A rays having a wavelength of 320 to 400 nm which cause browning of the skin, at the same time cause an alteration of the latter and can negatively and durably influence the appearance and the condition of the skin and more particularly of sensitive skin or parts of the skin continuously exposed to these rays. These can cause pathological changes, for example dermatosis.

It has been found that U.V.-A rays can potentiate the action of U.V.-B rays as has been described by several groups of authors and more particularly by J.

Willis et al in "The Journal of Investigative Dermatology" / (volume 59, n ° 6, pages 416, 1073) under the name of Photo aug-y-Λ mentation. J! / »I 2

It is also known that the constituents used in cosmetic preparations and in particular in make-up products such as nail varnishes, lipstick sticks, anhydrous foundations or oily compositions do not always have sufficient stability to light and they degrade under the action of light radiation.

1 Other products and compositions containing dyes, oils, oxidizable products, undergo a modification under the action of UV rays.

Therefore, it is desirable to have agents absorbing UV-A radiations and to be able to protect the various products sensitive to these radiations as well as the skin by means of these agents and to be able to incorporate these agents filtering the radiations. or ü.V.-A rays to products, preparations and compositions sensitive to these radiations.

The Applicant has discovered that certain beta-amino enone derivatives absorb UV-A radiation and are suitable for the protection of various products and compositions sensitive to these radiations as well as for the protection of the skin.

The invention relates to the application of beta amino “s; enones of general formula:

R H

o vUl IV <E2 '· »1 <ch2) J (I) where R represents a linear or branched alkyl group having from 1 to 20 carbon atoms, linear or branched slenyl having from 1 to 20 carbon atoms, substituted aryl or unsubstituted, aralkyl. substituted or unsubstituted, a substituted or unsubstituted alicyclic group, or substituted or unsubstituted heterocycle / 1 (

* I

! 3 j I the nitrogen atom and the adjacent carbon atom a substituted or unsubstituted heterocycle containing from 5 to 20 and preferably from 6 to 16 carbon atoms and 1 nitrogen atom; R. ^ represents a hydrogen atom, a linear or branched alkyl group having from 1 to 20 carbon atoms or else forms with R a ring as defined above; m denotes 0 (zero) or an integer from 1 to 3; R2 represents a linear or branched alkyl group having from 1 to 4 carbon atoms or else forms an adjacent saturated ring or a substituted or unsubstituted aromatic ring; when m is greater than lfR2 can represent identical groups

I or different; n denotes 0 (zero) or an integer from 1 to 15-

The compounds of formula (I) above can also be represented by formula (II): Ιΐ R- ^ \ ^ H N0 [j— (R2 "m <CH2> n <">

The substituents keep the same values as those indicated for formula (I) „ICe are excellent filtering agents for ultraviolet radiation and more particularly for DV - AI radiation. They are liposoluble, that is to say soluble in oils. ,

Wax islands and other fatty substances. They can be advantageously combined with liposoluble UV-B radiation filtering agents. The invention also relates to the application of the J compounds of formula (I) or (II) as a filtering agent. ! UV radiation - A as well as the compositions containing these compounds as filtering agents - Another object of the invention consists of a process for the protection of various organic, natural or synthetic materials from ultraviolet radiation, including using these compounds of formula (I) - 11 /

I I

4

It is understood in the following description that when talking about the compounds of formula (I), we will also include the tautomeric form of these compounds of formula (II) above indicated.

The compounds of formula (I) filter UV radiation in the area between 320 and 370 nm (nanometer). These compounds of formula (I) used as an agent for screening out UV radiation can be prepared by two methods hereinafter called methods A and B, Method A.

(1) Preparation of 1-hydroxymethyl-2-cyclohexanone.

2 liters of anhydrous ethyl ether, 98 g of cyclohexanone, 111 g of ethyl formate and 23 g of sodium are placed in a 3-liter reactor.

The mixture is stirred, 5 ml of ethanol are added thereto to initiate the reaction and the temperature is maintained at 20 ° C. for 6 hours. We then give up resting overnight. The following day, 25 ml of ethanol are added, the mixture is stirred until the sodium has completely disappeared and 200 ml of water are added. The ethereal phase is decanted, washed with water, dried and concentrated under reduced pressure. The residue is distilled under reduced pressure (Eb ^ Qmm = 83-84 ° C). 96 g of 2-hydroxymethylene cyclohexanone are obtained with a yield of 76%.

(2) Preparation of 2-laurylaminomethylenecyclohexanone

38 g of 2-hydroxy-methylene cyclohexanone and 100 ml of ethyl ether are introduced into a 500 ml reactor. A solution containing 7 6.5 g of laurylamine in 100 ml of ethyl ether is added, the addition being carried out dropwise, so that the temperature of the reaction mixture does not exceed 35 ° C. The mixture is stirred for 15 minutes and the compound is precipitated by cooling. The precipitate is separated by filtration, washed with ether and 55% of this laurylaminomethyiene-2-cyclohexanone is obtained with a yield of 62%. /

Elementary analysis: / /,

Λ I

i 5 î Theory Found 1%% I C 77.75 77.87 I H 12.02 12.13! N 4.77 4.82 J Absorption U.V. (EtOH) ^ max = 328 nm (£ = 17180)

I Method B

1 Preparation of 1 '(oxo-2-cyclohexylidene) -2-aza-1-I. cyclotridecane ..

236.7 g of oxime of cyclododecanone, 480 ml of dry dichloroethane and 150 g of pyridine are placed in a 2-liter reactor. The solution is cooled to -10 ° C. and added to it. in the space of 15 minutes, 212 g of benzene sulfochloride and I the reaction is maintained for 2 hours at 0 ° C.- I 600 g of 1-lino-1-cyclohexene is then added at this temperature. For 30 minutes, the reaction mixture is warmed to 30 ° C. and stirred at this temperature i for approximately 20 hours. I The reaction mixture is then hydrolyzed for 4 hours at 20 ° C. using 150 ml of 'Acetic acid 50%, i then added 1.2 liters of NaOH 6N. The mixture is decanted, the aqueous phase is treated with dichloroethane and the organic extracts are washed with water, dried over sodium sulfate and concentrated to dryness. The residue is distilled in vacuo (EbQ 5mm = 180-195 ° C) "i Obtain, with a yield of 70%, 233 g of 1 '(oxo-2-cy-" clohexylidene) -2-aza-1-cyclotridecane.

I Elementary analysis:, 1. Theory Found i%% CI 77.90 C 77.99 i H 11.19 H 11.24 1 N 5.05 N 5.16 I By the process (A) above indicated I is also prepared N (trimethyl -2,4,6-anilino) methylene-2-cyclohexanone and the: I cyclohexylamino-methylene-2-cyclohexanone "î By process (B) above, the / bxo-2-cyclojae- I xylidene is prepared. 2 aza-l-cycloheptane "/ / Ψ 6

The characteristics of the beta amino enones prepared are shown in Table I below.

These characteristics are: (1) structural formula, (2) gross formula and molecular weight, (3) elementary analysis: percentage C, H, N theorigue and found, (4) preparation process A or B, (5) length d 'wave corresponding to the maximum absorption (Λ max), expressed in nanometers, (6) molar extinction coefficient (£)' (7) solvent used, ji 7 SS tu -Γ1 pj PP OR o

H H H S

W W W U W

II | ° ο ο Ο o MJ 00 vo -et so vb

* - · Ό i — I SD

O cm m in

^ <N CS t — I rH

X

CD

Ë Q 'Ë oo os «t O r- N <^ C cs es co <t co s-—' co co co co <o c 0) o α · η

’4D

CP "α vj g <<<m pq O vl) tu u

FW FW

<u l ·) VU n- co M cn cn r-H 00 Os Os -tO l— cn in

• H> 00 r — I CO Γ ^ Γ> · Γ> · O ls VÛ OscnJi-I <f 00 H

COO “·> * --- - - - - - - -ti O t'- es) -t mosvo οι oo in r—” —i <f σι n C Fi r- 'i — t r' 'r- »Ir · -

0) AJ

B

seen H <- <_____ VD ---— —-! => m n η- OO P os η- O m cn m <! <u o) O r-- so ’osr ^ -r ^. ® η o γ-h m PQ cn-r) - - - - "- - - -„ in Cn cs> - <to Pi cs -t in P so cn co m in h in - - -

FprWO r ^ i-i Γ '-'- 1 n. c ^ tw sf osn <co vu r-- H ti Xi & -? & £ $ £ Β-Ϊ BS Β-Ϊ BS BS BS „„ <* j owa ο κ jg ü sg bwfe ^ UK g (UI 4J o D ü Fl VU Λ τ-Ι 2 0 is ja ω 6 ΐδ ο.ο Ο Ο τ ί ΙΠ τ—! »7 g» g iJ0 <Ν ΓΟ ^ rW. In F 2 Η W "W" es co co - t iH co ^ • rjv-i σ \ en mr * · ju «a ^ · wi OO flj r-1 θ '* r-iO VO CO CO Γ -' * cslro

FwFW-i O cS U es h 3 H n SS

O CS O CS u «-S

CO

K

o τ-S co î f Q àr, “9 = P> σ o S J g J3-0 7 ® é s \ - -Λ” - ° -v U3aMaw 8

The present invention also relates to the compositions containing at least one beta amino enone of formula (I) or (II) associated with an agent absorbing UV-B radiation of wavelength between 290 and 320 nm as well as possibly other UV-A absorbing agents. It is thus possible to obtain compositions filtering all of the UV-B and UV "-A" radiation. As an agent absorbing UV-B radiation, mention may be made of salicylic acid derivatives such as the salicy-late of 2 -ethyl-hexyl, homomenthyl salicylate, cinnamigue acid derivatives such as ethylhexyl-p-methoxy-cinnamate, 2-ethoxyethyl ~ p-methoxycinnamate, paraaminobenzoic acid derivatives such as paradimethylamino and amyl paraaminobenzoate, 2-ethyl hexylparadimethylamino-benzoate, benzophenone derivatives such as 2-hydroxy 4-methoxybenzophenone, 2,2'-dihydroxy 4-methoxybenzophen-none, camphor derivatives such as benzylidene camphor, (4-methylbenzylidene) -3 camphor optionally combined with 4-isopropyl-dibenzoylmethane, and liposoluble derivatives described in French patent application 2,383-904.

As fatty substances which can be combined with the compound of formula (I) or (II) according to the invention, mention may be made of mineral oils such as petrolatum oil or petro-latum, animal oils such as whale, drug, menhaden, halibut, cod liver, tuna, turtle, tallow, ox's foot, horse's foot, sheep's foot, mink, otter, groundhog and similar oils; vegetable oils such as almond, peanut, wheat germ, flax, apricot kernel, walnut, palm, pistachio, sesame, flaxseed, pine, castor oil , soy, avocado, safflower, coconut, hazelnut, olive, grape seed, sunflower, rapeseed, cade, corn germ, peach kernels, coffee, jojoba and similar oils; fatty acid glycerides such as fatty acid triglycerides having 6 to 12 carbon atoms, and concrete triglycerides at 25 ° C; fatty acid esters such as isopropyl esters of, /

U

. f '· i

U

; i, i 9 I myristic, palmitic and stearic acids, concrete fatty esters at 25 ° C; ozokerite, petrolatum, paraffin, lanolin, hydrogenated lanolin, acetylated lanolin, waxes such as lanolin wax, beeswax, candellila wax, microcrystalline wax, carnauba wax, spermaceti, cocoa butter, shea butter, silicone waxes such as methyloctade-cane-oxypolysiloxane and poly (dimethylsiloxy) stearoxysiloxane, hydrogenated oils concrete at 25 ° C; the sugar glycerides; the oleates, myristates, lanolates and stearates of Ca, Mg, Zr and Allés compositions according to the invention can be in various forms, in particular of solution, oily lotion, fatty gel, ointment and can be provided in the form of 'aerosol.

When the composition according to the invention is a cosmetic composition it can be used as a composition intended to protect the human epidermis against ultraviolet rays.

The cosmetic composition according to the invention can also be presented in other forms, in particular as an oily washing composition for the hair or the body, a make-up product such as a nail varnish, lipstick stick, background. complexion.

The cosmetic compositions according to the invention may contain adjuvants usually used in cosmetics, in particular thickeners, softeners, superfats, emollients, preservatives, antioxidants, perfumes, dyes, pigments, cosmetical polymers, oil-soluble surfactants.

The compounds of formula (I) or (II) are generally present in the compositions according to the invention in proportions by weight of 0.05 to 15% and preferably from 0.5 to 10%.

I The subject of the invention is also a method of protecting the human epidermis against UV rays, characterized in that a compound of formula 10 is applied to the skin (I) or (II) optionally combined with other agents absorbing U ”V” -A and / or U * V ”-B” rays. The invention also relates to a process for the protection of natural or synthetic organic materials consisting in incorporating them at least one compound of formula (I) or (II) or to associate them with such a compound * Among the materials which can be protected by compounds (I) or (II), mention may be made of synthetic plastics, edible oils such as as for example walnut oil, sunflower oil, as well as other oxidizable oils "The invention is illustrated by the nonlimiting application examples below" //

have

11 APPLICATION EXAMPLES Example 1; sun oil / oxo-2 cyclohexylidene. 7-2-aza-l cyclotridecane 4 g Benzylidene-3 camphor 3 g

Antioxidants q „s„ (sufficient quantity)

Perfume 0.5 g

Rapeseed oil q.s.p * 100 g * Example 2: solar stick / oxo-2-cyclohexylidene7-2-aza-l cycloheptane 2.5 g p-2-ethylhexyl methoxycinnamate 2.5 g

Cocoa butter 12 g

Ozokerite wax 8 g! Paraffin 3 g

Coffee oil 10 g

Lanolin 10 g

Antioxidants q „s„

Perfume 0.5 g

Vaseline oil q.s.p. 100g

Example 3; Sun ointment

Laurylaminomethylene-2-cyclohexanone 5 g

Octyl dimethyl p-aminobenzoic acid 4 g

Cocoa butter 10 g

Coconut oil 15-g. Shea butter 3 g

White petrolatum 45 g, Ozokerite wax 3 g

Antioxidants q.s.

I Perfume 1 g

Rapeseed oil q-s * p. 100g

EXAMPLE 4 Sun gel N / 2,4,4,6 anilino / methylene-2-cyclohexanone 3,5 g

White Vaseline 20 g

Silica 2 g

Magnesium stearate 10 g

Liquid Lanolin 3 g

Coffee oil 8 g 12

Benzylien-3 camphor 2.5 g

Perfume 1 g

Vaseline oil q-s.p. 100g

Example 5

This example is identical to Example 4 except that the 3.5 g of N (2,4,6,6-anilino) methylene-2 cyclohexanone are replaced by the same weight of 1 '(oxo-2-cyclohexylidene) -> 2-aza 1-cyclotridecane *

EXAMPLE 6 Sun Gel

Cyclohexylamino methylene-2-cyclohexanone 2.5 g

White Vaseline 30 g

Silica 3 g

Magnesium stearate 12 g

Liquid lanolin 1 g

Canola oil 12 g 2-ethylhexyl p-methoxy cinnamate 4.5 g

Preservatives q „s * /

Vaseline oil q.s-p- 100 g- / · /

T

Claims (14)

13 *! CLAIMS j - I! 1. Composition characterized in that it contains as a protective agent against light radiation, and in particular against ü „V„ -A rays at least one beta-amino enone of general formula: R .H '' u / O AA IV (R2> m L <CH2> £ (D can also be represented by the following tautomer formula: RH \ ^ • N 0 'ch2i; (II) where R represents a linear or branched alkyl group having from 1 to 20 atoms carbon, linear or branched alkenyl having from 1 to 20 carbon atoms, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, a substituted or unsubstituted alicyclic group, a substituted or unsubstituted heterocyclic group; R may also form with R ^ as well as with the nitrogen atom and the adjacent carbon atom a substituted or unsubstituted ring containing from 5 to 20 and preferably from 6 to 16 carbon atoms and one nitrogen atom; R ^ represents a hydrogen atom, a linear or branched alkyl group having from 1 to 20 carb atoms one or R ^ forms with R a cycle as defined above; m denotes zero or an integer from 1 to 3; R2 represents a linear or branched alkyl group having 1 to 4 carbon atoms or forms an adjacent saturated or substituted or unsubstituted aromatic ring; when m is greater than 1, can represent identical groups or! h different; / / * I 14 * n denotes zero or an integer from 1 to 15. 2. Cosmetic composition, characterized in that it contains as a protective agent against light radiation and in particular against UV rays. At least one beta amino enone of formula (I) or (II), according to claim 1. 3. Composition according to claims 1 and 2, characterized in that R denotes a substituted phenyl, lauryl, cyclohexyl or else, form with a heterocycle, aza-1 cyclotridecane or aza-1 cycloheptane. 4. Composition according to claims 1 or 2, characterized in that the compound of formula (I) is chosen from the group formed by laurylaminomethylene-2-cyclohexa-none, N (2,4,6-anilino trimethyl) methylene -2 cyclohexanone, cyclohexylamino methylene-2 cyclohexanone, 2 / oxo-2 cyclohexylidene7-2 aza-1 cyclotridecane, ^ 2-xo-2 cyclohexylidene7 * -2 aza-1 cycloheptane. 5. Composition according to any one of claims 1 to 4, characterized in that the compound of formula (I) or (II) is present in proportions of between 0.05 and 15% of the total weight of the composition. 6. Composition according to any one of claims 1 to 5, characterized in that it also contains. other liposoluble sun filters having a filtering action against UV radiation. 7. Composition according to any one of claims 1 to 6, characterized in that it also contains at least one fatty substance. 8. Composition according to Claim 7, characterized in that the fatty substance is chosen from: mineral-mineral oils, animal oils, vegetable oils, triglycerides of fatty acids having 6 to 12 carbon atoms, concrete triglycerides at 25 ° C; fatty acid esters, concrete fatty esters at 25 ° C; waxes, silicone waxes, hydrogenated oils concrete at 25 ° C, sucroglycerides; , oleates, myristates, lanolates and stearates of Ca, Mg, Zrj and Al. (.1 (f 15 * - »« 9. Cosmetic composition according to any one of claims 2 to 8, characterized in that it constitutes a sunscreen composition and that it is in the form of an oily solution or lotion, fatty gel or ointment, optionally packaged in aerosol. 10. Composition according to any one of claims 2 to 9, characterized in that it contains at least one cosmetic adjuvant chosen from thickeners, softeners, superfatters, emollients, * preservatives, perfumes, dyes , pigments, cosmetic polymers, oil-soluble surfactants. 11. Composition according to any one of claims! i 1 to 10, in the form of a colored cosmetic composition stabilized in light, characterized in that it consists of an oily washing composition for the hair or the body, a makeup product such as a varnish nail polish, lipstick concrete, or foundation. 12. A method of protecting the human epidermis against UV rays, characterized in that a compound of formula (I) or (II) according to claim 1, contained in a cosmetically acceptable medium. - 13. Process for the protection of natural organics. binders or synthetics, characterized in that there is incorporated in them an appropriate amount of at least one compound of j formula (I) or (II) according to claim 1. [14. Method according to claim 13, characterized by J organic matter is synthetic plastic. 15. The method of claim 13, characterized by the If has that the organic material is an oil. Drawings! - ^ L_ boards, - paaes of which —Λ ~~ cover page ^ V ~ pages of description 3. rs of claims - a ....... description tUXrr.hOîî'g, * 3 li 's Charles München