Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
  • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
  • C07D253/06—1,2,4-Triazines
  • C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
• • 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
  • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
  • A61K8/4966—Triazines or their condensed derivatives
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
  • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
  • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
  • C07D253/06—1,2,4-Triazines
  • C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
  • C07D253/07—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members with hetero atoms, or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms

Definitions

• the present invention relates to derivatives of 5,6-diphenyl-1,2,4-triazine, and in particular to their use as sun filters on human skin and hair or as light-protecting agents in industry synthetic materials such as plastics, glasses, textiles.
• the present invention also relates to cosmetic compositions containing said derivatives. It will be recalled briefly that the action of solar radiation on the skin essentially depends on the energy of the radiations which reach the various skin layers. In general, the most energetic radiations, ie having the shortest wavelength (E ⁇ hc / ⁇ ), cause erythema or "sunburn", while the less energetic radiations only generate simple browning of the skin.
• UV-A, UV-B and UV-C allow browning of the human epidermis. UV-B causes erythema and skin burns which can affect the development of natural tanning.
• UV-A rays are capable of inducing an alteration of the skin, in particular in the case of sensitive skin or skin continuously exposed to solar radiation. UV-A rays cause in particular a loss of elasticity in the skin and the appearance of wrinkles, leading to premature aging. They trigger the erythematous reaction or amplify this reaction in certain subjects and can even cause phototoxic or photoallergic reactions. It is therefore desirable to also filter UV-A radiation. UV-C, the most energetic, creates photokeratites.
• UV-C UV-C radiation
• UV-B which penetrate into the skin layer and in particular into the mucous body of the epidermis, cause solar erythemas. Consequently, all of the radiation (UV-B + UV-C) constitutes what is called the erythemal band with regard to which the sun filters must play the role of screen.
• UV-A produces direct pigmentation of the skin (melanogenesis), ie browning of the skin.
• Compounds derived from benzotriazoles and / or benzothiazoles are known as UV filters, in particular in the cosmetic field.
• Patent application FR 2 803 194 thus describes derivatives of S-triazines carrying phenylbenzothiazole or benzothiazole groups which are useful as UV filters in particulate form. These compounds cover the UV-A and UV-B domain but they have the major drawback of absorbing in the visible (wavelengths greater than 400 nm). These products are therefore strongly colored, which limits their use in cosmetic products.
• the present invention provides new derivatives of 5,6-diphenyl-1,2,4-triazine capable of absorbing in the field of UV-A and / or UV-B and / or UV-C, without absorbing in the visible domain. These compounds therefore have the advantage of being slightly colored. They also have the advantage of being able to be specific to one of these spectral domains.
• UV-A, UV-B or UV-C UV-A, UV-B or UV-C
• UV-A, UV-B or UV-C UV-A, UV-B or UV-C
• the subject of the present invention is the use as active sun filters in PUV-A and / or UV-B and / or PUV-C for human skin and / or hair, of 5,6-diphenyl-1 compounds , 2,4-triazine compounds of general formula (I):
• the penetrating links in the cycle indicate an indifferent substitution position in ortho, meta or para
• - Ri and R 2 identical or different, represent a hydrogen, fluorine, chlorine or bromine atom, a linear or branched C1 to C 12 alkyl group, hydroxy, linear or branched C1 to C 18 alkoxy group, poly (ethoxy) -alkoxy with a C 1 to C 4 alkyl fragment and the number of ethoxy units between 1 and 4, amino, or mono- or di-alkylamino with a C 1 to C 4 alkyl fragment,
• R 3 represents a chlorine atom, a hydroxy, amino or phenyl group optionally substituted 1 to 3 times by a hydroxy radical located at least in the para position or phenyl optionally substituted 1 to 3 times in the ortho, meta or para position, with a alkoxy C 12 or cyano and alkylirnino group with an alkyl moiety to C 7.
• the present invention also relates to the use of the compounds as defined above as light-protecting agents active in UV-A and / or PUV-B and / or PUV-C, useful in the synthetic materials industry , in particular as light-protecting agents used in the composition of plastics, glass or textile materials. These compounds which are the subject of the present invention can thus be used to protect photosensitive materials.
• the light protection agent can be incorporated into a substratum in order to protect this substratum against attack by ultraviolet rays, to prevent the modification of one or more physical properties of this substratum, such as for example the discoloration, a change in tear resistance, an increase in brittleness, etc. and / or chemical reactions caused by ultraviolet rays, for example in an oxidation process.
• the protective agent can be incorporated before and during the preparation of the substratum, or subsequently by a suitable method, for example a fixing method analogous to a dyeing operation.
• the light protection agent can also be incorporated into a substratum to protect one or more other substances incorporated in said substrate, for example dyes, auxiliary agents, etc.
• the light protection agent can also be incorporated into a filter layer which may be solid (film, sheet) or semi-solid (cream, oil, wax), which is applied to a substrate, in order to protect the latter from ultraviolet rays.
• a filter layer which may be solid (film, sheet) or semi-solid (cream, oil, wax), which is applied to a substrate, in order to protect the latter from ultraviolet rays.
• the compounds of the present invention are suitable not only as light protection agents for colorless materials, but also for pigmented materials. In this case, the protection against light is also exerted on the dyes, thus allowing in many cases a quite notable improvement in the stability to light.
• the present invention also relates to the 5,6-diphenyl-1,2,4-triazine compounds of general formula (la): in which :
• - Ri and R represent a CH 3 O- group
• - R 3 represents: - a phenyl substituted one or more times by a hydroxy radical located at least in the para position, - a phenyl substituted in the ortho, meta or para position, by a radical selected from alkoxy or C 12 or cyano, - or an alkylimino group with an alkyl moiety to C.
• the following compounds have led to particularly advantageous practical results:
• Ri and R 2 represent a CH 3 O group located in the para position
• the present invention also relates to cosmetic sunscreen compositions containing an effective amount of at least one compound of formula (la) in association with a cosmetically acceptable excipient, preferably between 0.1 and 20% by weight relative to the total weight of the composition.
• the anti-sun cosmetic compositions according to the invention may also contain one or more complementary sun filters active in PUV-A and / or in UV-B and / or in PUV-C (absorbents), hydrophilic or lipophilic.
• additional filters can in particular be chosen from cinnamic derivatives, dibenzoylmethane derivatives, salicylic derivatives, camphor derivatives and triazine derivatives other than those previously mentioned in the present invention.
• the compounds of general formula (I) can be prepared from 1,2-diketones of formula (II), by conventional methods known to those skilled in the art, such as those described in the examples which follow.
• diketone (II) where Ri and R have the same meanings as those given above.
• the diketones of formula (II) are commercially available (such as, for example, benzil (diphenylethan-1,2-dione), 4,4'-dimethylbenzil, 4,4'-dibromobenzil, 4,4'-diflurorobenzil or 4 , 4'-dichlorobenzil) or can be synthesized by conventional methods well known to those skilled in the art. For example, the following synthetic route can be used:
• RI, R2 hydrogen, halogen, -OH, linear or branched alkoxy Ci -C 18 (such as -OMe), linear or branched C1-C ⁇ 2, mono or dialkylamino with an alkyl moiety -C to C (such as -N (Et) 2 ).
• alkoxy C 12 such as -OMe or - OC ⁇ 2 H 25
• a cyano, alkylimino with an alkyl moiety -C to C 7 such as - NCH (CH 2 ) 5 CH 3
• FIGURES are a diagrammatic representation of FIGURES.
• FIG. 1 shows the absorption spectrum and PUVA PUVB Parsol ® 1789.
• 2 shows the absorption spectrum and PUVA PUVB compounds JRI 8, JR70 and JR65 in comparison with that of Parsol MCX ®.
• FIG. 3 represents the absorption spectrum in PUVA and PUVB of the compounds JR89, JRI 15, JR63, JR67, JR68 and JR77.
• 4 shows the absorption spectrum of PUVA and PUVB JRI compounds 07, 13 and JRI JRI 14 in comparison with those of Tinosorb ® S and Tinosorb M ®.
• the spectral characteristics of the compounds in comparison with commercial filters at a concentration of 10 ⁇ g.ml "1 are grouped in Tables 2- 1 and 2-2.
• the specfres are carried out using a double beam spectrophotometer (Varian CARY 50 Scan) between 290 nm and 400 nm.
• Example 24 The tested products are classified according to the spectral distribution in PUVA and PUVB in a range going from 290 to 400nm. It is possible to differentiate them according to their spectral distribution: Narrow spectrum products: • Absorbent products in the area between 280 nm and 320 nm (UVB) • Absorbent products in the area between 320 nm and 400 nm ( UVA)
• Example 24-1 Spectral distribution of the compounds of formula (T)
• Parsol 1789 ® only absorbs in PUVA (see Figure 1).
• JRI 8, JR70, JR65, JRI 73 absorb in PUVB (see Figure 2).
• JR89, JRI 15, JR63, JR68 and JR77 absorb in PUVB (280 nm - 320 nm) and PUVA-II (280 nm - 340 nm) (see Figure 3).
• JR107, JRI 13, JRI 14, Tinosorb S ® and Tinosorb M ® absorb in PUVB and PUVA (see Figure 4).
• Example 25 Evaluation of the sun protection factor (SPF) in vitro in a chemical solvent or in a primary formula
• the in vitro methods for determining the protective efficacy of sun products consist in measuring, by transmission spectrophotometry, the absorption spectrum of the filter in solution or of the product applied to a substrate intended to simulate the relief of the skin.
• the effectiveness against UVB rays, UVA rays or both, or their effects on the skin response, are then determined by calculation, taking into account or not the spectrum of action of UV radiation for the damage considered.
• Example 25-1 Evaluation of the sun protection factor (SPF in vitro in a chemical solvent
• the Sayre / Agin and Diffey / Robson method recommends a comparative measurement, using an integrating sphere spectroradiometer, of the transition from 290 nm to 400 nm in 5 nm bands, l the sample being subjected to UV radiation from a stable and known source covering the entire UV spectrum (non-filtered xenon). Diffey and Robson to evaluate by calculation is the erythema response.
• the formula is as follows: 00 ⁇ E ( ⁇ ) ⁇ 290 FPS ⁇ -y ⁇ E (A) * g FPM ( ⁇ )
• N ( ⁇ ) number of values for a determined wavelength
• the Diffey and Robson formula made it possible to determine the FPS from the measurement of the fransmittance between 290 nm and 400 nm.
• the fransmittance is measured in solution in ethyl acetate at a concentration of 10 ⁇ g.ml "1 using a UV-visible spectrophotometer (Varian CARY 50 Scan).
• T ( ⁇ ) the transmittance at a wavelength ⁇
• T ( ⁇ ) the transmittance at a wavelength ⁇
• Example 25-2 Evaluation of the sun protection factor (SPF) in vitro in a primary formula for mixtures comprising compounds of formula (la) and reference products
• the Suntest allows to reproduce the solar specfre and thus to realize exposures in interior section in good time and without meteorological constraints.
• the DEM Minimum Erythemal Dose: The irradiance of the solar simulator was carefully measured with a spectroradiometer (MSS 2044, Bielefeld, Germany). The UVB and UVA intensities were 0.49 mW / cm 2 and 6.32 mW / cm 2, respectively .
• the DEM value defined by COLIPA is 5.6 J / cm 2 in total UV (22). Total UV (UVA + UVB) represents 14.8% of the energy delivered by the lamp (power 460W / m 2 ).
• An irradiation dose equivalent to 1 DEM corresponds to 37.83 J / cm 2 (in total specfre) delivered by the lamp.
• the setting of the DEM on the Suntest and the correspondence with the sunshine of 3 seaside stations are shown in Table 6.
• the solutions of compounds are prepared in a concentration of 500 ⁇ g / ml in methanol. 50 ⁇ L (ie 25 ⁇ g) of each of the solutions are deposited in crystallizers, then irradiated in the Suntest at 5, 10 and / or 20DEM. A non-irradiated control is prepared (deposit of 50 ⁇ L of solution and addition of 2,450 ml of methanol). The solvent evaporating during the irradiation, the products are taken up in 2.5 ml of methanol. After irradiation, the absorbance of each solution is measured using a UV-visible spectrophotometer (Varian CARY 50 Scan). The results of measurement of the photostability of the compounds of formula (I) are collated in Table 7.

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• Organic Chemistry (AREA)
• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Public Health (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Veterinary Medicine (AREA)
• Epidemiology (AREA)
• Birds (AREA)
• Dermatology (AREA)
• Cosmetics (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2004
  • 2004-05-05 FR FR0404810A patent/FR2869906B1/fr not_active Expired - Fee Related
• 2005
  • 2005-05-04 CA CA2564493A patent/CA2564493C/fr not_active Expired - Lifetime
  • 2005-05-04 AU AU2005251975A patent/AU2005251975B2/en not_active Ceased
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