阅读说明：本技术 光稳定剂化合物、组合物和方法 (Light stabilizer compounds, compositions and methods ) 是由 C·A·邦达 于 2019-06-13 设计创作，主要内容包括：提供了杂环化合物。特别地,所述杂环化合物的杂原子可以是氮。所述杂环化合物可表现出稳定光敏化合物的能力。也提供了包含这些杂环化合物的局部组合物。特别地,这些局部组合物进一步包含光敏化合物。也提供了稳定光敏化合物的方法。这些方法包括将光敏化合物与光稳定剂杂环化合物混合。(Heterocyclic compounds are provided. In particular, the heteroatom of the heterocyclic compound may be nitrogen. The heterocyclic compound may exhibit the ability to stabilize the photosensitive compound. Topical compositions comprising these heterocyclic compounds are also provided. In particular, these topical compositions further comprise a photoactive compound. Methods of stabilizing photosensitive compounds are also provided. These methods include mixing a photosensitive compound with a light stabilizer heterocyclic compound.)

1. A heterocyclic compound having a structure according to formula I:

wherein A is¹、A²、A³、A⁴、A⁵、A⁶、A⁷And A⁸Each independently selected from CR³And N;

wherein R is³Selected from H, OH, a straight or branched chain alkyl group having from about 1 to about 20 carbon atoms, an alkoxy group having from about 1 to about 20 carbon atoms, an alkenyl group having from about 2 to about 20 carbon atoms, an alkynyl group having from about 2 to about 20 carbon atoms, and an aryl group having from about 6 to about 20 carbon atoms;

wherein A is¹、A²、A³、A⁴、A⁵、A⁶、A⁷And A⁸At least one of (a) is N;

wherein A is¹、A²、A³、A⁴、A⁵、A⁶、A⁷And A⁸Up to 4 of is N;

wherein R is¹And R²Each independently selected from CN, C (= O) OR⁴、C(=O)R⁴、F、CF₃Provided that R is¹And R²Are not all CN;

wherein R is⁴Selected from the group consisting of H, alkyl groups having from about 1 to about 20 carbon atoms, alkenyl groups having from about 2 to about 20 carbon atoms, alkynyl groups having from about 2 to about 20 carbon atoms, and aryl groups having from about 6 to about 20 carbon atoms.

2. The heterocyclic compound of claim 1, wherein R³Selected from H, straight chain having from about 1 to about 20 carbon atomsOr a branched alkyl group and an alkoxy group having from about 1 to about 20 carbon atoms.

3. The heterocyclic compound of claim 2, wherein R³Selected from H and straight or branched chain alkyl groups having from about 1 to about 20 carbon atoms.

4. The heterocyclic compound of claim 1, wherein R³Selected from H and a linear or branched alkyl group selected from methyl, ethyl, propyl, butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, pentyl, 2-methyl-2-butyl, hexyl, heptyl, octyl, decyl or dodecyl.

5. The heterocyclic compound of claim 1, wherein R¹And R²Each independently selected from CN and C (= O) OR⁴。

6. The heterocyclic compound of claim 5, wherein R¹And R²One is CN.

7. The heterocyclic compound of claim 5, wherein R⁴Is a straight or branched chain alkyl group having from about 1 to about 20 carbon atoms.

8. The heterocyclic compound of claim 5, wherein R⁴Is a straight or branched chain alkyl group having at least 8 and at most 12 carbon atoms.

9. The heterocyclic compound of claim 5, wherein R⁴Is a straight or branched chain alkyl group having 8 carbon atoms.

10. The heterocyclic compound of claim 1, wherein the compound is selected from the group consisting of:

。

11. the heterocyclic compound of claim 10, where the compound has a structure according to the following formula:

。

12. a composition comprising at least one heterocyclic compound having a structure according to formula I:

wherein A is¹、A²、A³、A⁴、A⁵、A⁶、A⁷And A⁸Each independently selected from CR³And N;

wherein R is³Selected from H, OH, straight or branched chain alkyl groups having from about 1 to about 20 carbon atoms, alkoxy groups having from about 1 to about 20 carbon atoms, alkenyl groups having from about 2 to about 20 carbon atoms, alkynyl groups having from about 2 to about 20 carbon atoms, aryl groups having from about 6 to about 20 carbon atoms;

wherein A is¹、A²、A³、A⁴、A⁵、A⁶、A⁷And A⁸At least one of (a) is N;

wherein A is¹、A²、A³、A⁴、A⁵、A⁶、A⁷And A⁸Up to 4 of is N;

wherein R is¹And R²Each independently selected from CN, C (= O) OR⁴、C(=O)R⁴、F、CF₃Provided that R is¹And R²Are not all the CN, but are all the CN,

wherein R is⁴Selected from the group consisting of H, straight or branched chain alkyl groups having from about 1 to about 20 carbon atoms, alkenyl groups having from about 2 to about 20 carbon atoms, alkynyl groups having from about 2 to about 20 carbon atoms, aryl groups having from about 6 to about 20 carbon atoms.

13. The composition of claim 12 wherein the heterocyclic compound is present in an amount of 0.01 to 25 weight percent of the total composition.

14. The composition of claim 12, further comprising at least one photosensitive compound.

15. The composition of claim 14, wherein the photosensitive compound is selected from the group consisting of retinoids, sunscreens, or mixtures thereof.

16. The composition of claim 15, wherein the photosensitive compound is a retinoid.

17. The composition of claim 16 wherein the retinoid is present in an amount from about 0.0001 to about 20% by weight of the total composition.

18. The composition of claim 15, wherein the photosensitive compound is a sunscreen.

19. The composition of claim 18, wherein the sunscreen agent is selected from the group consisting of UVA chemical sunscreen agents, UVB chemical sunscreen agents, physical sunscreen agents, and mixtures thereof.

20. The composition of claim 19, wherein the sunscreen is a UVA chemical sunscreen.

21. The composition of claim 20, wherein the UVA chemical sunscreen is present in an amount from about 0.001 to about 20% by weight of the total composition.

22. The composition of claim 19, wherein the sunscreen is a UVB chemical sunscreen.

23. The composition of claim 22 wherein the UVB chemical sunscreen is present in an amount of about 0.001 to about 45% by weight of the total composition.

24. The composition of claim 14, further comprising at least one ingredient selected from the group consisting of oils, surfactants, humectants, plant extracts, particulate materials, antioxidants, and other vitamins.

25. A method of stabilizing a photosensitive compound comprising mixing at least one photosensitive compound with at least one heterocyclic compound having a structure according to formula I:

wherein A is¹、A²、A³、A⁴、A⁵、A⁶、A⁷And A⁸Each independently selected from CR³And N;

wherein R is³Selected from H, OH, straight or branched chain alkyl groups having from about 1 to about 20 carbon atoms, alkoxy groups having from about 1 to about 20 carbon atoms, alkenyl groups having from about 2 to about 20 carbon atoms, alkynyl groups having from about 2 to about 20 carbon atoms, aryl groups having from about 6 to about 20 carbon atoms;

wherein A is¹、A²、A³、A⁴、A⁵、A⁶、A⁷And A⁸At least one of (a) is N;

wherein A is¹、A²、A³、A⁴、A⁵、A⁶、A⁷And A⁸Up to 4 of is N;

wherein R is¹And R²Each independently selected from CN, C (= O) OR⁴、C(=O)R⁴、F、CF₃Provided that R is¹And R²Are not all the CN, but are all the CN,

wherein R is⁴Selected from the group consisting of H, straight or branched chain alkyl groups having from about 1 to about 20 carbon atoms, alkenyl groups having from about 2 to about 20 carbon atoms, alkynyl groups having from about 2 to about 20 carbon atoms, aryl groups having from about 6 to about 20 carbon atoms.

Technical Field

The present disclosure is in the field of compounds that stabilize chemical sunscreen agents or other photosensitive compounds, and related compositions and methods.

BACKGROUND OF THE DISCLOSURE

Photosensitive compounds are widely used. For example, sunscreens are photoactive compounds. The most widely used UVA and UVB filters in sunscreens are Avobenzone (Avobenzone) (butyl methoxydibenzoylmethane) and octoxinol (Octoxinate) (ethylhexyl methoxycinnamate). While avobenzone and octocinoxate (Octinoxate) effectively block UVA and UVB radiation, respectively, they both degrade upon exposure to UV light. On exposure to UV light, the oxcinolate sometimes forms dimers with other oxcinolate molecules. These dimers no longer absorb UVB and lose UVB potency. The oxcinonide also reacts with the double bond of the predominant form of avobenzone to form cyclobutane, which then forms a ring-opened structure. With consequent loss of UVA efficacy.

Retinoids are also light-sensitive compounds. Upon exposure to UV light, retinoids undergo photoreactions such as photoisomerization, photopolymerization, photooxidation, and photodegradation. The photodecomposition products produced do not have the same level of biological activity. As a result, biological effectiveness is lost.

Light stabilizers, such as N-cyanodiphenylacrylates, such as Octocrylene (2-ethylhexyl 2-cyano-3, 3-diphenylacrylate), are known to inhibit UV-induced photodegradation of avobenzone. When avobenzone absorbs a photon of UV light, its electron enters a triplet energy state, which can lead to photo-degradation of avobenzone. Octocrylene is able to accept triplet excited state energy and restore avobenzone to its original unexcited state. However, when present, oxcinonide sometimes receives triplet excited state energy from avobenzone and then reacts with the double bond present in the predominant form of avobenzone. Therefore, octocrylene is sometimes, but not always, effective in achieving its intended purpose.

It is critical to address the problem of instability of photosensitive compounds. Sunscreens such as avobenzone and oxcinolate are widely used. In particular, avobenzone is one of the few UVA sunscreens approved for global use in sunscreen products. Retinoids are also promising for their biological benefits and potency. In particular, retinol is an important regulator in epidermal cell growth, normal cell differentiation and cell maintenance.

The present disclosure relates to heterocyclic compounds, compositions comprising these heterocyclic compounds, and related methods for stabilizing photosensitive compounds, which may include chemical sunscreens, such as avobenzone or oxcinoxate, among others, as well as other unstable compounds, such as retinol.

Summary of the disclosure

The present disclosure relates to heterocyclic compounds having a structure according to formula I:

in one embodiment, A is¹、A²、A³、A⁴、A⁵、A⁶、A⁷And A⁸Each independently selected from CR³And N.

In one aspect, R³Selected from H, OH, straight or branched chain alkyl groups having from about 1 to about 20 carbon atoms, alkoxy groups having from about 1 to about 20 carbon atoms, alkenyl groups having from about 2 to about 20 carbon atoms, alkynyl groups having from about 2 to about 20 carbon atoms, and aryl groups having from about 6 to about 20 carbon atoms. Preferably, R³Selected from H, having a largeA straight or branched alkyl group of from about 1 to about 20 carbon atoms, an alkoxy group having from about 1 to about 20 carbon atoms. More preferably, R³Selected from H, linear or branched alkyl groups having from about 1 to about 20 carbon atoms. Most preferably, R³Selected from H and straight or branched alkyl groups selected from methyl, ethyl, propyl, butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, pentyl, 2-methyl-2-butyl, hexyl, heptyl, octyl, decyl or dodecyl.

In an alternative embodiment, A¹、A²、A³、A⁴、A⁵、A⁶、A⁷And A⁸Each independently selected from CH and N.

In one embodiment, at least one of a1, a2, A3, a4, a5, a6, a7, and A8 is N. In another embodiment, up to 4 of a1, a2, A3, a4, a5, a6, a7, and A8 are N.

In one embodiment, R¹And R²Each independently selected from CN, C (= O) OR⁴、C(=O)R⁴、F、CF₃. In one aspect, R¹And R²Not all CN. Preferably, R¹And R²Each independently selected from CN and C (= O) OR⁴. More preferably, R¹And R²One is CN.

In one aspect, R⁴Selected from the group consisting of H, straight or branched chain alkyl groups having from about 1 to about 20 carbon atoms, alkenyl groups having from about 2 to about 20 carbon atoms, alkynyl groups having from about 2 to about 20 carbon atoms, and aryl groups having from about 6 to about 20 carbon atoms. Preferably, R⁴Is a straight or branched chain alkyl group having from about 1 to about 20 carbon atoms. More preferably, R⁴Is a straight or branched chain alkyl group having at least 8 and at most 12 carbon atoms. Most preferably, R⁴Is a straight or branched chain alkyl group having 8 carbon atoms.

In one embodiment, examples of the compound include, but are not limited to, compounds 1-8. The compound is preferably compound 1.

The present disclosure also relates to compositions comprising at least one heterocyclic compound having a structure according to formula I.

In one embodiment, the composition comprises a heterocyclic compound present in an amount of 0.01 to 25% by weight of the total composition. Preferably, the heterocyclic compound is present in the composition in an amount of 0.05 to 15% by weight of the total composition. More preferably, the heterocyclic compound is present in the composition in an amount of 0.1 to 5% by weight of the total composition.

In one embodiment, the composition further comprises at least one photoactive compound. Preferably, the photosensitive compound is selected from a retinoid, a sunscreen, or a mixture thereof.

In one aspect, the photosensitive compound is a retinoid. Preferably, the retinoid is retinol.

In one aspect, the retinoid is present in an amount from about 0.0001 to about 20% by weight of the total composition. Preferably, the retinoid is present in an amount from about 0.001 to about 10% by weight of the total composition. More preferably, the retinoid is present in an amount from about 0.01 to about 8% by weight of the total composition. Most preferably, the retinoid is present in an amount from about 0.05 to about 5% by weight of the total composition.

In one aspect, the photoactive compound is a sunscreen. Preferably, the sunscreen agent is selected from the group consisting of UVA chemical sunscreens, UVB chemical sunscreens, physical sunscreens and mixtures thereof.

In an alternative aspect, the sunscreen is a UVA chemical sunscreen. Preferably, the UVA chemical sunscreen is selected from dibenzoylmethane compounds and dicamphor sulfonic acid derivatives. More preferably, the UVA chemical sunscreen is selected from dibenzoylmethane compounds. Examples of dibenzoylmethane compounds include, but are not limited to, 4-methyldibenzoylmethane, 2-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, 2, 4-dimethyldibenzoylmethane, 2, 5-dimethyldibenzoylmethane, 4' -diisopropylbenzoylmethane, 4-tert-butyl-4 ' -methoxydibenzoylmethane, 4' -diisopropylbenzoylmethane, 2-methyl-5-isopropyl-4 ' -methoxydibenzoylmethane, 2-methyl-5-tert-butyl-4 ' -methoxydibenzoylmethane. Most preferably, the UVA chemical sunscreen is avobenzone.

In an alternative aspect, the UVA chemical sunscreen is present in an amount from about 0.001 to about 20% by weight of the total composition. Preferably, the UVA chemical sunscreen is present in an amount of from about 0.005 to about 5% by weight of the total composition. More preferably, the UVA chemical sunscreen is present in an amount of from about 0.005 to about 3% by weight of the total composition.

In an alternative aspect, the UVA chemical sunscreen is avobenzone and is present in up to about 3% by weight of the total composition.

In an alternative aspect, the sunscreen agent is a UVB chemical sunscreen agent. Preferably, the UVB chemical sunscreen is selected from the group consisting of α -cyano- β, β -diphenylacrylate, benzylidenecamphor derivatives, cinnamate derivatives, benzophenone derivatives, menthyl salicylate derivatives, aminobenzoic acid derivatives, salicylate derivatives, and esters of 2-phenylethanol and benzoic acid. More preferably, the UVB chemical sunscreen is selected from octocrylene, 4-methylbenzylidene camphor, octocinoxate, Cinoxate (Cinoxate), benzophenone 3, sulindac (Sulisobenzone), sulindac Sodium (sulindac Sodium), homosalate, ethylhexyl p-dimethylaminobenzoate, ethyl p-dihydroxypropylaminobenzoate, octyl salicylate, TEA-salicylate, DEA-salicylate, phenethylbenzoate. More preferably, the UVB chemical sunscreen is selected from octocrylene, 4-methylbenzylidene camphor, octocinol, benzophenone 3, homosalate, ethylhexyl p-dimethylaminobenzoate, octyl salicylate. Most preferably, the UVB chemical sunscreen is oxcinol ester.

In an alternative aspect, the UVB chemical sunscreen is present in an amount of about 0.001 to about 45% by weight of the total composition. Preferably, the UVB chemical sunscreen is present in an amount of about 0.005 to about 40% by weight of the total composition. More preferably, the UVA chemical sunscreen is present in an amount of about 0.01 to about 35% by weight of the total composition.

In one aspect, the composition is a sunscreen composition. Preferably, the sunscreen composition has an SPF value of from about 1 to about 50. More preferably, the sunscreen composition has an SPF value of from about 2 to about 45. Most preferably, the sunscreen composition has an SPF value of from about 5 to about 30.

The present disclosure also relates to a method of stabilizing a photoactive compound comprising mixing at least one photoactive compound with at least one heterocyclic compound having a structure according to formula I.

In one embodiment, the photosensitive compound is selected from avobenzone, oxcinonide, retinol, or mixtures thereof.