Chromatic compound and UV-absorbing composition

Abstract

The present invention provides UV absorbing chromophoric compounds and compositions comprising the same. One or more compounds may be formulated into cosmetic composition skin care products such as sunscreens, hair care products, and other personal care products. In addition, the compounds may be formulated into compositions such as paints, resins, dyes, and the like to protect surfaces from damage caused by UV exposure.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 435,372, filed December 27, 2022, which is hereby incorporated by reference in its entirety. Technical Field

[0003] The field of the disclosure relates to chromophoric compounds that absorb ultraviolet (UV) light, compositions thereof, and methods of use thereof. Background Art

[0004] Sunscreen compositions generally comprise one or more organic and / or inorganic compounds, to absorb the solar UV radiation (UV-A and UV-B), and thus provide protection from damage. For this reason, various compounds and preparations have been developed and commercialized.

[0005] The damage caused by exposure to UV radiation is not limited to human skin and other animals. It causes changes in the texture of hair, natural and synthetic fabrics, and wood products. In addition, it also causes discoloration of cloth and painted items. A common problem associated with many UV-absorbing compounds used in protection against UV radiation, such as 1,3-diketones and cinnamic acid derivatives, is that they photodegrade over time due to exposure, resulting in a decrease in their UV absorbance, especially UV-A absorbance.

[0006] Pentadecanoic acid esters have UV-Vis spectral absorption in the 280-400 nm range, which would make them ideal for protection against damage caused by exposure to sunlight. However, because they are photolabile and can photoisomerize, light exposure results in the formation of several products including cyclization and dimerization, which is accompanied by loss of the chromophore and reduced efficacy in protecting against UV radiation. To address this problem, US Pat. No. 4,847,073 (incorporated herein by reference in its entirety) discloses compounds with constrained structures of the pentadienoate chromophore for use in compositions for protection against UV radiation, these compounds having the following structures:

[0007]

[0008] wherein X and Y are independently selected from the group consisting of CN, COOR6, -PhNH(R6), CON(R6)2, -Ph-COOR6, -PhCOR6, and wherein only X or Y may be substituted by H; wherein R1, R2, R3, R4, and R5 are selected from the group consisting of H, OH, COOR6, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a hydroxyalkyl group, and R6 is selected from the group consisting of H, an alkyl group having 1 to 22 carbon atoms, an alkylaryl group, or an arylalkyl group. However, the patent does not disclose any compounds having an aromatic or heteroaromatic R4.

[0009] US 4,891,212 (incorporated herein by reference in its entirety) discloses compounds containing a pentadienoate chromophore having a constrained structure:

[0010]

[0011] wherein R1, R2, R3, R4 and R5 are selected from H or an alkyl group of 1 to 5 carbon atoms, X is O or NH, and R6 is selected from a divalent alkylene group of 2 to 16 carbon atoms, a cycloalkylene group of 5 to 8 carbon atoms, an arylene group of 6 to 12 carbon atoms or an alkylarylene group of 7 to 13 carbon atoms, and a sunscreen composition thereof.

[0012] US 10,836,777 (incorporated herein by reference in its entirety) relates to a synthetic process for preparing herbicides comprising synthesizing 2-(cyclohexenylidene)malonic acid derivatives by acid- or base-catalyzed cyclization:

[0013]

[0014] wherein R1, R2, R3, R4 and R5 are independently selected from H, Cl-C 10 Alkyl, C6-C 12 Aryl or containing one or two heteroaryl groups selected from N, O and sulfur atoms; and X1 and X2 are independently nitrile or COR6, wherein R6 is C1-C 10 Alkyl, C1-C 10 Alkoxy, etc.

[0015] Curti et al. [Synlett (2018), 29, 266-281] (incorporated herein by reference in its entirety) developed a specific synthetic method for compounds including (3-phenyl-2-cyclohexene-1-ylidene)malononitrile.

[0016] Staub et al. [J. Mat. Chem. (2003) 13, 825-833, herein incorporated by reference in its entirety] studied nonlinear polyene chromophores prepared from specific compounds such as [3-(4-aminophenyl)-2-cyclohexen-1-ylidene]malononitrile.

[0017] Since the compounds disclosed in US 4,847,073 and US 4,891,212 have a lambda of 305-306 最大 , which cannot efficiently absorb the entire UV-A range, and therefore the object of the present disclosure is to provide compounds comprising a constrained structure containing a pentadienoate chromophore. Summary of the Invention

[0018] The present disclosure provides chromophoric compounds containing constrained pentadienoate structures to minimize or eliminate their photochemical reactivity and having a lambda λ of 300-370 nm. 最大 Used to effectively absorb UV-A and UV-B.

[0019] The first aspect of the present disclosure is a compound having a chemical structure of Formula I and / or Formula II or a salt thereof:

[0020]

[0021] in:

[0022] R1 and R2 are independently selected from H, optionally substituted alkyl, optionally substituted alkynyl, optionally substituted aminoalkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxyalkyl, -CN, -C(O)R',

[0023] -C(O)OR', -C(O)NR'R”, -C(O)SR', -C(S)NR'R”, -NCO, -C(O)-XR y 、C(O)-XR z and -NO2; or

[0024] R1 and R2 together with the carbon atoms to which they are attached form a cyclic moiety of formula III or formula IV:

[0025]

[0026] in:

[0027] X is O or NR';

[0028] R 11 and R 12 are independently selected from H and optionally substituted alkyl;

[0029] R y and Rz are independently selected from H, optionally substituted C 1-15 Alkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxyalkyl, polyamides and polyethers;

[0030] R4 is selected from optionally substituted C6-C 10 Aryl, optionally substituted C2-C9 heteroaryl, the C2-C9 heteroaryl containing 0-4 heteroatoms selected from O, N and S;

[0031] Each of R3, R5, R6, R7, R8, R9 and R 10 are independently selected from H, halogen, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C 20 cycloalkenyl, optionally substituted C2-C7 heterocycloalkyl, optionally substituted C6-C 10 aryl, optionally substituted C2-C9 heteroaryl, -OR', -C(O)R', -C(O)OR', -C(O)NR'R", -C(=NR')NR'R", -C(=NR")R', -NR'R", -CN, -N=NR', cyanate, -OCN, -CNO, -NO2, -OC(O)NR'R", -SR', -S-SR', -S(O)R', -S(O)2R', -S(O)2OR', -S(O)2NR', -C(O)SR', -C(S)SR', -C(S)NR', ​​-B(OH)2, -B(OR')(OR"), PR'3, PR'2, -P(OR')2, -OP(OR')2, -P(O)(OR')2, -OP(O)(OR')2, polyamides and polyethers; and

[0032] Each R' and R" is independently selected from H, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C2-C 20 Cycloalkyl, optionally substituted C2-C 20 Cycloalkenyl, optionally substituted C2-C 20 Heterocycloalkyl, optionally substituted C6-C 10 aryl groups, optionally substituted C2-C9 heteroaryl groups, polyamides and polyethers.

[0033] In some embodiments of Formulas I and II, the compound has a cis and / or trans structure of Formula V or Formula VI:

[0034]

[0035] or a salt thereof,

[0036] in:

[0037] X is O or NR';

[0038] R1 is selected from H, -CN, alkyl isocyanate, alkyl isothiocyanate, aryl isocyanate, aryl isothiocyanate and C(O)-XR z ;

[0039] R y and R z are independently selected from H, optionally substituted C 1-15 Alkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxyalkyl, polyamides and polyethers;

[0040] Each R 13 、R 14 、R 15 、R 16 and R 17 are independently selected from H, halogen, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C 20 cycloalkenyl, optionally substituted C2-C7 heterocycloalkyl, optionally substituted C6-C 10 Aryl, optionally substituted C2-C9 heteroaryl, -OR', -C(O)R', -C(O)OR', -C(O)NR'R", -C(=NR')NR'R", -C(=NR")R', -NR'R", -CN, -N=NR', cyanate, -OCN, -NO2, -OC(O)NR'R", -SR', -S-SR', -S(O)R', -S(O)2R', -S(O)2OR', -S(O)2NR', -C(O)SR', -C(S)SR', -C(S)NR', ​​-B(OH)2, -B(OR')(OR"), -PR'2, -P(OR')2, -OP(OR')2, -P(O)(OR')2, -OP(O)(OR')2, polyamides and polyethers.

[0041] Each R' and R" is independently selected from H, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20Alkynyl, optionally substituted C2-C 20 Cycloalkyl, optionally substituted C2-C 20 Cycloalkenyl, optionally substituted C2-C 20 Heterocycloalkyl, optionally substituted C6-C 10 aryl groups, optionally substituted C2-C9 heteroaryl groups, polyamides and polyethers.

[0042] The second aspect of the present disclosure is a multimeric compound of Formula VII or Formula VIII:

[0043]

[0044] or a salt thereof,

[0045] in:

[0046] Each R1 is independently selected from H, -CN, alkyl isocyanate, alkyl isothiocyanate, aryl isocyanate, aryl isothiocyanate and C(O)-XR z ;

[0047] X is O or NR';

[0048] T is a linking moiety selected from the group consisting of: optionally substituted C1-C 20 Alkylene, optionally substituted C2-C 20 Alkenylene, optionally substituted C2-C 20 Alkynylidene, optionally substituted C2-C 20 Alkoxyalkylene, optionally substituted C2-C 20 Cycloalkylene, optionally substituted C2-C 20 Cycloalkenylene and optionally substituted C2-C 20 Heterocycloalkylene, wherein one or more carbon atoms of the main chain connecting the moiety T are optionally replaced by a divalent group each independently selected from the group consisting of oxygen (—O—), carbonyl (—CO—), optionally substituted alkylamino, optionally substituted cycloalkylene, optionally substituted heterocyclylene, optionally substituted heteroarylene, and optionally substituted arylene;

[0049] Each R z are independently selected from H, optionally substituted C 1-15 Alkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxyalkyl, polyamides and polyethers;

[0050] Each R3, R5, R6, R7, R8, R9, R 10 、R 13 、R 14 、R 15 、R 16 and R17 are independently selected from H, halogen, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C 20 cycloalkenyl, optionally substituted C2-C7 heterocycloalkyl, optionally substituted C6-C 10 Aryl, optionally substituted C2-C9 heteroaryl, -OR', -C(O)R', -C(O)OR', -C(O)NR'R", -C(=NR')NR'R", -C(=NR")R', -NR'R", -CN, -N=NR', cyanate, -OCN, -CNO, -NO2, -OC(O)NR'R", -SR', -S-SR', -S(O)R', -S(O)2R', -S(O)2OR', -S(O)2NR', -C(O)SR', -C(S)SR', -C(S)NR', ​​-B(OH)2, -B(OR')(OR"), PR'3, PR'2, -P(OR')2, -OP(OR')2, -P(O)(OR')2, -OP(O)(OR')2, polyamides and polyethers;

[0051] Each R' and R" is independently selected from H, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C2-C 20 Cycloalkyl, optionally substituted C2-C 20 Cycloalkenyl, optionally substituted C2-C 20 Heterocycloalkyl, optionally substituted C6-C 10 Aryl, optionally substituted C2-C9 heteroaryl, polyamide and polyether; and

[0052] n is selected from 2, 3, 4, 5 and 6.

[0053] A third aspect of the present disclosure is an oligomeric or polymeric compound of Formula IX or X:

[0054]

[0055] or its salt,

[0056] in:

[0057] Each X is independently O or NR';

[0058] L is a divalent linking moiety selected from the group consisting of: optionally substituted C1-C20 Alkylene, optionally substituted C1-C 20 Alkenylene, optionally substituted C2-C 20 Alkynylidene, optionally substituted C2-C 20 Alkoxyalkylene, optionally substituted C2-C 20 Cycloalkylene, optionally substituted C2-C 20 Cycloalkenylene, optionally substituted C2-C 20 Heterocycloalkylene, wherein one or more carbon atoms of the L backbone are optionally replaced by a divalent group each independently selected from the group consisting of oxygen (—O—), carbonyl (—CO—), optionally substituted alkylamino, optionally substituted cycloalkylene, optionally substituted heterocyclylene, optionally substituted heteroarylene, optionally substituted arylene, polyamide, and polyether;

[0059] Each R3, R5, R6, R7, R8, R9, R 10 、R 13 、R 14 、R 15 、R 16 and R 17 are independently selected from H, halogen, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C 20 cycloalkenyl, optionally substituted C2-C7 heterocycloalkyl, optionally substituted C6-C 10 Aryl, optionally substituted C2-C9 heteroaryl, -OR', -C(O)R', -C(O)OR', -C(O)NR'R", -C(=NR')NR'R", -C(=NR")R', -NR'R", -CN, -N=NR', cyanate, -OCN, -NCO, -NO2, -OC(O)NR'R", -SR', -S-SR', -S(O)R', -S(O)2R', -S(O)2OR', -S(O)2NR', -C(O)SR', -C(S)SR', -C(S)NR', ​​-B(OH)2, -B(OR')(OR"), PR'3, -PR'2, -P(OR')2, -OP(OR')2, -P(O)(OR')2, -OP(O)(OR')2, polyamides and polyethers;

[0060] Each R' and R" is independently selected from H, optionally substituted C1-C 20 Alkyl, optionally substituted C1-C 20 Alkenyl, optionally substituted C2-C 20Alkynyl, optionally substituted C2-C 20 Cycloalkyl, optionally substituted C2-C 20 Cycloalkenyl, optionally substituted C2-C 20 Heterocycloalkyl, optionally substituted C6-C 10 Aryl, optionally substituted C2-C9 heteroaryl, polyamides and polyethers;

[0061] n is at least 2, 3, 4, 5, 10, 20, 100, 150, 300, 500, or 1000 (e.g., n is an average degree of polymerization of 5-1000 or 10-100).

[0062] The present invention also provides UV absorbing compositions comprising one or more compounds of Formula I, II and / or VX.

[0063] A fourth aspect of the present disclosure relates to a method of providing UV photoprotection to the skin or hair of a subject, comprising applying a composition comprising one or more compounds of Formula I, II, and / or VX (such as, but not limited to, compounds E1-E64 of Table 6) to the skin or hair of a subject (such as, but not limited to, humans and other mammals).

[0064] A fifth aspect of the present disclosure relates to a composition stable against light-induced degradation, comprising an organic material subject to light-induced degradation and one or more compounds selected from compounds having the chemical structure of Formula I and / or II, such as, but not limited to, compounds E1-E64 of Table 6.

[0065] In some embodiments of the composition, the organic material is a coating, wax, resin, varnish, lacquer, enamel, paint, thermoplastic polymer, thermosetting polymer, polyester, protein, polysaccharide, adhesive, or blends thereof.

[0066] In preferred embodiments, the composition comprises one or more compounds of Formula I, II and / or VX in an amount ranging from 0.01% to 50% by weight of the organic material.

[0067] A sixth aspect of the present disclosure relates to a method of providing UV light protection to a UV light-sensitive material, comprising applying a composition containing one or more compounds of Formula I, II and / or VX (such as, but not limited to, compounds E1-E64 of Table 6) to the UV light-sensitive material.

[0068] A seventh aspect of the present disclosure relates to a composition for protecting fabrics from sun fading, the composition comprising one or more compounds selected from compounds having a chemical structure of Formula I, II and / or VX and salts thereof, such as but not limited to compounds E1-E64 of Table 6. BRIEF DESCRIPTION OF THE DRAWINGS

[0069] Figure 1 Shown is the UV absorption spectrum of a mixture of cis- and trans-(3-phenyl-2-cyclopenten-1-ylidene) 2-ethylhexyl cyanoacetate (E6).

[0070] Figure 2 The cis- and trans-isomer mixture of 2-ethylhexyl (3-phenyl-2-cyclohexene-1-ylidene)cyanoacetate (E5) in DMSO-d6 obtained using a 400 MHz NMR spectrometer is shown. 1 H-NMR spectrum.

[0071] Figure 3 The cis- and trans-isomer mixture of 2-ethylhexyl (3-phenyl-2-cyclopenten-1-ylidene)cyanoacetate (E6) in DMSO-d6 obtained using a 400 MHz NMR spectrometer is shown. 1 H-NMR spectrum.

[0072] Figure 4 The cis- and trans-isomer mixture of ethyl [3-(p-methoxyphenyl)-2-cyclohexene-1-ylidene]cyanoacetate (E7) in DMSO-d6 obtained using a 400 MHz NMR spectrometer is shown. 1 H-NMR spectrum.

[0073] Figure 5 The cis- and trans-isomer mixture of [3-(p-methoxyphenyl)-2-cyclopenten-1-ylidene]cyanoacetate (E8) in DMSO-d6 obtained using a 400 MHz NMR spectrometer is shown. 1 H-NMR spectrum. DETAILED DESCRIPTION

[0074] definition

[0075] In this specification, specific embodiments of the present disclosure are referred to in detail. Some embodiments or aspects thereof are shown in the accompanying drawings. Several aspects of the present disclosure are described herein with reference to exemplary applications for illustration. It should be understood that many specific details, relationships, and methods are set forth to provide a complete understanding of the features described herein. However, one of ordinary skill in the relevant art will readily recognize that the features described herein can be practiced without one or more of the specific details or with other methods. Unless expressly indicated otherwise, the features described herein are not limited to the ordering shown of the actions or events, as some actions can occur in different orders and / or simultaneously with other actions or events. In addition, not all of the actions or events shown are required to implement the methods according to the features described herein.

[0076] The compounds of the present disclosure include the compounds generally described above and are further illustrated by the categories, subclasses and species disclosed herein. Unless otherwise indicated, as used herein, the following definitions shall apply. For the purposes of the present disclosure, chemical elements are identified according to the periodic table, CAS version, Handbook of Chemistry and Physics, 75th edition. In addition, the general principles of organic chemistry are described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausalito: 1999 and "March's Advanced Organic Chemistry", 5th edition, editors: Smith, MB and March, J., John Wiley & Sons, New York: 2001, the entire contents of which are hereby incorporated by reference.

[0077] Abbreviations used herein have their conventional meanings in the chemical and biological arts.Chemical structures and formulae depicted herein are constructed according to standard rules of chemical valence known in the chemical arts.

[0078] As used herein, the term "aliphatic" or "aliphatic group" means a straight (i.e., unbranched) or branched, substituted or unsubstituted hydrocarbon chain that is fully saturated or contains one or more unsaturated units, or a monocyclic or bicyclic hydrocarbon (also referred to herein as "carbocycle," "cycloaliphatic," or "cycloalkyl") that is fully saturated or contains one or more unsaturated units but is not aromatic, having a single point of attachment to the rest of the molecule. Unless otherwise specified, an aliphatic group contains 1-6 aliphatic carbon atoms. In some embodiments, an aliphatic group contains 1-5 aliphatic carbon atoms. In some embodiments, an aliphatic group contains 1-4 aliphatic carbon atoms. In some embodiments, an aliphatic group contains 1-3 aliphatic carbon atoms. In some embodiments, an aliphatic group contains 1-2 aliphatic carbon atoms. In some embodiments, "cycloaliphatic" (or "carbocycle" or "cycloalkyl") refers to a monocyclic C3-C7 hydrocarbon that is fully saturated or contains one or more unsaturated units but is not aromatic, having a single point of attachment to the rest of the molecule. Suitable aliphatic groups include, but are not limited to, linear or branched, substituted or unsubstituted alkyl, alkenyl, alkynyl groups, and mixtures thereof, such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl, or (cycloalkyl)alkenyl.

[0079] The term "heteroatom" means one or more of oxygen, sulfur, nitrogen, phosphorus, or silicon (including any oxidized form of nitrogen, sulfur, phosphorus, or silicon; a quaternized form of any basic nitrogen; or a substituted nitrogen of a heterocyclic ring, such as N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl), or NR + (as in N-substituted pyrrolidinyl)).

[0080] As used herein, the term "unsaturated" means that a moiety has one or more units of unsaturation.

[0081] The term "alkylene" refers to a divalent alkyl group. An "alkylene chain" is a polymethylene group, i.e., -(CH2) n -, wherein n is a positive integer, preferably 1 to 6, 1 to 4, 1 to 3, 1 to 2 or 2 to 3. A substituted alkylene chain is a polymethylene group in which one or more methylene hydrogen atoms are replaced by a substituent. Suitable substituents include the substituents described below for substituted aliphatic groups.

[0082] The terms used herein are only used to describe the purpose of exemplary embodiments and are not intended to be restrictive. As used herein, unless the context clearly indicates otherwise, the singular "a", "an" and "the" are also intended to include plural forms. In addition, in the case of the terms "including / include" used in the detailed description and / or claims, "having / has / with" or its variants, such terms are intended to have inclusiveness in a manner similar to the term "comprising". Unless otherwise indicated, all technical terms and scientific terms used herein have the same meaning as those generally understood by those of ordinary skill in the art. Materials, methods and examples are only illustrative and are not intended to be restrictive.

[0083] As used herein, the term "about" or "approximately" means a range of up to 10%, preferably 5%, and more preferably 3% of a given value.

[0084] As used herein, the term "substantially" means that something can be done to a great extent or to a significant degree.

[0085] As used herein, the term "amount in the range of X% to Y%" includes all ranges within that range. For example, a compound having an amount in the range of 0.1% to 50% (w / w) includes ranges of 0.2% to 49% (w / w), 1.0% to 45% (w / w), 5% to 10% (w / w), 3% to 30% (w / w), 15% to 20% (w / w), and 20% to 45% (w / w). . . .

[0086] The terms "heteroaryl" and "heteroar-" refer to groups having 5 to 10 ring atoms, preferably 5, 6, or 9 ring atoms; sharing 6, 10, or 14 π electrons in a cyclic array; and having one to five heteroatoms in addition to carbon atoms. Heteroaryl groups include, but are not limited to, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl, naphthyridinyl, and pteridinyl. As used herein, the terms "heteroaryl" and "heteroar-" also include groups in which a heteroaromatic ring is fused to one or more aryl, cycloaliphatic, or heterocyclic rings, wherein the linking radical or point of attachment is on the heteroaromatic ring (or, in the case of a divalent fused heteroarylene ring system, at least one linking radical or point of attachment is on the heteroaromatic ring). Non-limiting examples include: indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzothiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl and pyrido[2,3-b]-1,4-oxazin-3(4H)-one. The heteroaryl group can be monocyclic or bicyclic. The term "heteroaryl" is used interchangeably with the term "heteroaryl ring," "heteroaryl group," or "heteroaromatic," any of which includes an optionally substituted ring.

[0087] As used herein, the terms "heterocyclyl," "heterocyclic group," and "heterocyclic ring" are used interchangeably and refer to a stable 5- to 7-membered monocyclic or 7- to 10-membered bicyclic heterocyclic moiety that is saturated or partially unsaturated and has, in addition to carbon atoms, one or more, preferably one to four, heteroatoms as defined above. When in the context of ring atoms, the term "nitrogen" includes substituted nitrogen. As an example, in a saturated or partially unsaturated ring having 0-3 heteroatoms selected from oxygen, sulfur, or nitrogen, nitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl), or NR + (such as in N-substituted pyrrolidinyl).

[0088] The heterocyclic ring may be attached to its side group at any heteroatom or carbon atom to produce a stable structure, and any ring atom may be optionally substituted. Examples of such saturated or partially unsaturated heterocyclic groups include, but are not limited to, tetrahydrofuranyl, tetrahydrothiophenyl, pyrrolidinyl, piperidinyl, pyrrolidinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxane, dioxolane, diazepine, oxadiazolyl ... Oxazolin Thiazepine The terms "heterocyclyl," "heterocyclyl ring," "heterocyclic group," "heterocyclic moiety," and "heterocyclic radical" are used interchangeably herein and also include groups in which a heterocyclyl ring is fused to one or more aryl, heteroaryl, or cycloaliphatic rings, such as indolinyl, 3H-indolyl, chromanyl, phenanthridinyl, or tetrahydroquinolinyl, wherein the linking group or point of attachment is located on the heterocyclyl ring. The heterocyclyl group may be monocyclic or bicyclic. The term "heterocycloalkyl" refers to an alkyl group substituted with a heterocyclyl, wherein the alkyl and heterocyclyl moieties are independently optionally substituted.

[0089] As used herein, the term "partially unsaturated" refers to a ring moiety containing at least one double or triple bond. The term "partially unsaturated" is intended to encompass rings having multiple sites of unsaturation, but is not intended to include aryl or heteroaryl moieties, as defined herein.

[0090] As used herein and unless otherwise specified, the suffix "-ene" is used to describe a divalent group. Thus, any of the above terms can be modified with the suffix "-ene" to describe the divalent form of the moiety. For example, a divalent carbocyclic ring is a "carbocyclylene," a divalent aromatic ring is an "arylene," a divalent benzene ring is a "phenylene," a divalent heterocyclic ring is a "heterocyclylene," a divalent heteroaryl ring is a "heteroarylene," a divalent alkyl chain is an "alkylene," a divalent alkenyl chain is an "alkylene," a divalent alkynyl chain is an "alkynylene," and the like.

[0091] As used herein, the terms "may," "optionally," "optionally," or "may optionally" mean that the subsequently described event may or may not occur, such that the description includes instances where the event occurs as well as instances where the event does not occur. For example, the phrase "optionally substituted" means that a non-hydrogen substituent may or may not be present on a given atom, and thus, the description includes structures with and without the non-hydrogen substituent.

[0092] When the term "substituted" appears before or after a list of possible substituted groups, it is intended that the term apply to every member of that group. For example, the phrase "substituted alkyl and aryl" should be interpreted as "substituted alkyl and substituted aryl."

[0093] In addition to the disclosure herein, the term "substituted" when used to modify a specified group or radical may also mean that one or more hydrogen atoms of the specified group or radical are each independently replaced with the same or different substituents as defined herein.

[0094] In addition to the disclosure herein, in certain embodiments, a substituted group has 1, 2, 3, or 4 substituents, 1, 2, or 3 substituents, 1 or 2 substituents, or 1 substituent.

[0095] Unless otherwise indicated, substituents not specifically defined herein are named by naming the terminal portion of the functionality followed by the adjacent functionality toward the point of attachment. For example, the substituent "hydroxyalkyl" refers to the group HO-(alkyl)-.

[0096] "Halo" and "halogen" refer to fluoro, chloro, bromo and iodo.

[0097] For any group disclosed herein that contains one or more substituents, it will of course be understood that these groups do not contain any substitutions or substitution patterns that are sterically impractical and / or synthetically infeasible. In addition, the subject compounds include all stereochemical isomers produced by the substitutions of these compounds.

[0098] As described herein, compounds of the present disclosure may (when specified) contain "optionally substituted" moieties. In general, the term "substituted," whether preceded by the term "optionally" or not, means that one or more hydrogen atoms of the designated moiety are replaced with a suitable substituent. "Substituted" applies to one or more hydrogen atoms that are explicitly or implicitly removed from the structure (e.g., At least and means at least ). In addition, in polycyclic ring systems, unless otherwise indicated, substituents may replace hydrogen on any individual ring (e.g. means at least ). Unless otherwise indicated, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituents may be the same or different at each position. The substituent combinations contemplated by the present disclosure are preferably those that result in the formation of stable or chemically feasible compounds. As used herein, the term "stable" refers to a compound that does not substantially change when subjected to conditions that allow its production, detection, and in certain embodiments, its recovery, purification, and use for one or more of the purposes disclosed herein.

[0099] Suitable monovalent substituents on the substitutable carbon atoms of an "optionally substituted" group are independently halogen; -(CH2) 0-4 R o ; -(CH2) 0-4 OR o ;-O(CH2) 0-4 R o ;-O(CH2) 0-4 C(O)OR o ;-O(CH2) 0-4 OR o ; -(CH2) 0-4 CH(OR o )2;-(CH2) 0-4 SR o ; -(CH2) 0-4 Ph, which can be R o Substitution; -(CH2) 0-4 O(CH2) 0-1 Ph (which can be R o substituted), -CH=CHPh (which may be replaced by R o substituted); -(CH2) 0-4 O(CH2) 0-1 -pyridyl, which may be replaced by R o Substitution; -NO2; -CN; -N3; ​​-(CH2) 0-4 N(R o )2;-(CH2) 0-4 N(R o )C(O)R o ;-N(R o )C(S)R o ; -(CH2) 0-4 N(R o )C(O)N(R o )2;-N(R o )C(S)N(R o )2;-(CH2) 0-4 N(R o)C(S)N(R o )2;-(CH2) 0-4 N(R o )C(O)OR o ;-N(R o )N(R o )C(O)R o ;-N(R o )N(R o )C(O)N(R o )2;-N(R o )N(R o )C(O)OR o ;-(CH2) 0-4 C(O)R o ;-C(S)R o ;-(CH2) 0-4 C(O)OR o ;-(CH2) 0- 4C(O)SR o ;-(CH2) 0-4 C(O)OSi(R o )3;-(CH2) 0-4 OC(O)R o ;-OC(O)(CH2) 0-4 SR o ;-SC(S)SR o ;-(CH2) 0- 4SC(O)R o ;-(CH2) 0-4 C(O)N(R o )2;-C(S)N(R o )2;-C(S)SR o ;-SC(S)SR o ;-(CH2) 0-4 OC(O)N(R o )2;-C(O)N(OR o )R o ;-C(O)C(O)R o ;-C(O)CH2C(O)R o ;-C(NOR o )R o ;-(CH2) 0-4 SSR o ;-(CH2) 0-4 S(O)2R o ;-(CH2) 0-4 S(O)2OR o ;-(CH2) 0-4 OS(O)2R o;-S(O)2NR o ; -(CH2) 0-4 S(O)R o ;-N(R o )S(O)2N(R o )2;-N(R o )S(O)2R o ;-N(OR o )R o ;-C(NH)N(R o )2;-P(OR o )2;-P(O)(R o )2;-OP(O)(R o )2;-OP(O)(OR o )2;-SiR o 3;-(C 1-4 linear or branched alkylene)ON(R o )2; or -(C 1-4 linear or branched alkylene) C(O)ON(R o )2, where each R o can be defined as follows: substituted and independently hydrogen, C 1-6 Aliphatic, -CH2Ph, -O(CH2) 0-1 Ph, -CH2-(5- to 6-membered heteroaryl ring), or a 5- to 6-membered saturated, partially unsaturated or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen and sulfur, or, notwithstanding the above definitions, two independent occurrences of R o Together with the atoms between them form a 3 to 12 membered saturated, partially unsaturated or aromatic monocyclic or bicyclic ring having 0 to 4 heteroatoms independently selected from nitrogen, oxygen and sulfur, which may be substituted as defined below.

[0100] R o (or two independent occurrences of R o Suitable monovalent substituents on the ring formed by taking together with the atoms between them are independently halogen; -(CH2) 0-2 R · ;-(haloR · ), -(CH2) 0-2 OH; -(CH2) 0-2 OR · ; -(CH2) 0-2 CH(OR · )2;-O(haloR · ); -CN; -N3; ​​-(CH2) 0-2 C(O)R · ; -(CH2) 0-2 C(O)OH; -(CH2)0-2 C(O)OR · ; -(CH2) 0-2 SR · ; -(CH2) 0-2 SH; -(CH2) 0-2 NH2; -(CH2) 0-2 NHR · ; -(CH2) 0-2 NR · 2; -NO2, -SiR · 3;-OSiR · 3;-C(O)SR · ;-(C 1-4 linear or branched alkylene)C(O)OR · or -SSR · , where each R · is unsubstituted, or is substituted only with one or more halogens before "halo", and is independently selected from C 1-4 Aliphatic, -CH2Ph, -O(CH2) 0-1 Ph, or a 5- to 6-membered saturated, partially unsaturated or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen and sulfur. o Suitable divalent substituents on a saturated carbon atom of include =0 and =S.

[0101] Suitable divalent substituents on a saturated carbon atom of an "optionally substituted" group include the following: =0; =S; =NNR # 2; =NNHC(O)R # 2; =NNHC(O)OR # 2; =NNHS(O)2R # 2; =NR # ; =NOR # ;-O(C(R # 2)) 2-3 O-; or -S(C(R # 2)) 2-3 S-; where each independent occurrence of R # is selected from hydrogen, C which may be substituted as defined below 1-6 aliphatic, or an unsubstituted 5- to 6-membered saturated, partially unsaturated, or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. Suitable divalent substituents attached to the ortho-substitutable carbon of an "optionally substituted" group include: -O(CR # 2) 2-3 O-, where each independent occurrence of R # is selected from hydrogen, C which may be substituted as defined below 1-6aliphatic, or an unsubstituted 5- to 6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

[0102] R # Suitable substituents on the aliphatic group include halogen, -R · 、-(haloR · ), -OH, -OR · 、-O(haloR · )、-CN、-C(O)OH、-C(O)OR · 、-NH2、-NHR · 、-NR · 2 or -NO2, where each R · unsubstituted or, when preceded by "halo", substituted only by one or more halogens, and independently C 1-4 Aliphatic, -CH2Ph, -O(CH2) 0-1 Ph or a 5- to 6-membered saturated, partially unsaturated or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen and sulfur.

[0103] Suitable substituents on a substitutable nitrogen of an "optionally substituted" group include or Each of these are independently: hydrogen, C1-6 aliphatic which may be substituted as defined below, unsubstituted -OPh, or an unsubstituted 5- to 6-membered saturated, partially unsaturated or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen and sulfur; or, in addition to the above definitions, two independent occurrences of Together with its central atoms, it forms an unsubstituted 3- to 12-membered saturated, partially unsaturated or aromatic monocyclic or bicyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen and sulfur.

[0104] Suitable substituents on the aliphatic group are independently halogen, -R · 、-(haloR · ), -OH, -OR · 、-O(haloR · )、-CN、-C(O)OH、-C(O)OR · 、-NH2、-NHR · 、-NR · 2 or -NO2, where each R · unsubstituted or, when preceded by "halo", substituted only by one or more halogens, and independently C 1-4 Aliphatic, -CH2Ph, -O(CH2) 0-1Ph or a 5- to 6-membered saturated, partially unsaturated or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen and sulfur.

[0105] As used herein, unless otherwise indicated, the term compound refers to cis, trans isomers, or mixtures thereof. Unless otherwise indicated, reference to a compound containing an ionizable group (such as, but not limited to, a carboxyl group, a sulfonic acid group, or an amino group) includes both the acidic and basic forms of the compound, i.e., any counterions. For example, the counterion of a negatively charged acidic group can be any positively charged ion, such as, but not limited to, an alkali metal ion or an alkaline earth metal, such as lithium, sodium, potassium, zinc, calcium, etc.; an ammonium ion or an alkylammonium ion, such as, but not limited to, methylammonium, dimethylammonium, trimethylammonium, tetramethylammonium, etc.; or an arylammonium ion, such as, but not limited to, aniline, N-methyl-N-aniline, etc. Similarly, for a basic group, the counterion can be any negatively charged ion, such as, but not limited to, acetate, oxalate, tartrate, propionate, hexanoate, fluoride, chloride, bromide, iodide, sulfate, nitrate, etc.

[0106] As used herein, the term "pharmaceutically acceptable salt" refers to salts that are suitable for use in contact with the tissues of humans and lower animals without undue toxicity, irritation, allergic response, etc., within the scope of sound medical judgment and commensurate with a reasonable benefit-risk ratio. Pharmaceutically acceptable salts are well known in the art. For example, SM Berge et al. describe pharmaceutically acceptable salts in detail in J. Pharmaceutical Sciences, 1977, 66, 1-19, which is incorporated herein by reference.

[0107] In certain embodiments, the neutral form of the compound is regenerated by contacting the salt with a base or acid and isolating the parent compound in a conventional manner. In certain embodiments, the parent form of the compound differs from the various salt forms in certain physical properties (such as solubility in polar solvents).

[0108] Unless otherwise indicated, structures depicted herein are also meant to include all isomeric (e.g., enantiomeric, diastereomeric, and geometric (or conformational)) forms of the structure; for example, the R and S configurations for each asymmetric center, Z and E double bond isomers, and Z and E conformational isomers. Thus, the present disclosure encompasses single stereochemical isomers as well as enantiomeric, diastereomeric, and geometric (or conformational) mixtures of the compounds of the invention. For example, a wavy bond in a bonded chemical structure is used to represent unknown stereochemistry and is intended to encompass all possible stereochemical and geometric isomers, such as express

[0109] Unless otherwise indicated, all tautomeric forms of the disclosed compounds are within the scope of the present disclosure. In addition, unless otherwise indicated, structures depicted herein are also meant to encompass compounds that differ only in the presence of one or more isotopically enriched atoms. For example, a structure having the present structure (including replacement of hydrogen by deuterium or tritium or by 13 C or 14 Compounds containing C-enriched carbon replacement carbon) are within the scope of the present disclosure. Such compounds are useful as, for example, analytical tools, probes in biological assays, or therapeutic agents according to the present disclosure. In some embodiments, the compounds of the present disclosure are provided in the form of single enantiomers or single diastereomers. A single enantiomer refers to an enantiomeric excess of 80% or greater, such as 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99%.

[0110] As used herein, the term "oxo" means an oxygen double bonded to a carbon atom, thereby forming a carbonyl group.

[0111] The articles "a" and "an" herein refer to one or to more than one (ie, to at least one) of the grammatical object of the article. For example, "an element" means one element or more than one element.

[0112] A "dosing regimen" (or "therapeutic regimen"), as the term is used herein, is a group of unit doses (usually more than one) that are administered individually to a subject, typically separated by time periods. In some embodiments, a given therapeutic agent has a recommended dosing regimen that may involve one or more doses. In some embodiments, the dosing regimen includes multiple doses, each separated by a time period of the same length; in some embodiments, the dosing regimen includes multiple doses separated by at least two different time periods.

[0113] As will be understood from the context, a "reference" compound refers to a compound that is sufficiently similar to a particular compound of interest to allow for a relevant comparison. In some embodiments, information about the reference compound is obtained simultaneously with information about the particular compound. In some embodiments, by comparing a particular compound of interest to a reference compound, the identity, similarity, or difference of the particular compound relative to the compound can be determined.

[0114] As used herein, the phrase "therapeutic agent" refers to any agent that has a therapeutic effect and / or elicits a desired biological and / or pharmacological effect when administered to a subject.

[0115] As used herein, the term "therapeutically effective amount" refers to the amount of a therapeutic agent that imparts therapeutic effect to a subject in a reasonable benefit / risk ratio applicable to any medical treatment. Curative effect can be objective (i.e., it can be measured by a test or marker) or subjective (i.e., the subject gives an indication of the effect or feels the effect). Specifically, "therapeutically effective amount" refers to an amount of a therapeutic agent that effectively treats, slows down or prevents a specific disease or condition, or shows a detectable therapeutic or preventive effect (such as by slowing down the symptoms associated with the disease, preventing or delaying the onset of the disease or condition, and / or also reducing the severity or frequency of the symptoms of the disease or condition). A therapeutically effective amount is typically administered in a dosage regimen that may include multiple doses. For any specific therapeutic agent, a therapeutically effective amount (and / or an appropriate unit dose within an effective dosage regimen) can vary, for example, depending on the route of administration, and in combination with other agents. Furthermore, the specific therapeutically effective amount (and / or unit dose) for any particular subject may depend on a variety of factors, including the condition being treated and the severity of that condition; the activity of the specific therapeutic agent being used; the specific composition being used; the age, weight, general health, sex, and diet of the subject; the time of administration, route of administration, and / or rate of excretion or metabolism of the specific therapeutic agent being used; the duration of the treatment; and like factors well known in the medical arts.

[0116] As used herein, the term "treatment" (also "treat" or "treating") refers to any administration of a substance (e.g., a provided composition) that partially or completely alleviates, ameliorates, alleviates, inhibits, delays the onset of, reduces the severity of, and / or reduces the incidence of one or more symptoms, characteristics, and / or causes of a particular disease, disorder, and / or condition. Such treatment may be for a subject who does not exhibit signs of the disease, disorder, and / or condition. Alternatively or additionally, such treatment may be for a subject who exhibits one or more established signs of the relevant disease, disorder, and / or condition. In some embodiments, treatment may be for a subject who has been diagnosed with the relevant disease, disorder, and / or condition. In some embodiments, treatment may be for an individual known to have one or more susceptibility factors that are statistically associated with an increased risk of developing the relevant disease, disorder, and / or condition.

[0117] All references disclosed herein are incorporated by reference in their entirety.

[0118] Compound

[0119] One aspect of the present disclosure relates to compounds and compositions comprising one or more of such compounds or salts thereof that are capable of absorbing UV-A and / or UV-B radiation.

[0120] The compound or its salt may have the chemical structure of Formula I and / or II:

[0121]

[0122] in:

[0123] R1 and R2 are independently selected from H, optionally substituted alkyl, optionally substituted alkynyl, optionally substituted aminoalkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxyalkyl, -CN, -C(O)R', -C(O)OR', -C(O)NR'R", -C(O)SR', -C(S)NR'R", -NCO, -C(O)-XR y 、C(O)-XR z and -NO2; or

[0124] R1 and R2 together with the carbon atoms to which they are attached form a cyclic moiety of formula III or formula IV:

[0125]

[0126] in:

[0127] X is O or NR';

[0128] R 11 and R 12 are independently selected from H and optionally substituted alkyl;

[0129] R y and R z are independently selected from H, optionally substituted C 1-15 Alkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxyalkyl, polyamides and polyethers;

[0130] R4 is selected from optionally substituted C6-C 10 Aryl, optionally substituted C2-C9 heteroaryl, the C2-C9 heteroaryl containing 0-4 heteroatoms selected from O, N and S;

[0131] Each of R3, R5, R6, R7, R8, R9 and R 10 are independently selected from H, halogen, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C 20 cycloalkenyl, optionally substituted C2-C7 heterocycloalkyl, optionally substituted C6-C 10aryl, optionally substituted C2-C9 heteroaryl, -OR', -C(O)R', -C(O)OR', -C(O)NR'R", -C(=NR')NR'R", -C(=NR")R', -NR'R", -CN, -N=NR', cyanate, -OCN, -CNO, -NO2, -OC(O)NR'R", -SR', -S-SR', -S(O)R', -S(O)2R', -S(O)2OR', -S(O)2NR', -C(O)SR', -C(S)SR', -C(S)NR', ​​-B(OH)2, -B(OR')(OR"), PR'3, PR'2, -P(OR')2, -OP(OR')2, -P(O)(OR')2, -OP(O)(OR')2, polyamides and polyethers; and

[0132] Each R' and R" is independently selected from H, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C2-C 20 Cycloalkyl, optionally substituted C2-C 20 Cycloalkenyl, optionally substituted C2-C 20 Heterocycloalkyl, optionally substituted C6-C 10 aryl groups, optionally substituted C2-C9 heteroaryl groups, polyamides and polyethers.

[0133] In some embodiments, the compound has the structure of Formula I.

[0134] In some embodiments, the compound has the structure of Formula II.

[0135] In a preferred embodiment of the composition, the compound is selected from compounds E1-E64 of Table 6.

[0136] In some embodiments, R4 is optionally substituted phenyl.

[0137] In some embodiments, at least one of R1 and R2 is -C(O)-XR y .

[0138] In some embodiments, the compounds of the present disclosure have the structure of Formula I and / or II:

[0139]

[0140] or its salts;

[0141] in:

[0142] R1 and R2 are independently H, substituted or unsubstituted C1-C8 alkyl, C1-C8 alkenyl, C1-C8 alkynyl, C1-C8 aminoalkyl, C1-C8 hydroxyalkyl, C1-C8 alkylisocyanate, C1-C8 alkylisothiocyanate, CN, C(O)R', C(O)OR', C(O)NR'R", C(O)SR', C(S)NR'R", or NO2; or

[0143] R1 and R2 form a cyclic moiety, wherein the cyclic moiety is of Formula III or Formula IV:

[0144]

[0145] in:

[0146] R 11 and R 12 Is H or C1-C 15 Alkyl groups such as, but not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, and isomers and variations thereof.

[0147] R4 is substituted or unsubstituted C6-C 10 Aryl, such as but not limited to phenyl, biphenyl, naphthyl, benzyl, benzoyl; 2-, 3- and / or 4-hydroxyphenyl; 2-, 3- and / or 4-mercaptophenyl; 2-, 3- and / or 4-aminophenyl; 2-, 3- or 4-benzenesulfonic acid and its salts; 2-, 3- and / or 4-nitrophenyl; 2-, 3- and / or 4-halogenated phenyl, such as fluorophenyl, chlorophenyl, bromophenyl and iodophenyl; alkoxyphenyl, such as but not limited to methoxy, ethoxy, etc.; phenylalkyl, such as 2-, 3- and / or 4-phenylsulfonic acid and its salts; or 4-methyl, -ethyl, -propyl, -butyl, -isobutyl, tert-butyl, etc.; mono-, di- and trihalomethylphenyl, such as trifluoromethyl, trichloromethyl and tribromomethyl; or substituted or unsubstituted C2-C9 heteroaryl, which contains one or more atoms selected from O, N and S, such as but not limited to pyrrolyl, pyridyl, pyrrolidinyl, pyrrolidonyl, thienyl; indolyl, isoindolyl, imidazolyl, thiazolyl, pyrimidinyl, triazolyl, triazolyl, triazinyl, etc. In addition, the aryl or heteroaryl group can be mono-, di- or trisubstituted, such as but not limited to di- or trifluorophenyl, di- or triisocyanate, di- or triisothiocyanate, di- or trimethyl, etc.

[0148] R3, R5, R6, R7, R8, R9 and R 10 are independently H, halogen; or substituted or unsubstituted C1-C 20Alkyl, such as, but not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, or isomers and variations thereof; C2-C 20 Alkenyl groups such as, but not limited to, vinyl,

[0149] 2-methylvinyl, butadienyl, isoprene, etc.; C2-C 20 Alkynyl groups such as, but not limited to, ethynyl,

[0150] 2-methylethynyl, etc.; C3-C8 cycloalkyl, such as but not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.; C2-C7 heterocycloalkyl, such as but not limited to aziridinyl, azetidinyl, pyrrolidinyl, tetrahydrofuranyl, sulfolanyl, tetrahydrothiophenyl, etc., aryl as defined for R4, heteroaryl as defined for R4, OR', C(O)R', C(O)OR', C(O)NR'R", R'R"NC=NR',

[0151] R'C=NR", NR'R", CN, N=NR', cyanate, NO2, OC(O)NR'R", SR', S-SR',

[0152] S(O)R', S(O)2R', S(O)2OR', S(O)2NR', C(O)SR', C(S)SR', C(S)NR', ​​B(OH)2, B(OR')(OR"), PR'3, PR'2, P(OR')2, OP(OR')2, P(O)(OR')2, OP(O)(OR')2, polyamide or polyether; and

[0153] Each R' and R" is independently H, substituted or unsubstituted C1-C 20 Alkyl, C1-C 20 Alkenyl, C2-C 20 Alkynyl, C2-C 20 Cycloalkyl, C2-C 20 Cycloalkenyl, C2-C 20 Heterocycloalkyl, C6-C 10 The aryl group, C2-C9 heteroaryl group, polyamide or polyether are as defined above.

[0154] In some embodiments, each R1 and R2 is independently selected from optionally substituted C1-C8 aminoalkyl, optionally substituted C1-C 20 Hydroxyalkyl, optionally substituted C1-C 20 Alkyl isocyanate and optionally substituted C1-C 20 Alkyl isothiocyanate.

[0155] In some embodiments, one or more compounds have the cis form, trans form, or mixtures thereof of Formula V, or a salt thereof:

[0156]

[0157]

[0158] in:

[0159] R1 is H, CN, alkyl isocyanate, alkyl isothiocyanate, aryl isocyanate, aryl isothiocyanate or C(O)-XR z ;

[0160] X is O or NR';

[0161] R y and R z are independently H, substituted or unsubstituted C1-C 15 Alkyl groups such as, but not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-isopentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, etc.; hydroxyalkyl groups such as, but not limited to, 2-hydroxyethyl, 3-hydroxypropyl, etc.; alkoxyalkyl groups such as, but not limited to, 3-methoxypropyl or 2-ethoxyethyl, etc., polyamides (including peptides) or polyethers;

[0162] R3, R5, R6, R7, R8, R9 and R 10 As described herein above for Formula I;

[0163] R 13 、R 14 、R 15 、R 16 and R 17 are independently H, halogen, substituted or unsubstituted C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C8 cycloalkyl, C2-C 20 Cycloalkenyl, C2-C7 heterocycloalkyl, C6-C 10aryl, C2-C9 heteroaryl, OR', C(O)R', C(O)OR', C(O)NR'R", R'R"NC=NR', R'C=NR", NR'R", CN, N=NR', cyanate, NO2, OC(O)NR'R", SR', S-SR', S(O)R', S(O)2R', S(O)2OR', S(O)2NR', C(O)SR', C(S)SR', C(S)NR', ​​B(OH)2, B(OR')(OR"), PR'3, PR'2, P(OR')2, OP(OR')2, P(O)(OR')2, OP(O)(OR')2, polyamide, or polyether; and

[0164] R' and R" are independently H, substituted or unsubstituted C1-C 20 Alkyl, C1-C 20 Alkenyl, C2-C 20 Alkynyl, C2-C 20 Cycloalkyl, C2-C 20 Cycloalkenyl, C2-C 20 Heterocycloalkyl, C6-C 10 Aryl, C2-C9 heteroaryl, polyamide or polyether.

[0165] In some other embodiments, one or more compounds have the structure of Formula VI or a salt thereof:

[0166]

[0167] in:

[0168] R1 is H, CN, alkyl isocyanate, alkyl isothiocyanate, aryl isocyanate, aryl isothiocyanate or

[0169] C(O)-XR z ,

[0170] X is O or NR';

[0171] R y and R z are independently H, substituted or unsubstituted C1-C 15 Alkyl groups such as, but not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, 3-methylbutyl, pentyl, neopentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, etc.; hydroxyalkyl groups such as, but not limited to, 2-hydroxyethyl, 3-hydroxypropyl, etc.; alkoxyalkyl groups such as, but not limited to, 3-methoxypropyl or 2-ethoxyethyl, etc., polyamides (including peptides) or polyethers;

[0172] R3, R5, R6, R7 and R8 are as described herein above for Formula II;

[0173] Each R 13 、R 14 、R 15 、R 16 and R 17 are independently selected from H, halogen, substituted or unsubstituted C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C8 cycloalkyl, C2-C 20 Cycloalkenyl, C2-C7 heterocycloalkyl, C6-C 10 Aryl, C2-C9 heteroaryl, OR', R'OR", C(O)R', C(O)OR', C(O)NR'R",

[0174] R'R"NC=NR'、R'C=NR",NR'R",CN、N=NR'、cyanate、NO2、OC(O)NR'R",

[0175] SR', S-SR', S(O)R', S(O)2R', S(O)2OR', S(O)2NR', C(O)SR', C(S)SR', C(S)NR', ​​B(OH)2, B(OR')(OR"), PR'3, PR'2, P(OR')2, OP(OR')2, P(O)(OR')2, OP(O)(OR')2, polyamide or polyether;

[0176] R' and R" are independently selected from H, substituted or unsubstituted C1-C 20 Alkyl, C1-C 20 Alkenyl, C2-C 20 Alkynyl, C2-C 20 Cycloalkyl, C2-C 20 Cycloalkenyl, C2-C 20 Heterocycloalkyl, C6-C 10 Aryl, C2-C9 heteroaryl, polyamide and polyether.

[0177] In some embodiments, R1 and R2 of the compounds of Formula I and II are independently selected from H, substituted or unsubstituted C1-C8 aminoalkyl, C1-C8 hydroxyalkyl, C1-C8 alkyl isocyanate, C1-C8 alkyl isothiocyanate, COOR' or COSR'; and salts thereof; or R1 and R2 form a cyclic moiety, wherein the cyclic moiety is Formula III or Formula IV:

[0178]

[0179] in:

[0180] R 11 and R 12 are independently H or alkyl; and

[0181] R' and R" are independently H, substituted or unsubstituted C1-C 20 Alkyl, C1-C 20 Alkenyl, C2-C 20 Alkynyl, C2-C 20 Cycloalkyl, C2-C 20 Cycloalkenyl, C2-C 20 Heterocycloalkyl, C6-C 10 Aryl, C2-C9 heteroaryl, polyamide or polyether.

[0182] In some embodiments, the compounds of Formula I and Formula II or their salts are multimers, such as dimers or trimers.

[0183] One aspect of the present disclosure relates to cis and / or trans compounds having the structure of Formula V and / or VI, or salts thereof:

[0184]

[0185] in:

[0186] R1 is H, CN, alkyl isocyanate, alkyl isothiocyanate, aryl isocyanate, aryl isothiocyanate or C(O)-XR z , X is O or NR';

[0187] R y and R z are independently H, substituted or unsubstituted C1-C 15 Alkyl, C1-C 15 Hydroxyalkyl, C1-C 15 Alkoxyalkyl, polyamide or polyether;

[0188] R 13 、R 14 、R 15 、R 16 and R 17 are independently H, halogen, substituted or unsubstituted C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C8 cycloalkyl, C2-C 20 Cycloalkenyl, C2-C7 heterocycloalkyl, C6-C 10Aryl, C2-C9 heteroaryl, OR', C(O)R', C(O)OR', C(O)NR'R", R'R"NC=NR', R'C=NR", NR'R", CN, N=NR', cyanate, NO2, OC(O)NR'R", SR', S-SR', S(O)R', S(O)2R', S(O)2OR', S(O)2NR', C(O)SR', C(S)SR', C(S)NR', ​​B(OH)2, B(OR')(OR"), PR'3, PR'2, P(OR')2, OP(OR')2, P(O)(OR')2, OP(O)(OR')2, polyamide or polyether;

[0189] R' and R" are independently H, substituted or unsubstituted C1-C 20 Alkyl, C1-C 20 Alkenyl, C2-C 20 Alkynyl, C2-C 20 Cycloalkyl, C2-C 20 Cycloalkenyl, C2-C 20 Heterocycloalkyl, C6-C 10 Aryl, C2-C9 heteroaryl, polyamide or polyether;

[0190] R3, R5, R6, R7, R8, R9 and R 10 As defined for Formula I.

[0191] R y and R z is independently H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-isopentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, 2-ethoxyethyl, 3-methoxypropyl, a polyamide, or a polyether; and

[0192] R 13 、R 14 、R 15 、R 16 and R 17 and independently H, halogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, hydroxy, methoxy, ethoxy, 2-ethoxyethyl, 3-methoxypropyl, amino, methylamino, dimethylamino, trimethylammonium, trifluoromethyl, or NO2.

[0193] In some embodiments of Formulas I and II, the compound having a cis and / or trans structure has Formula V or Formula VI:

[0194]

[0195] or a salt thereof,

[0196] in:

[0197] R1 is selected from H, -CN, alkyl isocyanate, alkyl isothiocyanate, aryl isocyanate, aryl isothiocyanate and C(O)-XR z ;

[0198] Each R 13 、R 14 、R 15 、R 16 and R 17 are independently selected from H, halogen, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C 20 cycloalkenyl, optionally substituted C2-C7 heterocycloalkyl, optionally substituted C6-C 10 Aryl, optionally substituted C2-C9 heteroaryl, -OR', -C(O)R', -C(O)OR', -C(O)NR'R", -C(=NR')NR'R", -C(=NR")R', -NR'R", -CN, -N=NR', cyanate, -OCN, -NO2, -OC(O)NR'R", -SR', -S-SR', -S(O)R', -S(O)2R', -S(O)2OR', -S(O)2NR', -C(O)SR', -C(S)SR', -C(S)NR', ​​-B(OH)2, -B(OR')(OR"), -PR'2, -P(OR')2, -OP(OR')2, -P(O)(OR')2, -OP(O)(OR')2, polyamides and polyethers.

[0199] In some embodiments of Formulas V and VI, R1 is -CN.

[0200] In some embodiments of Formulas V and VI, R1 is -C(O)-XR z .

[0201] In some embodiments of Formulas V and VI, R y and R z is an optionally substituted C 1-15 alkyl.

[0202] In some embodiments of Formulas V and VI, X is O.

[0203] In some embodiments of Formulas V and VI, X is NH.

[0204] In some embodiments of Formulas I, II, V, and VI:

[0205] Each R y and R z is independently selected from H, methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, 2-ethoxyethyl, and 3-methoxypropyl; and

[0206] Each R3, R5, R6, R7, R8, R9, R 10 、R 13 、R 14 、R 15 、R 16 and R 17 independently selected from H, halogen, methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, hydroxy, methoxy, ethoxy, 2-ethoxyethyl, 3-methoxypropyl, amino, methylamino, dimethylamino, trimethylammonium, trifluoromethyl, and -NO

[0207] In some embodiments of Formulas I, II, V, and VI, R y and R z Independently selected from

[0208]

[0209] In some embodiments of Formulas I, II, V, and VI, R4 is selected from

[0210]

[0211] In some embodiments, the compounds of Formula I and II or their salts are in multimeric form.

[0212] Aspects of the present disclosure include multimeric compounds of Formula VII or Formula VIII:

[0213]

[0214] or a salt thereof,

[0215] in:

[0216] Each R1 is independently selected from H, -CN, alkyl isocyanate, alkyl isothiocyanate, aryl isocyanate, aryl isothiocyanate and C(O)-XR z ;

[0217] X is O or NR';

[0218] T is a linking moiety selected from the group consisting of: optionally substituted C1-C 20 Alkylene, optionally substituted C2-C 20 Alkenylene, optionally substituted C2-C 20 Alkynylidene, optionally substituted C2-C 20 Alkoxyalkylene, optionally substituted C2-C 20 Cycloalkylene, optionally substituted C2-C 20 Cycloalkenylene and optionally substituted C2-C 20 Heterocycloalkylene, wherein one or more carbon atoms of the backbone of the linking moiety T are optionally replaced by a divalent group each independently selected from the group consisting of oxygen (—O—), carbonyl (—CO—), optionally substituted alkylamino, optionally substituted cycloalkylene, optionally substituted heterocyclylene, optionally substituted heteroarylene, and optionally substituted arylene;

[0219] Each R z are independently selected from H, optionally substituted C 1-15 Alkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxyalkyl, polyamides and polyethers;

[0220] Each R3, R5, R6, R7, R8, R9, R 10 、R 13 、R 14 、R 15 、R 16 and R 17 are independently selected from H, halogen, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C 20 cycloalkenyl, optionally substituted C2-C7 heterocycloalkyl, optionally substituted C6-C 10Aryl, optionally substituted C2-C9 heteroaryl, -OR', -C(O)R', -C(O)OR', -C(O)NR'R", -C(=NR')NR'R", -C(=NR")R', -NR'R", -CN, -N=NR', cyanate, -OCN, -CNO, -NO2, -OC(O)NR'R", -SR', -S-SR', -S(O)R', -S(O)2R', -S(O)2OR', -S(O)2NR', -C(O)SR', -C(S)SR', -C(S)NR', ​​-B(OH)2, -B(OR')(OR"), PR'3, PR'2, -P(OR')2, -OP(OR')2, -P(O)(OR')2, -OP(O)(OR')2, polyamides and polyethers;

[0221] Each R' and R" is independently selected from H, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C2-C 20 Cycloalkyl, optionally substituted C2-C 20 Cycloalkenyl, optionally substituted C2-C 20 Heterocycloalkyl, optionally substituted C6-C 10 Aryl, optionally substituted C2-C9 heteroaryl, polyamide and polyether; and

[0222] n is selected from 2, 3, 4, 5 and 6.

[0223] In some embodiments, R1 is -CN.

[0224] In some embodiments, R1 is -C(O)-XR z .

[0225] In some embodiments, R z is independently optionally substituted C 1-15 alkyl.

[0226] In some embodiments, X is O.

[0227] In some embodiments, X is NH.

[0228] In some embodiments, the compound has Formula VII. In some embodiments, the compound has Formula VIII.

[0229] It will be understood that any of the embodiments of the chromophores of the compounds of Formulas I and II may also be applicable to multimeric and polymeric forms of the compounds.

[0230] In some embodiments, the compounds of Formulas I and II or their salts are conjugated to oligomers such as, but not limited to, oligopeptides, polypeptides, proteins, polyethylene glycol (PEG), polypropylene glycol (PPG), polyamides, polycarbonates, polyurethanes, polyureas, polyesters, oligosaccharides or polysaccharides, etc. Examples of polysaccharides include, but are not limited to, chitin, chitosan, cotton, cellulose, hemicellulose, pectin, etc. In some other embodiments, the compounds or their salts are copolymerized with ethylene oxide, propylene oxide, hydroxy acids, carboxylic acids, amines, isocyanate alcohols / amines, isothiocyanate alcohols / amines, etc. For example, when R1 and R2 are selected from polymerizable functional groups such as, but not limited to, carboxyl, C1-C8 aminoalkyl, such as aminomethyl, 2-aminoethyl, 3-aminopropyl, 4-aminopentyl, 6-aminohexyl and isomers thereof, etc.; C1-C8 hydroxyalkyl, such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxypentyl, 6-hydroxyhexyl and isomers thereof, etc.; C1-C8 alkyl isocyanate, such as methyl isocyanate, 2-ethyl isocyanate, 3-propyl isocyanate, 4-pentyl isocyanate, 6-hexyl isocyanate and isomers thereof, etc., and C1-C8 alkyl isothiocyanates, such as methyl thioisocyanate, 2-ethyl thioisocyanate, 3-propyl thioisocyanate, 4-pentyl thioisocyanate, 6-hexyl thioisocyanate and isomers thereof, which can be copolymerized with compounds such as but not limited to ethylene glycol, ethylene oxide, propylene glycol, propylene oxide, glycerol, C4-C6 polyols, ethylenediamine, propylenediamine, 1,4-butanediamine (putrescine), 1,5-diaminopentane (cadaverine), 1,6-hexanediamine, dithiocyanates and diisocyanate derivatives by methods well known in the art.

[0231] In some embodiments, the oligomer or polymer comprises a chromophore of Formula XI or XII:

[0232]

[0233] in:

[0234] Each R3, R5, R6, R7, R8, R9, R 10 、R 13 、R 14 、R 15 、R 16 and R 17 are independently selected from H, halogen, substituted or unsubstituted C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C8 cycloalkyl, C2-C 20 Cycloalkenyl, C2-C7 heterocycloalkyl, C6-C 10Aryl, C2-C9 heteroaryl, OR', C(O)R', C(O)OR', C(O)NR'R", R'R"NC=NR', R'C=NR", NR'R", CN, N=NR', cyanate, NO2, OC(O)NR'R", SR', S-SR', S(O)R', S(O)2R', S(O)2OR', S(O)2NR', C(O)SR', C(S)SR', C(S)NR', ​​B(OH)2, B(OR')(OR"), PR'3, PR'2, P(OR')2, OP(OR')2, P(O)(OR')2, OP(O)(OR')2, polyamides and polyethers; and

[0235] R' and R" are independently H, substituted or unsubstituted C1-C 20 Alkyl, C1-C 20 Alkenyl, C2-C 20 Alkynyl, C2-C 20 Cycloalkyl, C2-C 20 Cycloalkenyl, C2-C 20 Heterocycloalkyl, C6-C 10 Aryl, C2-C9 heteroaryl, polyamide or polyether.

[0236] The present disclosure provides oligomers and polymers comprising monomer repeat units of formula XI and / or XII, these monomer repeat units being linked together using suitable linking chemistry or linking moieties. Exemplary linking moieties are described herein. In certain embodiments, the oligomers and polymers are characterized by polyethers, polyesters, polyamides, polycarbonates, polyurethanes, polyureas or polysaccharides. In certain embodiments, the monomer precursors of the oligomers and polymers of the present disclosure are compounds of formula I and / or II.

[0237] The present disclosure provides copolymers comprising monomer repeat units of formula XI and / or XII, and one or more additional comonomers of interest and / or terminal groups or conjugated moieties of interest. The copolymers can be random copolymers or block copolymers.

[0238] In some embodiments, the oligomer or polymer has an average length or degree of polymerization in the range of 5-5000 repeat units (such as 5-1000, 5-500, 5-100, or 10-100). In some embodiments, the length is 5-100 (such as 5-50, 10-50, 10-40, 10-30, or 10-20) repeat units.

[0239] In oligomer or polymer, the amount of chromophore (for example, the number of repeating units of formula) will vary depending on required application.In certain embodiments, oligomer or polymer can be a homologous oligomer or homopolymer of formula I or II compound.Oligomer or polymer are obtained by copolymerization with different mol ratios of formula I or II compound or its salt and other monomers, and these mol ratios are such as but not limited to 1:1,1:10,1:20,1:30,1:50,1:100,1:150,1:200,1:300,1:400,1:500,1:700,1:1000,1:1500 or 1:200.

[0240] In a preferred embodiment, the one or more compounds have the structural formula IX:

[0241]

[0242] in:

[0243] X is O or NR';

[0244] L is C1-C 20 Alkyl, alkenyl, alkynyl, alkoxyalkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, aryl, heteroaryl, polyamide or polyether;

[0245] R3, R5, R6, R7, R8, R9, R 10 、R 13 、R 14 、R 15 、R 16 and R 17 As defined herein for Formula V;

[0246] and

[0247] n is any number of at least 2, 3, 4, 5, 10, 20, 100, 150, 300, 500, 1000 or more repeating units.

[0248] In a second preferred embodiment, one or more compounds have the structure of formula X:

[0249]

[0250] in:

[0251] X is O or NR';

[0252] L is a substituted or unsubstituted C1-C 20 Alkyl, alkenyl, alkynyl, alkoxyalkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, aryl, heteroaryl, polyamide or polyether;

[0253] R3, R5, R6, R7, R8, R 13、R 14 、R 15 、R 16 and R 17 As defined herein for Formula VI; and

[0254] n is any number of at least 2, 3, 4, 5, 10, 20, 100, 150, 300, 500, 1000 or more repeating units.

[0255] In some embodiments, the oligomeric or polymeric compound has Formula IX or X:

[0256]

[0257] or its salt,

[0258] in:

[0259] Each X is independently O or NR';

[0260] L is a divalent linking moiety selected from the group consisting of: optionally substituted C1-C 20 Alkylene, optionally substituted C1-C 20 Alkenylene, optionally substituted C2-C 20 Alkynylidene, optionally substituted C2-C 20 Alkoxyalkylene, optionally substituted C2-C 20 Cycloalkylene, optionally substituted C2-C 20 Cycloalkenylene, optionally substituted C2-C 20 Heterocycloalkylene, wherein one or more carbon atoms of the L backbone are optionally replaced by a divalent group each independently selected from the group consisting of oxygen (—O—), carbonyl (—CO—), optionally substituted alkylamino, optionally substituted cycloalkylene, optionally substituted heterocyclylene, optionally substituted heteroarylene, optionally substituted arylene, polyamide, and polyether;

[0261] Each R3, R5, R6, R7, R8, R9, R 10 、R 13 、R 14 、R 15 、R 16 and R 17 are independently selected from H, halogen, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C 20 cycloalkenyl, optionally substituted C2-C7 heterocycloalkyl, optionally substituted C6-C 10Aryl, optionally substituted C2-C9 heteroaryl, -OR', -C(O)R', -C(O)OR', -C(O)NR'R", -C(=NR')NR'R", -C(=NR")R', -NR'R", -CN, -N=NR', cyanate, -OCN, -NCO, -NO2, -OC(O)NR'R", -SR', -S-SR', -S(O)R', -S(O)2R', -S(O)2OR', -S(O)2NR', -C(O)SR', -C(S)SR', -C(S)NR', ​​-B(OH)2, -B(OR')(OR"), PR'3, -PR'2, -P(OR')2, -OP(OR')2, -P(O)(OR')2, -OP(O)(OR')2, polyamides and polyethers;

[0262] Each R' and R" is independently selected from H, optionally substituted C1-C 20 Alkyl, optionally substituted C1-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C2-C 20 Cycloalkyl, optionally substituted C2-C 20 Cycloalkenyl, optionally substituted C2-C 20 Heterocycloalkyl, optionally substituted C6-C 10 Aryl, optionally substituted C2-C9 heteroaryl, polyamides and polyethers;

[0263] n is at least 2, 3, 4, 5, 10, 20, 100, 150, 300, 500 or 1000.

[0264] In some embodiments, the oligomer or polymer has an n value representing the average degree of polymerization. In some embodiments, n is in the range of 5-5000 (such as 5-1000, 5-500, 5-100 or 10-100). In some embodiments, n is 5-50, such as 10-50, 10-40, 10-30 or 10-20.

[0265] In some embodiments, the compound is a homo-oligomer or homopolymer. In some embodiments, the compound is an oligomer or polymer that is a polyether, polyester, polyamide, polycarbonate, polyurethane, polyurea, or polysaccharide.

[0266] In some embodiments, the one or more compounds capable of absorbing UV-A and / or UV-B are selected from the compounds listed in Table 6.

[0267] Typically, the compounds of the present disclosure have an absorption maximum (λ) in the range of 270-400 nm, preferably 280-390 nm, preferably 290-380 nm, more preferably 295-375, even more preferably 300-375 nm, and most preferably 315-375 nm. 最大 ), and in λ 最大 The M of the present invention is at least 10,000, preferably at least 12,000, preferably at least 14,000, preferably at least 16,000, more preferably at least 18,000, and most preferably at least 20,000. -1 cm -1 In some formulations of the composition, the ability of the UV absorbing compound is expressed as a mass absorption coefficient (i.e., at λ over a one centimeter optical path length). 最大 A maximum concentration of 1 g / dL of absorption may be more convenient and is designated herein and hereinafter as E 1％ Thus, suitable compounds for use in the composition have a kinetic energy of at least 400, preferably at least 500, more preferably at least 600, more preferably at least 700, even more preferably at least 800, and most preferably at least 900 dL·g -1 cm -1 E 1％ .

[0268] Cosmetic composition:

[0269] Composition

[0270] The present disclosure provides UV absorbing compositions comprising one or more compounds of Formula I, II, and / or VX (eg, as described above).

[0271] In some embodiments of the composition, one or more compounds have the structure of Formula I.

[0272] In some other embodiments of the composition, one or more compounds has the structure of Formula II.

[0273] In yet another embodiment of the composition, two or more compounds have the structures of Formula I and Formula II.

[0274] In a preferred embodiment of the composition, one or more compounds are selected from compounds E1-E64 in Table 6.

[0275] In another preferred embodiment, the one or more compounds have a cis and / or trans structure of Formula V or a salt thereof:

[0276]

[0277] in:

[0278] R1 is H, CN, alkyl isocyanate, alkyl isothiocyanate, aryl isocyanate, aryl isothiocyanate or C(O)-XR z ;

[0279] X is O or NR';

[0280] Each R y and R z are independently selected from H, substituted or unsubstituted C1-C 15 Alkyl, C1-C 15 Hydroxyalkyl, C1-C 15 Alkoxyalkyls, polyamides, and polyethers;

[0281] Each R 13 、R 14 、R 15 、R 16 and R 17 are independently selected from H, halogen, substituted or unsubstituted C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C8 cycloalkyl, C2-C 20 Cycloalkenyl, C2-C7 heterocycloalkyl, C6-C 10 Aryl, C2-C9 heteroaryl, OR', C(O)R', C(O)OR', C(O)NR'R", R'R"NC=NR', R'C=NR", NR'R", CN, N=NR', cyanate, NO2, OC(O)NR'R", SR', S-SR', S(O)R', S(O)2R', S(O)2OR', S(O)2NR', C(O)SR', C(S)SR', C(S)NR', ​​B(OH)2, B(OR')(OR"), PR'3, PR'2, P(OR')2, OP(OR')2, P(O)(OR')2, OP(O)(OR')2, polyamides and polyethers;

[0282] Each R' and R" is independently selected from H, substituted or unsubstituted C1-C 20 Alkyl, C1-C 20 Alkenyl, C2-C 20 Alkynyl, C2-C 20 Cycloalkyl, C2-C 20 Cycloalkenyl, C2-C 20 Heterocycloalkyl, C6-C 10 Aryl, C2-C9 heteroaryl, polyamide, and polyether; and

[0283] R3, R5, R6, R7, R8, R9 and R 10 As defined for Formula I.

[0284] In some embodiments of the composition, R y and R z R is independently H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-isopentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, 2-ethoxyethyl, 3-methoxypropyl, a polyamide, or a polyether; and R 13 、R 14 、R 15 、R 16 and R 17 and independently H, halogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, hydroxy, methoxy, ethoxy, 2-ethoxyethyl, 3-methoxypropyl, amino, methylamino, dimethylamino, trimethylammonium, trifluoromethyl, or NO2.

[0285] In another preferred embodiment, the one or more compounds have the cis and / or trans structure of Formula VI or a salt thereof:

[0286]

[0287] in:

[0288] R1 is H, CN, alkyl isocyanate, alkyl isothiocyanate, aryl isocyanate, aryl isothiocyanate or C(O)-XR z ;

[0289] X is O or NR';

[0290] Each R y and R z are independently selected from H, substituted or unsubstituted C1-C 15 Alkyl, C1-C 15 Hydroxyalkyl, C1-C 15 Alkoxyalkyls, polyamides, and polyethers;

[0291] Each R 13 、R 14 、R 15 、R 16 and R 17 are independently selected from H, halogen, substituted or unsubstituted C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C8 cycloalkyl, C2-C 20Cycloalkenyl, C2-C7 heterocycloalkyl, C6-C 10 Aryl, C2-C9 heteroaryl, OR', C(O)R', C(O)OR', C(O)NR'R", R'R"NC=NR', R'C=NR", NR'R", CN, N=NR', cyanate, NO2, OC(O)NR'R", SR', S-SR', S(O)R', S(O)2R', S(O)2OR', S(O)2NR', C(O)SR', C(S)SR', C(S)NR', ​​B(OH)2, B(OR')(OR"), PR'3, PR'2, P(OR')2, OP(OR')2, P(O)(OR')2, OP(O)(OR')2, polyamides and polyethers;

[0292] Each R' and R" is independently selected from H, substituted or unsubstituted C1-C 20 Alkyl, C1-C 20 Alkenyl, C2-C 20 Alkynyl, C2-C 20 Cycloalkyl, C2-C 20 Cycloalkenyl, C2-C 20 Heterocycloalkyl, C6-C 10 Aryl, C2-C9 heteroaryl, polyamide, and polyether; and

[0293] R3, R5, R6, R7 and R8 are as defined for Formula II.

[0294] In some embodiments of the composition, R y and R z R is independently H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-isopentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, 2-ethoxyethyl, 3-methoxypropyl, a polyamide, or a polyether; and R 13 、R 14 、R 15 、R 16 and R 17 and independently H, halogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, hydroxy, methoxy, ethoxy, 2-ethoxyethyl, 3-methoxypropyl, amino, methylamino, dimethylamino, trimethylammonium, trifluoromethyl, or NO2.

[0295] In another preferred embodiment, the one or more compounds have the cis and / or trans structure of Formula VII or a salt thereof:

[0296]

[0297] in:

[0298] Each R1 is independently selected from H, -CN, alkyl isocyanate, alkyl isothiocyanate, aryl isocyanate, aryl isothiocyanate and C(O)-XR z ;

[0299] X is O or NR';

[0300] T is a linking moiety selected from the group consisting of: optionally substituted C1-C 20 Alkylene, optionally substituted C2-C 20 Alkenylene, optionally substituted C2-C 20 Alkynylidene, optionally substituted C2-C 20 Alkoxyalkylene, optionally substituted C2-C 20 Cycloalkylene, optionally substituted C2-C 20 Cycloalkenylene and optionally substituted C2-C 20 Heterocycloalkylene, wherein one or more carbon atoms of the backbone of the linking moiety T are optionally replaced by a divalent group each independently selected from the group consisting of oxygen (—O—), carbonyl (—CO—), optionally substituted alkylamino, optionally substituted cycloalkylene, optionally substituted heterocyclylene, optionally substituted heteroarylene, and optionally substituted arylene;

[0301] Each R z are independently selected from H, optionally substituted C 1-15 Alkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxyalkyl, polyamides and polyethers;

[0302] Each R3, R5, R6, R7, R8, R9, R 10 、R 13 、R 14 、R 15 、R 16 and R 17 are independently selected from H, halogen, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C 20 cycloalkenyl, optionally substituted C2-C7 heterocycloalkyl, optionally substituted C6-C 10Aryl, optionally substituted C2-C9 heteroaryl, -OR', -C(O)R', -C(O)OR', -C(O)NR'R", -C(=NR')NR'R", -C(=NR")R', -NR'R", -CN, -N=NR', cyanate, -OCN, -CNO, -NO2, -OC(O)NR'R", -SR', -S-SR', -S(O)R', -S(O)2R', -S(O)2OR', -S(O)2NR', -C(O)SR', -C(S)SR', -C(S)NR', ​​-B(OH)2, -B(OR')(OR"), PR'3, PR'2, -P(OR')2, -OP(OR')2, -P(O)(OR')2, -OP(O)(OR')2, polyamides and polyethers;

[0303] Each R' and R" is independently selected from H, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C2-C 20 Cycloalkyl, optionally substituted C2-C 20 Cycloalkenyl, optionally substituted C2-C 20 Heterocycloalkyl, optionally substituted C6-C 10 Aryl, optionally substituted C2-C9 heteroaryl, polyamide and polyether; and

[0304] n is selected from 2, 3, 4, 5 and 6.

[0305] In some embodiments of the composition, T is ethylene, trimethylene, tetramethylene, pentamethylene, 3,3-dimethylpentamethylene, 2,2,3,3-tetramethyltetramethylene, 1,2,3-propanetriyl, benzene-1,2-ylidene, benzene-1,3-ylidene, benzene-1,4-ylidene, bis(ethylene) or 1,3,5-triazine-2,4,6-triyl; each R z are independently selected from H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-isopentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, 2-ethoxyethyl, 3-methoxypropyl, polyamides, and polyethers; and each R 13 、R 14 、R 15 、R 16 and R 17independently selected from H, halogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, hydroxy, methoxy, ethoxy, 2-ethoxyethyl, 3-methoxypropyl, amino, methylamino, dimethylamino, trimethylammonium, trifluoromethyl, and NO2.

[0306] In another preferred embodiment, the one or more compounds have the cis and / or trans structure of Formula VIII or a salt thereof:

[0307]

[0308] in:

[0309] Each R1 is independently selected from H, -CN, alkyl isocyanate, alkyl isothiocyanate, aryl isocyanate, aryl isothiocyanate and C(O)-XR z ;

[0310] X is O or NR';

[0311] T is a linking moiety selected from the group consisting of: optionally substituted C1-C 20 Alkylene, optionally substituted C2-C 20 Alkenylene, optionally substituted C2-C 20 Alkynylidene, optionally substituted C2-C 20 Alkoxyalkylene, optionally substituted C2-C 20 Cycloalkylene, optionally substituted C2-C 20 Cycloalkenylene and optionally substituted C2-C 20 Heterocycloalkylene, wherein one or more carbon atoms of the backbone of the linking moiety T are optionally replaced by a divalent group each independently selected from the group consisting of oxygen (—O—), carbonyl (—CO—), optionally substituted alkylamino, optionally substituted cycloalkylene, optionally substituted heterocyclylene, optionally substituted heteroarylene, and optionally substituted arylene;

[0312] Each R z are independently selected from H, optionally substituted C 1-15 Alkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxyalkyl, polyamides and polyethers;

[0313] Each R3, R5, R6, R7, R8, R 13 、R 14 、R 15 、R 16 and R 17 are independently selected from H, halogen, optionally substituted C1-C 20Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C 20 cycloalkenyl, optionally substituted C2-C7 heterocycloalkyl, optionally substituted C6-C 10 Aryl, optionally substituted C2-C9 heteroaryl, -OR', -C(O)R', -C(O)OR', -C(O)NR'R", -C(=NR')NR'R", -C(=NR")R', -NR'R", -CN, -N=NR', cyanate, -OCN, -CNO, -NO2, -OC(O)NR'R", -SR', -S-SR', -S(O)R', -S(O)2R', -S(O)2OR', -S(O)2NR', -C(O)SR', -C(S)SR', -C(S)NR', ​​-B(OH)2, -B(OR')(OR"), PR'3, PR'2, -P(OR')2, -OP(OR')2, -P(O)(OR')2, -OP(O)(OR')2, polyamides and polyethers;

[0314] Each R' and R" is independently selected from H, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C2-C 20 Cycloalkyl, optionally substituted C2-C 20 Cycloalkenyl, optionally substituted C2-C 20 Heterocycloalkyl, optionally substituted C6-C 10 Aryl, optionally substituted C2-C9 heteroaryl, polyamide and polyether; and

[0315] n is selected from 2, 3, 4, 5 and 6.

[0316] In some embodiments of the composition, T is ethylene, trimethylene, tetramethylene, pentamethylene, 3,3-dimethylpentamethylene, 2,2,3,3-tetramethyltetramethylene, 1,2,3-propanetriyl, benzene-1,2-ylidene, benzene-1,3-ylidene, benzene-1,4-ylidene, bis(ethylene) or 1,3,5-triazine-2,4,6-triyl; each R z are independently selected from H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-isopentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, 2-ethoxyethyl, 3-methoxypropyl, polyamides, and polyethers; and each R 13 、R14 、R 15 、R 16 and R 17 independently selected from H, halogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, hydroxy, methoxy, ethoxy, 2-ethoxyethyl, 3-methoxypropyl, amino, methylamino, dimethylamino, trimethylammonium, trifluoromethyl, and NO2.

[0317] In yet another preferred embodiment, one or more compounds have the cis and / or trans structure of Formula IX or a salt thereof:

[0318]

[0319] in:

[0320] X is O or NR';

[0321] L is a substituted or unsubstituted C1-C 20 Alkyl, alkenyl, alkynyl, alkoxyalkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, aryl, heteroaryl, polyamide or polyether;

[0322] Each R 13 、R 14 、R 15 、R 16 and R 17 are independently selected from H, halogen, substituted or unsubstituted C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C8 cycloalkyl, C2-C 20 Cycloalkenyl, C2-C7 heterocycloalkyl, C6-C 10 Aryl, C2-C9 heteroaryl, OR', C(O)R', C(O)OR', C(O)NR'R", R'R"NC=NR', R'C=NR", NR'R", CN, N=NR', cyanate, NO2, OC(O)NR'R", SR', S-SR', S(O)R', S(O)2R', S(O)2OR', S(O)2NR', C(O)SR', C(S)SR', C(S)NR', ​​B(OH)2, B(OR')(OR"), PR'3, PR'2, P(OR')2, OP(OR')2, P(O)(OR')2, OP(O)(OR')2, polyamides and polyethers;

[0323] Each R' and R" is independently selected from H, substituted or unsubstituted C1-C 20Alkyl, C1-C 20 Alkenyl, C2-C 20 Alkynyl, C2-C 20 Cycloalkyl, C2-C 20 Cycloalkenyl, C2-C 20 Heterocycloalkyl, C6-C 10 Aryl, C2-C9 heteroaryl, polyamide, and polyether; and

[0324] Each of R3, R5, R6, R7, R8, R9 and R 10 As defined for Formula I.

[0325] In some embodiments of the compositions, each R 13 、R 14 、R 15 、R 16 and R 17 independently selected from H, halogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, hydroxy, methoxy, ethoxy, 2-ethoxyethyl, 3-methoxypropyl, amino, methylamino, dimethylamino, trimethylammonium, trifluoromethyl, and NO2.

[0326] In some embodiments, the composition is a sunscreen comprising one or more selected from moisturizers, emollients, preservatives, buffers, chelating agents, fragrances, antioxidants, antimicrobials, thickeners, dry feel modifiers, and solvents.

[0327] In some embodiments, the sunscreen composition comprises cis and / or trans compounds of Formula V, VI, VII, VIII, IX, and / or X in an amount ranging from 0.01 wt% to 50 wt%.

[0328] In preferred embodiments, the sunscreen composition is a solution, lotion, emulsion, cream, gel, aerosol, or spray.

[0329] In another preferred embodiment, the composition is a cosmetic composition formulated as a solution, emulsion, lotion, cream, lotion, foam, gel, ointment, paste, suspension, stick, powder, wax, tablet, aerosol or spray.

[0330] In a more preferred embodiment, the cosmetic composition is a hair product.

[0331] In another more preferred embodiment, the cosmetic composition is formulated for application on the lips.

[0332] In yet another more preferred embodiment, the cosmetic composition is formulated for hair removal.

[0333] preparation

[0334] The UV absorbing compounds or salts thereof described herein can be formulated into the compositions of the present disclosure individually or in any combination by methods well known in the art. In addition, the compounds of the present disclosure can be formulated with other known UV absorbing compounds and other ingredients used in sunscreen compositions and other cosmetic products to produce the desired cosmetic compositions. Examples of UV absorbing compounds approved by U.S. and / or European regulatory agencies for use in cosmetic compositions (including over-the-counter sunscreens) are listed in Tables 1 and 2. Such cosmetic compositions include, but are not limited to, sunscreen compositions with different sun protection factors (SPF), tanning preparations, skin conditioners; hair care compositions including, but not limited to, hair tonics, styling preparations, pomades, shampoos, conditioners, hair dyes, care packs, hair treatments, hair straightening preparations, hair styling preparations, face foundations (loose powder or pressed powder), eye shadows, eyeliners, eye creams, eye-fix creams, and mascara; lip care products such as, but not limited to, lipsticks, lip balms, lip glosses, lip liners, and the like; nail care products including, but not limited to, nail polishes, nail polish removers, nail hardeners, nail polishes, and nail polishes. polish) or cuticle remover; foot cream, foot balm, foot bath, foot powder, insect repellent, deodorant, antiperspirant, shaving products, such as but not limited to soap, cream, foaming cream, foam, gel, aftershave, aftershave lotion, fragrance, etc. are well known in different forms, such as but not limited to spray, lotion, gel, emulsion, cream, foam, spray, solid, wax, etc. For sunscreen and cosmetic compositions, see, for example, U.S. Patent Nos. 20040062729, 20040136932, 20050013782, 20080014155, 20080305057, 20090035234, 20100135939, 20110200543, 20120148647, 20130078204 and 20160256371;U.S. Patents 2,104,492, 2,276,204, 2,327,899, 2,395,665, 2,853,423, 2,874,090, 2,974,089, 3,004,896, 3,175,950, 3,238,138, 3,244,708, 3,269,903, 3,275,520, 3,403,207, 3,479,428, 3,529,055, 3,697,642, 3,864,473, 3,895,104, 4,036,951, 4,069,309, 4, 107,290, 4,401,649, 4,489,057, 4,559,225, 4,663,155, 4,671,955, 4,686,099, 4,710,371, 4,710,373, 4,810,489, 4,826,978, 4,891,212, 4,940,574, 4,935,533, 5,152,983, 5,217,709, 5,372,805, 5,338,539, 5,429,820, 5,447,715, 5,516,506, 5,538,71 6, 5,573,753, 5,587,150, 5,605,680, 5,945,090, 5,945,091, 6,048,517, 6,103,221, 6,165,449, 6,197,281, 6,416,773, 6,419,907, 6,890,521, 6,899,866, 6,919,473, 6,962,692, 7,087,692, 7,166,273; 7,108,860, 7,235,587, 7,361,785, 7,446,230, 7,50 4,528, 7,550,134, 7,713,519, 7,611696, 7,893,292, 7,959,834, 8,039,532, 8,044,058, 8,158,678, 8,829,192, 8,236,287, 8,540,972, 8,557,227, 8,628,757, 8,697,035, 8,877,166, 8,992,895, 9,539,194, 9,539,195, 9,550,730, 10,632,096, 11,291,621;and CH350461A, DE202010006005U1, EP0376511A2, EP0950398A2, FR2526658A2, FR2768730A1, FR2818142B1, FR2852840A1, GB2081716A, WO1992019208A1, WO1994007460A1, WO1996041614 A1, WO2008811701A1, and WO2010020668A1, each of which is herein incorporated by reference in its entirety. For hair care products, such as, but not limited to, shampoo, hair dye, and conditioner compositions, see, for example, U.S. Patents 4,551,330, 5,553,630, 6,190,645, 8,044,058, and 8,829,192; and EP 0 165 710 A1 and DE 102 40 863 A1, each of which is incorporated herein by reference in its entirety.;

[0335] Effective UV protection requires the use of a combination of UV-A and / or UV-B absorbing compounds to cover the entire erythemal action spectrum (290-400 nm). Typically, the formulation will contain at least one effective UV-absorbing compound for each segment of the erythemal action spectrum, such as UV-B (290-320 nm), UV-A II (320-340 nm), and UV-A I (340-400 nm). Some compounds absorb UV radiation in two or more segments of the erythemal action spectrum, allowing a reduced concentration of sunscreen ingredients to produce an effective UV-absorbing formulation. Disclosed herein are compounds of the present disclosure or salts thereof for use in formulating cosmetic compositions comprising sunscreens in an amount ranging from 0.01-50 wt.%, preferably 0.03-40 wt.%, preferably 0.07-30 wt.%, preferably 0.10-25 wt.%, preferably 0.15-20 wt.%, more preferably 0.2-15 wt.%, even more preferably 0.3-12 wt.%, and most preferably 0.5-10 wt.%, of the total weight of the composition. In some embodiments, the amount of UV absorbing compound will be in the range of 1.0 wt.% to 7.5 wt.% of the total weight of the composition. In some cases, one or more of the compounds of the present disclosure may be sufficient to produce the desired cosmetic composition. In some other cases, one or more compounds or salts thereof may be combined with other known UV absorbing ingredients currently on the market to produce a composition that provides broad-spectrum UV protection. Some cosmetic compositions of the present disclosure may contain one or more SPF boosters, sunscreen solvents, and photostabilizers, such as, but not limited to, those listed in Table 3.

[0336] Sunscreen compositions comprising only one or more compounds of the present disclosure, or salts thereof, use less than 24 wt.%, preferably less than 20 wt.%, preferably less than 18 wt.%, more preferably less than 15 wt.%, more preferably less than 14 wt.%, even more preferably less than 13 wt.%, even more preferably less than 12 wt.%, and most preferably less than 10 wt.% of total UV-absorbing ingredients, based on the total weight of the composition, to achieve an SPF of 50, 45, 40, 35, 30, 25, 20, 15, or 10. In combination with other sunscreen ingredients, the amount can be reduced to less than 15 wt.%, preferably less than 12 wt.%, more preferably less than 10 wt.%, or even less than 7 wt.%, based on the total weight of the composition.

[0337] Table 1

[0338] FDA-approved over-the-counter (OTC) sunscreen ingredients

[0339]

[0340] Table 2

[0341] EU approved ingredients

[0342]

[0343]

[0344]

[0345] Table 3

[0346] SPF boosters / sunscreen solvents / light stabilizers that can be used.

[0347]

[0348] In some embodiments, the cosmetic compositions of the present disclosure may contain skin tanning and / or browning agents (self-tanning agents), such as, but not limited to, dihydroxyacetone (DHA).

[0349] In addition, the compositions of the present disclosure may comprise one or more cosmetic additives such as, but not limited to, fatty substances, vegetable oils, water, organic solvents, ionic or nonionic thickeners, softeners, humectants, antioxidants, emollients, peeling agents, free radical scavengers, anti-pollution agents, antibacterial agents, anti-inflammatory agents, depigmenting agents, pro-pigmenting agents, sunscreens, stabilizers, moisturizers, silicones, antifoaming agents, insect repellents, fragrances, preservatives, anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic or amphoteric surfactants, fillers, pigments, polymers, propellants, acidifying or alkalizing agents, or any other ingredient commonly used in cosmetics and / or dermatological applications.

[0350] The fatty substance may consist of an oil, a wax or a mixture thereof. The term "oil" means a compound that is liquid at room temperature. The term "wax" means a compound that is solid or substantially solid at room temperature and whose melting point is generally above 35°C. Oils that may be mentioned include: mineral oils such as paraffin; vegetable oils, including but not limited to sweet almond oil, macadamia oil, blackcurrant seed oil or jojoba oil; synthetic oils such as perhydrosqualene, fatty alcohols, fatty acids or fatty acid esters (e.g. FINSOLV TN TM Examples of the present invention include C12-C15 alcohol benzoates (sold under the trademark Benzyl Alcohol (C12-C15)), octyl palmitate, isopropyl lanoate, triglycerides (including capric / caprylic triglyceride), oxyethylenated or oxypropylated fatty esters and ethers; silicone oils, such as cyclomethicone, polydimethylsiloxane (PDMS); fluorinated oils and polyolefins. Waxy compounds that may be mentioned include paraffin, carnauba wax, beeswax and hydrogenated castor oil.

[0351] The cosmetic composition may contain one or more solvents selected from water or organic solvents, such as but not limited to ethyl acetate, acetone, or lower alcohols, such as but not limited to ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, isopentanol, hexanol and isomers thereof, etc. Polyols, such as but not limited to diols, including but not limited to ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol (two isomers) or diethylene glycol; glycerol, reducing sugars and their derivatives, such as but not limited to their methyl ether or ethyl ether.

[0352] Many suitable thickeners can be used to formulate the compositions of the present disclosure, such as, but not limited to, cross-linked acrylic acid polymers (such as, but not limited to, carbomers), acrylates / C10-C30 alkyl acrylate crosspolymers (such as, but not limited to, CO. under the name VISCOPHOBE TM PEMULEN sold by DB 1000 TM or polyacrylate-3), polyacrylamide (such as Under the name SEPIGEL 305 TM emulsions of polyacrylamide, C13-C14 isoparaffin and laureth-7 sold by Sales AMPS), modified or unmodified guar gum and cellulose (such as hydroxypropyl guar gum, methyl hydroxyethyl cellulose and hydroxypropyl methyl cellulose), xanthan gum and nano-sized silica of the Aerosil type (such as 200).

[0353] The composition of the present disclosure can be prepared as comprising one or more compounds of the present disclosure or its salt by technology well known to those skilled in the art, such as those intended to prepare oil-in-water or water-in-oil emulsions. Especially, the composition can be in the form of simple or complex emulsion (O / W, W / O, O / W / O or W / O / W emulsion), such as cream or milk, in the form of gel or cream-gel, or in the form of skin care lotion, oil, powder or solid tube, and can optionally be packaged as aerosol and can be in the form of mousse or spray. In certain embodiments, the composition is preferably in the form of oil-in-water or water-in-oil emulsion. The aqueous phase of the emulsion can include nonionic vesicle dispersions prepared according to known methods (see, for example, Bangham, Standish and Watkins, J.Mol.Biol.13,238 (1965), FR-2,315,991 and FR-2,416,008, each of which is incorporated by reference in its entirety). For human skin care products, the composition may be in the form of a suspension or dispersion in a solvent or a fatty substance, in the form of a non-ionic vesicular dispersion or in the form of an emulsion (preferably of the oil-in-water type, such as a cream or milk), or in the form of an ointment, a gel, a cream-gel, a sunscreen, a solid tube, a powder, an aerosol mousse or a spray.

[0354] In some embodiments, the composition is a hair care product. It can be in the form of a shampoo, lotion, gel, emulsion, or nonionic vesicle dispersion and can constitute, for example, a rinse-off composition for use before or after shampooing, before or after dyeing or bleaching, or before, during, or after permanently waving or smoothing hair; a styling or conditioning lotion or gel; a blow-drying or styling lotion or gel; or a composition for permanently waving, smoothing, dyeing, or bleaching hair.

[0355] In some other embodiments, the composition is a makeup composition, such as, but not limited to, nail polish, eyelash, eyebrow, or skin care products, including cuticle care creams, foundations, lipstick tubes, eye shadows, mascara, or eyeliners, which can be in solid or pasty, anhydrous or aqueous form, such as oil-in-water or water-in-oil emulsions, non-ionic vesicle dispersions or suspensions.

[0356] Disclosed herein is a sunscreen formulation of the oil-in-water emulsion type, wherein the water phase content is in the range of 50 wt.% to 95 wt.%, preferably in the range of 60 wt.% to 90 wt.%, and more preferably in the range of 70 wt.% to 90 wt.%; the oil phase is in the range of 5 wt.% to 50 wt.%, preferably in the range of 10 wt.% to 40 wt.%, and more preferably in the range of 15 wt.% to 30 wt.%, and the emulsifier is in the range of 0.5 wt.% to 20 wt.%, preferably in the range of 2 wt.% to 10 wt.%, and more preferably in the range of 3 wt.% to 7 wt.%.

[0357] A second aspect of the present disclosure relates to a method for protecting a subject from UV-A and UV-B radiation using a cosmetic composition. The method comprises applying an effective amount of the composition of the present disclosure to the skin or lips of the subject. Application can be by spray, aerosol, cream, lotion, stick, or the like. The subject can be any animal, preferably a mammal, and most preferably a human.

[0358] Composition for protecting surfaces from UV damage:

[0359] The UV absorbing compounds and salts thereof described herein can be incorporated into any well-known composition in the art for protecting surfaces from environmental damage, including but not limited to coatings, paints, resins, adhesives, polymers, shoe polishes, varnishes, floor washes and polishes, waxes, dyes, household products (such as, but not limited to, detergents, fabric softeners, etc.), abrasive cleaners; glass washers; neutral cleaners (such as all-purpose cleaners); kitchen and bathroom household cleaners; rinsers; dishwashing detergents; kitchen cleaners; oven cleaners; metal, glass and ceramic cleaners; fabric care products; carpet cleaners; rug shampoos; rust removing compositions, stains; furniture polishes; all-purpose polishes; leather and vinyl dressing compositions; etc. Furthermore, they can also be incorporated into materials (such as polymers) used in automobiles, aircraft, spacecraft, ships and boats, see, for example, publication US20050171253 and U.S. Patents 3,004,896, 3,134,748, 3,201,366, 3,205,193, 3,211,696, 3,213,058, 3,214,436, 3,218,285 、3,230,194、3,239,483、3,253,921、3,271,339、3,282,886、3,284,387、3,301,816、3,322,718、3,368,916、3,429,732、3,467,482、3,499,869、3,900,442、3,925,509、3,9 36,418, 3,954,706, 4,323,633, 4,344,830, 4,381,360, 4,431,762, 4,749,643, 4,816,504, 4,839,405, 5,086,097, 5,204,390, 5,330,672, 5,380,774, 5,674,670, 6,191,1 99, 6,194,493, 6,268,415, 6,296,674, 6,401,724, 6,797,751, 6,916,867, 6,930,136, 7,153,588, 7,695,643, 8,906,987, 10,596,087, and 10,619,098, each of which is incorporated herein by reference in its entirety. Additionally, fabric care compositions, such as, but not limited to, fabric softeners and detergents, are well known in the art, see, for example, U.S. Patents 4,153,744, 5,134,223, 5,330,672, 5,374,362, 5,474,691, 5,705,474, 5,723.435, 6,916,778, and 7,087,692, each of which is incorporated herein by reference in its entirety.

[0360] The UV absorbing compounds of the present disclosure and their salts, used alone or in combination with other known UV absorbing ingredients (such as, but not limited to, those listed in Table 4), can also be used as additives or to chemically modify organic materials such as, but not limited to, natural or synthetic organic polymers, adhesives, paints, etc. Examples include, but are not limited to, polymers of monoolefins and diolefins, mixtures of polymers of monoolefins and diolefins; copolymers of monoolefins and diolefins with each other or with other vinyl monomers; hydrocarbon resins, including hydrogenated modifications thereof (e.g., tackifiers) and mixtures of polyolefins and starch; polystyrene, poly(p-methylstyrene), poly(α-methylstyrene); aromatic homopolymers and copolymers derived from vinyl aromatic monomers, copolymers of vinyl aromatic monomers and comonomers such as, but not limited to, ethylene, propylene, dienes, nitriles, acids, maleic anhydride, maleimide, vinyl acetate, and vinyl chloride or acrylic acid derivatives, and mixtures thereof, aromatic homopolymers and copolymers derived from vinyl aromatic monomers. Hydrogenated aromatic polymers of copolymers of vinyl aromatic monomers, copolymers of vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydride, maleimide, vinyl acetate and vinyl chloride or acrylic acid derivatives, and mixtures thereof; graft copolymers of vinyl aromatic monomers; halogen-containing polymers, especially polymers of halogen-containing vinyl compounds, such as but not limited to polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, and copolymers thereof, such as but not limited to vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers; polymers derived from α,β-unsaturated acids and their derivatives; α.Copolymers of β-unsaturated acids and their derivatives with each other or with other unsaturated monomers; polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, and their copolymers with polymers of monoolefins and diolefins; homopolymers and copolymers of cyclic ethers, such as polyolefin diols, polyethylene oxide, polypropylene oxide, or copolymers thereof with bisglycidyl ethers; polyacetals, such as polyoxymethylene containing ethylene oxide as a comonomer, polyacetals modified with thermoplastic polyurethanes, acrylates, MBS, etc.; polyphenylene ethers and polyphenylene sulfides, and mixtures of polyphenylene ethers with styrene polymers or polyamides; polyethers, polyesters or polybutadienes terminated with hydroxy groups on the one hand, and aliphatic or aromatic polyisocyanates on the other hand, and precursors thereof; Polyamides and copolyamides from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams; polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles; polyesters derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids or the corresponding lactones or lactides, and copolyetheresters derived from hydroxy-terminated polyethers, and polyesters modified with polycarbonate or MBS; polycarbonates and polyester carbonates; polyketones; polysulfones, polyethersulfones and polyetherketones; crosslinked polymers derived from the polymerization of aldehydes with phenols, urea and melamine (such as, but not limited to, phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins); drying and non-drying alkyd resins; Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyols and vinyl compounds as crosslinking agents, and also their low-flammability halogen-containing modifications; crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates; alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins; crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds (such as, but not limited to, the diglycidyl ethers of bisphenol A and bisphenol F, which are reacted with customary hardeners such as anhydrides or amines, with or without accelerators); ) cross-linked); natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof (such as, but not limited to, cellulose acetate, cellulose propionate and cellulose butyrate, or cellulose ethers such as methyl cellulose), rosin and rosin derivatives; polymer blends (such as, but not limited to, PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC); naturally occurring and synthetic organic materials, either pure monomeric compounds or mixtures of such compounds; and aqueous emulsions of natural or synthetic rubber (e.g., natural latex or latex of carboxylated styrene / butadiene copolymers). As indicated above, the UV absorbing compounds of the present invention or their salts can be derivatized for copolymerization with ethylene oxide, propylene oxide, diisocyanate derivatives, dithiocyanate derivatives, and the like. In some embodiments of the present invention, suitable derivatives of the compounds disclosed herein can be used in copolymers during the polymerization of the polymers mentioned herein.

[0361] Table 4 Examples of UV absorbing additives for paints, plastics, adhesives and coatings

[0362]

[0363]

[0364] Table 5. Photolabile ingredients already available on the market that can be stabilized by the compounds of the present disclosure.

[0365]

[0366] In some embodiments, one or more compounds of the present disclosure may be added to a photolabile compound, such as, but not limited to, those in Table 5 and combinations thereof.

[0367] The compounds of the present disclosure can photostabilize photolabile compounds by quenching the excited state of unstable chemicals and then dissipating the energy through non-radiative internal conversion processes. In order to achieve photostabilization of photolabile compounds, the concentration of the compounds of the present disclosure relative to the photolabile compounds must be in the range of 1 mol% to 400 mol%, preferably in the range of 25 mol% to 300 mol%, more preferably in the range of 50 mol% to 200 mol%, and most preferably in the range of 70 mol% to 100 mol%.

[0368] Examples

[0369] Example 1 Synthesis of UV absorbing compounds:

[0370] Compounds E1-E11 and E14-E39 were synthesized by the Knoevenagel condensation method. In a typical synthesis, a solution of ketone X (1.0 equivalent), compound Y (1.1 equivalent) selected from malononitrile, malonate, 2,2-dimethyl-1,3-dioxane-4,6-dione (Meldrum acid), cyanoacetic acid ester, etc., and ammonium carboxylate (such as ethylenediamine diacetate or ammonium acetate) (0.2 equivalent) was heated under reflux in a mixture of carboxylic acid (42%) (such as acetic acid or propionic acid) and a hydrocarbon solvent (such as cyclohexane or toluene) in a round-bottom flask, and the water product of the reaction was removed by a Dean Stark water trap optionally containing molecular sieves. The reaction progress was monitored by changes in TLC and / or UV-Vis spectroscopy until completion. The reaction mixture was then concentrated in vacuo and the residue was dissolved in ethyl acetate. The organic solution was then subjected to standard post-treatment to produce a solid or oily residue. The oily residue was adsorbed onto celite and subjected to silica gel chromatography, eluting the product using a mixture of hexane and ethyl acetate. Appropriate fractions were collected and concentrated in vacuo to obtain the product. All prepared compounds were characterized by spectroscopic methods, including UV-Vis spectroscopy, which was performed at 0.01 g·L -1 Table 6 lists the names of the prepared compounds, 最大 , ε and E1%. Figure 1 The UV absorption spectrum of (E5) is shown. Figure 2 Shown is (E5) 1 H-NMR spectrum. Figure 3 Shown is (E6) 1 H-NMR spectrum. Figure 4 Shown is (E7) 1 H-NMR spectrum. Figure 5 Shown is (E8) 1 H-NMR spectrum. Table 7 lists the structures of the compounds used in the above method and the starting materials of compounds X and Y.

[0371] Compounds E40-E44 can be synthesized by the above-described method using the starting materials listed in Table 7.

[0372] Example 2 Synthesis of UV absorbing compounds:

[0373] Compounds E45-E47 and E49 were synthesized by the Horner-Wadsworth-Emmons method. In a typical reaction, a solution of ketone X (1.0 equivalent), diethylphosphonoacetate Y (1.1 equivalent), lithium chloride (3.0 equivalent) and 1,8-diazabicyclo (5.4.0) undec-7-ene (3.0 equivalent) in acetonitrile (0.1M) was heated under reflux and stirred for 16 hours in a nitrogen atmosphere. The reaction mixture was concentrated in vacuo, and the residue was dissolved in ethyl acetate. The organic solution was then subjected to standard post-treatment to produce a solid or oily residue. The solid or oily residue was adsorbed onto diatomaceous earth and analyzed by chromatography to purify and characterize the product as described in Example 1. Table 6 includes the names of the compounds prepared, λ 最大 , ε and E 1％ Table 7 lists the structures of the compounds used in the above method and the starting materials of compounds X and Y. Compounds E48 and E50-E64 can be synthesized by the above method using the starting materials listed in Table 7.

[0374] Table 6

[0375] Exemplary compounds, their absorbance maxima (λ 最大 ), molar absorption coefficient (ε) and mass absorption coefficient (E 1％ )

[0376]

[0377]

[0378]

[0379]

[0380]

[0381]

[0382]

[0383] Table 7 List of exemplary compounds and starting materials used to prepare the above compounds

[0384]

[0385]

[0386]

[0387]

[0388]

[0389]

[0390]

[0391]

[0392]

[0393]

[0394]

[0395]

[0396]

[0397] a Three equivalents of ketone X and one equivalent of compound Y. b Two equivalents of ketone X and one equivalent of compound Y.

[0398] Table 8 Compounds and their appearance and thin layer chromatography (TLC) retention factors (R F )

[0399]

[0400]

[0401]

[0402]

[0403]

[0404]

[0405] Example 3

[0406] Compounds E12 and E13 were prepared from the above compound E11 by transesterification.

[0407] (a) Dimethyl (3-phenyl-2-cyclohexene-1-ylidene)malonate (E12):

[0408]

[0409] Compound 12 was obtained by dissolving 2,2-dimethyl-5-(3-phenyl-2-cyclohexene-1-ylidene)-1,3-dioxane-4,6-dione (E11, 812.7 mg, 2.724 mmol) and p-toluenesulfonic acid monohydrate (110.4 mg, 0.5803 mmol) in 30 mL of methanol and heating the solution under reflux. The reaction was monitored by thin layer chromatography or UV-Vis spectroscopy. After completion, the reaction was cooled to room temperature. Methanol was evaporated in vacuo. The resulting oil was subjected to standard post-treatment to produce a yellow oil (0.2019 g, 26%).

[0410] (b) Synthesis of polyethylene (3-phenyl-2-cyclohexene-1-ylidene) malonate (E13):

[0411]

[0412] Compound 13 can be obtained by heating a mixture of 2,2-dimethyl-5-(3-phenyl-2-cyclohexene-1-ylidene)-1,3-dioxane-4,6-dione (E11, 305.1 mg, 1.023 mmol), ethylene glycol (0.15 mL, 2.68 mmol), zinc acetate (0.9 mg, 0.005 mmol), pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (0.8 mg, 0.0007 mmol) and triphenyl phosphite (0.5 mg, 0.002 mmol) to 140° C. under a nitrogen atmosphere with stirring. The reaction can be monitored by UV / Vis spectroscopy, and acetone and acetal byproducts should be removed by distillation. Then, under positive nitrogen pressure, polycondensation catalyst antimony trioxide (1.0 mg, 0.0034 mmol) is added to the reaction mixture as a suspension in diol, subsequently heated to 190 ° C, and diol is distilled during 30 min under 50 mTorr pressure to drive the polycondensation reaction. The reaction can be completed within 12 hours, and is cooled to room temperature (about 23 ° C) and dissolved in a small amount of chloroform. The resulting solution is added dropwise to the stirred isopropanol solution to precipitate the product polymer (E13), which can be collected by filtration.

[0413] Example 4

[0414] Sunscreen composition:

[0415] Weigh and combine the ingredients of Phases A, B, C, D, and E separately. After mixing Phases A and B and heating them to 80°C, add Phases C and D sequentially while homogenizing the mixture and heating it to 75°C. Then, slowly add Phase E and homogenize the mixture thoroughly for 3 minutes. Cool the homogenized mixture to <50°C and add the components of Phase F sequentially with continuous mixing until uniform. Finally, cool the mixture to room temperature.

[0416] (a) SPF 15 sunscreen:

[0417]

[0418] (b) SPF 15 sunscreen:

[0419]

[0420]

[0421] (c) SPF 30 sunscreen:

[0422] Mix the ingredients of Phase A and heat to 80°C, followed by the sequential addition of the mixture of Phases B and C. In a separate container, combine the ingredients of Phase D with mixing and heat to 75°C, then add the ABC mixture to Phase D. Homogenize the ABCD mixture for 3 minutes, cool to <50°C, and add the ingredients of Phase E with mixing. Finally, cool the mixture to room temperature.

[0423]

[0424]

[0425] Example 5

[0426] Sunscreen Conditioner:

[0427] After thoroughly mixing the ingredients of phases A and B and heating them to 71°C, the two phases were mixed and homogenized. The mixture was then cooled to 40°C and the ingredients of phase C were added in sequence with stirring. The pH of the mixture was adjusted to between 4 and 5.5 with citric acid.

[0428]

[0429] Equivalents and Incorporation by Reference

[0430] While aspects of the disclosure have been particularly shown and described with reference to certain embodiments and various alternative embodiments, it will be understood by those skilled in the relevant art that various changes in form and details may be made without departing from the spirit and scope of the disclosure.

[0431] All references, issued patents, and patent applications cited in the text of this specification are hereby incorporated by reference in their entirety for all purposes.

Claims

1. A composition comprising a compound of formula I or formula II: or its salt, in: R1 and R2 are independently selected from H, optionally substituted alkyl, optionally substituted alkynyl, optionally substituted aminoalkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxyalkyl, -CN, -C(O)R', -C(O)OR', -C(O)NR'R", -C(O)SR', -C(S)NR'R", -NCO, -C(O)-XR y 、C(O)-XR z and -NO2; or R1 and R2 together with the carbon atoms to which they are attached form a cyclic moiety of formula III or formula IV: in: X is O or NR'; R 11 and R 12 are independently selected from H and optionally substituted alkyl; R y and R z are independently selected from H, optionally substituted C 1-15 Alkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxyalkyl, polyamides and polyethers; R4 is selected from optionally substituted C6-C 10 Aryl, optionally substituted C2-C9 heteroaryl, the C2-C9 heteroaryl containing 0-4 heteroatoms selected from O, N and S; Each of R3, R5, R6, R7, R8, R9 and R 10 are independently selected from H, halogen, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C 20 cycloalkenyl, optionally substituted C2-C7 heterocycloalkyl, optionally substituted C6-C 10 aryl, optionally substituted C2-C9 heteroaryl, -OR', -C(O)R', -C(O)OR', -C(O)NR'R", -C(=NR')NR'R", -C(=NR")R', -NR'R", -CN, -N=NR', cyanate, -OCN, -CNO, -NO2, -OC(O)NR'R", -SR', -S-SR', -S(O)R', -S(O)2R', -S(O)2OR', -S(O)2NR', -C(O)SR', -C(S)SR', -C(S)NR', ​​-B(OH)2, -B(OR')(OR”), PR'3, PR'2, -P(OR')2, -OP(OR')2, -P(O)(OR')2, -OP(O)(OR')2, polyamides and polyethers; and Each R' and R" is independently selected from H, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C2-C 20 Cycloalkyl, optionally substituted C2-C 20 Cycloalkenyl, optionally substituted C2-C 20 Heterocycloalkyl, optionally substituted C6-C 10 aryl groups, optionally substituted C2-C9 heteroaryl groups, polyamides and polyethers.

2. The composition of claim 1, wherein the compound has formula I.

3. The composition of claim 1, wherein the compound has Formula II.

4. The composition according to any one of claims 1 to 3, wherein R4 is optionally substituted phenyl.

5. The composition according to any one of claims 1 to 4, wherein at least one of R1 and R2 is -C(O)-XR y .

6. The composition of claim 5, wherein the composition comprises one or more compounds having a cis and / or trans structure of Formula V or Formula VI: or a salt thereof, in: R1 is selected from H, -CN, alkyl isocyanate, alkyl isothiocyanate, aryl isocyanate, aryl isothiocyanate and C(O)-XR z ; Each R 13 、R 14 、R 15 、R 16 and R 17 are independently selected from H, halogen, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C 20 cycloalkenyl, optionally substituted C2-C7 heterocycloalkyl, optionally substituted C6-C 10 aryl, optionally substituted C2-C9 heteroaryl, -OR', -C(O)R', -C(O)OR', -C(O)NR'R", -C(=NR')NR'R", -C(=NR")R', -NR'R", -CN, -N=NR', cyanate, -OCN, -NO2, -OC(O)NR'R", -SR', -S-SR', -S(O)R', -S(O)2R', -S(O)2OR', -S(O)2NR', -C(O)SR', -C(S)SR', -C(S)NR', ​​-B(OH)2, -B(OR')(OR”), -PR'2, -P(OR')2, -OP(OR')2, -P(O)(OR')2, -OP(O)(OR')2, polyamides and polyethers.

7. The composition of claim 6, wherein R1 is -CN.

8. The composition of claim 6, wherein R1 is -H.

9. The composition of claim 6, wherein R1 is -C(O)-XR z .

10. The composition according to any one of claims 1 to 9, wherein R y and R z is an optionally substituted C 1-15 alkyl.

11. The composition according to any one of claims 1 to 10, wherein X is O.

12. The composition of any one of claims 1 to 10, wherein X is NH.

13. The composition according to any one of claims 6 to 12, wherein: Each R y and R z is independently selected from H, methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, 2-ethoxyethyl, and 3-methoxypropyl; and Each R3, R5, R6, R7, R8, R9, R 10 、R 13 、R 14 、R 15 、R 16 and R 17 independently selected from H, halogen, methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, hydroxy, methoxy, ethoxy, 2-ethoxyethyl, 3-methoxypropyl, amino, methylamino, dimethylamino, trimethylammonium, trifluoromethyl, and -NO2.

14. The composition according to any one of claims 1 to 13, wherein R y and R z Independently selected from 15. A composition according to any one of claims 1 to 14, wherein R4 is selected from 16. The composition of claim 1, wherein the composition comprises one or more compounds selected from E1-E64 of Table 6.

17. A cis- and / or trans-compound having a structure of Formula V or VI: or a salt thereof, in R1 is H, -CN, alkyl isocyanate, alkyl isothiocyanate, aryl isocyanate, aryl isothiocyanate or C(O)-XR z ; X is O or NR'; Each R y and R z are independently selected from H, optionally substituted C1-C 15 Alkyl, optionally substituted C1-C 15 Hydroxyalkyl, optionally substituted C1-C 15 Alkoxyalkyls, polyamides, and polyethers; Each R3, R5, R6, R7, R8, R9, R 10 、R 13 、R 14 、R 15 、R 16 and R 17 are independently selected from H, halogen, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C 20 cycloalkenyl, optionally substituted C2-C7 heterocycloalkyl, optionally substituted C6-C 10 aryl, optionally substituted C2-C9 heteroaryl, OR', C(O)R', C(O)OR', C(O)NR'R", -C(=NR')NR'R", -C(=NR")R', NR'R", CN, N=NR', cyanate, NO2, OC(O)NR'R", SR', S-SR', S(O)R', S(O)2R', S(O)2OR', S(O)2NR', C(O)SR', C(S)SR', C(S)NR', ​​B(OH)2, B(OR')(OR"), PR'3, PR'2, P(OR')2, OP(OR')2, P(O)(OR')2, OP(O)(OR')2, polyamides and polyethers; and Each R' and R" is independently selected from H, optionally substituted C1-C 20 Alkyl, optionally substituted C1-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C2-C 20 Cycloalkyl, optionally substituted C2-C 20 Cycloalkenyl, optionally substituted C2-C 20 Heterocycloalkyl, optionally substituted C6-C 10 aryl groups, optionally substituted C2-C9 heteroaryl groups, polyamides and polyethers.

18. The compound of claim 17, wherein R1 is -CN.

19. The compound of claim 17, wherein R1 is -H.

20. The compound of claim 17, wherein R1 is -C(O)-XR z .

21. A compound according to any one of claims 17 to 20, wherein R y and R z is independently an optionally substituted C 1-15 alkyl.

22. The compound of any one of claims 17 to 21, wherein X is O.

23. A compound according to any one of claims 17 to 21, wherein X is NH.

24. A compound according to any one of claims 17 to 23, wherein: Each R y and R z is independently selected from H, methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, 2-ethoxyethyl, and 3-methoxypropyl; and Each R3, R5, R6, R7, R8, R9, R 10 、R 13 、R 14 、R 15 、R 16 and R 17 independently selected from H, halogen, methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-ethylhexyl, 2-butyloctyl, hydroxy, methoxy, ethoxy, 2-ethoxyethyl, 3-methoxypropyl, amino, methylamino, dimethylamino, trimethylammonium, trifluoromethyl, and -NO, 25. A compound according to any one of claims 17 to 24, wherein R y and R z Independently selected from 26. The compound according to any one of claims 17 to 25, wherein the compound comprises 13 、R 14 、R 15 、R 16 and R 17 One of the following substituted phenyl groups defined:

27. The compound of claim 17, wherein the compound is selected from the compounds of Table 6.

28. A compound of formula VII or formula VIII: or a salt thereof, in: Each R1 is independently selected from H, -CN, alkyl isocyanate, alkyl isothiocyanate, aryl isocyanate, aryl isothiocyanate and C(O)-XR z ; X is O or NR'; T is a linking moiety selected from the group consisting of: optionally substituted C1-C 20 Alkylene, optionally substituted C2-C 20 Alkenylene, optionally substituted C2-C 20 Alkynylidene, optionally substituted C2-C 20 Alkoxyalkylene, optionally substituted C2-C 20 Cycloalkylene, optionally substituted C2-C 20 Cycloalkenylene and optionally substituted C2-C 20 Heterocycloalkylene, wherein one or more carbon atoms of the backbone of the linking moiety T are optionally replaced by a divalent group each independently selected from the group consisting of oxygen (—O—), carbonyl (—CO—), optionally substituted alkylamino, optionally substituted cycloalkylene, optionally substituted heterocyclylene, optionally substituted heteroarylene, and optionally substituted arylene; Each R z are independently selected from H, optionally substituted C 1-15 Alkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxyalkyl, polyamides and polyethers; Each R3, R5, R6, R7, R8, R9, R 10 、R 13 、R 14 、R 15 、R 16 and R 17 are independently selected from H, halogen, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C 20 cycloalkenyl, optionally substituted C2-C7 heterocycloalkyl, optionally substituted C6-C 10 Aryl, optionally substituted C2-C9 heteroaryl, -OR', -C(O)R', -C(O)OR', -C(O)NR'R", -C(=NR')NR'R", -C(=NR")R', -NR'R", -CN, -N=NR', cyanate, -OCN, -CNO, -NO2, -OC(O)NR'R", -SR', -S-SR', -S(O)R', -S(O)2R', -S(O)2OR', -S(O)2NR', -C(O)SR', -C(S)SR', -C(S)NR', ​​-B(OH)2, -B(OR')(OR"), PR'3, PR'2, -P(OR')2, -OP(OR')2, -P(O)(OR')2, -OP(O)(OR')2, polyamides and polyethers; Each R' and R" is independently selected from H, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C2-C 20 Cycloalkyl, optionally substituted C2-C 20 Cycloalkenyl, optionally substituted C2-C 20 Heterocycloalkyl, optionally substituted C6-C 10 Aryl, optionally substituted C2-C9 heteroaryl, polyamide and polyether; and n is selected from 2, 3, 4, 5 and 6.

29. The compound of claim 28, wherein R1 is -CN.

30. The compound of claim 28, wherein R1 is -H.

31. The compound of claim 28, wherein R1 is -C(O)-XR z .

32. A compound according to any one of claims 28 to 31, wherein R z is an optionally substituted C 1-15 alkyl.

33. A compound according to any one of claims 28 to 32, wherein X is O.

34. A compound according to any one of claims 28 to 32, wherein X is NH.

35. according to the compound described in any one of claim 28 to 34, wherein said compound comprises R 13 、R 14 、R 15 、R 16 and R 17 One of the following substituted phenyl groups defined:

36. A compound according to any one of claims 28 to 35, wherein the compound has formula VII.

37. The compound of any one of claims 28 to 35, wherein the compound has formula VIII.

38. An oligomeric or polymeric compound of formula IX or X: or its salt, in: Each X is independently O or NR'; L is a divalent linking moiety selected from the group consisting of: optionally substituted C1-C 20 Alkylene, optionally substituted C1-C 20 Alkenylene, optionally substituted C2-C 20 Alkynylidene, optionally substituted C2-C 20 Alkoxyalkylene, optionally substituted C2-C 20 Cycloalkylene, optionally substituted C2-C 20 Cycloalkenylene, optionally substituted C2-C 20 Heterocycloalkylene, wherein one or more carbon atoms of the L backbone are optionally replaced by a divalent group each independently selected from the group consisting of oxygen (—O—), carbonyl (—CO—), optionally substituted alkylamino, optionally substituted cycloalkylene, optionally substituted heterocyclylene, optionally substituted heteroarylene, optionally substituted arylene, polyamide, and polyether; Each R3, R5, R6, R7, R8, R9, R 10 、R 13 、R 14 、R 15 、R 16 and R 17 are independently selected from H, halogen, optionally substituted C1-C 20 Alkyl, optionally substituted C2-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C 20 cycloalkenyl, optionally substituted C2-C7 heterocycloalkyl, optionally substituted C6-C 10 Aryl, optionally substituted C2-C9 heteroaryl, -OR', -C(O)R', -C(O)OR', -C(O)NR'R", -C(=NR')NR'R", -C(=NR")R', -NR'R", -CN, -N=NR', cyanate, -OCN, -NCO, -NO2, -OC(O)NR'R", -SR', -S-SR', -S(O)R', -S(O)2R', -S(O)2OR', -S(O)2NR', -C(O)SR', -C(S)SR', -C(S)NR', ​​-B(OH)2, -B(OR')(OR"), PR'3, -PR'2, -P(OR')2, -OP(OR')2, -P(O)(OR')2, -OP(O)(OR')2, polyamides and polyethers; Each R' and R" is independently selected from H, optionally substituted C1-C 20 Alkyl, optionally substituted C1-C 20 Alkenyl, optionally substituted C2-C 20 Alkynyl, optionally substituted C2-C 20 Cycloalkyl, optionally substituted C2-C 20 Cycloalkenyl, optionally substituted C2-C 20 Heterocycloalkyl, optionally substituted C6-C 10 Aryl, optionally substituted C2-C9 heteroaryl, polyamides and polyethers; n is at least 2, 3, 4, 5, 10, 20, 100, 150, 300, 500, or 1000 (e.g., n is an average degree of polymerization of 5-1000 or 10-100).

39. The compound of claim 38, wherein the compound is a homo-oligomer or a homopolymer.

40. The compound of claim 38 or 39, wherein the compound is an oligomer or polymer that is a polyether, polyester, polyamide, polycarbonate, polyurethane, polyurea, or polysaccharide.

41. A composition comprising one or more compounds according to any one of claims 17 to 40.

42. The composition of any one of claims 1 to 16 or 41, wherein the composition is a sunscreen.

43. The sunscreen composition of claim 42, further comprising one or more additional components selected from moisturizers, emollients, preservatives, buffers, chelating agents, fragrances, antioxidants, antimicrobials, thickeners, dry feel modifiers, UV filters, and solvents.

44. A sunscreen composition according to claim 42 or 43, wherein the compound is present in an amount ranging from 0.01 wt% to 50.0 wt%.

45. The sunscreen composition of claim 42, wherein the composition is formulated as a solution, lotion, emulsion, cream, gel, aerosol, or spray.

46. ​​The composition of any one of claims 1 to 16 or 41, wherein the composition is a cosmetic composition.

47. The cosmetic composition of claim 46, wherein the composition is a solution, emulsion, lotion, cream, lotion, foam, gel, ointment, paste, suspension, stick, powder, wax, tablet, aerosol, or spray.

48. The cosmetic composition of claim 46, wherein the composition is a hair product.

49. The cosmetic composition of claim 46, wherein the composition is formulated for application to the lips.

50. The cosmetic composition of claim 46, wherein the composition is formulated for hair removal.

51. A method of providing UV photoprotection to the skin or hair of a subject, the method comprising applying a composition according to any one of claims 1 to 16 or 41 to the skin or hair of the subject.

52. The method of claim 51, wherein the composition comprises one or more of compounds E1-E64 of Table 6.

53. A composition stabilized against light-induced degradation according to any one of claims 1 to 16 or 41, further comprising an organic material susceptible to light-induced degradation.

54. The composition of claim 53, wherein the organic material is a thermoplastic polymer, a thermosetting polymer, a polyester, a protein, a polysaccharide, a binder, or a blend thereof.

55. The composition of claim 53, wherein the organic material is a coating, wax, resin, varnish, lacquer, enamel, or paint.

56. The composition of claim 55, wherein the coating is applied to a substrate that is sensitive to UV light.

57. A composition according to any one of claims 53 to 56, wherein the composition comprises one or more compounds of formula I or formula II in an amount of 0.01% to 50% by weight of the organic material.

58. A composition according to any one of claims 53 to 57, wherein the composition comprises one or more compounds selected from compounds E1-E64 of Table 6.

59. A composition according to any one of claims 1 to 16 or 41 formulated for protecting fabrics from photodegradation.

60. A method of providing UV light protection to a UV light sensitive material, the method comprising applying a composition according to any one of claims 1 to 16 or 41 to a UV light sensitive material.

61. The method of claim 60, wherein the composition comprises one or more compounds selected from Compounds E1-E64 of Table 6.

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