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US 11,129,782 B2Granted
Derivatives of PPD useful for coloring hair and skin
AssigneesNational University of Singapore, Agency for Science, Technology and Research, National University Hospital (Singapore) Pte Ltd
InventorsGiorgia Pastorin, Paul Bigliardi, Suresh Valiyaveettil, Gopalakrishnan Venkatesan, Arup Sinha, Yuri Herbert Dancik, Mei Bigliardi-Qi
Life of this patent
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Abstract
The is provided a compound of formula I or II or physiologically acceptable salts or solvates, or oxidised derivatives thereof: where R1 to R3, R13 and R14 are as defined herein. Also disclosed herein are methods of dyeing hair or (temporarily) tattooing the skin using the compounds of formula I or II (or physiologically acceptable salts or solvates, or oxidised derivatives thereof) in a suitable composition.
Claims21
A compound of formula I:
- wherein:
- R1 and R2 independently represent H, CH2Phenyl or C5-10 alkyl, which phenyl group is substituted by NO2, OCH3, CH3 or OH, and which C5-15 alkyl group is unsubstituted or substituted with one or more substituents selected from:
- C1-10 alkyl, which group is unsubstituted or substituted by one or more substituents selected from OH, nitro, CN, OR4a, NR4bR4c, aryl and Het1;
- Cy1, which Cy1 group is unsubstituted or substituted by one or more substituents selected from nitro, CN, C1-10 alkyl (which C1-10 alkyl group is unsubstituted or substituted by one or more substituents selected from OH, ═O, C1-4 alkyl and C1-4 alkoxy), and OR5a, S(O)qR5b, S(O)2NR5cR5d, NR5eS(O)2R5f, NR5gR5h;
- Heta, which Heta group is unsubstituted or substituted by one or more substituents selected from nitro, CN, C1-6 alkyl (which C1-6 alkyl group is unsubstituted or substituted by one or more substituents selected from OH, ═O, halo, C1-4 alkyl and C1-4 alkoxy), OR6a, S(O)qR6b, S(O)2NR6cR6d, NR6eS(O)2R6f, NR6gR6h;
- and
- OR7a, S(O)qR7b, S(O)2NR7cR7d, NR7eS(O)2R7f and NR7gR7h,
- R3 represents H, OC1-10 alkyl, C(O)OC1-10 alkyl or OC(O)C1-10 alkyl, which OC1-10 alkyl, C(O)OC1-10 alkyl and OC(O)C1-10 alkyl groups are unsubstituted or substituted with one or more substituents selected from:
- C1-10 alkyl, which group is unsubstituted or substituted by one or more substituents selected from OH, nitro, CN, OR8a, NR8bR8c, aryl and Het2;
- Cy2, which Cy2 group is unsubstituted or substituted by one or more substituents selected from nitro, CN, C1-6 alkyl (which C1-6 alkyl group is unsubstituted or substituted by one or more substituents selected from OH, ═O, C1-4 alkyl and C1-4 alkoxy), and OR9a, S(O)qR9b, S(O)2NR9cR9d, NR9eS(O)2R9f, NR9gR9h;
- Hetb, which Hetb group is unsubstituted or substituted by one or more substituents selected from nitro, CN, C1-6 alkyl (which C1-6 alkyl group is unsubstituted or substituted by one or more substituents selected from OH, ═O, halo, C1-4 alkyl and C1-4 alkoxy), OR10a, S(O)qR10b, S(O)2NR10cR10d, NR10eS(O)2R10f, NR10gR10h;
- and
- OR11a, S(O)qR11b, S(O)2NR11cR11d, NR11eS(O)2R11f and NR11gR11h,
- Het1 and Het2 represent, independently at each occurrence, a 4- to 14-membered heterocyclic group containing one or more heteroatoms selected from O, S and N, which heterocyclic groups may comprise one, two or three rings and may be substituted by one or more substituents selected from OR12a and C1-10 alkyl, which C1-10 alkyl group is unsubstituted;
- Cy1 and Cy2 represent, independently at each occurrence, a 3- to 6-membered aromatic, fully saturated or partially unsaturated carbocyclic ring;
- R4a to R4c, R5a to R5h, R6a to R6h, R7a to R7h, R8a to R8c, R9a to R9h, R10a to R10h, R11a to R11h, independently represent, at each occurrence, H, or C1-10 alkyl (which C1-10 alkyl group is unsubstituted or substituted by one or more substituents selected from C1-6 alkyl, OR12b), or R5-7c and R5-7d, R9-11c and R9-11d, R5-7g and R5-7h, R9-11g and R9-11h represent, together with the nitrogen atom to which they are attached, a 3- to 14-membered heterocyclic ring that may be aromatic, fully saturated or partially unsaturated and which may additionally contain one or more heteroatoms selected from O, S and N, which heterocyclic ring is optionally substituted by one or more substituents selected from halo, nitro, CN, and C1-6 alkyl;
- Heta and Hetb independently represent 4- to 14-membered heterocyclic groups containing one or more heteroatoms selected from O, S and N;
- R12a-b independently represents, at each occurrence, H or C1-4 alkyl, and
- n represents 0 to 4,
- or a physiologically acceptable salt or solvate, or an oxidised derivative thereof of the compound of formula I,
- provided that when R1 and R2 are H, and n is 0, 1 or 2, R3 is not H.
18 more elements
A method of dyeing hair or of applying a temporary tattoo, which method comprises applying a composition comprising a compound of formula I or a physiologically acceptable salt or solvate, or an oxidised derivative thereof, to the hair or skin of a subject, wherein the compound of formula I has the structure:
- wherein:
- R1 and R2 independently represent H, CH2Phenyl or C5-10 alkyl, which phenyl group is substituted by NO2, OCH3, CH3 or OH, and which C5-10 alkyl group is unsubstituted or substituted with one or more substituents selected from:
- C1-10 alkyl, which group is unsubstituted or substituted by one or more substituents selected from OH, nitro, CN, OR4a, NR4bR4c, aryl and Het1;
- Cy1, which Cy1 group is unsubstituted or substituted by one or more substituents selected from nitro, CN, C1-6 alkyl (which C1-6 alkyl group is unsubstituted or substituted by one or more substituents selected from OH, ═O, C1-4 alkyl and C1-4 alkoxy), and OR5a, S(O)qR5b, S(O)2NR5cR5d, NR5eS(O)2R5f, NR5gR5h;
- Heta, which Heta group is unsubstituted or substituted by one or more substituents selected from nitro, CN, C1-6 alkyl (which C1-6 alkyl group is unsubstituted or substituted by one or more substituents selected from OH, ═O, halo, C1-4 alkyl and C1-4 alkoxy), OR6a, S(O)qR6b, S(O)2NR6cR6d, NR6eS(O)2R6f, NR6gR6h;
- and
- OR7a, S(O)qR7b, S(O)2NR7cR7d, NR7eS(O)2R7f and NR7gR7h,
- R3 represents H, C1-10 alkyl, OC1-10 alkyl, C(O)OC1-10 alkyl or OC(O)C1-10 alkyl, which C1-10 alkyl, OC1-10 alkyl, C(O)OC1-10 alkyl or OC(O)C1-10 alkyl groups are unsubstituted or substituted with one or more substituents selected from:
- C1-10 alkyl, which group is unsubstituted or substituted by one or more substituents selected from OH, nitro, CN, OR8a, NR8bR8c, aryl and Het2;
- Cy2, which Cy2 group is unsubstituted or substituted by one or more substituents selected from nitro, CN, C1-6 alkyl (which C1-6alkyl group is unsubstituted or substituted by one or more substituents selected from OH, ═O, C1-4 alkyl and C1-4 alkoxy), and OR9a, S(O)qR9b, S(O)2NR9cR9d, NR9eS(O)2R9f, NR9gR9h;
- Hetb, which Hetb group is unsubstituted or substituted by one or more substituents selected from nitro, CN, C1-6 alkyl (which C1-6 alkyl group is unsubstituted or substituted by one or more substituents selected from OH, ═O, halo, C1-4 alkyl and C1-4 alkoxy), OR10a, S(O)qR10b, S(O)2NR10cR10d, NR10eS(O)2R10f, NR10gR10h;
- and
- OR11a, S(O)qR11b, S(O)2NR11cR11d, NR11eS(O)2R11f and NR11gR11h,
- Het1 and Het2 represent, independently at each occurrence, a 4- to 14-membered heterocyclic group containing one or more heteroatoms selected from O, S and N, which heterocyclic groups may comprise one, two or three rings and may be substituted by one or more substituents selected from OR12a and C1-10 alkyl, which C1-10 alkyl group is unsubstituted;
- Cy1 and Cy2 represent, independently at each occurrence, a 3- to 6-membered aromatic, fully saturated or partially unsaturated carbocyclic ring;
- R4a to R4c, R5a to R5h, R6a to R6h, R7a to R7h, R8a to R8c, R9a to R9h, R10a to R10h, R11a to R11h, independently represent, at each occurrence, H, or C1-10 alkyl (which C1-10 alkyl group is unsubstituted or substituted by one or more substituents selected from C1-6 alkyl, OR12b), or R5-7c and R5-7d, R9-11c and R9-11d, R5-7g and R5-7h, R9-11g and R9-11h represent, together with the nitrogen atom to which they are attached, a 3- to 14-membered heterocyclic ring that may be aromatic, fully saturated or partially unsaturated and which may additionally contain one or more heteroatoms selected from O, S and N, which heterocyclic ring is optionally substituted by one or more substituents selected from halo, nitro, CN, and C1-10 alkyl;
- Heta and Hetb independently represent 4- to 14-membered heterocyclic groups containing one or more heteroatoms selected from O, S and N;
- R12a-b independently represents, at each occurrence, H or C1-4 alkyl,
- n represents 0 to 4,
- or a physiologically acceptable salt or solvate, or an oxidised derivative thereof of the compound of formula I,
- provided that when R1 and R2 are H, and n is 0, R3 is not H.
18 more elements
A compound of formula II:
- wherein:
- R13 represents H or C6-10 alkyl, which C6-10 alkyl group is unsubstituted or substituted with one or more substituents selected from:
- C1-10 alkyl, which group is unsubstituted or substituted by one or more substituents selected from OH, nitro, CN, OR15a, NR15bR15c, aryl and Het3;
- Cy3, which Cy3 group is unsubstituted or substituted by one or more substituents selected from nitro, CN, C1-6 alkyl (which C1-6 alkyl group is unsubstituted or substituted by one or more substituents selected from OH, ═O, C1-4 alkyl and C1-4 alkoxy), and OR16a, S(O)qR16b, S(O)2NR16cR16d, NR16eS(O)2R16f, NR16gR16h;
- Hetc, which Hetc group is unsubstituted or substituted by one or more substituents selected from nitro, CN, C1-6 alkyl (which C1-6 alkyl group is unsubstituted or substituted by one or more substituents selected from OH, ═O, halo, C1-4 alkyl and C1-4 alkoxy), OR17a, S(O)qR17b, S(O)2NR17cR17d, NR17eS(O)2R17f, NR17gR17h;
- and
- OR18a, S(O)qR18b, S(O)2NR18cR18d, NR18eS(O)2R18f and NR18gR18h,
- R14 represents C1-10 alkyl, OC1-10 alkyl, C(O)OC1-10 alkyl or OC(O)C1-10 alkyl, which OC1-10 alkyl is substituted with one or more substituents selected from:
- Cy4, which Cy4 group is unsubstituted or substituted by one or more substituents selected from nitro, CN, C1-6 alkyl (which C1-6 alkyl group is unsubstituted or substituted by one or more substituents selected from OH, ═O, C1-4 alkyl and C1-4 alkoxy), and OR20a,S(O)qR20b, S(O)2NR20cR20d, NR20eS(O)2R20f,NR20gR20h;
- Hetd, which Hetd group is unsubstituted or substituted by one or more substituents selected from nitro, CN, C1-10 alkyl (which C1-10 alkyl group is unsubstituted or substituted by one or more substitutents selected from OH, ═O, halo, C1-4 alkyl and C1-4 alkoxy), OR21a, S(O)qR21b, S(O)2NR21c, R21d, NR21eS(O)2R21f,NR21gR21h;and
- OR22a, S(O)qR22b,S(O)2NR22cR22d, NR22eS(O)2R22f and NR22gR22h;
- and p1 and which C1-10 alkyl, C(O)OC1-10 alkyl and OC(O)C1-10 alkyl groups are unsubstituted or substituted with one or more substituents selected from:
- C1-10 alkyl, which group is unsubstituted or substituted by one or more substituents selected from OH, nitro, CN, OR19a, NR19bR19c, aryl and Het4;
- Cy4, which Cy4 group is unsubstituted or substituted by one or more substituents selected from nitro, CN, C1-6 alkyl (which C1-6 alkyl group is unsubstituted or substituted by one or more substituents selected from OH, ═O, C1-4 alkyl and C1-4 alkoxy), and OR20a, S(O)qR20b, S(O)2NR20cR20d, NR20eS(O)2R20f, NR20gR20h;
- Hetd, which Hetd group is unsubstituted or substituted by one or more substituents selected from nitro, CN, C1-10 alkyl (which C1-6 alkyl group is unsubstituted or substituted by one or more substituents selected from OH, ═O, halo, C1-4 alkyl and C1-4 alkoxy), OR21a, S(O)qR21b, S(O)2NR21cR21d, NR21eS(O)2R21f, NR21gR21h;
- and
- OR22a, S(O)qR22b, S(O)2NR22cR22d, NR22eS(O)2R22f and NR22gR22h,
- Het3 and Het4 represent, independently at each occurrence, a 4- to 14-membered heterocyclic group containing one or more heteroatoms selected from O, S and N, which heterocyclic groups may comprise one, two or three rings and may be substituted by one or more substituents selected from OR23a and C1-10 alkyl, which C1-10 alkyl group is unsubstituted;
- Cy3 and Cy4 represent, independently at each occurrence, a 3- to 6-membered fully saturated or partially unsaturated carbocyclic ring;
- R15a to R15c, R16a to R16h, R17a to R17h, R18a to R18h, R19a to R19c, R20a to R20h, R21a to R21h, R22a to R22h, independently represent, at each occurrence, H, or C1-10 alkyl (which C1-10 alkyl group is unsubstituted or substituted by one or more substituents selected from C1-6 alkyl, OR23b), or R16-18c and R16-18d, R20-22c and R20-22d, R16-18g and R16-18h, R20-22g and R20-22h represent, together with the nitrogen atom to which they are attached, a 3- to 14-membered heterocyclic ring that may be aromatic, fully saturated or partially unsaturated and which may additionally contain one or more heteroatoms selected from O, S and N, which heterocyclic ring is optionally substituted by one or more substituents selected from halo, nitro, CN, and C1-6 alkyl;
- Hetc and Hetd independently represent 4- to 14-membered heterocyclic groups containing one or more heteroatoms selected from O, S and N;
- R23a-b independently represents, at each occurrence, H or C1-4 alkyl, or an oxidised derivative thereof of the compound of formula II, provided that when R13 is H, R14 is not n-hexyl.
19 more elements
A method of dyeing hair or of applying a temporary tattoo, which method comprises applying a composition comprising a compound of formula II or a physiologically acceptable salt or solvate, or an oxidised derivative thereof, to the hair or skin of a subject, wherein the compound of formula II has the structure:
- wherein:
- R13 represents H or C6-10 alkyl, which C6-10 alkyl group is unsubstituted or substituted with one or more substituents selected from:
- C1-10 alkyl, which group is unsubstituted or substituted by one or more substituents selected from OH, nitro, CN, OR15a, NR15bR15c, aryl and Het3;
- Cy3, which Cy3 group is unsubstituted or substituted by one or more substituents selected from nitro, CN, C1-6 alkyl (which C1-6 alkyl group is unsubstituted or substituted by one or more substituents selected from OH, ═O, C1-4 alkyl and C1-4 alkoxy), and OR16a, S(O)qR16b, S(O)2NR16cR16d, NR16eS(O)2R16f, NR16gR16h;
- Hetc, which Hetc group is unsubstituted or substituted by one or more substituents selected from nitro, CN, C1-6 alkyl (which C1-6 alkyl group is unsubstituted or substituted by one or more substituents selected from OH, ═O, halo, C1-4 alkyl and C1-4 alkoxy), OR17a, S(O)qR17b, S(O)2NR17cR17d, NR17eS(O)2R17f, NR17gR17h;
- and
- OR18a, S(O)qR18b, S(O)2NR18cR18d, NR18eS(O)2R18f and NR18gR18h,
- R14 represents C1-10 alkyl, OC1-10 alkyl, C(O)OC1-10 alkyl or OC(O)C1-10 alkyl, which C1-10 alkyl, OC1-10 alkyl, C(O)OC1-10 alkyl and OC(O)C1-10 alkyl groups are unsubstituted or substituted with one or more substituents selected from:
- C1-10 alkyl (which group is unsubstituted or substituted by one or more substituents selected from OH, nitro, CN, OR19a, NR19bR19c, aryl and Het4);
- Cy4 (which Cy4 group is unsubstituted or substituted by one or more substituents selected from nitro, CN, C1-6 alkyl (which C1-6 alkylgroup is unsubstituted or substituted by one or more substituents selected from OH, ═O, C1-4 alkyl and C1-4 alkoxy), and OR20a, S(O)qR20b, S(O)2NR20cR20d, NR20eS(O)2R20f, NR20gR20h);
- Hetd (which Hetd group is unsubstituted or substituted by one or more substituents selected from nitro, CN, C1-10 alkyl (which C1-10 alkyl group is unsubstituted or substituted by one or more substituents selected from OH, ═O, halo, C1-4 alkyl and C1-4 alkoxy), OR21a, S(O)qR21b, S(O)2NR21cR21d, NR21eS(O)2R21f, NR21gR21h);
- and
- OR22a, S(O)qR22b, S(O)2NR22cR22d, NR22eS(O)2R22f and NR22gR22h,
- Het3 and Het4 represent, independently at each occurrence, a 4- to 14-membered heterocyclic group containing one or more heteroatoms selected from O, S and N, which heterocyclic groups may comprise one, two or three rings and may be substituted by one or more substituents selected from OR23a and C1-10 alkyl, which C1-10 alkyl group is unsubstituted;
- Cy3 and Cy4 represent, independently at each occurrence, a 3- to 6-membered fully saturated or partially unsaturated carbocyclic ring;
- R15a to R15c, R16a to R16h, R17a to R17h, R18a to R18h, R19a to R19c, R20a to R20h, R21a to R21h, R22a to R22h, independently represent, at each occurrence, H, or C1-10 alkyl (which C1-10 alkyl group is unsubstituted or substituted by one or more substituents selected from C1-6 alkyl, OR23b), or R16-18c and R16-18d, R20-22c and R20-22d, R16-18g and R16-18h, R20-22g and R20-22h represent, together with the nitrogen atom to which they are attached, a 3- to 14-membered heterocyclic ring that may be aromatic, fully saturated or partially unsaturated and which may additionally contain one or more heteroatoms selected from O, S and N, which heterocyclic ring is optionally substituted by one or more substituents selected from halo, nitro, CN, and C1-6 alkyl;
- Hetc and Hetd independently represent 4- to 14-membered heterocyclic groups containing one or more heteroatoms selected from O, S and N;
- R23a-b independently represents, at each occurrence, H or C1-4 alkyl, or an oxidised derivative thereof of the compound of formula II.
15 more elements
A compound selected from the list:
- (i) 4-2-((2-ethylhexyl)oxy)benzene-1,4-diamine;
- (ii) hexyl-2,5-diaminobenzoate;
- and
- (iii) (N1-hexyl)(2-hexyloxy)-1,4-diaminobenzene.
1 more element
Dependencies are inferred from the claim text.