# US 7,744,657 B2 · Styrl tetrahydroquinolinium thiol/disulfide dye compound and method for lightening keratin materials using the same

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- Number: US 7,744,657 B2
- Document ID: US7744657B2
- Status: Granted
- Kind: B2
- Application number: 12/234,135
- Filed: 2008-09-19
- Published: 2009-05-21
- Granted: 2010-06-29
- Earliest claimed: 2007-09-21
- Assignees: L'oreal
- Inventors: Andrew Greaves; Nicolas Daubresse; Franco Manfre
- Web page: https://patentgrep.com/patent/US7744657B2

## CPC

- C09B 23/145: {the ethylene chain carrying an heterocyclic residue, e.g. heterocycle-CH=CH-C6H5}
- A61K 8/4926: {having six membered rings}
- A61K 8/4933: {having sulfur as an exocyclic substituent, e.g. pyridinethione}
- A61Q 5/065: {Preparations for temporary colouring the hair, e.g. direct dyes}
- A61Q 5/08: Preparations for bleaching the hair
- A61Q 5/10: Preparations for permanently dyeing the hair
- C09B: ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES {, e.g. PIGMENTS}; MORDANTS; LAKES (fermentation or enzyme using processes to synthesise a desired chemical compound C12P)
- A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D)
- A61Q: SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS

## Abstract

The present disclosure relates to the dyeing of keratin materials using thiol/disulfide styryl tetrahydroquinolinium fluorescent dyes. Disclosed herein is a dye composition comprising a thiol/disulfide styryl tetrahydroquinolinium fluorescent dye and a dyeing process with, for instance, a lightening effect on keratin materials such as hair, using said composition. Disclosed herein are thiol fluorescent dyes and the uses thereof in lightening keratin materials. This composition can be used to obtain a lightening effect which can be resistant and visible on dark keratin fibers.

## Claims

### Claim 1

A fluorescent dye of formula (I) or (II):
the organic or mineral acid salts thereof, optical isomers and geometric isomers thereof, or the solvates thereof:
wherein:
is chosen from an aryl, a heterocyclic, and a heteroaryl group fused to the phenyl ring; or is absent from the phenyl ring;
G and G′, which may be identical or different, are chosen from an —NRcRd group and a (C1-C6)alkoxy group, which is optionally substituted; or G or G′ is absent;
Rc and Rd, which may be identical or different, are chosen from a hydrogen atom, an optionally substituted (C1-C6)alkyl group, an aryl(C1-C4)alkyl group, and a (C1-C6)alkoxy(C1-C6)alkyl group; or the two Rc and Rd radicals may form, together with the nitrogen atoms to which they are attached, a heterocyclic or heteroaryl group;
Rg, R′g, R″g, R′″g, Rh, and R′″h, which may be identical or different, are chosen from a hydrogen atom, a halogen atom, an amino, a (di)(C1-C4)alkylamino, a cyano, a carboxyl, a hydroxyl, a trifluoromethyl, a acylamino, a C1-C4 alkoxy, a C2-C4 (poly)hydroxyalkoxy, a (C1-C4)alkylcarbonyloxy, a (C1-C4)alkoxycarbonyl, a (C1-C4)alkylcarbonylamino, a acylamino, a carbamoyl, a (C1-C4)alkylsulfonylamino group, an aminosulfonyl radical, and a (C1-C16)alkyl radical optionally substituted with a group chosen from (C1-C12)alkoxy, hydroxyl, cyano, carboxyl, amino, and (di)(C1-C4)alkylamino wherein optionally the two alkyl radicals borne by the nitrogen atom of the amino group form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical to or different from that of the nitrogen atom;
or two groups Rg and R′g, or R″g and R′″g, together with the two adjacent carbon atoms to which they are attached, form a benzo, an indeno ring, a fused heterocycloalkyl, or a fused heteroaryl group; wherein the benzo, indeno, heterocycloalkyl, or heteroaryl ring being optionally substituted with at least one radical chosen from a halogen atom, a (C1-C4)alkyl, an amino, a (C1-C4)alkylamino, a (C1-C4)dialkylamino, a cyano, a carboxyl, a hydroxyl, a trifluoromethyl group, an acylamino, a C1-C4 alkoxy, a C2-C4 (poly)hydroxyalkoxy, a alkylcarbonyloxy, a alkoxycarbonyl, a alkylcarbonylamino, an acylamino, a carbamoyl, a alkylsulfonylamino radical, an aminosulfonyl radical, and a (C1-C16) alkyl radical optionally substituted with a group chosen from (C1-C12)alkoxy, hydroxyl, cyano, carboxyl, amino, (C1-C4)alkylamino, (C1-C4) dialkylamino, and (C1-C4) dialkylamino wherein the two alkyl radicals borne by the nitrogen atom of the amino group form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical to or different from that of the nitrogen atom;
or when G and/or G′ are —NRcRd, two groups Rc and R′g, Rd and Rg, and/or Rc and R″g, Rd and R′″g together form a saturated heteroaryl or heterocycle, optionally substituted with at least one (C1-C6)alkyl group;
R′i and R′″i, which may be identical or different, are chosen from a hydrogen atom and a (C1-C4)alkyl group;
R′h with R″i and R″h with R′″i form, together with the carbon atoms which bear them, an optionally substituted C5-C7 cycloalkyl group fused to the pyridinium group, wherein the R′h or R″h radical and the styryl group bearing the R′i or R′″i radical are positioned on adjacent carbon atoms of the pyridinium groups;
R1, R2, R3, R4, R′1, R′2, R′3, and R′4, which may be identical or different, are chosen from:
a hydrogen atom,
a (C1-C4)alkyl group,
a (C1-C12)alkoxy,
a hydroxyl,
a cyano,
a —C(O)O−M+ wherein M+ is an alkali metal or M+ and An− are absent,
a carboxyl,
a (di)(C1-C4)(alkyl)amino, wherein the two alkyl radicals may optionally form, with the nitrogen atom which bears them, a heterocycle comprising from 5 to 7 members, optionally comprising another heteroatom which may or may not be different from nitrogen;
Ta and Tb, which may be identical or different, are chosen from:
i) a σ covalent bond;
ii) at least one radical or combination thereof, chosen from —SO2—, —O—, —S—, —N(R)—, —N+(R)(Ro)—, and —C(O)—, wherein R and Ro, which may be identical or different, are chosen from a hydrogen atom, a C1-C4 alkyl radical, a C1-C4 hydroxyalkyl radical, and an aryl(C1-C4)alkyl; and
(iii) a monocyclic, cationic or noncationic, heterocycloalkyl or heteroaryl radical;
m, m′, n, and n′, which may be identical or different, are integers ranging from 0 to 6, wherein m+n and m′+n′, which may be identical or different, are integers ranging from 1 to 10;
An− is an anionic counterion; and
Y is chosen from:
i) a hydrogen atom;
ii) an alkali metal;
iii) an alkaline earth metal;
iv) an ammonium group: N+RαRβRγRδ or a phosphonium group: P+RαRβRγRδ wherein Rα, Rβ, Rγ, and Rδ, which may be identical or different, are chosen from a hydrogen atom and a (C1-C4)alkyl group; and
v) a thiol-function-protecting group;
wherein when the compound of formula (I) or (II) comprises at least one other cationic part, it is associated with at least one anionic counterion allowing formula (I) or (II) to achieve electroneutrality.

### Claim 2 (depends on 1)

The fluorescent dye of formula (II) according to claim 1, wherein Y is chosen from a hydrogen atom and an alkali metal.

### Claim 3 (depends on 1)

The fluorescent dye of formula (II) according to claim 1, wherein Y is chosen from a thiol-function-protecting group.

### Claim 4 (depends on 3)

The fluorescent dye of formula (II) according to claim 3, wherein Y is chosen from a thiol-function-protecting group chosen from the following radicals:
(C1-C4)alkylcarbonyl;
(C1-C4)alkylthiocarbonyl;
(C1-C4)alkoxycarbonyl;
(C1-C4)alkoxythiocarbonyl;
(C1-C4)alkylthiothiocarbonyl;
(di)(C1-C4)(alkyl)aminocarbonyl;
(di)(C1-C4)(alkyl)aminothiocarbonyl;
arylcarbonyl;
aryloxycarbonyl;
aryl(C1-C4)alkoxycarbonyl;
(di)(C1-C4)(alkyl)aminocarbonyl;
(C1-C4)(alkyl)arylaminocarbonyl;
carboxyl;
SO3−; M+, wherein M+ is an alkali metal or An− of formula (II) and M+ are absent;
optionally substituted aryl;
optionally substituted heteroaryl;
optionally cationic, optionally substituted heterocycloalkyl,
the following group:
wherein R′c, R′d, R′e, R′f, R′g, and R′h, which may be identical or different, are chosen from hydrogen atoms and (C1-C4) alkyl groups, or two groups R′g with R′h, and/or R′e with R′f form an oxo or thioxo group, or R′g with R′e together form a cycloalkyl; and v is an integer ranging from 1 to 3; and An′− is an anionic counterion;
isothiouronium;
—C(NR′cR′d)═N+R′eR′f; An′−, wherein R′c, R′d, R′e, and R′f, which may be identical or different, are chosen from a hydrogen atom and a (C1-C4)alkyl group, and An− is an anionic counterion;
isothiourea;
—C(NR′cR′d)═NR′e; An′−, wherein R′c, R′d, R′e, and An− are defined above;
optionally substituted (di)aryl(C1-C4)alkyl;
optionally substituted (di)heteroaryl(C1-C4)alkyl;
—CR1R2R3, wherein R1, R2, and R3, which may be identical or different, are chosen from:
i) halogen atom
ii) (C1-C4)alkyl;
iii) (C1-C4)alkoxy;
iv) optionally substituted aryl;
v) optionally substituted heteroaryl; and
vi) P(Z1)R′1R′2R′3, wherein R′1 and R′2, which may be identical or different, are chosen from a hydroxyl, a (C1-C4)alkoxy, and a alkyl group; R′3 is chosen from a hydroxyl and a (C1-C4)alkoxy group; and Z1 is chosen from an oxygen atom and a sulfur atom;
a sterically hindered cyclic group; and
optionally substituted alkoxyalkyl.

### Claim 5 (depends on 1)

The fluorescent dye of formula (II) according to claim 1, wherein Y is chosen from an alkali metal and a protecting group chosen from:
(C1-C4)alkylcarbonyl;
arylcarbonyl;
(C1-C4)alkoxycarbonyl;
aryloxycarbonyl;
aryl(C1-C4)alkoxycarbonyl;
(di)(C1-C4)(alkyl)aminocarbonyl;
(C1-C4)(alkyl)arylaminocarbonyl;
optionally aryl;
5- or 6-membered cationic monocyclic heteroaryl optionally substituted with at least one (C1-C4)alkyl group which may be identical or different;
8- to 11-membered cationic bicyclic heteroaryl optionally substituted with at least one (C1-C4)alkyl group which may be identical or different;
cationic heterocycle of the following formula:
isothiouronium;
—C(NH2)═N+H2; An′−;
isothiourea;
—C(NH2)═NH; and
SO3−; M+, wherein M+ is an alkali metal or An− of formula (II) and M+ are absent.

### Claim 6 (depends on 1)

The fluorescent dye of formula (I) according to claim 1, comprising a C2 axis of symmetry between the two sulfur atoms of the central disulfide radical.

### Claim 7 (depends on 1)

The fluorescent dye according to claim 1, comprising at least one of the two formulae (Ia) and (IIa):
wherein:
R3 and R4, which may be identical or different, are chosen from:
a hydrogen atom;
a (C1-C4)alkyl group;
a —C(O)O−M+, wherein M+ is an alkali metal, or M+ and An− are absent;
carboxyl;
Rg, R′g, and Rh, which may be identical or different, are chosen from a hydrogen atom, a halogen atom, a (di)(C1-C4)(alkyl)amino, a hydroxyl, an acylamino, a (C1-C4)alkoxy group, a (C1-C4)alkylcarbonylamino group, and a (C1-C6)alkyl radical;
two groups Rc and R′g and/or Rd and Rg together form a saturated heterocycle or a heteroaryl, optionally substituted with at least one (C1-C6)alkyl group;
Rc and Rd, which may be identical or different, are chosen from a hydrogen atom, an optionally substituted (C1-C6)alkyl group, and an aryl(C1-C4)alkyl;
or the two radicals Rc and Rd, together with the nitrogen atoms to which they are attached, form a heterocyclic or heteroaryl group;
Ta is chosen from a σ covalent bond and a group chosen from: —N(R)—, —C(O)—N(R)—, and N(R)—C(O)—;
m and n, which may be identical or different, are chosen from an integer ranging from 1 to 6, wherein the sum m+n is an integer ranging from 2 to 6;
An− is an anionic counterion; and
Y is as defined in claim 1;
wherein, when the compounds of formula (Ia) or (IIa) comprise other cationic parts, they are associated with at least one anionic counterion allowing formula (Ia) or (IIa) to achieve electroneutrality.

### Claim 8 (depends on 1)

The fluorescent dye according to claim 1, chosen from one of the following formulae:
wherein An−, which may be identical or different, is chosen from an anionic counterion.

### Claim 9 (depends on 1)

A dye composition, comprising, in a cosmetically acceptable medium, at least one fluorescent dye of formula (I) or (II) according to claim 1.

### Claim 10 (depends on 1)

A process for dyeing keratin materials, comprising applying to the keratin materials a dye composition comprising at least one fluorescent dye of formula (I) or (II) according to claim 1, optionally in the presence of a reducing agent.

### Claim 11 (depends on 10)

The process for dyeing keratin materials according to claim 10, wherein said keratin materials are dark human keratin fibers.

### Claim 12 (depends on 10)

The process for dyeing keratin materials according to claim 10, wherein the keratin materials are dark keratin fibers comprising a tone height of less than or equal to 6.

### Claim 13 (depends on 12)

The process for dyeing keratin materials according to claim 12, wherein said dark human keratin fibers comprise a tone height of less than 6.

### Claim 14 (depends on 10)

The process for dyeing keratin materials according to claim 10, wherein said dark human keratin fibers are lightened.

### Claim 15 (depends on 10)

The process for dyeing keratin materials according to claim 10, further comprising applying an oxidizing agent to the keratin fibers.

### Claim 16 (depends on 1)

A multicompartment device comprising a first compartment and a second compartment, wherein the first compartment comprises a dye composition comprising at least one fluorescent dye of formula (I) or (II) according to claim 1, and the second compartment comprises a reducing agent.

### Claim 17 (depends on 16)

The multicompartment device according to claim 16, further comprising a third compartment comprising an oxidizing agent.