USE FOR DYEING KERATIN FIBRES OF A COMPOUND OF AZOMETHINE TYPE BEARING TWO PYRAZOLOPYRIDINE UNITS
20170349753 · 2017-12-07
Inventors
Cpc classification
A61K8/494
HUMAN NECESSITIES
A61Q5/065
HUMAN NECESSITIES
International classification
C09B69/10
CHEMISTRY; METALLURGY
Abstract
The invention relates to a compound chosen from the compounds of formulae (I) and (II), the leucoforms thereof, the optical and geometrical isomers thereof and the tautomers thereof, and also the addition salts thereof with an acid or a base, and the solvates thereof. The invention also relates to the use of these particular compounds for dyeing keratin fibres.
##STR00001##
Claims
1. Compound chosen from dyes of azomethine type comprising two pyrazolopyridine units of formulae (I) and (II), the leuco forms, optical and geometrical isomers, and tautomers thereof, and also the addition salts thereof with an acid or a base and the solvates thereof such as hydrates: ##STR00048## in which formulae (I) and (II): Z.sub.1 represents an oxygen atom or a group —N(R.sub.6)—; Z′.sub.1 represents an oxygen atom or a group —N(R′.sub.6)—; when Z.sub.1 represents —N(R.sub.6)— and/or Z′.sub.1 represents —N(R′.sub.6)— then R.sub.1 and R.sub.6 and/or R′.sub.1 and R′.sub.6, respectively, may form, together with the nitrogen atom to which they are attached, an optionally substituted, 5- to 8-membered, optionally cationic, saturated, unsaturated or aromatic heterocycle; R.sub.1, R′.sub.1, R.sub.6, and R′.sub.6 each independently represent: a hydrogen atom, a C.sub.1-C.sub.10 alkyl radical optionally interrupted with one or more non-adjacent heteroatoms, preferably oxygen, and/or optionally substituted, preferably with one or more groups chosen from i) hydroxyl, ii) optionally substituted, 5- to 8-membered, cationic or non-cationic, saturated, unsaturated or aromatic (hetero)cycle, iii) —N(R′)R″, iv) —N.sup.+R′R″R′″ with R′, R″ and R′″ each independently representing a C.sub.1-C.sub.6 alkyl group; an optionally substituted, 5- to 8-membered, cationic or non-cationic, saturated, unsaturated or aromatic (hetero)cyclic radical; R.sub.2, R.sub.3, R.sub.4, R.sub.5, R′.sub.2, R′.sub.3, R′.sub.4 and R′.sub.5 each independently represent: a hydrogen atom, an optionally substituted C.sub.1-C.sub.4 alkyl radical, a group chosen from —NH.sub.2, —N(H)R.sub.10, —N(R.sub.11)R.sub.12, OH and —OR.sub.9, with R.sub.9 and R.sub.10 representing an optionally substituted, linear or branched C.sub.1-C.sub.6 alkyl, R.sub.11 and R.sub.12, which may be identical or different, representing an optionally substituted, linear or branched C.sub.1-C.sub.6 alkyl, it being possible for R.sub.11 and R.sub.12 to form, together with the nitrogen atom to which they are attached, a saturated, unsaturated or aromatic 5- to 8-membered heterocycle optionally containing one or more other heteroatoms or groups chosen from N, O, S, S(O).sub.2 and C(O), the heterocycle being optionally substituted; R.sub.2, R.sub.3, R.sub.4, R.sub.5, R′.sub.2, R′.sub.3, R′.sub.4 and R′.sub.5 may form, in pairs with adjacent radicals, an optionally substituted, saturated or unsaturated (hetero)cycle; it being understood that when the compound of formula (I) or (II) is positively charged, then it comprises as many anionic counterions as cationic charges to achieve the electrical neutrality of the molecule.
2. Compound according to claim 1, characterized in that R.sub.1 and R′.sub.1 are chosen from the following groups: i) C.sub.1-C.sub.6 alkyl; ii) C.sub.1-C.sub.10 alkyl substituted with one or more hydroxyl groups; iii) C.sub.1-C.sub.6 alkyl substituted with one or more amino or (di)(C.sub.1-C.sub.4)alkylamino groups such as dimethylamino; iv) C.sub.1-C.sub.6 alkyl substituted with a nitrogenous heterocycle, for example piperazinyl, imidazolyl, pyrrolidinyl, morpholinyl or piperidyl; v) —[(CH.sub.2).sub.m—O].sub.p-L-Y with p=1, 2 or 3, preferably 1 or 2, m=1, 2 or 3, preferably 2, L denoting a linear or branched, saturated C.sub.1-C.sub.6 divalent hydrocarbon-based group, and Y denoting a hydroxyl group or a hydrogen atom.
3. Compound according to claim 1 or 2, characterized in that R.sub.2, R′.sub.2, R.sub.3, R′.sub.3, R.sub.4, R′.sub.4, R.sub.5 and R′.sub.5 independently represent a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical such as methyl, ethyl, propyl, isopropyl, butyl or tert-butyl, or R.sub.4 and R.sub.5 and R′.sub.4 and R′.sub.5 together form a 5- to 8-membered ring.
4. Compound according to any one of the preceding claims, characterized in that it is chosen from those of formula (I′) or (II′): ##STR00049## in which formulae (I′) and (II′): Z″.sub.1 is chosen from an oxygen atom and a group —N(R″.sub.6)—; when Z″.sub.1 represents —N(R″.sub.6)—, then R″.sub.1 and R″.sub.6 may form, together with the nitrogen atom to which they are attached, an optionally substituted, 5- or 6-membered, saturated, unsaturated or aromatic heterocycle; R″.sub.1 represents a C.sub.1-C.sub.6 alkyl radical, optionally interrupted with one or more non-adjacent oxygen atoms, and/or optionally substituted with: a hydroxyl radical, a di(C.sub.1-C.sub.4)alkylamino radical, a heterocycle optionally substituted with one or more C.sub.1-C.sub.4 alkyl and/or hydroxyl radicals and chosen from pyrrolidine, piperidine, morpholine, piperazine and imidazole; R″.sub.6 represents: a hydrogen atom; a C.sub.1-C.sub.10 alkyl radical optionally substituted with a hydroxyl radical; R″.sub.2, R″.sub.3, R″.sub.4 and R″.sub.5 each independently represent: a hydrogen atom; a C.sub.1-C.sub.4 alkyl radical; and the leuco forms, isomers and tautomers thereof, and also the addition salts thereof with an acid or a base and the solvates thereof.
5. Compound according to claim 4, characterized in that Z″.sub.1 represents an oxygen atom, R″.sub.1 denotes a linear or branched C.sub.1-C.sub.6 alkyl radical, a C.sub.1-C.sub.6 hydroxyalkyl radical; a di(C.sub.1-C.sub.4 alkyl)amino(C.sub.1-C.sub.6 alkyl) radical; a radical —[(CH.sub.2).sub.m′—O].sub.p′-L′-Y′ with p′=1, 2, 3, preferably 1 or 2, m′=2 or 3, L′ denoting a saturated linear C.sub.1-C.sub.6 divalent hydrocarbon-based radical, and Y′ denoting a hydroxyl radical or a hydrogen atom; an alkyl radical substituted with a heterocycle chosen from pyrrolidinyl, piperidyl, morpholinyl, piperazinyl and imidazolyl, said heterocycle being optionally substituted with one or more C.sub.1-C.sub.4 alkyl radicals such as methyl, or hydroxyl.
6. Compound according to claim 4, characterized in that Z″.sub.1 represents NH, R″.sub.1 denotes a C.sub.1-C.sub.6 hydroxyalkyl radical, a di(C.sub.1-C.sub.4 alkyl)amino(C.sub.1-C.sub.6 alkyl) radical, an alkyl radical substituted with a heterocycle chosen from pyrrolidinyl, piperidyl, morpholinyl, piperazinyl and imidazolyl, said heterocycle being optionally substituted with one or more C.sub.1-C.sub.4 alkyl radicals such as methyl, or hydroxyl.
7. Compound according to claim 4, characterized in that Z″.sub.1 represents —N(R″.sub.6)—, R″.sub.1 and R″.sub.6 each independently denote a C.sub.1-C.sub.6 alkyl radical or a C.sub.1-C.sub.6 hydroxyalkyl radical, and preferably R′.sub.1 and R′.sub.6 are identical; or R″.sub.1 forms with R″.sub.6 a ring, this ring being chosen from pyrrolidinyl, piperidyl, morpholinyl and piperazinyl rings optionally substituted with one or more C.sub.1-C.sub.4 alkyl and/or hydroxyl radicals.
8. Composition for dyeing keratin fibres comprising, in a medium that is suitable for dyeing keratin fibres, one or more compounds as defined in any one of claims 1 to 7.
9. Composition according to claim 8, characterized in that the compound(s) as defined in any one of claims 1 to 7 are present in an amount ranging from 0.01% to 15% by weight and preferably from 0.05% to 10% by weight relative to the total weight of the composition.
10. Composition according to claim 8 or 9, characterized in that it also comprises one or more oxidizing agents.
11. Use of one or more compounds as defined in any one of claims 1 to 7, for dyeing keratin fibres.
12. Process for dyeing keratin fibres, characterized in that at least one dye composition according to any one of claims 8 to 10 is applied to these fibres.
13. Process for preparing compounds of formulae (I) and (II) as defined in any one of claims 1 to 7, according to the following scheme: A) in the case where formulae (I) and (II) are symmetrical: ##STR00050## which consists: a) in a first stage, in reacting at least two molar equivalents of pyrazolo[1,5-a]pyridine compound A.sub.1 comprising an amino group in position 3 with a pyridine compound A.sub.2 which is free in position 6 and comprising in position 2 either a hydrogen atom or an electrofugal group, preferably, this reaction is performed i) in a polar protic solvent such as in water or a mixture of water/C.sub.1-C.sub.10 alcohol such as ethanol, ii) and/or in the presence of one or more mineral or organic basifying agents, as defined below, chosen in particular from sodium hydroxide, potassium hydroxide, a mineral carbonate such as potassium carbonate, or an acetate, iii) and/or in the presence of a chemical oxidizing agent such as peroxides or persulfates, iv) and/or at a temperature between room temperature; i.e. 25° C., and the reflux temperature of the solvent, preferably at room temperature; and then b) in a second stage, in maintaining the reaction medium under stirring for a time of between 5 minutes and 48 hours, more particularly between 30 minutes and 24 hours if the reaction is performed at room temperature; and then c) the reaction products (I) and (II) are optionally purified via a standard technique such as recrystallization, filtration or chromatography; it being understood that, in formulae A.sub.1, A.sub.2, (I) and (II), the radicals R.sub.1 to R.sub.5 and Z.sub.1 are as defined in claims 1 to 3, and Y represents a hydrogen atom or an electrofugal group such as halogen, (poly)halo(C.sub.1-C.sub.6 alkoxy), or (poly)(halo)(C.sub.1-C.sub.6 alkyl)-SO.sub.3—; B) in the case where formulae (I) and (II) are symmetrical or dissymmetrical: ##STR00051## which consists: a) in a first stage, in reacting one molar equivalent of pyrazolo[1,5-a]pyridine compound A.sub.1 comprising an amino group in position 3 with a pyridine compound A.sub.2 which is free in position 6 and comprising in position 2 either a hydrogen atom or an electrofugal group, preferably, this reaction is performed i) in a polar protic solvent such as in water or a mixture of water/C.sub.1-C.sub.10 alcohol such as ethanol, ii) and/or in the presence of one or more mineral or organic basifying agents, as defined below, chosen in particular from sodium hydroxide, potassium hydroxide, a mineral carbonate such as potassium carbonate, or an acetate, iii) and/or in the presence of a chemical oxidizing agent such as peroxides or persulfates, iv) and/or at a temperature between room temperature, i.e. 25° C., and the reflux temperature of the solvent, preferably at room temperature; and then b) in a second stage, in maintaining the reaction medium under stirring for a time of between 5 minutes and 48 hours, more particularly between 30 minutes and 24 hours if the reaction is performed at room temperature; and then c) the reaction product A.sub.3 is optionally purified via a standard technique such as recrystallization, filtration or chromatography; d) according to a variant, compound A.sub.3 once purified reacts with a molar equivalent of pyrazolo[1,5-a]pyridine compound A′.sub.1 comprising an amino group in position 3, under the same conditions as steps a) and b), to give the products (I) and (II), which are optionally purified via a standard technique such as recrystallization, filtration or chromatography; e) according to another variant, compound A.sub.3 is not purified, and reacts with a molar equivalent of pyrazolo[1,5-a]pyridine compound A′.sub.1 comprising an amino group in position 3, under the same conditions as steps a) and b), to give the products (I) and (II), which are optionally purified via a standard technique such as recrystallization, filtration or chromatography; it being understood that, in formulae A.sub.1, A.sub.2, A.sub.3, (I) and (II), the radicals R.sub.1 to R.sub.5, Z.sub.1, R′.sub.1 to R′.sub.5, Y and Z′.sub.1 are as defined previously.
14. Compound of formula A.sub.3 as defined in claim 13, the optical isomers thereof, geometrical isomers thereof and the tautomers thereof, and also the addition salts thereof with an acid or a base, and the solvates thereof such as hydrates.
Description
EXAMPLES
Example 1: Synthesis of the Dye Having the Following Formula
[0159] ##STR00036##
[0160] 500 ml of ethanol are placed in a 1-litre one-necked round-bottomed flask equipped with a calcium chloride guard tube, followed by addition, with stirring, of g (0.2177 mol) of 2-[(3-aminopyrazolo[1,5-a]pyridin-2-yl)oxy]ethanol hydrochloride.
[0161] 14.2 g (0.986 mol) of 2-chloropyridine-3,5-diamine and 60.3 ml (0.346 mol) of N-ethyl-N-(propan-2-yl)propan-2-amine are added to this solution.
[0162] The solution thus obtained is stirred at room temperature for 4 days. The black precipitate formed is isolated by filtration, washed with water and dried in a desiccator under vacuum at 30° C. in the presence of a desiccant, to constant weight. A black solid is thus obtained.
[0163] The spectrometric analyses show that the compound obtained corresponds to the above structure.
Example 2: Synthesis of 3,3-[(5-amino-3-iminopyridine-2,6-(1H,3H)-diylidene)-bis(nitrilopyrazolo[1,5-a]pyridine-3,2-diyloxy)]dipropan-1-ol hydrochloride
[0164] ##STR00037##
[0165] 150 ml of ethanol are placed in a 500-ml one-necked round-bottomed flask equipped with a calcium chloride guard tube, followed by addition, with stirring, of 10.4 g (0.04268 mol) of 3-[(3-aminopyrazolo[1,5-a]pyridin-2-yl)oxy]propan-1-ol hydrochloride.
[0166] 2.78 g (0.01940 mol) of 2-chloropyridine-3,5-diamine and 11.8 ml (0.06790 mol) of N-ethyl-N-(propan-2-yl)propan-2-amine are added to this solution.
[0167] The solution thus obtained is then stirred at room temperature for 4 days. The black precipitate formed is isolated by filtration, washed with water and dried in a desiccator under vacuum at 30° C. in the presence of a desiccant, to constant weight. A solid in the form of a black powder is thus obtained.
[0168] The spectrometric analyses show that the compound obtained corresponds to 3,3′-[(5-amino-3-iminopyridine-2,6-(1H,3H)-diylidene)bis(nitrilopyrazolo[1,5-a]-pyridine-3,2-diyloxy)]dipropan-1-ol hydrochloride
Example 3: Synthesis of N,N′-(5-amino-3-iminopyridine-2,6-(1H,3H)-diylidene)-bis{2-[2-(dimethylamino)ethoxy]pyrazolo[1,5-a]pyridin-3-amine}dihydrochloride
[0169] ##STR00038##
[0170] 550 ml of ethanol are placed in a 1-litre one-necked round-bottomed flask equipped with a calcium chloride guard tube, followed by addition, with stirring, of 55 g (0.1876 mol) of 2-[2-(dimethylamino)ethoxy]pyrazolo[1,5-a]pyridin-3-amine dihydrochloride.
[0171] 12.24 g (0.085 mol) of 2-chloropyridine-3,5-diamine and 52 ml (0.346 mol) of N-ethyl-N-(propan-2-yl)propan-2-amine are added to this solution.
[0172] The solution thus obtained is stirred at room temperature for 4 days. The viscous black oil obtained after removal of the solvent by evaporation under vacuum is chromatographed on a column of silica in normal phase with an eluent consisting of 50% dichloromethane and 50% methanol.
[0173] After removal of the solvent by evaporation under vacuum, the viscous black oil crystallizes in the form of a black solid.
[0174] The black solid formed is isolated by filtration, washed with water and then dried in a desiccator under vacuum at 30° C. in the presence of a desiccant, to constant weight.
[0175] The spectrometric analyses show that the compound obtained corresponds to N,N′-(5-amino-3-iminopyridine-2,6-(1H,3H)-diylidene)bis {2-[2-(dimethylamino)ethoxy]pyrazolo[1,5-a]pyridin-3-amine}dihydrochloride.
Example 4: Synthesis of N,N′-(5-amino-3-iminopyridine-2,6-(1H,3H)-diylidene)bis[2-(propan-2-yloxy)pyrazolo[1,5-a]pyridin-3-amine]hydrochloride
[0176] ##STR00039##
[0177] 80 ml of ethanol are placed in a 250-ml one-necked round-bottomed flask equipped with a calcium chloride guard tube, followed by addition, with stirring, of 4.11 g (18.1 mmol) of 2-(propan-2-yloxy)pyrazolo[1,5-a]pyridin-3-amine hydrochloride.
[0178] 1.18 g (8.21 mmol) of 2-chloropyridine-3,5-diamine and 5.0 ml (29 mol) of N-ethyl-N-(propan-2-yl)propan-2-amine are added to this solution.
[0179] The solution is then stirred at room temperature for 4 days. The black precipitate formed is isolated by filtration, washed with water and dried in a desiccator under vacuum at 30° C. in the presence of a desiccant, to constant weight. The compound is thus obtained in the form of a black powder.
[0180] The spectrometric analyses show that the compound obtained corresponds to N,N′-(5-amino-3-iminopyridine-2,6-(1H,3H)-diylidene)bis[2-(propan-2-yloxy)pyrazolo[1,5-a]pyridin-3-amine]hydrochloride.
Example 5: Synthesis of N,N′-(5-amino-3-iminopyridine-2,6-(1H,3H)-diylidene)-bis[2-(propan-2-yloxy)ethoxy]pyrazolo[1,5-a]pyridin-3-amine}hydrochloride
[0181] ##STR00040##
[0182] 150 ml of ethanol are placed in a 500-ml one-necked round-bottomed flask equipped with a calcium chloride guard tube, followed by addition, with stirring, of 11 g (48.5 mmol) of 2-[2-(propan-2-yloxy)ethoxy]pyrazolo[1,5-a]pyridin-3-amine hydrochloride.
[0183] 2.64 g (18.4 mmol) of 2-chloropyridine-3,5-diamine and 11.2 ml (64.4 mmol) of N-ethyl-N-(propan-2-yl)propan-2-amine are added to this solution.
[0184] The solution is then stirred at room temperature for 4 days. The black precipitate formed is isolated by filtration, washed with water and dried in a desiccator under vacuum at 30° C. in the presence of a desiccant, to constant weight. The compound is thus obtained in the form of a black powder.
[0185] The spectrometric analyses show that the compound obtained corresponds to N,N′-(5-amino-3-iminopyridine-2,6-(1H,3H)-diylidene)bis {2-[2-(propan-2-yloxy)ethoxy]pyrazolo[1,5-a]pyridin-3-amine}hydrochloride.
Example 6: Synthesis of N,N′-(5-amino-3-iminopyridine-2,6-(1H,3H)-diylidene)-bis{2-[2-(2-ethoxyethoxy)ethoxy]pyrazolo[1,5-a]pyridin-3-amine}hydrochloride
[0186] ##STR00041##
[0187] 150 ml of ethanol are placed in a 500-ml one-necked round-bottomed flask equipped with a calcium chloride guard tube, followed by addition, with stirring, of 10.0 g (33.14 mmol) of 2-[2-(2-ethoxyethoxy)ethoxy]pyrazolo[1,5-a]pyridin-3-amine hydrochloride.
[0188] 2.16 g (15.06 mmol) of 2-chloropyridine-3,5-diamine and 9.2 ml (52.71 mmol) of N-ethyl-N-(propan-2-yl)propan-2-amine are added to this solution.
[0189] The solution is then stirred at room temperature for 4 days. The black precipitate formed is isolated by filtration, washed with water and dried in a desiccator under vacuum at 30° C. in the presence of a desiccant, to constant weight. The compound is obtained in the form of a black powder.
[0190] The spectrometric analyses show that the compound obtained corresponds to N,N′-(5-amino-3-iminopyridine-2,6-(1H,3H)-diylidene)bis {2-[2-(2-ethoxyethoxy)ethoxy]pyrazolo[1,5-a]pyridin-3-amine}hydrochloride.
Example 7: Examples of Dyeing at Neutral pH
[0191] The following dye compositions are prepared from the ingredients indicated in the table below:
TABLE-US-00001 Dye.sup.(1) 10.sup.−3 mol pH 7 dye support .sup.(2) Demineralized water qs 100 g .sup.(1) Dye synthesized in one of Examples 1 to 6 above: Dye 1 (synthesized in Example 1)
[0192] Each mixture obtained was applied to locks of grey hair containing 90% white hairs. After a leave-on time of 30 minutes, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.
[0193] The shades obtained are given in the table below:
TABLE-US-00002 Dye 1 2 3 4 5 6 Shade Grey Grey Grey Grey Grey Grey observed neutral dark neutral dark light light
[0194] For the colourings in the presence of an oxidizing agent: at the time of use, each of the compositions described above was mixed with an equal weight of 20-volumes aqueous hydrogen peroxide solution (6% by weight relative to the total weight of 100 grams). A final pH of 7 is obtained.
[0195] The shades obtained are given in the table below:
TABLE-US-00003 Dye 1 2 3 4 5 6 Shade Grey Grey Grey Grey Grey Grey observed neutral
Example 8: Examples of Dyeing in Basic Medium
[0196] The following dye compositions are prepared:
TABLE-US-00004 Dye 1, 2, 3, 4, 5 or 6 10.sup.−3 mol pH 9.5 dye support .sup.(3) Demineralized water qs 100 g .sup.(3): pH 9.5 dye support 96° ethyl alcohol 20.8 g Pentasodium salt of diethylenetriaminepentaacetic acid as 0.48 g AM* an aqueous 40% solution C.sub.8-C.sub.10 alkyl polyglucoside as an aqueous 60% solution 3.6 g AM* Benzyl alcohol 2.0 g Polyethylene glycol containing 8 units of ethylene oxide 3.0 g NH.sub.4Cl 4.32 g Aqueous ammonia containing 20% NH.sub.3 2.94 g *AM: Active material
[0197] Each mixture obtained was applied to locks of grey hair containing 90% white hairs. After a leave-on time of 30 minutes, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.
[0198] The shades obtained are given in the table below:
TABLE-US-00005 Dye 1 2 3 4 5 6 Shade Grey Grey Grey Grey Grey Grey observed neutral dark
[0199] For the colourings in the presence of an oxidizing agent: at the time of use, each of the compositions described above was mixed with an equal weight of 20-volumes aqueous hydrogen peroxide solution. A final pH of 9.5 is obtained.
[0200] The shades obtained are given in the table below:
TABLE-US-00006 Dye 1 2 3 4 5 6 Shade Grey Grey Grey Grey Grey Grey observed neutral dark
[0201] The colours of the locks thus obtained with dyes 1 to 6 and also with compound 35 used in the same pH 9.5 dye support as that described above, and in the presence of an oxidizing agent, were evaluated in the CIE L* a* b* system, using a Minolta Spectrophotometer CM2600D colorimeter (specular components included, illuminant D65, angle 10°).
[0202] In this L* a* b* system, the three parameters denote, respectively, L*: the colour intensity, a*: the green/red colour axis, and b*: the blue/yellow colour axis. For the intensity, the lower the value, the darker and more intense the colour.
[0203] The variation in colouring or gain in colour build-up is the difference in colour between the locks of natural grey hair (NG) treated with the composition according to the invention, and the untreated locks, and is measured by (ΔE) according to the following equation:
ΔE=√{square root over ((L*−L.sub.o*).sup.2+(a*−a.sub.o*).sup.2+(b*−b.sub.o*).sup.2)}
[0204] In this equation, L*, a* and b* represent the values measured on NG dyed hair according to the invention, and L.sub.0*, a.sub.0* and b.sub.0* represent the values measured on the untreated locks.
[0205] The higher the value of ΔE, the greater the gain in colour build-up.
[0206] The results are given in the table below:
TABLE-US-00007 Dye L a b ΔE 1 24.54 0.41 1.36 37.98 2 22.21 0.26 1.05 40.25 3 25.78 −0.39 1.8 36.69 4 21.74 −0.31 1.27 40.63 5 23.67 1.96 3.85 37.91 6 25.06 0.54 1.59 37.4 Compound 35 25.64 1.36 3.2 36.27