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Publication numberCN101684204 B
Publication typeGrant
Application numberCN 200810168074
Publication date25 Jun 2014
Filing date22 Sep 2008
Priority date21 Sep 2007
Also published asCN101684204A, EP2062945A2, EP2062945A3, EP2062945B1, US7727287, US20090211038
Publication number200810168074.0, CN 101684204 B, CN 101684204B, CN 200810168074, CN-B-101684204, CN101684204 B, CN101684204B, CN200810168074, CN200810168074.0
InventorsA·格里夫斯, N·多布雷斯
Applicant莱雅公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Hemicyanin styryl thiol/disulfide dye, dye composition comprising this dye, process for lightening keratin materials using this dye
CN 101684204 B
Abstract  translated from Chinese
本发明涉及使用半花青苷苯乙烯基硫醇和二硫化物染料使角蛋白材料染色。 The present invention relates to the use of semi anthocyanin styrene mercaptan and disulfide dye staining keratin material. 本发明涉及包含半花青苷苯乙烯基发色团硫醇或二硫化物染料的染料组合物和使用所述组合物使角蛋白材料、特别是使角蛋白纤维、尤其是使人角蛋白纤维,例如毛发具有亮泽效果的染色方法。 The dye composition and use of the compositions of the present invention relates to a semi-anthocyanin styryl chromophore thiol or disulfide dye keratin materials, especially keratin fibers, in particular keratin fibers make , such as dyeing hair with a glossy effect method. 本发明还涉及新的半花青苷苯乙烯基发色团硫醇染料及其在亮化角蛋白材料中的用途。 The present invention also relates to a new semi-anthocyanin styryl chromophore thiol dyes and their use in lighting keratin material. 本发明的组合物能够获得具有特别持久牢固并且在暗色角蛋白纤维上明显可见的亮泽效果的着色。 The compositions of the invention can be obtained with a particular firm and lasting on dark keratin fibers visible colored glossy effect.
Claims(13)  translated from Chinese
1.一种下式(I)或式(II)的荧光染料、其有机或无机酸盐、旋光异构体和几何异构体: A following formula (I) or formula (II), a fluorescent dye, an organic or inorganic acid salts thereof, optical isomers and geometrical isomers:
Figure CN101684204BC00021
式⑴和式(II)中: >η表示I或2 ; >m表示O或I ; > Ra和Rb可相同或不同,表不氢原子或C1-C4烷基; > R1表不氢原子或(C1-C6)烷基; > R2和R3可相同或不同,表示氢原子、(C1-C6)烷基;或者R2和R3与携带它们的碳原子一起形成任选取代的苯并环; > R\ R5和R6可相同或不同,表示: •氢原子; • C1-C6 烷基; •氨基; •被一个或两个可相同或不同的C1-C6烷基取代的氨基, >或者两个相邻基团R4与R5和/或R5与R6与携带它们的碳原子一起形成任选取代的、与苯基稠合的苯并环; > L表示C1-C2tl 二价烃型链; > X表示氧原子或NR基团,其中R表示氢原子或(C1-C6)烷基; > Y表不:i)氢原子; >1表示殿'基团,其中R'表示氢原子或(C1-C4)烷基; > Q-表示选自如下的阴离子抗衡离子:i)卤离子;ii)硝酸根; UDC1-C6烷基磺酸根;iv)柠檬酸根;v)琥珀酸根;vi)酒石酸根; vii)乳酸根;viii)烷基硫酸根;ix)磷酸根;x)乙酸根;xi)三氟甲磺酸根;和xii)硼酸根; 要理解,如果η为2,则m为O,如果η为I,则m为I。 Type ⑴ and formula (II) are:> η = I or 2;> m represents O or I;> Ra and Rb may be the same or different, a hydrogen atom or a table is not C1-C4 alkyl;> R1 table is not a hydrogen atom or (C1-C6) alkyl;> R2 and R3 may be the same or different, represent a hydrogen atom, (C1-C6) alkyl; or R2 and R3 together with the carbon atoms carrying them form an optionally substituted benzo ring;> R \ R5 and R6 may be the same or different means: • a hydrogen atom; • C1-C6 alkyl; • amino; • by one or two may be the same or different C1-C6 alkyl substituted amino,> or two adjacent groups R4 and R5 and / or R6 and R5 and the carbon atoms carrying them form an optionally substituted benzo fused to a phenyl ring;> L represents C1-C2tl divalent hydrocarbon type chain;> X It represents an oxygen atom or NR group, wherein R represents a hydrogen atom or a (C1-C6) alkyl;> Y table is not: i) a hydrogen atom;> represents a temple 'group, wherein R' represents a hydrogen atom or a (C1- C4) alkyl;> Q- represents an anionic counter ion selected from: i) a halide ion; ii) nitrate; UDC1-C6 alkyl sulfonate; iv) citrate; v) succinate; vi) tartrate; vii) lactate; viii) alkyl sulfate; ix) phosphate; x) acetate; xi) triflate; and xii) borate; to be understood that, if η is 2, m is O, if η is I, then m is I.
2.上述权利要求的式(I)或式(II)的荧光染料,其中m和η为1,Y表示氢原子。 2. the preceding claims of formula (I) or formula (II), a fluorescent dye, wherein m and η is 1, Y represents a hydrogen atom.
3.权利要求1的式(I)或式(II)的二硫化物荧光染料,其中η = 2,m = O。 Of formula (I) 1 or Formula (II) according to claim disulfide fluorescent dye, wherein η = 2, m = O.
4.权利要求1的下式(Ia)、(IIa)、(Ib)和(IIb)的荧光染料: 1 of formula (Ia), (IIa) 4. claim, (Ib) and (IIb) fluorescent dye:
Figure CN101684204BC00031
在式(Ia)、(IIa)、(Ib)和(IIb)中: > Ra、R1至R6、W、Y和Q_同权利要求1中定义; > η'和m'可相同或不同,表不I和6之间的整数,含I和6,n' +m'之和介于2和4之间,含2和4 ; > X表不选自以下的基团:-G_,其中G表不氧原子,或NR,其中R表不氢原子或(C1-C6)烷基; > Ta表示σ共价键。 In the formula (Ia), (IIa), (Ib) and (IIb) in:> Ra, R1 to R6, W, Y and Q_ as defined in claim 1;> η 'and m' may be the same or different, Table integers between I and 6, containing I and 6, n '+ m' of and between 2 and 4, with 2 and 4;> X table is not selected group: -G_, wherein G table is not an oxygen atom, or NR, wherein R represents a hydrogen atom or not (C1-C6) alkyl;> Ta denote σ covalent bond.
5.权利要求1的式(I)或式(II)的荧光染料,选自下列染料: A fluorescent dye of formula (I) or formula (II) 1 of claim, the dye is selected from the following:
Figure CN101684204BC00041
Figure CN101684204BC00051
其中ArT可相同或不同,表示权利要求1中所定义的Q—。 ArT which may be the same or different and each represents Q- 1 as defined in the claims.
6.一种染料组合物,所述染料组合物在化妆品用介质中含有权利要求1的式(I)或式(II)的荧光染料。 A dye composition comprising the dye composition according to claim 1 of the formula (I) or formula (II) with a fluorescent dye in a cosmetic medium.
7.一种给角蛋白材料染色的方法,其中将包含至少一种权利要求1的式(I)或式(II)的荧光染料的染料组合物应用于所述材料。 7. A method for dyeing keratin materials, which will contain at least one claim of formula (I) 1 or Formula (II) of the dye composition is applied to the material of a fluorescent dye.
8.权利要求7的给角蛋白材料染色的方法,其中所述角蛋白材料是色调高度小于或等于6的暗色角蛋白纤维。 The method for dyeing keratin material according to claim 7, wherein the keratin material is a tone height of less than or equal to 6 dark keratin fibers.
9.权利要求7的方法,其中在使用权利要求1的式(I)或式(II)的荧光染料之前或之后使用还原剂。 The method of claim 7, wherein prior to use claims of formula (I) 1 or Formula (II) or a fluorescent dye after using a reducing agent.
10.权利要求7的方法,其中所述组合物包含氧化剂。 10. The method of claim 7, wherein said composition comprises an oxidizing agent.
11.权利要求1的式(I)或式(II)的荧光染料在暗色角蛋白纤维染色中的用途。 Formula (I) 1 of claim or formula (II) is a fluorescent dye in a dark keratin fiber dyeing purposes.
12.权利要求11的用途,用于暗色角蛋白纤维亮化。 12. The use of claim 11 for lighting dark keratin fibers.
13.权利要求11或12的用途,其中所述角蛋白纤维的色调高度小于6。 13. The use of claim 11 or claim 12, wherein said keratin fibers tone height of less than 6.
Description  translated from Chinese

半花青苷苯乙烯基硫醇/ 二硫化物染料、包含该染料的染料组合物以及使用该染料亮化角蛋白材料的方法 Semi anthocyanin styrene thiol / disulfide dyes, dye composition containing the dye and the use of lighting the dye keratin material

[0001] 本发明涉及使用半花青苷苯乙烯基硫醇/ 二硫化物荧光染料给角蛋白材料染色。 [0001] The present invention relates to the use of semi anthocyanin styrene thiol / disulfide fluorescent dyes for dyeing keratin material.

[0002] 通过直接染色法使角蛋白纤维、特别是使人角蛋白纤维染色是已知的通行做法。 [0002] by direct staining keratin fibers, in particular keratin fibers dyed people are known practices. 常规用于直接染色的方法包括将直接染料应用于角蛋白纤维,使其扩散,然后冲洗该纤维,所述直接染料是对角蛋白纤维具有亲和性的有色分子或着色分子。 Conventional methods for the direct dyeing comprises direct dyes applied to the keratin fibers to spread, then rinse the fiber, said direct dye is having an affinity for keratin fibers colored molecule or coloring molecules.

[0003] 常用的直接染料为例如硝基苯型染料、蒽醌型染料、硝基吡啶型染料或偶氮型染料、咕吨型染料、吖啶型染料、吖嗪型染料或三芳基甲烷型染料。 [0003] The direct dyes used, for example, nitrobenzene dyes, anthraquinone dyes, nitropyridine dyes or azo dyes, xanthene dyes, acridine dyes, azine dyes or triarylmethane type dyes.

[0004] 采用半花青苷苯乙烯基直接染料对角蛋白纤维进行强效染色也是已知的通行做法。 [0004] The half anthocyanin styryl direct dyes to the keratin fiber dyeing is also known potent practices. 这些苯并噻唑鎗或苯并咪唑鎗杂芳基染料参见例如专利申请EP1166753或EP1166757。 These guns benzothiazole, or benzimidazole dye gun heteroaryl see e.g. EP1166753 or patent application EP1166757.

[0005] 使用这些常规直接染料对角蛋白纤维着色时,无法使角蛋白纤维有明显的光泽。 When [0005] The use of these conventional direct dyes for coloring keratin fibers, keratin fibers can not make a clear gloss.

[0006] 将暗色角蛋白纤维的颜色亮化为较亮的色度(shade),任选改变其色度,是一项重要的需求。 [0006] The color dark keratin fibers lighting is brighter shades (shade), optionally change its color, is an important requirement.

[0007] 按照惯例,为了获得较亮的色彩而采用化学漂白方法。 [0007] Conventionally, in order to obtain a lighter color and the use of chemical bleaching process. 该方法包括,通常在碱性介质中,用通常包括过氧化氢,可能与过酸盐联用的强氧化系统,对角蛋白纤维(例如毛发)进行处理。 The method includes, generally in an alkaline medium, using typically include hydrogen peroxide, may be too strong acid oxidation system, in conjunction with keratin fibers (such as hair) for processing.

[0008] 这一漂白系统的缺点是破坏角蛋白纤维,对其化妆品性质产生不利影响。 Disadvantage [0008] The bleaching system is to undermine keratin fibers, adversely affecting their cosmetic properties. 角蛋白纤维实际上往往易变得粗糙,更难于梳理,更易脆裂。 Keratin fibers in fact often easy to become rough, more difficult to sort out, more brittle. 结果,用氧化剂使角蛋白纤维变得有光泽或漂白与用于改变所述纤维形状的处理,特别是拉直毛发的处理互不相容。 As a result, the keratin fibers with an oxidizing agent or bleaching becomes shiny and processing for changing the shape of the fibers, especially hair straightening treatment incompatible.

[0009] 另一项亮化技术包括将荧光直接染料应用于暗色毛发。 [0009] Another lighting technique involves a fluorescent dye is applied directly to the dark hair. 该技术详细记载于专利文献W003/028685和W02004/091473中。 The technique described in detail in Patent Document W003 / 028685 and W02004 / 091473 in. 该技术使得能够在处理时保持角蛋白纤维的质量。 This technique makes it possible to maintain the angle when dealing with the quality of the protein fibers. 然而,这些荧光直接染料不具备作为外用物质的令人满意的坚牢度。 However, these fluorescent direct dyes do not have a satisfactory fastness external substance.

[0010]为了提高直接染色的坚牢度,已知的做法是使用二硫化物染料,特别是专利申请TO2005/097051或EP1647580中的咪唑鎗发色团染料及专利申请W02006/134043和W02006/136617中的吡啶鎗/ 二氢吲哚鎗(indolinium)苯乙烯基发色团染料。 [0010] In order to improve direct dyeing fastness, it is known practice to use disulfide dyes, especially patent application TO2005 / 097051 or EP1647580 imidazole gun chromophore dye and patent application W02006 / 134043 and W02006 / 136617 The pyridine gun / indoline gun (indolinium) styryl dye chromophore. 专利申请W02007/039527公开了用于染发的具体的苯乙烯基硫醇染料,该染料带有吲哚部分,在吲哚基1,2-位上被取代。 Patent application W02007 / 039527 discloses a hair thiol specific styryl dye, the dye having an indole moiety, indolyl substituted in the 1,2-position. 这些文献都没有提到亮化角蛋白纤维而又无需使用化学氧化剂问题。 These documents are not mentioned lighting keratin fibers but without the use of chemical oxidants problem.

[0011] 本发明的目的是提供用于使角蛋白材料,特别是人角蛋白纤维,尤其是暗色毛发染色的新的系统,该系统没有现有漂白方法的缺点。 [0011] The present invention is to provide a disadvantage for keratin materials, in particular human keratin fibers, especially dark hair dyed the new system, the system is no existing method of bleaching.

[0012] 具体地说,本发明的一个目的是提供用于获得亮泽效果(尤其是对于天然或人造的暗色角蛋白纤维)的直接染色系统,该系统可耐受连续的洗发操作,不会损坏角蛋白纤维,不会对染色系统的化妆品性质造成不利影响。 [0012] In particular, an object of the present invention is to provide a means for obtaining glossy effects (especially for natural or man-made dark keratin fibers) direct dyeing system, which can withstand continuous operation of shampoo, not it will damage the keratin fibers, will not adversely affect the staining system cosmetic properties.

[0013] 本发明的另一个目的是使角蛋白材料染色,并且染色方式对于外部侵蚀而言是持久牢固的。 [0013] Another object of the present invention is to dyeing keratin materials, and coloration is strong for enduring external corrosion is concerned.

[0014] 本发明的另一个目的是能够扩大可用于角蛋白纤维、特别是用于亮色毛发或用于暗色毛发的染料范围,能够脱去通过该处理已染上的色彩,同时又不损伤所述纤维。 [0014] Another object of the present invention is to be used to expand the keratinous fibers, in particular for light-colored hair or for hair dye dark range, it is possible by this process to have contracted off color, without damage to the said fibers.

[0015] 可以用本发明达到该目的,本发明的一个主题是用于使角蛋白材料、特别是角蛋白纤维、尤其是人角蛋白纤维(例如毛发)、更特别是暗色毛发的染色方法,该方法包括将 [0015] The present invention may be used to achieve this purpose, a subject of the invention is used to keratin materials, in particular keratin fibers, especially human keratin fibers (such as hair), more particularly dark hair dyeing method, The method includes

染料组合物应用于角蛋白材料,所述染料组合物包含合适化妆品用介质中的至少一种二硫 Dye composition applied to the keratin material, the dye composition comprises a suitable cosmetic medium, at least one disulfide

化物或硫醇荧光染料,所述染料选自下式(I)和式(II)的染料、其有机酸盐或无机酸盐、旋 Thiol compound or a fluorescent dye, a dye selected from the dyes of the formula (I) and formula (II), which is an organic acid salt or inorganic acid salt, spin

光异构体和几何异构体以及溶剂合物(例如水合物): Optical isomers and geometric isomers and solvates (eg hydrates):

[0016] [0016]

Figure CN101684204BD00071

[0017]式(I)或式(II)中: [0017] Formula (I) or formula (II) are:

[0018] >n 表示I 或2 ; [0018]> n represents I or 2;

[0019] >m 表示O 或I ; [0019]> m represents O or I;

[0020] > Ra和Rb可相同或不同,表示氢原子或C1-C4烷基;特别地,Rb表示氢原子,更特别地,Ra和Rb表不氢原子; [0020]> Ra and Rb may be the same or different, represent a hydrogen atom or a C1-C4 alkyl; in particular, Rb represents a hydrogen atom, more particularly, Ra and Rb are not hydrogen atom table;

[0021] ^R1表不氢原子或(C1-C6)烷基,任选被选自以下的基团取代:素、C1-C4^氧基、C1-C4(二)(烷基)氨基、苯基、甲苯基和甲氧基苯基; [0021] ^ R1 table is not a hydrogen atom or a (C1-C6) alkyl, optionally substituted with a group selected from the following: prime, C1-C4 ^ alkoxy, C1-C4 (b) (alkyl) amino, phenyl, tolyl and methoxyphenyl;

[0022] >或者R1和Ra —起形成(C3`-C6)亚烷基链,例如亚乙基或亚丙基或(C3-C7)亚烯基链例如-CH = CH-; [0022]> or R1 and Ra - together form a (C3`-C6) alkylene chain, such as ethylene or propylene or (C3-C7) alkenylene chain such as -CH = CH-;

[0023] >R2和R3可相同或不同,表不氢原子或齒原子、任选取代的(C「C6)烷基、(C1-C6)烷氧基或(C1-C6)烷硫基;或者R2和R3与携带它们的碳原子一起形成任选取代的苯并环; [0023]> R2 and R3 may be the same or different, a hydrogen atom or a table without teeth atoms, optionally substituted (C 'C6) alkyl, (C1-C6) alkoxy or (C1-C6) alkylthio; or R2 and R3 together with the carbon atoms carrying them form an optionally substituted benzo ring;

[0024] > R4、R5和R6可相同或不同,表不: [0024]> R4, R5 and R6 may be the same or different, and the table does not:

[0025].氢原子; . [0025] a hydrogen atom;

[0026].任选被一个或多个选自以下的基团取代的C1-C6烷基、优选C1-C2烷基:羟基、C1-C2烷氧基、c2-c4(多)羟基烷氧基、酰氨基和被可相同或不同的两个C1-C4烷基取代的氨基; . [0026] optionally substituted with one or more substituents selected from the following group of C1-C6 alkyl, preferably C1-C2 alkyl: hydroxy, C1-C2 alkoxy, c2-c4 (poly) hydroxy alkoxy group, an amido group, and may be the same or different two C1-C4 alkyl substituted amino;

[0027].卤原子例如氯、氟或溴; . [0027] a halogen atom such as chlorine, fluorine or bromine;

[0028].羟基; . [0028] hydroxy;

[0029].C1-C2 烷氧基; [0029] .C1-C2 alkoxy;

[0030].C1-C2 烧硫基; [0030] .C1-C2 burning sulfur;

[0031] •氨基; [0031] • amino;

[0032].5或6元杂环烷基,其可被1-3个可相同或不同的选自以下的基团取代:羟基、氨基、(二)烷基氨基和C1-C4羟基烷基,例如吗啉代、(羟乙基)哌嗪-1基、(二)(羟基)吡咯烷-1基、(二)(羟基)哌啶-1基; [0032] .5 or 6-membered heterocyclic group which may be substituted by 1-3 same or different substituents selected from the following groups: hydroxyl, amino, (di) alkylamino and C1-C4 hydroxyalkyl , e.g., morpholino, (hydroxyethyl) piperazine -1-yl, (b) (hydroxy) pyrrolidin-1-yl, (b) (hydroxy) piperidin-1-yl;

[0033].被一个或两个可相同或不同、任选带有至少以下基团的C1-C6烷基取代的氨基:[0034] i)羟基、 [0033] one or two may be the same or different, C1-C6 alkyl optionally substituted amino group with at least the following:. [0034] i) hydroxy,

[0035] ii)任选被一个或两个C1-C3烷基取代的氨基,所述烷基可与它们所连接的氮原子一起形成含有5-7元、饱和或不饱和的、任选取代的杂环,该杂环任选包含至少一个与氮可相同或不同的其它杂原子、 [0035] ii) optionally substituted with one or two C1-C3 alkyl substituted amino group, the alkyl group with the nitrogen atom to which they are attached form a 5-7 membered containing, saturated or unsaturated, optionally substituted The heterocyclic ring optionally containing at least one nitrogen may be the same or different additional heteroatoms and,

[0036] .-N(R)-C(O)-R'其中R基团为氢原子或任选带有至少一个羟基的C1-C4烷基,R'基团为C1-C2烷基; [0036] (R) -C (O) -R 'group wherein R is a hydrogen atom or an optionally C1-C4 alkyl, R having at least one hydroxyl' group is a C1-C2 alkyl-N.;

[0037].酸或成盐形式(优选与碱金属或铵成盐,所述铵是取代或未取代的)的羧基; . [0037] an acid or a salt form (preferably with an alkali metal or ammonium salt formation, the ammonium is a substituted or unsubstituted) carboxy;

[0038].含有1-6个碳原子和1-6个可相同或不同齒原子的多卤代烷基;多卤代烷基例如三氟甲基; [0038] 1-6 carbon atoms and 1-6 may be the same or different teeth atoms containing polyhaloalkyl;. Polyhaloalkyl such as trifluoromethyl;

[0039] -R4和R5优选为氢原子,R6优选位于苯基环4位碳原子上,R6特别表示取代氨基; [0039] -R4 and R5 is preferably a hydrogen atom, R6 is preferably located on the phenyl ring 4 carbon atoms, R6 represents a substituted amino group in particular;

[0040] >或者两个相邻基团R4与R5和/或R5与R6与携带它们的碳原子一起形成任选取代的、与苯基稠合的苯并环或杂环,杂环特别选自吗啉基、哌嗪基、哌啶基或吲哚基,后者优选在b-[3,4]上与式(I)或式(II)的苯基稠合,或者R4和R5,特别与携带它们的式(I)或式(II)的苯基一起,形成咔唑基; [0040]> or two adjacent groups R4 and R5 and / or R5 and R6 and the carbon atoms carrying them form an optionally substituted phenyl fused with benzo or heterocyclic ring, heterocyclic special election from morpholinyl, piperazinyl, piperidinyl, or indolyl, which is preferably in the b- [3,4] of the formula (I) or formula (II) is fused to a phenyl, or R4 and R5, Special and carrying them phenyl of formula (I) or formula (II) together form a carbazolyl group;

[0041];>或者R4、R5和R6与式(II)的苯基一起形成下式的久洛尼定型三环单元: [0041];> or R4, R5 and R6 phenyl formula (II) are taken together to form a long Maloney stereotypes tricyclic unit:

[0042] [0042]

Figure CN101684204BD00081

[0043] 其中Re和Rd表示氢原子或C1-C4烷基; [0043] wherein Re and Rd represents a hydrogen atom or a C1-C4 alkyl;

[0044] > L表示C1-C2tl 二价烃型链,该链任选被以下基团取代、被以下基团任选中断和/或在其两端的一端或另一端被以下基团任选终止:i) 一个或多个选自以下的二价基团或其组合:-N(R) -「N.(R) (R° ) -、An' _0_、-S-、-CO-和-SO2-,其中R 和R。可相同或不同,选自氢和C1-C4烷基、羟基烷基或氨基烷基,ArT表示阴离子抗衡离子,或者ii)阳离子杂环或阳离子杂芳基Het+, ArT,其中ArT如上定义,Het+表示5_10元饱和或不饱和的杂环,或者5-10元杂芳基,例如咪唑鎗、吡啶鎗、哌嗪鎗、哌啶鎗、吡咯烷鎗或苯并咪唑鎗;L特别表示(C1-C6)亚烷基链例如亚甲基、亚乙基、亚丙基或亚丁基; [0044]> L represents C1-C2tl divalent hydrocarbon type chain which is optionally substituted with, optionally interrupted and / or one or the other of its two ends are optionally terminated following groups following groups : i) one or more groups selected from the following divalent groups or combinations thereof: -N (R) - "N. (R) (R °) -, An '_0 _, - S -, - CO- and - SO2-, wherein R and R. may be the same or different, selected from hydrogen and C1-C4 alkyl, hydroxyalkyl or aminoalkyl, ArT represents an anionic counterion, or ii) a cationic heterocycle or cationic heteroaryl Het +, ArT, wherein ArT is as defined above, Het + represents 5_10 membered saturated or unsaturated heterocyclic ring, or 5-10 membered heteroaryl group, such as imidazole gun, gun pyridine, piperazine gun, gun piperidine, pyrrolidine, or benzimidazole gun gun; L expressed particular (C1-C6) alkylene chain such as methylene, ethylene, propylene or butylene;

[0045] > X表不氧原子或硫原子或NR基团,其中R表不氢原子或(C1-C6)烷基; [0045]> X table is not an oxygen atom or a sulfur atom or NR group, wherein R represents a hydrogen atom or not (C1-C6) alkyl;

[0046] >Y表示:i)氢原子;ii)碱金属;iii)碱土金属;iv)铵基团:N+R°ReRYRs,An'”或鱗基团P+ITR0RyRs, An”_,其中R°、Re、Ry和Rs可相同或不同,表示氢原子或(C1-C4)烷基,An”_为阴离子抗衡离子;或V)硫醇官能保护基; [0046]> Y indicates: i) hydrogen; ii) an alkali metal; iii) an alkaline earth metal; iv) ammonium groups: N + R ° ReRYRs, An '"or scale group P + ITR0RyRs, An" _, which R °, Re, Ry and Rs may be the same or different, represent a hydrogen atom or a (C1-C4) alkyl, An "_ is an anionic counterion; or V) protected thiol functional groups;

[0047] > W表示氧原子或硫原子或NR'基团,其中R'表示氢原子或(C1-C4)烷基; [0047]> W represents an oxygen atom or a sulfur atom or a NR 'group, wherein R' represents a hydrogen atom or a (C1-C4) alkyl;

[0048] >Q表示阴离子抗衡离子; [0048]> Q represents an anionic counter ion;

[0049] 要注意的是,如果η为2,则m为0,如果n为1,则m为1, [0049] It should be noted that if η is 2, m is 0 if n is 1, m is 1,

[0050] 本发明的另一个主题是具有亮泽效果的用于角蛋白纤维染色的染料组合物,其包含合适化妆品用介质中的至少一种如上定义的式(I)或式(II)的半花青苷苯乙烯基二硫化物或硫醇荧光染料,和任选还原剂。 [0050] Another subject of the invention is a keratin fiber dyeing composition has a glossy effect dye, which comprises a suitable cosmetic medium, at least one compound of formula (I) or formula (II), Semi anthocyanin styryl disulfide or thiol fluorescent dye, and optionally a reducing agent. [0051] 本发明一个主题是新的如上定义的式(I)或式(II)的半花青苷苯乙烯基二硫化物或硫醇荧光染料。 [0051] The present invention is a new topic is a compound of formula (I) or formula (II) semi anthocyanin styryl disulfide or thiol fluorescent dye.

[0052] 本发明还涉及多室装置,其中第一室装有包含至少一种如上定义的式(I)或式(II)荧光染料的染料组合物,第二室装有还原剂;任选第三室装有氧化剂。 [0052] The present invention further relates to a multi-chamber apparatus, wherein the first chamber comprises at least one containing a compound of formula (I) or formula (II) dye composition fluorescent dye, a second compartment containing a reducing agent; optionally The third room is equipped with an oxidizing agent.

[0053] 本发明的染色方法可以使暗色角蛋白材料、特别是使暗色人角蛋白纤维、尤其是使暗色毛发明显着色。 [0053] The dyeing process of the present invention can make dark keratin materials, especially so dark human keratin fibers, in particular, make clear colored dark hair. 此外,本发明的方法可以使毛发着色,而不会损伤毛发,这种着色对于洗发操作、普通侵蚀(日光、汗水)和其它毛发处理是持久牢固的。 Further, the method of the present invention can make hair coloring, without damaging the hair, the hair coloring for operation, ordinary erosion (sunlight, perspiration) and other hair treatment lasting solid. 本发明的方法还可使角蛋白材料例如角蛋白纤维、特别是暗色角蛋白纤维,更特别是暗色毛发获得光泽。 The method of the present invention may also make keratin materials such as keratin fibers, in particular dark keratin fibers, more particularly dark hair get shiny.

[0054] 本发明的新染料具有令人满意的耐光性和化学稳定性。 The new dye [0054] The present invention has a satisfactory light resistance and chemical stability. 这些染料溶于适于毛发染色的化学品用介质,更特别溶于水/乙醇混合物。 These dyes are dissolved in suitable chemicals with hair coloring medium, and more particularly soluble in water / ethanol mixture. 这些染料可以扩大可获得的色彩范围(黄色、橙色、红色、紫色、蓝色染料),而同时又能脱去已染上的色彩且不会损伤纤维。 These dyes can expand the range of available colors (yellow, orange, red, purple, blue dye), while still off the colors have been infected and will not damage the fiber. 该方法还能以强效和色彩丰富的方式给漂白的角蛋白纤维染色。 The method can to powerful and colorful way to bleach keratin fiber dyeing.

[0055] 使用本发明的染料所获得的染色范围也包括染发领域最多需求的基本色度(shade)。 Dyeing range [0055] The present invention also includes dyes obtained hair needs the most basic chromaticity areas (shade).

[0056] 对于本发明的目的,术语“暗色角蛋白材料”是指用C.1.EHVi系统测量的光亮度L* < 45、优选< 40的材料,此外还假定I/ = O等于黑色,L* = 100等于白色。 [0056] For the purposes of this invention the term "dark keratin material" means brightness with C.1.EHVi system measured L * <45, preferably <material 40, also assumed I / = O equals black, L * = 100 is equal to white.

[0057] 对于本发明的目的,术语“天然或人造的暗色毛发”是指其色调高度(toneheight)为< 6(暗棕黄色(dark blond)),优选< 4 (褐棕色(chestnut-brown))。 [0057] For purposes of the present invention, the term "natural or artificial dark hair" means a tone height (toneheight) was <6 (dark brown (dark blond)), preferably <4 (brown brown (chestnut-brown) ).

[0058] 通过式(I)或式(II)化合物使用前后“色调高度”的差异来评价毛发的光泽。 [0058] The formula (I) or formula (II) Difference "tone height" of the compounds was evaluated before and after the hair sheen. “色调(tone) ”的含义基于天然色度的分类,一种色调将各种色度与紧靠其前后的色度区分。 "Tone (tone)" the meaning of classification based on natural color, a wide range of color and hue will immediately distinguish its color before and after. 这种天然色度的定义和分类是美发专业人员所熟知的,并记载于“Science des traitementscapillaires” [毛发调理科学]一书中(Charles Zviakl988, Masson 出版,第215 和278页)。 This natural color definition and classification of hairdressing professionals in the art, and are described in "Science des traitementscapillaires" [hair conditioning Sciences] book (Charles Zviakl988, Masson publishing, and 278 215).

[0059] 色调高度范围为I (黑色)至10 (很亮的棕黄色),一个单位相对于一种色调;数值越大,色度越亮。 [0059] tone height ranges from I (black) to 10 (very light brown), a unit with respect to a tone; the larger the value, the brighter the color.

[0060] 人工染色的毛发是通过染色处理(例如用直接染料或氧化染料染色)颜色发生改变的毛发。 [0060] The artificial hair is dyed by a dyeing treatment (e.g., with direct dyes or oxidation dye) color change of the hair.

[0061] 对于本发明的目的,术语“漂白的毛发”是指色调高度大于6,优选大于8的毛发。 [0061] For purposes of the present invention, the term "bleached hair" means that the tone height greater than 6, preferably greater than 8 in the hair.

[0062] 对于本发明的目的,术语“脱去”角蛋白纤维的色彩是指包括使用化学或物理刺激因素,使毛发能够回复到其最初颜色的方法。 [0062] The present invention, the term "off" color of keratin fibers is meant to include the use of chemical or physical stimulus, the hair can be restored to its original color approach. 举例来说,可在适度碱性的PH下,即7和12之间,优选8和10.5之间,使用过氧化氢型、过硫酸钠型、过硫酸钾型或过硫酸铵型的氧化组合物达到褪色目的。 For example, in moderate alkaline PH, i.e. between 7 and 12, preferably between 8 and 10.5, using hydrogen peroxide type, type sodium persulfate, potassium persulfate, ammonium persulfate type or combination type oxide The purpose was to achieve the fade.

[0063] 在应用本发明的荧光染料后测定毛发所获得的亮泽效果的一种方法是利用毛发反射度的现象。 A method [0063] Determination of the hair glossy effect obtained after the application of fluorescent dyes of the invention is the use of hair reflectance phenomenon.

[0064] 优选该组合物在应用于暗色毛发后应导致下列结果。 [0064] Preferably, the composition is applied after dark hair should lead to the following results.

[0065]-重点关注当所述毛发用波长范围为400-700纳米的可见光照射时,毛发的反射度性能水平。 [0065] - when the focus when the hair is irradiated with visible light in the wavelength range 400-700 nm, the reflection of the performance level of the hair.

[0066]-反射度曲线随波长而变化,则用本发明组合物处理的毛发的反射度曲线与未处理毛发的进行比较。 [0066] - reflectance curve varies with wavelength, the reflectance curves of the composition of the present invention is treated hair were compared with untreated hair. [0067]-在波长范围500-700纳米内,处理毛发的反射度曲线应显示出高于未处理毛发的曲线的反射度。 [0067] - in a wavelength range of 500-700 nm, the reflectance curve should exhibit treating hair reflectance curve is higher than the untreated hair.

[0068]-这就是说,在540-700纳米的波长范围内,在至少一个范围内,处理毛发的反射度曲线高于未处理毛发的反射度曲线。 [0068] - that is to say, in the wavelength range 540-700 nm, in at least one range, the reflectance curves of the hair treatment than untreated hair reflectance curve. 术语“高于”是指反射度差异为至少0.05%,优选至少0.1 %。 The term "higher" means that the reflectance difference of at least 0.05%, preferably at least 0.1%. 尽管如此,在540-700纳米的波长范围内,仍可能在至少一个范围内,处理毛发的反射度曲线重叠于或低于未处理毛发的反射度曲线。 Nevertheless, in the wavelength range 540-700 nm, it may still be within the scope of at least one processing reflectance curves superimposed on the hair or untreated hair below reflectance curve.

[0069] 优选处理毛发的反射度曲线与未处理毛发的反射度曲线之间差异最大时的波长在500-650纳米的波长范围内,优选在550-620纳米的波长范围内。 The difference between the [0069] preferred hair treatment reflectance curves with the reflectance curve of the untreated hair maximum wavelength in the wavelength range 500-650 nm, preferably in the wavelength range 550-620 nm.

[0070] 对于本发明的目的,除非另有说明,否则: [0070] For the purposes of this invention, unless otherwise noted:

[0071]- “芳基”或“杂芳基”或基团的芳基或杂芳基部分可被至少一个选自以下的取代基取代: [0071] - "aryl" or "heteroaryl" or aryl group or heteroaryl moieties may be at least one selected from the following substituents:

[0072] -C1-C16烷基,优选C1-C8烷基,任选被选自以下的一个或多个基团取代^SX1-C2烷氧基、c2-c4(多)羟基烷氧基、酰氨基和氨基,其中氨基被两个可相同或不同、任选带有至少一个羟基的C1-C4烷基取代,或两个基团可与它们所连接的氮原子一起形成含有5-7元、优选5或6元饱和或不饱和的、任选取代的并且任选含有与氮原子相同或不同的另外的杂原子的杂环; [0072] -C1-C16 alkyl, preferably C1-C8 alkyl, optionally substituted with one or more selected from the group ^ SX1-C2 alkoxy, c2-c4 (poly) hydroxyalkoxy, amido and amino, wherein amino is two may be the same or different, optionally C1-C4 alkyl substituted with at least one hydroxyl group, or two groups can form together with the nitrogen atom to which they are attached a 5-7 membered containing , preferably 5 or 6-membered saturated or unsaturated, optionally substituted and optionally containing a nitrogen atom and are the same or different additional hetero atom heterocycle;

[0073].齒原子,例如氯、氟或溴; . [0073] teeth atom, e.g., chlorine, fluorine or bromine;

[0074].羟基; . [0074] hydroxy;

[0075].C1-C2 烷氧基; [0075] .C1-C2 alkoxy;

[0076].C1-C2 烧硫基; [0076] .C1-C2 burning sulfur;

[0077].C2-C4 (多)羟基烷氧基; [0077] .C2-C4 (poly) hydroxyalkoxy;

[0078].氨基; . [0078] amino;

[0079].5或6元杂环烷基; [0079] .5 or 6-membered heterocyclic group;

[0080].任选阳离子5或6元杂芳基,优选咪唑鎗,任选被C1-C4烷基、优选甲基取代; . [0080] optionally cationic 5- or 6-membered heteroaryl, preferably imidazole gun, optionally substituted with C1-C4 alkyl, preferably methyl substituents;

[0081].被一个或两个可相同或不同的、任选带有至少以下基团的C1-C6烷基取代的氨基: . [0081] one or two may be the same or different, C1-C6 alkyl optionally substituted amino group with at least the following:

[0082] i) 一个羟基; [0082] i) a hydroxyl group;

[0083] ii) 一个氨基,任选被一个或两个任选取代的C1-C3烷基取代,所述烷基可与它们所连接的氮原子一起形成含有5-7元、饱和或不饱和的、任选取代的并且任选含有至少一个可与氮相同或不同的其它杂原子的杂环; [0083] ii) an amino group, optionally substituted by one or two optionally substituted C1-C3 alkyl substituted, the alkyl group with the nitrogen atom to which they are attached form a 5-7 membered containing, saturated or unsaturated , optionally substituted and optionally containing at least one nitrogen heterocycle with other identical or different hetero atoms;

[0084] ^-N(R)-C(O)-R'其中R基团为氢原子或任选带有至少一个羟基的C1-C4烷基,R'基团为C1-C2烷基; [0084] ^ -N (R) -C (O) -R 'group wherein R is a hydrogen atom or an optionally C1-C4 alkyl, R having at least one hydroxyl' group is a C1-C2 alkyl;

[0085].(R)2N-C(O)-,其中R基团可相同或不同,表示氢原子或任选带有至少一个羟基的C1-C4烷基; . [0085] (R) 2N-C (O) -, wherein R groups may be the same or different, represent a hydrogen atom or a hydroxyl group optionally having at least one C1-C4 alkyl;

[0086] *R' S (O)2-N(R)-,其中R基团表示氢原子或任选带有至少一个羟基的C1-C4烷基,R'基团表示C1-C4烷基或苯基; [0086] * R 'S (O) 2-N (R) -, wherein R represents a hydrogen atom or a radical optionally having at least one hydroxyl C1-C4 alkyl, R' represents a group C1-C4 alkyl or phenyl;

[0087].(R)2N-S(O)2-,其中R基团可相同或不同,表示氢原子或任选带有至少一个羟基的C1-C4烷基; . [0087] (R) 2N-S (O) 2-, wherein R groups may be the same or different, represent a hydrogen atom or a hydroxyl group optionally having at least one C1-C4 alkyl;

[0088].酸或成盐形式(优选与碱金属或铵成盐,所述铵是取代或未取代的)的羧基;[0089].氰基; . [0088] an acid or a salt form (preferably with an alkali metal or ammonium salt formation, the ammonium is a substituted or unsubstituted) carboxy; [0089] a cyano group.;

[0090] •多卤代烷基,含有1-6个碳原子和1-6个可相同或不同的卤原子;多卤代烷基为例如三氟甲基; [0090] • polyhaloalkyl group, containing 1-6 carbon atoms and 1-6 identical or different halogen atoms; polyhaloalkyl, for example, trifluoromethyl;

[0091]-非芳族基团的环部分或杂环部分可被至少一个选自以下基团的取代基取代: Substituted heterocyclic ring moiety or part of the non-aromatic groups may be at least one selected from the group of substituents - [0091]:

[0092].羟基; . [0092] hydroxy;

[0093].C1-C4 烷氧基; [0093] .C1-C4 alkoxy;

[0094].C1-C4 烷基; [0094] .C1-C4 alkyl;

[0095].C2-C4 (多)羟基烷氧基; [0095] .C2-C4 (poly) hydroxyalkoxy;

[0096].C1-C2 烧硫基; [0096] .C1-C2 burning sulfur;

[0097].RC(0)-N(R')_,其中R'基团为氢原子或任选带有至少一个羟基的C1-C4烷基,R基团为C1-C2烷基或被两个可相同或不同、任选带有至少一个羟基的C1-C4烷基取代的氨基; [0097] .RC (0) -N (R ') _, wherein R' group is a hydrogen atom or a hydroxyl group optionally having at least one C1-C4 alkyl, R group is a C1-C2 alkyl or two may be the same or different, C1-C4 alkyl optionally substituted amino group having at least one hydroxyl group;

[0098].RC(O)-O-,其中R基团为C1-C4烷基或被一个或两个可相同或不同、任选带有至少一个羟基的C1-C4烷基取代的氨基,所述烷基可与它们所连接的氮原子一起形成含有5-7元、饱和或不饱和的、任选取代的并且任选含有至少一个可与氮相同或不同的其它杂原子的杂环; [0098] .RC (O) -O-, wherein R group is a C1-C4 alkyl or one or two of the same or different, C1-C4 alkyl group optionally having at least one hydroxyl-substituted amino group, The alkyl group with the nitrogen atom to which they are attached form a 5-7 membered containing, saturated or unsaturated, optionally substituted and optionally containing at least one nitrogen heterocyclic ring other identical or different hetero atoms;

[0099].RO-C (O) _,其中R基团为任选带有`至少一个羟基的C1-C4烷基; [0099] .RO-C (O) _, wherein R 'group is optionally substituted with at least one hydroxyl C1-C4 alkyl;

[0100]-环状基团或杂环基;或芳基或杂芳基的非芳族部分还可被一个或多个氧代基或硫代基取代; [0100] - cyclic group or a heterocyclic group; or a non-aromatic portion of the aryl group or heteroaryl group may also be substituted with one or more oxo or thioxo substituents;

[0101]- “芳基”基团表示含有6-22个碳原子、稠合或非稠合的单环或多环基团,且至少一个环为芳环;优选芳基为苯基、联苯基、萘基、茚基、蒽基或四氢萘基; [0101] - "aryl" group containing from 6 to 22 carbon atoms, fused or non-fused monocyclic or polycyclic group, and at least one ring is an aromatic ring; preferably aryl is phenyl, biphenyl phenyl, naphthyl, indenyl, anthryl, or tetrahydronaphthyl;

[0102] 二芳基烷基”基团表示在烷基的同一个碳原子上含有两个可相同或不同的芳基的基团,例如联苯基甲基或1,1-联苯基乙基; [0102] diarylalkylamine "group represents the same carbon atom in the alkyl group contains two may be the same or different aryl groups such as biphenyl or 1,1-biphenyl methyl acetate group;

[0103]- “杂芳基”表示含有5-22元和1-6个选自氮、氧、硫和硒原子的杂原子、任选阳离子的、稠合或非稠合的单环或多环基团,且其中至少一个环为芳环;优选杂芳基选自吖啶基、苯并咪唑基、苯并双三唑基、苯并吡唑基、苯并哒嗪基、苯并喹啉基、苯并噻唑基、苯并三唑基、苯并噁唑基、吡啶基、四唑基、二氢噻唑基、咪唑并吡啶基、咪唑基、吲哚基、异喹啉基、萘并咪唑基、萘并噁唑基、萘并吡唑基、噁二唑基、噁唑基、噁唑并吡啶基、吩嗪基、苯并噁唑基、吡嗪基、吡唑基、pyrilyUpyrazoyltriazyl、吡啶基、吡啶并咪唑基、吡咯基、喹啉基、四唑基、噻二唑基、噻唑基、噻唑并吡啶基、噻唑并咪唑基、thiopyrylyl、三唑基、咕吨基及其铵盐; [0103] - "heteroaryl" represents containing 5-22 yuan and 1-6 groups selected from nitrogen, hetero atoms of oxygen, sulfur and selenium atoms, optionally cationic, condensed or non-fused monocyclic or cycloalkyl group, and wherein at least one ring is an aromatic ring; preferably heteroaryl is selected from acridinyl, benzimidazolyl, benzo-bis-triazolyl, benzo pyrazolyl, benzo pyridazinyl, benzoquinoline isoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridyl, tetrazolyl, dihydro-thiazole, imidazolyl and pyridyl, imidazolyl, indolyl, isoquinolyl, naphthyl and imidazolyl, and oxazolyl naphthyl, naphthyl and pyrazolyl, oxadiazolyl, oxazolyl, pyridyl and oxazolyl, phenazine group, benzoxazolyl, pyrazinyl, pyrazolyl, pyrilyUpyrazoyltriazyl , pyridyl, pyridyl and imidazolyl, pyrrolyl, quinolinyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolyl and pyridyl, thiazolyl and imidazolyl, thiopyrylyl, triazolyl, xanthene group and ammonium salt;

[0104] 二杂芳基烷基”基团表示在烷基的同一碳原子上含有两个可相同或不同的杂芳基的基团,例如二呋喃基甲基、1,1-二呋喃基乙基、二吡咯基甲基或二噻吩基甲基; [0104] bis heteroarylalkyl "group on the same carbon atom represent an alkyl group containing two may be the same or different, heteroaryl group, e.g., methyl-di-furyl, 1,1-furyl ethyl, di-methyl or di-pyrrolyl thienylmethyl;

[0105]- “环状基团”是稠合或非稠合的单环或多环非芳族环烷基,含有5-22个碳原子,可能含有一个或多个不饱和键;环状基团特别为环己基; [0105] - "cyclic group" is fused or non-fused monocyclic or polycyclic non-aromatic ring group containing 5-22 carbon atoms, may contain one or more unsaturated bonds; cyclic groups especially cyclohexyl;

[0106]- “位阻环状”基团是含有6-14元、取代或未取代的、芳族或非芳族的、受位阻效应或约束阻碍、可被桥接的环状基团;作为位阻基团,可以提及的有二环[1.1.0] 丁烷、莱基类例如1,3,5-三甲基苯基、1,3,5-三叔丁基苯基、1,3,5-异丁基苯基、1,3,5-三甲基甲硅烷基苯基和金刚烷基;[0107]- “杂环基或杂环”是含有5-22元、包含1-6个选自氮、氧、硫和硒的杂原子的稠合或非稠合的单环或多环非芳族基团; [0106] - "hindered cyclic" group having a 6-14 membered, optionally substituted, aromatic or non-aromatic, by steric hindrance or constraint obstacles can be bridged cyclic group; As a sterically hindered group, there may be mentioned bicyclo [1.1.0] butane, Leckie class e.g. 1,3,5-trimethylphenyl, 1,3,5-tri-t-butylphenyl, isobutyl-phenyl-1,3,5, 1,3,5-trimethyl benzene and adamantyl silicon; [0107] - "heterocyclic or heterocyclic ring" containing 5-22 yuan, comprised of 1-6 atoms selected from nitrogen, thick oxygen, sulfur and selenium hetero atoms or non-fused monocyclic or polycyclic non-aromatic group;

[0108]- “烷基”为直链或支链C1-C16、优选C1-C8的烃类基团; [0108] - "alkyl" is a straight chain or branched chain C1-C16, preferably C1-C8 hydrocarbon group;

[0109]- “亚烷基”基团为如上定义的二价烷基; [0109] - "alkylene" group is a divalent alkyl group, as defined above;

[0110]- “亚烯基”基团为含有1-3个碳-碳双键的二价烃类基团,特别地,双键是共轭的,例如-CH = CH-、-CH = CH-CH = CH-、-CH = CH-CH = CH-CH = CH-; [0110] - "alkenylene" radical containing from 1 to 3 carbon - carbon double bond, a divalent hydrocarbon group, particularly, a conjugated double bond, e.g., -CH = CH -, - CH = CH-CH = CH -, - CH = CH-CH = CH-CH = CH-;

[0111]-在烷基上标有术语“任选取代的”是指所述烷基可被选自以下的一个或多个基团取代:i)羟基JDC1-C4烷氧基;iii)酰氨基;iv)任选被一个或两个可相同或不同的C1-C4烷基取代的氨基,所述烷基可能与携带它们的氮原子一起形成含有5-7元、任选含有与氮可相同或不同的另外的杂原子的杂环;v)或季铵基团-N+R' R”R”',M_,其中R'、R”、R”'可相同或不同,表示氢原子或C1-C4烷基,或者-N+R' R”R”'形成杂芳基,例如任选被C1-C4烷基取代的咪唑鎗,M—表示相应的有机酸、无机酸或卤化物的抗衡离子; [0111] - in the alkyl has superscript term "optionally substituted" means that the alkyl group may be selected from groups substituted with one or more of: i) hydroxy JDC1-C4 alkoxy; iii) acyl amino; iv) may be optionally substituted by one or two identical or different C1-C4 alkyl substituted amino, the alkyl group may be the nitrogen atom carrying them together form a 5-7 membered containing, optionally containing nitrogen may identical or different additional hetero atom heterocycle; v) or a quaternary ammonium group -N + R 'R "R"', M_, wherein R ', R ", R"' may be the same or different, represent a hydrogen atom or a C1 -C4 alkyl, or -N + R 'R "R"' is formed heteroaryl group, e.g., C1-C4 alkyl optionally substituted imidazol-gun, M- indicate corresponding organic acid, mineral acid or halide counterion ions;

[0112]- “烷氧基”为烷基氧基或烷基-0-,其中烷基为直链或支链C1-C16、优选C1-C8的烃类基团; [0112] - "alkoxy" as a group or a group -0- alkyl, wherein alkyl is a straight chain or branched chain C1-C16, preferably C1-C8 hydrocarbon group;

[0113]- “烷硫基”为烷基-S-,其中烷基为直链或支链C1-C16、优选C1-C8的烃类基团; [0113] - "alkylthio" is an alkyl group -S-, wherein the alkyl group is a straight chain or branched chain C1-C16, preferably C1-C8 hydrocarbon group;

[0114] 如果烷硫基是任选取代的,则是指烷基任选被如上定义的取代基取代; [0114] If an alkyl group is optionally substituted, it refers to an alkyl group optionally substituted as defined above;

[0115] 限定取值范围的端值也包括在取值范围内; [0116]有机酸盐或无机酸盐”更特别选自衍生自以下成分的盐:i)盐酸HCl ;ii)氢溴酸HBr ;iii)硫酸H2SO4 ;iv)烷基磺酸:烷基-S (O) 20H,例如甲磺酸和乙磺酸;v)芳基磺酸:芳基-S(O)2OH,例如苯磺酸和甲苯磺酸;vi)柠檬酸;vii)琥珀酸;viii)酒石酸;ix)乳酸;X)烷氧基亚磺酸:烷基-OS (0)0H,例如甲氧基亚磺酸和乙氧基亚磺酸;xi)芳氧基亚磺酸,例如甲苯氧基亚磺酸和苯氧基亚磺酸;xii)磷酸H3PO4 ;xiii)乙酸CH3C (O) OH ;xiv)三氟甲磺酸CF3SO3H和XV)四氟硼酸HBF4 ; [0115] defining the range end values are also included within the range; [0116] an organic acid salt or inorganic acid salt "is more particularly selected from salts derived from the following ingredients: i) hydrochloric acid HCl; ii) hydrobromide HBr; iii) sulfuric acid H2SO4; iv) alkylsulfonic acids: alkyl -S (O) 20H, such as methanesulfonic acid and ethanesulfonic acid; v) arylsulfonic acids: aryl group -S (O) 2OH, such as benzene sulfonic acid and p-toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid; X) alkoxyimino acid: alkyl -OS (0) 0H, e.g. methoxyimino acid sulfinic acids and ethoxy; xi) aryloxyimino acids, e.g., toluene sulfonic acid and oxyalkylene phenoxy sulfinic acid; xii) phosphoric acid H3PO4; xiii) acetic acid CH3C (O) OH; xiv) trifluoromethyl mesylate CF3SO3H and XV) tetrafluoroborate HBF4;

[0117]- “阴离子抗衡离子”是与染料的阳离子电荷结合的阴离子或阴离子基团;阴离子抗衡离子更特别选自:i)卤离子,例如氯离子或溴离子;ii)硝酸根;iii)磺酸根,其中有C1-C6烷基磺酸根:烷基-S (O) ,O,,例如甲基磺酸根或甲磺酸根或乙基磺酸着色。 [0117] - "anionic counterion" is cationic charge anionic dyes or anionic binding group; anionic counterion more particularly from: i) halides, such as chloride ion or bromide ion; ii) nitrate; iii) sulfonate, including C1-C6 alkyl sulfonate: alkyl -S (O), O ,, e.g. methanesulfonate or ethyl methanesulfonate or a sulfonic acid coloring.

[0118] ;iv)芳基磺酸根:芳基-S(0)20_,例如苯磺酸根或甲苯磺酸根;v)柠檬酸根;vi)琥拍酸根;vii)酒石酸根;viii)乳酸根;ix)烷基硫酸根:烷基_0_S (O) 0_,例如甲基硫酸根和乙基硫酸根;x)芳基硫酸根:芳基-OS(O)CT,例如苯硫酸根和甲苯硫酸根;xi)烧氧基硫酸根:烷基-0-S(0)20_,例如甲氧基硫酸根和乙氧基硫酸根;xii)芳氧基硫酸根:芳基-OS(O)2CT ;xiii)磷酸根;xiv)乙酸根;xv)三氟甲磺酸根;和xvi)硼酸根,例如四硼酸根; [0118]; iv) aryl sulfonate: aryl -S (0) 20_, e.g. benzenesulfonate or p-toluenesulfonate; v) citrate; vi) succinic acid radical beat; vii) tartrate; viii) lactate; ix) alkyl sulfate: alkyl _0_S (O) 0_, such as methyl sulfate and ethyl sulfate; x) aryl sulfate: an aryl group -OS (O) CT, such as benzene and toluene, sulfuric acid sulfate Root; xi) burning oxy sulfate: alkyl group -0-S (0) 20_, such as methoxy sulfate and ethoxy sulfate; xii) aryloxy sulfate: an aryl group -OS (O) 2CT ; xiii) phosphate; xiv) acetate; xv) triflate; and xvi) borates, such as tetra borate;

[0119]- “溶剂合物”表示水合物,以及与直链或支链C1-Ca醇(例如乙醇、异丙醇或正丙醇)的缔合物。 [0119] - "solvate" represents hydrate, and with a straight or branched chain C1-Ca alcohols (such as ethanol, isopropanol or n-propanol) in association complex.

[0120] 如上定义的式(I)或式(II)的半花青苷苯乙烯基二硫化物或硫醇染料是荧光染料,即在UV幅射或可见区波长Yabs介于250nm和800nm之间能够吸收;并且在发射波长Y™介于400nm和800nm之间,在可见区能够重发射的染料。 [0120] a compound of formula (I) or formula (II) semi anthocyanin styryl disulfide or thiol dye is a fluorescent dye, namely between 250nm and 800nm of UV radiation in the visible wavelength or Yabs Inter can absorb; and between 400nm and 800nm emission wavelength between Y ™, capable of re-emitted in the visible region of the dye.

[0121] 优选本发明式⑴或式(II)的荧光化合物是在Yabs介于400nm和800nm之间的可见区能够吸收并且在Y em介于400nm和800nm可见区能够再发射的染料。 [0121] Preferred compounds of the invention of formula fluorescent present ⑴ or formula (II) is capable of absorbing at 400nm and 800nm Yabs between the visible region and between 400nm and 800nm Y em capable of re-emitting in the visible region of the dye. 更优选式(I)或式(II)的染料是在Yabs介于420nm和550nm之间能够吸收并且在Yem介于470nm和600nm的可见区能够再发射的染料。 More preferably the dye of formula (I) or formula (II) is capable of absorbing at Yabs interposed between 420nm and 550nm and between 470nm and 600nm Yem area can be re-emitting visible dye.

[0122] 本发明的式⑴或式(II)化合物当η和m为I时,含有可以是共价键形式_S_Y或离子形式-S_Y+的SY官能团,这取决于Y的性质和介质的pH。 [0122] ⑴ a compound of formula or formula (II) of the present invention, when η and m is I, contains can be covalently _S_Y or ionic form of SY -S_Y + functional groups, depending on the nature of Y and medium pH .

[0123] 一个具体的实施方案涉及其中η和m为1,且Y表示氢原子或碱金属的式(I)或式(II)的半花青苷苯乙烯基二硫化物或硫醇荧光染料。 [0123] A specific embodiment relates to where η and m is 1, and Y represents a hydrogen atom or an alkali metal of formula (I) or formula (II) is half anthocyanin styryl disulfide or thiol fluorescent dyes . Y最好表示氢原子。 Y preferably represents a hydrogen atom.

[0124] 根据本发明的另外的具体实施方案,在上述式⑴或(II)中,Y为本领域技术人员已知的保护基,例如下列书中记载的保护基:“Protective Groups in OrganicSynthesis”,TWGreene, John Wiley & Sons 编辑,NY, 1981,第193-217 页!“ProtectingGroups”,P.Kocienski,Thieme,第3版,2005,第5章。 [0124] According to a further embodiment of the present invention, in the above formula ⑴ or (II), Y is known to those skilled in the protection of groups such as protecting groups described in the following books: "Protective Groups in OrganicSynthesis" , TWGreene, John Wiley & Sons edit, NY, 1981, p. 193-217! "ProtectingGroups", P.Kocienski, Thieme, 3rd Edition, 2005, Chapter 5. 应理解,作为保护基的Y不能与其连接的硫原子构成二硫化物染料,即不能构成n = m = I的式(I)或(II)。 It should be understood, a sulfur atom as a protecting group Y can not be connected thereto constitute disulfide dyes, i.e. not constitute n = m = I of formula (I) or (II). 作为保护基团的Y不能表示通过另一个非氧化的硫原子直接与式(I)和(II)的硫原子连接的基团。 As protective group Y can not be represented by another non-oxidized sulfur atom directly with the formula (I) and (II) a sulfur atom attached to the group.

[0125] 特别当Y表示硫醇官能保护基时,Y选自以下基团: [0125] In particular, when Y represents a thiol-functional protective group, Y is selected from the following groups:

[0126] (C1-C4)烷基羰基; [0126] (C1-C4) alkylcarbonyl;

[0127] (C1-C4)烷硫基羰基; [0127] (C1-C4) alkylthio carbonyl group;

[0128] (C1-C4)烷氧基羰基; [0128] (C1-C4) alkoxycarbonyl group;

[0129] (C1-C4)烷氧基硫代羰基; [0129] (C1-C4) alkoxy-thiocarbonyl;

[0130] (C1-C4)烷硫基硫代羰基; [0130] (C1-C4) alkylthio thiocarbonyl group;

[0131] (二) (C1-C4)(烷基)氨基羰基; [0131] (b) (C1-C4) (alkyl) aminocarbonyl;

[0132] (二) (C1-C4)(烷基)氨基硫代羰基; [0132] (b) (C1-C4) (alkyl) amino thiocarbonyl group;

[0133] 芳基擬基,例如苯基擬基; [0133] aryl intends groups such as phenyl proposed group;

[0134] 芳氧基羰基; [0134] aryloxycarbonyl group;

[0135] 芳基(C1-C4)烷氧基羰基; [0135] aryl (C1-C4) alkoxycarbonyl group;

[0136] (二)(C1-C4)(烷基)氨基羰基,例如二甲氨基羰基; [0136] (b) (C1-C4) (alkyl) aminocarbonyl, e.g., dimethylamino-carbonyl;

[0137] (C1-C4)(烷基)芳基氨基羰基; [0137] (C1-C4) (alkyl) aryl aminocarbonyl;

[0138] 羧基 [0138] carboxyl

[0139] SO3' M+,其中M+表示碱金属,例如钠或钾,或者式(I)或(II)的GT或An' _和M不存在; [0139] SO3 'M +, where M + represents an alkali metal such as sodium or potassium, or of formula (I) or (II) of GT or An' _ and M does not exist;

[0140] 任选取代的芳基,例如苯基、二苯并辛二酸基(dibenzosuberyl)或I, 3,5-环庚 [0140] optionally substituted aryl, such as phenyl, diphenyl and suberic acid group (dibenzosuberyl) or I, 3,5- cycloheptyl

二烯基; Dienyl;

[0141] 任选取代的杂芳基;特别包括以下含有1-4个杂原子的阳离子或非阳离子杂芳基: [0141] optionally substituted heteroaryl; particularly comprising cationic or cationic-containing heteroaryl group with 1-4 heteroatoms:

[0142] i)含有5、6或7元的单环,例如呋喃基(furanyl/furyl)、吡咯基(pyrrolyl/pyrryl)、噻吩基(thiophenyl/thienyl)、批唑基、嚼唑基、嚼唑鐵、异嚼唑基、异嚼唑鐵、噻唑基、噻唑鎗、异噻唑基、异噻唑鎗、I,2,4-三唑基、I,2,4-三唑鎗、I,2,3-三唑基、I,2,3-三唑鎗、1,2,4-噁唑基、1,2,4-噁唑鎗、1,2,4-噻二唑基、1,2,4-噻二唑鎗、吡喃鎗、硫代吡啶基、吡啶鎗、嘧啶基、嘧啶鎗、吡嗪基、吡嗪鎗、哒嗪基、哒嗪鎗、三嗪基、三嗪鎗、四嗪基、四嗪鐵、氮杂蕈、氮杂蕈鐵、氧杂氮杂蕈基(oxazepinyl)、氧杂氮杂蕈鐵(oxazepinium)、硫杂氮杂蕈基(thiepinyl)、硫杂氮杂蕈鐵(thiepinium)、咪唑基、咪唑鐵; [0142] i) contain 5, 6 or 7-membered single ring, such as furyl (furanyl / furyl), pyrrolyl (pyrrolyl / pyrryl), thienyl (thiophenyl / thienyl), approved oxazolyl, thiazolyl chew, chew azole iron, iso-oxazolyl chew, chew different azole iron, thiazolyl, thiazolyl gun, isothiazolyl, isothiazole gun, I, 2,4- triazolyl, I, 2,4- triazole gun, I, 2 , 3-triazolyl, I, 2,3- triazol-gun, 1,2,4-oxazolyl, 1,2,4-gun oxazole, 1,2,4-thiadiazolyl, 1, 2,4-thiadiazol-gun, guns pyran, thio pyridyl, pyridyl gun, pyrimidinyl, pyrimidinyl gun, pyrazinyl, pyrazine gun, pyridazinyl, pyridazine gun, triazinyl, triazine gun , tetrazine group, tetrazine iron, aza mushroom, mushroom aza iron, oxazepino mushroom base (oxazepinyl), oxazepino mushroom iron (oxazepinium), thiazepine mushroom base (thiepinyl), thia aza mushroom iron (thiepinium), imidazolyl, imidazole iron;

[0143] ϋ)含有8-11元的双环,例如吲哚基、二氢吲哚鎗、苯并咪唑基、苯并咪唑鎗、苯并噁唑基、苯并噁唑鎗、二氢苯并噁唑啉基、苯并噻唑基、苯并噻唑鎗、吡啶并咪唑基、吡啶并咪唑鎗、噻吩并环庚二烯基,这些单环或双环基团任选被一个或多个例如以下的基团取代:(C1-C4)烷基(例如甲基)或多卤代(C1-C4)烷基(例如三氟甲基); [0143] ϋ) containing 8-11 membered bicyclic, for example, indolyl, indolinyl gun, benzimidazolyl, benzimidazol-gun, benzoxazolyl, benzoxazole gun, dihydrobenzo oxazolinyl, benzothiazolyl, benzothiazole gun, imidazolyl and pyridyl, pyrido gun imidazole, thiophene and cycloheptadienyl, which monocyclic or bicyclic group is optionally substituted with one or more of the following e.g. substituted with: (C1-C4) alkyl (e.g. methyl) or halo (C1-C4) alkyl (e.g. trifluoromethyl);

[0144] iii)或以下的三环ABC: [0144] iii) or less tricyclic ABC:

[0145] [0145]

Figure CN101684204BD00141

[0146] 其中A、£两个环任选含有杂原子,S环为5、6或7元,特别为6元环,并含有至少一个杂原子,例如哌啶基或吡喃基; [0146] wherein A, £ two rings optionally containing hetero atoms, S 5, 6 or 7-membered ring, especially a 6-membered ring, and containing at least one hetero atom, such as piperidyl or pyranyl;

[0147] 任选阳离子,任选取代的杂环烷基,所述杂环烷基特别为5、6或7元、含有1-4个选自氧、硫和氮的杂原子的饱和或部分饱和的单环基团,例如二氢/四氢呋喃基、二氢/四氢噻吩基、二氢/四氢吡咯基、二氢/四氢吡喃基、二氢/四氢/六氢噻喃基、二氢吡啶基、哌嗪基、哌啶基、四甲基哌啶基、吗啉基、二氢/四氢/六氢氮杂草基或二氢/四氢嘧啶基,这些基团任选被一个或多个以下的基团取代:例如(C1-C4)烷基、氧代基或硫代基;或者 [0147] optionally cationic, optionally substituted heterocycloalkyl, the heterocycloalkyl specifically for 5,6 or 7-membered, contain 1-4 heteroatoms selected from oxygen, or partially saturated heteroatom sulfur and nitrogen saturated monocyclic groups, e.g., dihydro-/ tetrahydrofuranyl, dihydro / tetrahydrothienyl, dihydro / pyrrolidine group, dihydro / tetrahydropyranyl, dihydro / tetrahydro- / hexahydro-thiopyran-yl , dihydro pyridyl, piperazinyl, piperidinyl, tetramethyl piperidinyl, morpholinyl, dihydro / tetrahydro- / hexahydro-dihydro-diazepine group or / tetrahydropyrimidinyl, any of these groups optionally substituted with one or more of the following substituents groups: for example (C1-C4) alkyl, oxo or thioxo group; or

杂环表示以下基团: Heterocyclic represent the following groups:

[0148] [0148]

Figure CN101684204BD00142

[0149] 其中R' c、R' d、R' % R' f、R' g和R' h可相同或不同,表示氢原子或(C1-C4)烷基,或者两个基团R' g与R' h和/或R' e与R' f 一起形成氧代基或硫代基,或者R' g与R' e —起形成环烷基表示介于I和3之间的整数(含I和3);优选R' e至R' h表示氢原子;An”'_表示抗衡离子; [0149] wherein R 'c, R' d, R '% R' f, R 'g and R' h may be the same or different, represent a hydrogen atom or a (C1-C4) alkyl, or two groups R ' g and R 'h, and / or R' e and R 'f together form an oxo group or a thioxo group, or R' g and R 'e - together form a cycloalkyl group represents an integer between I and 3 between ( containing I and 3); preferably R 'e to R' h represent a hydrogen atom; An "'_ represents a counter ion;

[0150] 异硫脲鎗-C (NR,CR,d) = N+R,eR,f,An”,_,其中R'。、R,d、R,6和R,f 可相同 [0150] -isothiourea gun -C (NR, CR, d) = N + R, eR, f, An ", _, in which R '., R, d, R, 6, and R, f may be the same

或不同,表示氢原子或(C1-C4)烷基;优选R' ^至!?' f表示氢原子;An”' _表示抗衡离子; Or different, represent a hydrogen atom or a (C1-C4) alkyl; '!? ^ To' R f preferably represents a hydrogen atom; An "'_ represents a counter ion;

[0151] 异硫脲_C(NR' CR,d) = NR,e ;其中R,C、R,d 和R,e 如上定义; [0151] -isothiourea _C (NR 'CR, d) = NR, e; wherein R, C, R, d and R, e is as defined above;

[0152] 任选取代的(二)芳基(C1-C4)烷基,例如任选被一个或多个特别选自以下的基团取代的9-蒽基甲基、苯基甲基或联苯基甲基=(C1-C4)烷基、(C1-C4)烷氧基(例如甲氧基)、羟基、烷基擬基和(~) (C1-C4)(烷基)氣基(例如二甲氣基); [0152] optionally substituted (ii) aryl (C1-C4) alkyl, e.g., optionally substituted with one or more particularly selected from the group methyl substituted 9- anthracenyl group, a phenyl group or a biphenyl methyl phenylmethyl = (C1-C4) alkyl, (C1-C4) alkoxy (e.g. methoxy), a hydroxyl group, an alkyl group and a quasi (~) (C1-C4) (alkyl) Gas group ( such as dimethyl gas-yl);

[0153] 任选取代的(二)杂芳基(C1-C4)烷基,该杂芳基特别为含有5或6元和1-4个选自氮、氧和硫的杂原子的阳离子或非阳离子的单环,例如基团吡咯基、呋喃基、噻吩基、批啶基、吡啶基N-氧化物(例如4-吡啶基N-氧化物或2-吡啶基N-氧化物)、批喃鎗、吡啶鎗或三嗪基,任选被一个或多个基团(例如烷基,特别是甲基)取代,(二)杂芳基(C1-C4)烷基最好为(二)杂芳基甲基或(二)杂芳基乙基;[0154] CR1R2R3,其中R1、R2和R3可相同或不同,表示卤原子或选自以下基团: [0153] optionally substituted (ii) heteroaryl (C1-C4) alkyl, the heteroaryl group containing a cationic especially 5 or 6-membered and 1-4 atoms selected from nitrogen, oxygen and sulfur atoms or monocyclic non-cationic, e.g., pyrrolyl group, furyl, thienyl, piperidinyl batch, pyridyl N- oxide (e.g., 4-pyridyl N- oxide or 2-pyridyl N- oxide), batch furans gun, gun or pyridine triazinyl, optionally substituted with one or more groups (e.g., alkyl, especially methyl), (ii) heteroaryl (C1-C4) alkyl, preferably (b) heteroaryl-methyl or (ii) heteroaryl ethyl; [0154] CR1R2R3, wherein R1, R2 and R3 may be the same or different, represent a halogen atom or a group selected from the following:

[0155] -(C1-C4)烷基; [0155] - (C1-C4) alkyl;

[0156] - (C1-C4)烷氧基; [0156] - (C1-C4) alkoxy;

[0157]-任选取代的芳基,例如任选被一个或多个以下基团取代的苯基:例如(C1-C4)烷基、(C1-C4)烷氧基或羟基; [0157] - an optionally substituted aryl group, e.g., optionally substituted with one or more phenyl groups: for example (C1-C4) alkyl, (C1-C4) alkoxy or hydroxy;

[0158]-任选取代的杂芳基,例如任选被(C1-C4)烷基取代的噻吩基、呋喃基、吡咯基、批喃基或吡啶基; [0158] - optionally substituted heteroaryl, such as optionally substituted (C1-C4) alkyl substituted thienyl, furyl, pyrrolyl, or pyridyl batch furans;

[0159] -P(Z1)IT 1IT 2R' 3,其中R' 1和R' 2可相同或不同,表示羟基、(C「C4)烷氧基或烷基,R' 3表示羟基或(C1-C4)烷氧基,Z1表示氧原子或硫原子; [0159] -P (Z1) IT 1IT 2R '3, wherein R' 1 and R '2 may be the same or different, represent a hydroxyl, (C "C4) alkoxy or alkyl, R' 3 represents a hydroxyl group or a (C1 -C4) alkoxy group, Z1 represents an oxygen atom or a sulfur atom;

[0160] 位阻的环状基团,和 [0160] hindered cyclic group, and

[0161] 任选取代的烷氧基烷基,例如甲氧基甲基(Μ0Μ)、乙氧基乙基(EOM)或异丁氧基甲基。 [0161] an optionally substituted alkoxy group, such as methoxymethyl (Μ0Μ), ethoxyethyl (EOM) or isobutoxymethyl.

[0162] 根据一个具体的实施方案,m和η为I的被保护的式(I)或式(II)的硫醇荧光染料包含以下基团Y:1) 5或6元阳离子的芳族单环杂芳基,含有1-4个选自氧、硫和氮的杂原子,例如噁唑鎗、异噁唑鎗、噻唑鎗、异噻唑鎗、I,2,4-三唑鎗、I,2,3-三唑鎗、I,2,4-噁唑鎗、I,2,4-噻二唑鎗、吡喃鎗、吡啶鎗、嘧啶鎗、吡嗪基、吡嗪鎗、哒嗪鎗、三嗪鎗、四嗪鎗、氧杂風杂金翁(oxazepinium)、硫杂氮杂草基(thiepinyl)、硫杂氮杂草鐵(thiepinium)或 [0162] According to a particular embodiment, m and η as I protected the formula (I) or formula (II) thiol fluorescent dye contains the following groups Y: 1) 5 or 6-membered aromatic cation single heteroaryl containing 1-4 hetero atoms selected from oxygen, sulfur and nitrogen, such as gun oxazole, isoxazole gun, gun thiazole, isothiazole gun, I, 2,4- triazole gun, I, 2,3-triazol-gun, I, 2,4- oxazole gun, I, 2,4- thiadiazole gun, gun pyran, pyridine gun, gun pyrimidinyl, pyrazinyl, gun pyrazine, pyridazine gun , triazine guns, gun tetrazines, oxa wind hybrid gold Weng (oxazepinium), thia diazepine group (thiepinyl), thia diazepin iron (thiepinium) or

咪唑鎗;ii)8-ll元的阳离子双环杂芳基,例如二氢吲哚鎗、苯并咪唑鎗、苯并噁唑鎗或苯并噻唑鎗,这些单环或双环杂芳基任选被以下一个或多个基团取代:例如烷基(例如甲基)或多卤代(C1-C4)烷基(例如三氟甲基);iii)或以下杂环基: Imidazole gun; ii) 8-ll membered cationic bicyclic heteroaryl, e.g. indoline gun, the gun-benzimidazole, benzoxazole or benzothiazole gun gun, these monocyclic or bicyclic heteroaryl optionally substituted with one or more substituted: such as alkyl (e.g. methyl) or halo (C1-C4) alkyl (e.g. trifluoromethyl); iii) a heterocyclic group, or the following:

[0163] [0163]

Figure CN101684204BD00151

[0164] 其中R' R' d可相同或不同,表示氢原子或(C1-C4)烷基;优选R'。 [0164] wherein R 'R' d may be the same or different, represent a hydrogen atom or a (C1-C4) alkyl; preferably R '. 至R' <1表示(C1-C4)烷基(如甲基);An”' _表示阴离子抗衡离子。 To R '<1 represents (C1-C4) alkyl (e.g. methyl); An "' _ represents an anionic counterion.

[0165] Y特别为选自以下的基团:噁唑鎗、异噁唑鎗、噻唑鎗、异噻唑鎗、I,2,4-三唑鎗、1,2,3-三唑鎗、1,2,4-噁唑鎗、1,2,4-噻二唑鎗、吡喃鎗、吡啶鎗、嘧啶鎗、吡嗪鎗、哒嗪鎗、三嗪鎗和咪唑鎗、苯并咪唑鎗、苯并噁唑鎗、苯并噻唑鎗,这些基团任选被一个或多个(C1-C4)烷基、特别是甲基取代。 [0165] Y is selected from the particular group: gun oxazole, isoxazole gun, gun thiazole, isothiazole gun, I, 2,4- triazole gun, gun 1,2,3-triazole, 1 , 2,4-oxazole gun, gun 1,2,4-thiadiazole, pyran gun, gun pyridine, pyrimidine gun, gun pyrazine, pyridazine gun, guns and triazine gun imidazole, benzimidazole gun, gun benzoxazole, benzothiazole gun, these groups optionally substituted with one or more (C1-C4) alkyl, especially methyl substituted.

[0166] Y特别为碱金属或保护基,例如: [0166] Y in particular is an alkali metal or a protecting group, for example:

[0167] > (C1-C4)烷基擬基,例如甲基擬基或乙基擬基; [0167]> (C1-C4) alkyl group proposed, for example, a methyl or ethyl group proposed quasi-yl;

[0168] >芳基擬基,例如苯基擬基; [0168]> aryl intends groups such as phenyl proposed group;

[0169] > (C1-C4)烷氧基羰基; [0169]> (C1-C4) alkoxycarbonyl group;

[0170] >芳氧基羰基; [0170]> an aryloxycarbonyl group;

[0171] >芳基(C1-C4)烷氧基羰基; [0171]> aryl (C1-C4) alkoxycarbonyl group;

[0172] > ( 二) (C1-C4)(烷基)氨基羰基,例如二甲氨基羰基;[0173] > (C1-C4)(烷基)芳基氨基羰基; [0172]> (b) (C1-C4) (alkyl) aminocarbonyl, e.g., dimethylamino-carbonyl; [0173]> (C1-C4) (alkyl) aryl aminocarbonyl;

[0174] >任选取代的芳基,例如苯基; [0174]> an optionally substituted aryl group such as phenyl;

[0175] > 5或6元单环杂芳基,例如咪唑基或吡啶基; [0175]> 5 or 6-membered monocyclic heteroaryl, such as imidazolyl or pyridyl;

[0176] >5或6兀阳尚子的单环杂芳基,例如吡喃鐵、吡淀鐵、喃淀鐵、吡嚷鐵、啦嚷鐵、二嗪鎗或咪唑鎗;这些基团任选被一个或多个相同或不同的(C1-C4)烷基(例如甲基)取代; [0176]> 5 or 6 Wu Yang Naoko monocyclic heteroaryl, such as pyran iron, iron as pyridine, furans lake iron, iron topiramate cried, cried la Fe, diazinon gun or imidazole gun; these groups are optionally by one or more identical or different (C1-C4) alkyl (e.g., methyl) substituted;

[0177] >8-11元阳离子的双环杂芳基,例如苯并咪唑鎗或苯并噁唑鎗;这些基团任选被一个或多个相同或不同的(C1-C4)烷基(例如甲基)取代; [0177]> 8-11 membered cationic bicyclic heteroaryl group, e.g., a gun-benzimidazole or benzoxazole gun; these groups being optionally substituted by one or more identical or different (C1-C4) alkyl (e.g. methyl) groups;

[0178] >下式的阳离子杂环: [0178]> cationic heterocycle of the formula:

[0179] [0179]

Figure CN101684204BD00161

[0180] >异硫脲鎗-C(NH2) = N+H2 ;An”,^ ; [0180]> -isothiourea gun -C (NH2) = N + H2; An ", ^;

[0181 ] >异硫脲-C (NH2) = NH ; [0181]> -isothiourea -C (NH2) = NH;

[0182] >S03_,M+,其中M+表示碱金属,例如钠或钾,或者式(I)或式(II)的Q-或An,-和M+不存在。 [0182]> S03_, M +, wherein M + represents an alkali metal, e.g., sodium or potassium, or of formula (I) or formula (II), or Q- An, - and M + are absent.

[0183] 根据本发明的一个具体实施方案,式(I)或式(II)的荧光染料为其中n = 2,m =O的二硫化物染料。 [0183] In accordance with one specific embodiment of the present invention, of formula (I) or formula (II) in which a fluorescent dye n = 2, m = O disulfide dyes.

[0184] 本发明式⑴的二硫化物荧光染料特别选自下式(Ia)、(IIa)、(Ib)和(IIb)的二 [0184] The present invention of formula ⑴ disulfide fluorescent dye is particularly selected from the formula (Ia), (IIa), (Ib) and (IIb) II

硫化物荧光染料: Sulfide fluorescent dyes:

[0185] [0185]

Figure CN101684204BD00171

[0186]在式(Ia)、式(IIa)、式(Ib)或式(IIb)中: [0186] In the formula (Ia), formula (IIa), formula (Ib) or formula (IIb) in:

[0187] > R^R1-ABj 或Q—如上定义 [0187]> R ^ R1-ABj or Q- as defined above,

[0188] >n和m可相同或不同,表不I和6之间的整数(含I和6), n+m之和介于2和4之间(含2和4),对于(IIa)特别为2或3 ; [0188]> n and m are the same or different, are not I watch between integer and 6 (including I and 6), n + m of and between (containing 2 and 4) between 2 and 4, for (IIa ) specifically for 2 or 3;

[0189] > X表不选自以下的基团:_G_、-G,_C (G)-或_C (G) -G,_,其中G和G,可相同或不同,表不氧原子或硫原子,或NR,其中R表不氢原子或(C1-C6)烷基;X最好表不基团-NR-、-NR-CO-、-C (O) -NR-、-S (O) 2_、-S (O) 2_NR_ ;或-NR-S (O) 2_ 或-NR-;特别地,式(Ia)的X 在未取代的或被基团R4和R5取代的苯基的4位上连接; [0189]> X table is not selected from the group: _G _, - G, _C (G) - or _C (G) -G, _, where G and G, may be the same or different, and the table is not an oxygen atom or a sulfur atom, or NR, wherein R represents a hydrogen atom or do not (C1-C6) alkyl; X is preferably a group tables are not -NR -, - NR-CO -, - C (O) -NR -, - S ( O) 2 _, - S (O) 2_NR_; or -NR-S (O) 2_ or -NR-; in particular, the formula (Ia) of X in unsubstituted or groups R4 and R5 substituted phenyl 4 on the connection;

[0190]:> Ta 表示σ 共价键;基团-N(R' a) - ;-N+(R' a) (R' b) _,An_ ;-C(O) -N(Rja)-或-N(R'a) -C(O)-,或含有5_7元的二价阳离子杂芳基(例如咪唑鎗),其中R' a、R'b可相同或不同,表示氢原子或(C1-C4)烷基,ArT表示阴离子抗衡离子;Ta特别表示-C (O) -N (R' J -和-N (R' a) -C (O) _。 [0190]:> Ta denote σ covalent bond; a group -N (R 'a) -; -N + (R' a) (R 'b) _, An_; -C (O) -N (Rja) - or -N (R'a) -C (O) -, or contains a divalent cation 5_7 membered heteroaryl (e.g., imidazole gun), wherein R 'a, R'b may be the same or different, represent a hydrogen atom or a ( C1-C4) alkyl, ArT represents an anionic counterion; Ta particular represents -C (O) -N (R 'J - and -N (R' a) -C (O) _.

[0191 ] 特别地,本发明的染料具有表示苯基4位NR基团的基团X,R4和R5表示氢原子,或者一起形成任选被烷基取代的苯并基团或吗啉基,R2和R3表示氢原子或卤原子,或者一起形成任选被1-3个卤原子取代的苯并基团,L最好表示亚乙基、亚丙基或亚丁基,更特别是 [0191] In particular, the dye of the present invention has a means phenyl group NR 4 group X, R4 and R5 represent a hydrogen atom, an alkyl group or taken together form an optionally substituted benzo group or a morpholino group, R2 and R3 represent a hydrogen atom or a halogen atom, or taken together form an optionally substituted 1-3 halogen atoms benzo group, L preferably represents ethylene, propylene or butylene, more particularly

亚乙基。 Ethylene.

[0192] 举例来说,可能提及的有下式(I)或(II)的荧光染料: [0192] For example, there may be mentioned the following formula (I) or (II), fluorescent dyes:

[0193] [0193]

Figure CN101684204BD00181
Figure CN101684204BD00191
Figure CN101684204BD00201

[0196] [0196]

Figure CN101684204BD00211
Figure CN101684204BD00221
Figure CN101684204BD00231
Figure CN101684204BD00241
Figure CN101684204BD00251
Figure CN101684204BD00261
Figure CN101684204BD00271

[0203] 其中An_可相同或不同,表示阴离子抗衡离子。 [0203] wherein An_ may be the same or different and each represents an anionic counterion.

[0204] 对于下面所有的用于制备新的式(I)或式(II)的硫醇和二硫化物半花青苷苯乙烯基荧光染料的实施方案,本领域技术人员了解如何通过已知的保护/脱保护方法,预先保护发色团的反应官能团(例如酮官能团),然后根据合成反应的需要使之脱保护,有关方法参见例如上述参考书(TwGreene,John Willey & Sons出版社,NY,1981或P.Kocienski “Protecting Groups”,P.Kocienski, Thieme,第3 版,2005)。 [0204] For all of the following embodiments of the preparation for the new formula (I) or formula (II) thiol and disulfide half anthocyanin styryl fluorescent dyes, those skilled in the art will appreciate how known protection / deprotection methods previously protected chromophore reactive functional groups (such as a ketone functional group), and then need to make the synthesis reaction deprotected See related methods such as the aforementioned reference (TwGreene, John Willey & Sons Press, NY, 1981 or P.Kocienski "Protecting Groups", P.Kocienski, Thieme, 3rd edition, 2005).

[0205] 其中m和η为I的被保护的式(Ι_Υ)或式(ΙΙ_Υ)的硫醇染料可以分两个步骤合成。 [0205] wherein m and η of the formula I to be protected (Ι_Υ) or formula (ΙΙ_Υ) thiol dye synthesis can be divided into two steps. 第一步包括按照本领域技术人员已知方法(例如“Thiols and organic sulfides”,uThiocyanates and isothiocyanates, organic,,,UllmannJ s Encyclopedia, ffiley-VCH,Weinheim,2005),来制备未保护的硫醇染料(1-H)或(I1-H)。 The first step includes according to methods known to those skilled in the art (e.g., "Thiols and organic sulfides", uThiocyanates and isothiocyanates, organic ,,, UllmannJ s Encyclopedia, ffiley-VCH, Weinheim, 2005), to prepare the unprotected thiol dye (1-H) or (I1-H). 然后,第二步包括按照本领域技术人员已知常规方法对硫醇官能团进行保护,以便得到被保护的式(1-Y)或式(I1-Y)的硫醇染料。 Then, the second step involves known to those skilled in the art in accordance with conventional methods of thiol functional group be protected in order to obtain the protected formula (1-Y) or formula (I1-Y) thiol dyes. 举例来说,为了保护硫醇染料的硫醇官能团-SH,可以采用下列书中的方法:“Protective Groups inOrganic Synthesis”,TWGreene, John Willey & Sons 编辑,NY,1981,第193-217 页!“Protecting Groups”, P.Kocienski, Thieme,第3 版,2005,第5 章。 For example, in order to protect thiol dye thiol functional group -SH, the following method may be employed in the book: "Protective Groups inOrganic Synthesis", TWGreene, John Willey & Sons Editor, NY, 1981, p. 193-217 "! Protecting Groups ", P.Kocienski, Thieme, 3rd Edition, 2005, Chapter 5. 该方法可以通过包括以下的方法加以说明:i)通过带有二硫化物官能团-SS-的半花青苷苯乙烯基二发色团染料(例如(1-S)或(I1-S))的还原反应,得到式(1-H)或式(I1-H)的半花青苷苯乙烯基硫醇染料,和ii)为了获得被保护的式(1-Y)或式(I1-Y)的半花青苷苯乙烯基硫醇染料,按照常规方法,用反应剂ZY'R对所述(1-H)或(I1-H)的硫醇官能团进行保护。 The method can be illustrated by a method comprising: i) through the second half of anthocyanin styryl dye chromophores having -SS- disulfide functional groups (for example, (1-S) or (I1-S)) reduction reaction, to give the formula (1-H) or formula (I1-H) of the thiol half anthocyanin styryl dyes, and ii) in order to obtain a protected compound of formula (1-Y) or formula (I1-Y ) semi anthocyanin styryl thiol dyes, according to the conventional method, using reagents ZY'R protection of the (1-H) or (I1-H) thiol functional group. 硫醇化合物(1-H)或(I1-H)还可以与碱金属或碱土金属Met*进行金属化反应,从而得到式(1-Met)或式(I1-Met)的硫醇盐荧光染料。 Thiol compound (1-H) or (I1-H) also may be an alkali metal or alkaline earth metal Met * metallization reaction, thereby obtaining the formula (1-Met) or formula (I1-Met) the thiolate fluorescent dye .

[0206] [0206]

Figure CN101684204BD00291
Figure CN101684204BD00301

[0208] 其中,Y'表示硫醇官能团保护基;Met*表示碱金属或碱土金属,特别为钠或钾,要理解的是,如果金属是碱土金属,则包含硫醇盐_S_官能团的2个发色团可与I个金属2+缔合;其中R1-R^WajIP L如上定义;Y'表示硫醇官能团保护基洱表示离核体离去基团,例如甲磺酸基、甲苯磺酸基、三氟甲磺酸基或卤基。 [0208] wherein, Y 'represents a thiol functional group protecting group; Met * represents an alkali metal or alkaline earth metal, especially sodium or potassium, to be understood that if the metal is an alkaline earth metal, contains a functional group thiolate _S_ two chromophores can and I metal 2+ association; wherein R1-R ^ WajIP L as defined above; Y 'represents a thiol functional group protecting groups from the nucleus er represents a leaving group, such as mesylate, toluene a sulfonic acid group, a trifluoromethanesulfonic acid group or a halogen group.

[0209] 另一种可行方法是,按照上述书中记载的一种方法制备的、用如上定义的保护基Y'保护的被保护的硫醇化合物皿所述被保护的硫醇化合物包含至少一个亲核官能团),可与足够量的、优选等摩尔的半花青苷苯乙烯基发色团M或1¾!进行反应,所述发色团包含亲电子官能团,从而形成Σ连接基团中的共价键,式(I' -Y)和式(I' -Y)染料的制备见下: [0209] Another possible approach is described in accordance with a method of the preparation of the book, with a protecting group as defined above, Y 'is protected by the protected thiol compound dish protected thiol compound containing at least one nucleophilic functional group), with a sufficient amount, preferably equimolar half anthocyanin styryl chromophore M or 1¾! reacted, the chromophore containing electrophilic functional groups to form a linking group of Σ a covalent bond, of formula (I '-Y) and formula (I' -Y) preparing the dye below:

[0210] [0210]

Figure CN101684204BD00311

[0211] 其中R1-RfUJl如上定义;m'和η'为1_6之间的整数,m' +η'之和为2和6之 [0211] wherein R1-RfUJl as defined above; m 'and η' is an integer between 1_6, m '+ η' the sum of 2 and 6 of the

间的整数,Nu表示亲核基团出表示亲电子基团;Σ表示在亲核试剂攻击亲电子试剂后产生的连接基团。 Integer between, Nu represents a nucleophilic group representing electrophilic group; Σ represents the nucleophile attack electrophiles generated after linking group.

[0212] 举例来说,基于亲电子试剂与亲核试剂的缩合可以形成的Σ共价键见下表: [0212] For example, based on the condensation of electrophiles and nucleophiles may be formed by a covalent bond Σ table below:

[0213] 亲电子试剂E 亲核试剂Nu Σ共价键 [0213] E electrophile nucleophile Nu Σ covalent bond

[0214] 活性酯* 胺 羧酰胺 [0214] amine carboxamides active ester *

[0215] 酰基氮化物# 胺 羧酰胺 [0215] acyl nitrides # amine carboxamides

[0216] 酰卤胺 羧酰胺 [0216] amine carboxamides halide

[0217] 酰卤醇 酯 [0217] acid halide ester

[0218] 酰基氰醇 酯 [0218] acyl cyanohydrin ester

[0219] 酰基氰胺 羧酰胺 [0219] acyl Cyanamid carboxamide

[0220] 烷基齒胺 烷基胺 [0220] alkyl amines alkyl amines tooth

[0221] 烷基卤羧酸 酯 [0221] alkyl halide carboxylate

[0222] 烷基卤硫醇 硫酯 [0222] alkyl halide thiol thioester

[0223] 烷基卤醇 醚 [0223] alkyl halide alcohol ether

[0224] 磺酸及其盐硫醇 硫醚 [0224] thiol sulfide acid and its salts

[0225] 磺酸及其盐羧酸 酯 [0225] acid and its salts carboxylate

[0226] 磺酸及其盐醇 醚 [0226] alcohol ether sulfonic acid and its salts

[0227] 酐醇 酯 [0227] anhydride ester

[0228] 酐胺 羧酰胺 [0228] anhydride amine carboxamide

[0229] 芳基卤硫醇 硫醚 [0229] aryl halides thiols sulfide

[0230] 芳基卤胺 芳基胺 [0230] aryl halide amine arylamine

[0231] 氮丙唳硫醇 硫醚 [0231] ethylenimine Li thiol sulfide

[0232] 羧酸胺 羧酰胺 [0232] carboxylic acid amide carboxamide

[0233] 羧酸醇 酯 [0233] carboxylic acid ester

[0234] 碳二亚胺羧酸 N-酰基脲或酐 [0234] carbodiimide acid or anhydride N- acylurea

[0235] 重氮烷羧酸 酯 [0235] diazoalkane carboxylate

[0236] 环氧化物硫醇 硫醚[0237] 卤代乙酰胺 硫醇 硫醚 [0236] epoxides thiols thioethers [0237] haloacetamides thiols thioethers

[0238] 酰亚胺酯 胺 脒 [0238] ester amine amidine

[0239] 异氰酸酯 胺 脲 [0239] amine isocyanate urea

[0240] 异氰酸酯 醇 氨基甲酸酯 [0240] isocyanate-alcohol urethane

[0241] 异硫氰酸酯 胺 硫脲 [0241] isothiocyanate amine thiourea

[0242] 马来酰亚胺 硫醇 硫醚 [0242] maleimide thiol sulfide

[0243] 磺酸酯 胺 烷基胺 [0243] amine alkyl amines sulfonate

[0244] 磺酸酯 硫醇 硫醚 [0244] sulfonic acid ester thiols thioethers

[0245] 磺酸酯 羧酸 酯 [0245] sulfonate carboxylate

[0246] 磺酸酯 醇 醚 [0246] sulfonic acid ester alcohol ether

[0247] 磺酰卤 胺 磺酰氨 [0247] sulfonyl halide amine sulfonamide

[0248] *通式-CO-部分的活性酯,其中“部分”表示离去基团,例如氧基琥珀酰亚胺基、氧基苯并三唑基、任选取代的芳氧基; [0248] * active ester of the general formula -CO- portion, wherein "part" represents a leaving group, such as succinimidyl group, benzotriazolyl group, an optionally substituted aryloxy;

[0249] **酰基氮化物可以重排得到异氰酸酯。 [0249] ** acyl nitrides may rearrange to give isocyanates.

[0250] 该方法的一种变通方法是利用具有亲电子丙烯酸酯官能团(-0C0-C = C-)的半花青苷苯乙烯基发色团,在该丙烯酸酯官能团上进行可形成Σ键的加成反应。 [0250] An alternative to this approach is to use half of anthocyanin styryl chromophore having an electrophilic acrylate functional groups (-0C0-C = C-), and performed on the acrylate functional groups may form Σ bond The addition reaction.

[0251] 还可以采用硫醇反应剂(α):包含如上定义的Y'基团的Y' -SH,其亲核SH官能团可在相对于(a' )或(a/ )的半花青苷苯乙烯基发色团所带卤原子的α位与基团L的碳原子反应,从而得到被保护的以上式(ι-y)或式(i1-ϋ)的硫醇染料: [0251] You can also use a thiol reactant (α): contains as defined above Y 'group Y' -SH, its nucleophilic functional group may SH relative to (a ') or (a /) is hemicyanine glycosides styryl chromophore brought halogen atom α position with the group L carbon reaction, resulting in the above formula is protected (ι-y) or formula (i1-ϋ) thiol dyes:

[0252] [0252]

Figure CN101684204BD00321

[0253] 其中R1-R6UiQ' (1-Y)或(I1-Y)如上定义,Hal表示离核体卤原子,例如溴、碘或氯。 [0253] wherein R1-R6UiQ '(1-Y) or (I1-Y) are as defined above, Hal represents a halogen atom from the nucleus, such as bromine, iodine or chlorine.

[0254] 更具体地讲,离核体离去基团可用硫脲的衍生物(S = C (NRR) NRR)或硫脲置换,从而得到异硫脲鎗。 [0254] More specifically, the nucleus from a leaving group can thiourea derivatives (S = C (NRR) NRR), or thiourea replacement, resulting isothiourea gun. 例如,基于如上定义的发色团ϋ或ϋα,如果硫脲基团是咪唑啉硫酮m(或其硫代脱氢咪唑鎗互变异构体),则得到s被咪唑啉鎗基团保护的染料α ” -Y)或(II,,-Y): For example, as defined above, based chromophore ϋ or ϋα, if the thiourea group is an imidazoline thione m (or thio dehydrogenation gun imidazole tautomers), the resulting s protected imidazoline gun group dyes α "-Y) or (II ,, - Y):

[0255] [0255]

Figure CN101684204BD00331

[0256]其中(a,)、(a/ )、R,c、R' d、R1-R6'W、X、L、Q'Hal 和ArT 如上定义。 [0256] wherein (a,), (a /), R, c, R 'd, R1-R6'W, X, L, Q'Hal and ArT are as defined above.

[0257] 另外的变通方法可以用硫代咪唑型环状硫脲衍生物(b' ),随后用R' d-Lg使所述咪唑烷基化得到化合物(I”-Y' )或(ΙΙ”-Υ'),其中Lg为离去基团,例如氯、溴、甲苯磺酸基或甲磺酸基: [0257] Another workaround can thioimidazole cyclic thiourea derivatives (b '), followed by R' d-Lg alkylating said imidazole compound (I "-Y ') or (ΙΙ "-Υ '), wherein Lg is a leaving group such as chloro, bromo, tosylate or mesylate:

[0258] [0258]

Figure CN101684204BD00332

[0259]其中 R1-R6IU (a')、(a' 立、Q_、Hal、Lg 如I:定义。 [0259] wherein R1-R6IU (a '), (a' stand, Q_, Hal, Lg such as I: Definition.

[0260] 一种变通方法是采用包含另外的类型的离核体(例如甲苯磺酸基或甲磺酸基)的发色团,取代包含卤基的荧光发色团ϋΐ或ϋα。 [0260] An alternative method is to use include additional types from the nucleus (such as tosylate or mesylate) is chromophore, a fluorescent chromophore containing a halogen substituent group ϋΐ or ϋα.

[0261] 按照另一种可行方法,可以按照常规方法,使被保护的硫醇化合物与带有两个被活化的羧酸官能团的化合物反应而获得某种被保护的硫醇染料(I' -Y)或(II' -Y)(例如与碳二亚胺或与亚硫酰氯反应)。 [0261] According to another possible way, in accordance with the conventional method, the protected compound is reacted with a thiol compound with two activated carboxylic acid functional group to obtain some kind of protected thiol dye (I '- Y) or (II '-Y) (e.g., reaction with carbodiimide or with thionyl chloride). 所得产物Iil随后与带有亲核官能团的半花青苷苯乙烯基发色团ϋ或例如伯胺型或仲胺型或脂族醇型的半花青苷苯乙烯基发色团)反应。 The resulting product is then Iil and half anthocyanin styryl chromophore with ϋ nucleophilic functional groups such as primary or secondary amine or aliphatic amine or alcohol type semi anthocyanin styryl chromophore) reaction.

[0262] [0262]

Figure CN101684204BD00341

[0263]其中 R1-R6, m\n\ff,X>Q\E, Nu, (I,_Y)或(II,-Y)如上定义。 [0263] wherein R1-R6, m \ n \ ff, X> Q \ E, Nu, (I, _Y) or (II, -Y) as defined above.

[0264] 另一种变通方法是采用硫内酯衍生物,基于特定的亲核发色团M和1^1,从而得到包含被酰胺官能团中断的连接基L的衍生物(I' -H)或(II' -H),反应流程如下: [0264] Another workaround is to use thiolactone derivatives, issued based on the specific pro-chromophore M and 1 ^ 1, thereby obtaining a derivative containing linker L interrupted by an amide functional group (I '-H) or (II '-H), the following reaction scheme:

[0265] [0265]

Figure CN101684204BD00342

[0266] 其中R1-ARUj'n'或m'如上定义,G'表示氧原子或硫原子,或NR'基团,其中R'表示氢原子或烷基,R表示氢原子、C1-C4烷基、C1-C4-基烷基或芳基(C1-C4)烷基。 [0266] wherein R1-ARUj'n 'or m' are as defined above, G 'represents an oxygen atom or a sulfur atom, or NR' group, wherein R 'represents a hydrogen atom or an alkyl group, R represents a hydrogen atom, C1-C4 alkyl group, C1-C4- alkyl or aryl (C1-C4) alkyl. 硫内酯衍生物优选选择η' = 3且G'表示氧原子。 Thiolactone derivative is preferably selected η '= 3 and G' represents an oxygen atom.

[0267] 包含游离SH官能团的衍生物(I' -H)或(II' -H)继而可按上述方法进行保护或 [0267] contains derivative (I '-H) or (II' -H) free SH functional group can then be protected or the method described above

金属化。 Metallization.

[0268] 按照另一种可行方法,可通过使含有被Y'基团保护的硫醇基团和离核体离去基团Lg的化合物m,与半花青苷苯乙烯基发色团w或反应,得到被保护的式α”'-Y)和式(ιY”-υ)硫醇染料,所述离去基团例如甲磺酸基、甲苯磺酸基、三氟甲磺酸基或卤基。 [0268] According to another possible way, it may be protected by containing Y 'groups and thiol groups from the nucleus compound leaving group Lg m, with half anthocyanin styryl chromophore w or to give a protected compound of formula α "'- Y) and formula (ιY" -υ) thiol dye, said leaving group such as mesylate, tosylate, triflate group or halo.

[0269] [0269]

Figure CN101684204BD00351

[0270] 其中#-1?6、? [0270] where # -1? 6 ,? '、13、1^和0_如上定义,2'表示氢原子或活化X的亲核性的基团。 ', 13,1 ^ 0_ as defined above and 2' represents a hydrogen atom or an activated X nucleophilic groups.

[0271] 式c'中,Ζ'还可表示叔胺基团或含氮杂环基团,与X缔合,能够取代离去基团Lg ;在这种情况下,化合物(I”' -Y)可包含作为除Q-以外的抗衡离子的基团Lg_。 [0271] where c 'in, Ζ' can also mean a tertiary amine group or a nitrogen-containing heterocyclic group, and X association, to replace the leaving group Lg; in this case, the compound (I "'- Y) may contain a counter ion other than Q- groups Lg_.

[0272] 举例来说,含有被保护的硫醇基团的化合物(I”' -Y)或(II”' -Y)含有离核体离去基团R,例如甲磺酸基、甲苯磺酸基或三氟甲磺酸基,可由半花青苷苯乙烯基发色团(c' )或(c”)的胺如下进行亲核攻击: [0272] For example, the compound (I "'-Y) or (II"' -Y) containing a protected thiol group-containing nucleus from a leaving group R, for instance mesylate, toluene sulfonamide acid group or a triflate group, by half anthocyanin styryl chromophore (c ') or (c ") amine nucleophilic attack follows:

Figure CN101684204BD00352

[0274] 有关上述方法所用操作条件的详情可参见以下参考书! [0274] For details on the method used by the operating conditions can be found in the following reference! Advanced OrganicChemistry,“Reactions,Mechanisms andStructures”,J.March,第4 片反,John Willey &Sons,1992 或TWGreene “Protective Groups in Organic Synthesis,,。 Advanced OrganicChemistry, "Reactions, Mechanisms andStructures", J.March, the first four anti, John Willey & Sons, 1992, or TWGreene "Protective Groups in Organic Synthesis ,,.

[0275] 釆用常规保护基对-SH硫醇进行保护,可以将所形成的半花青苷苯乙烯基硫醇染料转化成-SY'保护的硫醇荧光染料。 [0275] preclude the use of conventional protecting group for -SH thiol protect half anthocyanin styryl thiol dyes formed can be converted into -SY 'protected thiol fluorescent dye. 还通过釆用本领域技术人员已知的常规方法使硫醇荧光染料金属化,有关技术参见例如Advanced Organic Chemi StryZi React ions, MechanismsandStructures”,J.March,第4 版,John Willey & Sons,NY,1992。 Also preclude the use of conventional methods so that by the skilled artisan thiol fluorescent dye metalization, see for example the technical Advanced Organic Chemi StryZi React ions, MechanismsandStructures ", J.March, 4th edition, John Willey & Sons, NY, 1992.

[0276] 可以通过常规路线对被保护的半花青苷苯乙烯基硫醇染料进行脱保护,参见例如以下参考书! [0276] can be protected by a conventional route to the semi-anthocyanin dye styryl thiol deprotection, see for example the following reference! “Protective Groups in OrganicSynthesis,,,TWGreene, John Willey &Sons 编辑,NY,1981 ,Protecting Groups,,,P.Kocienski,Thieme,第3 版,2005。 "Protective Groups in OrganicSynthesis ,,, TWGreene, John Willey & Sons edit, NY, 1981, Protecting Groups ,,, P.Kocienski, Thieme, 3rd edition, 2005.

[0277] 起始的反应剂是市售的,或者可通过本领域技术人员已知常规方法获得。 [0277] starting reactants are commercially available or may be obtained by those skilled in the known conventional methods. [0278] 可通过对荧光硫醇染料进行氧化来合成式(I)或式(II)的荧光二硫化物染料。 [0278] thiol fluorescent dyes by oxidation to the synthesis of formula (I) or formula (II) disulfide fluorescent dye.

[0279] 该方法可如下例证,通过对半花青苷苯乙烯基硫醇染料(例如(1-H)或(I1-H))进行氧化,从而产生式(ι-s)或(I1-S)的半花青苷苯乙烯基二硫化物染料。 [0279] The following method can be exemplified by the thiol half anthocyanin styryl dyes (e.g., (1-H) or (I1-H)) is oxidized to produce the formula (ι-s) or (I1- S) semi anthocyanin styryl disulfide dyes.

[0280] 可用氧化剂任选结合碱性试剂来进行氧化反应。 [0280] optionally an oxidizing agent available for binding the alkaline reagent oxidation. 可以采用本领域常用的任何氧化剂类型。 Commonly used in the art may be employed in any type of oxidant. 因此,氧化剂可选自过氧化氢、过氧化脲、碱金属溴化物、过酸盐(例如过硼酸盐和过硫酸盐)以及酶,其中可能提及的酶有过氧化物酶、2电子氧化还原酶(例如尿酸酶)和4电子氧化酶(例如漆酶)。 Thus, the oxidizing agent selected from hydrogen peroxide, urea peroxide, alkali metal bromide, persalt (e.g., perborate and persulfate), and an enzyme, wherein the enzyme may be mentioned peroxidases, 2 electron oxidoreductase (such as uricase) and four-electron oxidase (eg laccase). 特别优选采用过氧化氢。 Particularly preferred to use hydrogen peroxide. 碱性试剂选自例如氨水、胺(特别是乙醇胺)、碳酸盐或碳氢酸盐。 E.g. alkaline agent is selected from ammonia, amines (especially amine), or a hydrocarbon carbonate salts.

[0281] [0281]

Figure CN101684204BD00361

[0282] 另一种可行方法是,二硫化物化合物Mi (所述二硫化物化合物包含2个亲核官能团)可与足够量的、优选2当量且包含亲电子官能团的半花青苷苯乙烯基发色团ϋ或1¾!反应,从而形成Σ共价连接基团;应理解(CH2)m-Σ -(CH2)n表示式I和式II定义的L的亚类。 [0282] Another possibility is that disulfide compound Mi (the disulfide compound containing two nucleophilic functional group) with a sufficient amount of, preferably 2 equivalents of styrene and contains half of anthocyanin electrophilic functional group base chromophore ϋ or 1¾ reaction to form a covalent linkage group Σ; it should be understood (CH2) m-Σ - (CH2) n L represents a subgroup of Formula I and Formula II defined!. 式(1-S)和(I1-S)染料的制备见下: Formula (1-S) and (I1-S) prepared dye below:

[0283] [0283]

Figure CN101684204BD00371

[0284]其中 或Nu 如上定义。 [0284] where or Nu is as defined above.

[0285] 该方法的一个变通方法是采用具有亲电子丙烯酸酯官能团(-0C0-C = C-)的半花青苷苯乙烯基发色团,在该丙烯酸酯官能团上进行的加成反应可产生Σ连接基团的共价键。 [0285] An alternative to this approach is the use of semi-anthocyanin styryl chromophore having an electrophilic acrylate functional groups (-0C0-C = C-), the addition reaction in the acrylate functional groups can be Σ linking group produced a covalent bond.

[0286] 另一种可行方法是,二硫化物化合物(所述二硫化物化合物包含2个亲电官能团)可与足够量的、优选2当量且包含亲核官能团的半花青苷苯乙烯基发色团M或g反应,从而形成Σ连接基团;式(1-S)和(I1-S)染料的制备见下: [0286] Another possibility is that the disulfide compound (the disulfide compound containing two electrophilic functional group) with a sufficient amount of, preferably 2 equivalents and comprise half of anthocyanin styryl nucleophilic functional groups chromophore M or g reaction, thereby forming a Σ linking group; formula (1-S) and (I1-S) prepared dye below:

[0287] [0287]

Figure CN101684204BD00372

[0288]其中 RlR'mW'W'X'Q'E'Nu、0- _Y)和(II' _Y)如上定义。 [0288] where RlR'mW'W'X'Q'E'Nu, 0- _Y) and (II '_Y) as defined above.

[0289] 按照另一种可行方法,可使包含二硫化物基团和2个离核体离去基团Lg的化合物(d”),与半花青苷苯乙烯基发色团MI或么泣反应,得到式(1-s)或式αι-s)的二硫化物染料,所述离去基团例如甲磺酸基、甲苯磺酸基、三氟甲磺酸基或卤基。 [0289] According to another possible way, it can contain disulfide groups and two groups from the nucleus Lg compound (d "), and half anthocyanin styryl chromophore MI or leave it weep to give the formula (1-s) or formula αι-s) disulfide dyes, the leaving group e.g. mesylate, tosylate, triflate or halo.

[0290] [0290]

Figure CN101684204BD00381

[0291] 其中RW'W'X'L'z,或GT如上定义。 [0291] where RW'W'X'L'z, or GT as defined above.

[0292] 按照另一种可行方法,可以使包含二硫化物基团和亲电子基团的化合物Ifi与包含亲核基团的杂环化合物反应,得到本发明的式(I)或式(II) 二硫化物染料。 [0292] According to another possible way to make a compound Ifi contain disulfide groups and electrophilic groups and nucleophilic groups containing heterocyclic compound to give the formula (I) or formula (II) of the present invention. disulfide dyes. 举例来说,当G'表示氧原子或硫原子时,醛或硫醛可与“活性亚甲基化合物”(例如阳离子杂芳基衍生物)M或M缩合,从而得到乙烯键〉C = c〈。 For example, when G 'represents oxygen atom or sulfur atom, with an aldehyde or aldehyde sulfur "active methylene compound" (e.g., cationic heteroaryl derivative) M or M condensation, thereby obtaining a vinyl bond> C = c <. 该反应通常被称为“克脑文盖尔”缩合反应(Knoevenagel condensation)。 The reaction is usually referred to as "gram brain Gaelic text" condensation reaction (Knoevenagel condensation).

[0293] [0293]

Figure CN101684204BD00382

[0294] 其中R1-R6、W、X、L和Q-如上定义。 [0294] wherein R1-R6, W, X, L and Q- are as defined above. G'表示氧原子或硫原子。 G 'represents an oxygen atom or a sulfur atom.

[0295] 有关上述方法所用操作条件的详情可参见以下参考书:Advanced OrganicChemistry, “Reactions, Mechanisms andStructures,,,J.March,第4 版,John Willey &Sons,1992。 [0295] For details on the method used by the operating conditions can be found in the following reference: Advanced OrganicChemistry, "Reactions, Mechanisms andStructures ,,, J.March, 4th edition, John Willey & Sons, 1992.

[0296] 起始的反应剂是市售的,或者可通过本领域技术人员已知常规方法获得。 [0296] starting reactants are commercially available or may be obtained by those skilled in the known conventional methods.

[0297] 举例来说,对于染料⑴的合成和随后的反应剂(I')或(I”),使用2当量衍生物M和I当量含有2个包含亲电子官能团(例如醛或硫醛)的芳基或杂芳基B的二硫化物反应剂2反应,或使用含有活性亚甲基的二硫化物反应剂2与2当量衍生自芳基或杂芳基的亲电子的反应剂(g' )反应,通过双克脑文盖尔缩合,从而得到苯乙烯基二硫化物衍生物IR。 [0297] For example, for the synthesis of dyes ⑴ and subsequent reaction agent (I ') or (I "), 2 equivalents derivative M and I equivalents containing two functional groups containing electron affinity (for example, sulfur aldehyde or aldehyde) aryl or heteroaryl disulfide reactant B 2 reaction, or an active methylene containing disulfide 2 and 2 equivalents of reactant derived from an electrophilic aryl or heteroaryl group of reactants (g ') reaction, by double-gram brain Gaelic text is condensed to obtain styrene disulfide derivative IR.

[0298] [0298]

Figure CN101684204BD00391

[0299]其中 R1-R6'An'L、X、G,和(I)和(II)如上定义。 [0299] wherein R1-R6'An'L, X, G, and (I) and (II) as defined above.

[0300] 本发明的组合物含有至少一种式(I)或式(II)的二硫化物、硫醇或被保护的硫醇半花青苷苯乙烯基荧光染料。 Disulfide [0300] The compositions of the invention contain at least one compound of formula (I) or formula (II), the thiol or protected thiol half anthocyanin styryl fluorescent dye. 除包含至少一种式(I)或式(II)荧光染料外,本发明的组合物还可含有还原剂。 In addition to comprising at least one compound of formula (I) or formula (II) fluorescent dye, the compositions of the present invention may also contain a reducing agent.

[0301] 该还原剂可选自硫醇,例如半胱氨酸、高半胱氨酸或硫代乙酸、这些硫醇的盐、磷化氢、亚硫酸氢盐、亚硫酸盐、巯基乙酸及其酯,特别是单巯基乙酸甘油酯和硫代甘油。 [0301] The reducing agent is selected from mercaptans, such as cysteine, homocysteine or thioacetic acid, salts of these thiols, phosphines, bisulfite, sulfite, thioglycolic acid and esters, especially single thioglycolic acid ester and thioglycerol. 该还原剂还可选自硼氢化物及其衍生物,例如硼氢化物、氰基硼氢化物、三乙酰氧基硼氢化物或三甲氧基硼氢化物的以下盐:钠盐、锂盐、钾盐、钙盐、季铵(四甲基铵、四乙基铵、四-η- 丁基铵或苄基三乙基铵)盐;和儿茶酚硼烷。 The reducing agent may also be selected from borohydrides and derivatives thereof, e.g., the following salts of borohydride, cyanoborohydride, triacetoxy borohydride or trimethoxy borohydride: sodium, lithium salt, potassium salt, calcium salt, quaternary ammonium (tetramethylammonium, tetraethylammonium, tetrabutylammonium or four -η- benzyl triethylammonium) salt; and catechol borane.

[0302] 可用于本发明的染料组合物一般含有式(I)或式(II)染料的量占组合物总重量的0.001%和50%之间。 [0302] may be used between the dye composition of the present invention is generally an amount of 0.001% and 50% of the composition containing the formula (I) or formula (II) of the total weight of the dye. 优选该含量介于0.005%和20% (重量)之间,甚至更优选占组合物总重量的0.01%和5% (重量)之间。 The content is preferably between 0.005% and 20% (by weight) between, and even more preferably between accounts (by weight) from 0.01% and 5% by weight of the total composition.

[0303] 染料组合物还可含有另外的直接染料。 [0303] The dye composition may also contain additional direct dyes. 这些直接染料选自例如中性、酸性或阳离子硝基苯直接染料;中性、酸性或阳离子偶氮直接染料;四氮杂五甲炔花青(tetraazapentamethine)染料;中性、酸性或阳离子醌;特别是蒽醌染料、B丫嗪直接染料、三芳基甲烷直接染料、吲哚胺直接染料和天然直接染料。 These direct dyes selected, for example neutral, acidic or cationic nitrobenzene direct dyes; neutral, acidic or cationic azo direct dyes; tetraaza pentamethine cyanine (tetraazapentamethine) dyes; neutral, acidic or cationic quinone; in particular anthraquinone dyes, B Ah oxazine direct dyes, triarylmethane direct dyes, direct dyes indole amines and natural direct dyes.

[0304] 天然直接染料中,可能提及的有指甲花醌、胡桃叶醌、茜素、红紫素、胭脂红酸、月因脂酮酸、红掊酚、原儿茶醛、靛蓝、靛红、姜黄素、小刺青霉素和芹菜定。 [0304] Natural direct dyes, there may be mentioned Lawsone, walnut leaf quinones, alizarin, purpurin, carminic acid, fatty acid because month, break up phenol red, protocatechuic aldehyde, indigo, indigo red, curcumin, a small thorn given penicillin and celery. 还可以使用含有这些天然染料的萃取物或熬剂,特别是泥罨剂或指甲花型萃取物。 You can also use the extract or boil agent containing these natural dyes, in particular poultices or henna-type extract.

[0305] 染料组合物可含有常用于给角蛋白纤维染色的一种或多种氧化碱和/或一种或多种成色剂(coupler)。 [0305] The dye composition may contain one or more oxidation bases commonly used in the dyeing of keratin fibers and / or one or more dye (coupler).

[0306] 氧化碱中,可能提及的有对苯二胺、双苯基亚烷基二胺、对氨基苯酚、双对氨基苯酚、邻氨基苯酚、杂环碱及其加成盐。 [0306] oxidation bases, may be mentioned p-phenylenediamine, bis alkyl phenyl diamine, aminophenol, double-aminophenol, o-aminophenol, heterocyclic bases and their addition salts.

[0307] 这些成色剂中,特别可能提及的有间苯二胺、间氨基苯酚、间联苯酚、萘成色剂、杂环成色剂及其加成盐。 [0307] These couplers, in particular, may be mentioned m-phenylenediamine, m-amino-phenol, biphenol, naphthalene couplers, heterocyclic couplers and their addition salts.

[0308] 各种成色剂存在的量一般占染料组合物总重量的0.001%和10%之间,优选介于0.005%和6% (重量)之间。 [0308] amount of each coupler presence usually accounts for between 0.001% and 10% of the total weight of the dye composition, preferably between 0.005% and 6% (by weight) between.

[0309] 染料组合物中存在的各氧化碱的量一般占染料组合物总重量的0.001%和10%之间,优选介于0.005%和6%之间。 The amount of each oxide base [0309] in the presence of the dye composition is generally between 0.001% and accounted for 10% of the total weight of the dye composition, between 0.005% and 6%, preferably between.

[0310] 一般而言,可用于本文全文中的氧化碱和成色剂的加成盐特别选自与酸的加成盐,例如盐酸盐、氢溴酸盐、硫酸盐、柠檬酸盐、琥珀酸盐、酒石酸盐、乳酸盐、甲苯磺酸盐、苯磺酸盐、磷酸盐和乙酸盐;与碱的加成盐,例如碱金属(例如钠或钾)的氢氧化物、氨水、胺或烷醇胺。 [0310] In general, the addition salts can be used herein in the entirety oxidation bases and couplers are chosen in particular from the addition salts with acids, such as hydrochloride, hydrobromide, sulfate, citrate, succinate , tartrate, lactate, tosylate, besylate, phosphate and acetate; addition salts with a base, such as alkali metal (e.g. sodium or potassium) hydroxides, ammonia, amine or alkanolamine.

[0311] 适于染色的介质,亦称染色载体(dye support),—般是由水或水与至少一种有机溶剂的混合物构成的化妆品用介质。 [0311] The medium suitable for dyeing, also called dye carrier (dye support), - cosmetic generally composed of water or a water mixture with at least one organic solvent with a medium constituted. 作为有机溶剂,可以提及的有例如C1-C4低级烷醇,例如乙醇和异丙醇;多元醇和多元醇醚,例如2-丁氧基乙醇、丙二醇、丙二醇单甲醚、二乙二醇单乙醚和二乙二醇单甲醚;以及芳族醇,例如苯甲醇或苯氧乙醇及其混合物。 As the organic solvent, there may be mentioned, for example C1-C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monomethyl ether; and aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

[0312] 溶剂如果存在的话,优选以占染料组合物总重量优选约1%和40%之间的比例存在,甚至更优选介于约5%和30% (重量)之间。 [0312] The solvent, if present, preferably to the total weight of the dye composition ratio is preferably from about 1% and 40% between the presence, even more preferably between about 5% and 30% (by weight).

[0313] 染料组合物还可含有常用于毛发染色组合物中的各种辅料,例如阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂、两性表面活性剂或两性离子表面活性剂或其混合物、阴离子聚合物、阳离子聚合物、非离子聚合物、两性聚合物或两性离子聚合物或其混合物、无机或有机增稠剂,特别是阴离子缔合聚合物增稠剂、阳离子缔合聚合物增稠剂、非离子缔合聚合物增稠剂和两性缔合聚合物增稠剂、抗氧化剂、渗透剂、螯合剂、香料、缓冲剂、分散剂、调理剂例如改性或未改性的、挥发或不挥发的硅酮(例如氨基硅酮)、成膜剂、神经酰胺、防腐剂、遮光剂或导电聚合物。 [0313] The dye composition may also contain conventional hair dye composition in the various materials, such as anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants or zwitterionic surfactants, or mixture, anionic polymers, cationic polymers, nonionic polymers, amphoteric polymers or zwitterionic polymers or mixtures thereof, inorganic or organic thickeners, in particular anionic associative polymer thickeners, cationic associative polymer thickeners, nonionic and amphoteric associative polymer thickeners associative polymer thickeners, antioxidants, penetrating agents, chelating agents, fragrances, buffers, dispersants, conditioning agents such as modified or unmodified , volatile or non-volatile silicones (e.g., amino silicones), film-forming agents, ceramides, preservatives, opacifiers, or a conductive polymer.

[0314] 上述各辅料一般存在的量占组合物重量的0.01%和20% (重量)之间。 [0314] 0.01% and 20% each of the above materials are generally present in an amount between weight of the composition (by weight).

[0315] 本领域技术人员当然应该谨慎地选择一种或一些可能的其它化合物,其方式应使预期的添加物不削弱或基本不削弱与本发明染料组合物有关的固有的有利性质。 [0315] Of course, the skilled person should be careful to choose one or a number of other compounds may in a manner such that the additive is not expected to weaken or not substantially impair the advantageous properties inherent with the dye composition of the present invention pertains.

[0316] 染料组合物的pH —般介于约3和14之间,优选介于约5和11之间。 [0316] The dye composition of pH - generally between about 3 and 14, preferably between about 5 and 11 between. 可以通过常用于角蛋白纤维染色的酸化剂或碱化剂或者通过常规缓冲系统调节PH至所需值。 PH can be adjusted or by conventional dyeing keratin fibers in acidifying agent or alkalizing agents by conventional buffer system to the desired value.

[0317] 酸化剂中,可以提及的实例有无机酸或有机酸,例如盐酸、磷酸、硫酸、羧酸(例如乙酸、酒石酸、柠檬酸或乳酸)或磺酸。 [0317] acidifying agents, examples may be mentioned inorganic or organic acid, such as hydrochloric acid, phosphoric acid, sulfuric acid, carboxylic acids (e.g. acetic acid, tartaric acid, citric acid or lactic acid) or sulfonic acid.

[0318] 碱化剂中,可以提及的实例有氨水,碱金属碳酸盐,烷醇胺(例如单乙醇胺、二乙醇胺和三乙醇胺)及其衍生物,氢氧化钠或氢氧化钾和下式(Y)的化合物: [0318] basifying agents, examples may be mentioned ammonia, alkali metal carbonates, alkanolamines (e.g., monoethanolamine, diethanolamine, and triethanolamine) and derivatives thereof, sodium hydroxide or potassium hydroxide and a lower The compounds of formula (Y) is:

[0319] [0319]

Figure CN101684204BD00401

[0320] 其中Wa为任选被羟基或C1-C4烷基取代的亚丙基残基;Ral、Ra2>Ra3和Ra4可相同或不同,表示氢原子、C1-C4烷基或C1-C4羟基烷基。 [0320] wherein Wa is optionally substituted by hydroxy or C1-C4 alkyl substituted propylene residues; Ral, Ra2> Ra3 and Ra4 may be the same or different, represent a hydrogen atom, C1-C4 alkyl or C1-C4 hydroxyalkyl alkyl.

[0321] 染料组合物还可呈不同形式,例如液体剂、乳膏剂或凝胶剂的形式,或者呈适于角蛋白纤维、特别是毛发染色的任何形式。 [0321] The dye composition may also be in different forms, e.g., in the form of liquids, creams or gels, or a form suitable for keratin fibers, in particular any form of hair coloring.

[0322] 本发明用于角蛋白材料、特别是暗色角蛋白材料染色的方法,包括将在合适的化妆品用介质中包含至少一种选自式(I)和式(II)染料的半花青苷苯乙烯基二硫化物或硫醇荧光染料的染料组合物应用于角蛋白材料。 [0322] The present invention is applied to keratin materials, particularly dark keratin material staining methods, including the use hemicyanine medium containing at least one selected from formula (I) and formula (II) in an appropriate cosmetic dyes styryl dye composition glycosides disulfide or thiol fluorescent dyes used in keratin material.

[0323] 根据本发明方法的一个具体实施方案,还可以在使用含有至少一种式(I)或式(II)的半花青苷苯乙烯基荧光染料的组合物之前应用还原剂进行预处理。 [0323] According to a particular embodiment of the inventive method, the composition may contain at least one before the formula (I) or formula (II) semi anthocyanin styryl fluorescent dye reducing agent pretreatment application in use .

[0324] 用上述还原剂的这种预处理可以是短时间的,特别为I秒钟至30分钟,优选I分钟至15分钟。 [0324] In this pre-treatment of the reducing agent may be a short period of time, specifically for I second to 30 minutes, preferably from I to 15 minutes.

[0325] 按照另一种方法,包含至少一种式(I)或式(II)半花青苷苯乙烯基荧光染料的组合物还含有至少一种如上定义的还原剂。 [0325] According to another method, a composition comprising at least one compound of formula styryl half anthocyanins (I) or formula (II) further contains a fluorescent dye at least one reducing agent as defined above. 然后将该组合物应用于毛发。 The composition is then applied to the hair.

[0326] 如果m和η为I的式(I)或(II)的半花青苷苯乙烯基硫醇荧光染料包括硫醇官能团保护基Y,则可在用本发明的方法之前进行脱保护步骤,目的在于原位使SH官能团复原。 [0326] If m and η as I formula (I) or (II) semi anthocyanin styryl thiol fluorescent dyes include a thiol functional group-protecting group Y, may be in use before the method of the present invention will be deprotected step aimed at making SH functional group in situ recovery.

[0327] 举例来说,可如下调节pH以便使具有Y保护基的SY官能团脱保护: [0327] For example, the pH can be adjusted as follows so that the Y SY functional group having a protecting group deprotection:

[0328] [0328]

Figure CN101684204BD00411

[0329] 脱保护步骤还可在毛发预处理步骤中进行,例如毛发的还原预处理。 [0329] deprotection steps can be performed in the hair pretreatment step, such as reducing pretreatment of the hair.

[0330] 按照一种变通方法,将还原剂在使用时加到含有至少一种式(I)或式(II)半花青苷苯乙烯基荧光染料的染料组合物中。 [0330] According to one alternative method, the reducing agent is added when using the dye composition containing at least one compound of formula (I) or formula (II) and a half anthocyanin styryl fluorescent dye.

[0331] 按照另一种方法,包含至少一种式(I)或式(II)半花青苷苯乙烯基荧光染料的组合物还含有至少一种如上定义的还原剂。 [0331] According to another method, a composition comprising at least one compound of formula styryl half anthocyanins (I) or formula (II) further contains a fluorescent dye at least one reducing agent as defined above. 然后将该组合物应用于毛发。 The composition is then applied to the hair.

[0332] 按照另一种变通方法,在应用含有至少一种式(I)或式(II)半花青苷苯乙烯基荧光染料的组合物之后使用还原剂作为后处理。 [0332] According to another workaround, after application of a composition comprising at least one compound of formula (I) or formula (II) and a half anthocyanin styryl fluorescent dye used as a reducing agent after treatment. 用上述还原剂后处理的时间可较短,例如为I秒钟至30分钟,优选为I分钟至15分钟。 After a short time can be used in the above-described reducing agent, for example, I second to 30 minutes, preferably from I to 15 minutes. 根据一个具体的实施方案,还原剂为上述硫醇或硼氢化物型还原剂。 According to a particular embodiment, said reducing agent is a thiol reducing agent or a boron hydride type.

[0333] 本发明的一个具体实施方案涉及一种方法,其中式(I)或式(II)的半花青苷苯乙烯基荧光染料可以直接应用于毛发而无需还原剂,免去了还原预处理或还原后处理。 [0333] An embodiment of the present invention relates to a method in which the formula (I) or formula (II) semi anthocyanin styryl fluorescent dye can be directly applied to the hair without reducing agents, eliminating the need to restore the pre- After treatment or reduction treatment.

[0334] 可任选结合用氧化剂的处理。 [0334] optionally in combination with an oxidizing agent in the process. 优选本发明的染色方法包括将氧化剂应用于角蛋白纤维的额外步骤。 Dyeing process of the invention preferably includes an additional step of oxidizing agent applied to the keratin fibers. 可以采用本领域常用的任何氧化剂类型。 Commonly used in the art may be employed in any type of oxidant. 因此,氧化剂可选自过氧化氢、过氧化脲、碱金属溴化物、过酸盐(例如过硼酸盐和过硫酸盐)以及酶,其中可能提及的有过氧化物酶、2电子氧化还原酶(例如尿酸酶)和4电子氧化酶(例如漆酶)。 Thus, the oxidizing agent selected from hydrogen peroxide, urea peroxide, alkali metal bromide, persalt (e.g., perborate and persulfate), and the enzyme, which may be mentioned peroxidases, 2-electron oxidation reductase (such as uricase) and four-electron oxidase (eg laccase). 特别优选采用过氧化氢。 Particularly preferred to use hydrogen peroxide. 该处理的时间介于I秒钟和40分钟之间,优选介于15秒钟和15分钟之间。 The treatment time is between I seconds and 40 minutes, and preferably between 15 seconds and 15 minutes.

[0335] 一般在环境温度下使用本发明的染料组合物。 [0335] Usually at ambient temperature using a dye composition of the present invention. 然而,可以在20_180°C的温度范围内使用。 However, it can be used within 20_180 ° C temperature range. [0336] 本发明还有一个主题是多室染料装置或染料“盒”,其中第一室装有包含至少一种式(I)或式(II)半花青苷苯乙烯基荧光染料的染色组合物,第二室装有能够还原角蛋白材料和/或式(I)或式(II)半花青苷苯乙烯基二硫化物荧光染料的二硫化物官能团的还原剂。 [0336] Another subject of the present invention is a multi-chamber apparatus dye or dye "box", which contains the first chamber has at least one compound of formula (I) or formula (II) and a half anthocyanin styryl fluorescent dye staining reducing composition, the second chamber has keratin material capable of reducing and / or formula (I) or formula (II) and a half anthocyanin styryl disulfide fluorescent dye disulfide functional groups.

[0337] 这些隔室之一还可装有一种或多种直接染料型或氧化染料型的其它染料。 [0337] One of these compartments may also be provided with one or more direct dyes dye oxidation dye type or other type.

[0338] 本发明还涉及多室装置,其中第一室装有包含至少一种式(I)或式(II)半花青苷苯乙烯基荧光染料的染料组合物;第二室装有能够还原角蛋白材料和/或式(I)或式(II)半花青苷苯乙烯基二硫化物荧光染料的二硫键的还原剂;第三室装有氧化剂。 [0338] The present invention further relates to a multi-chamber apparatus, wherein the first chamber comprises at least one semi-containing anthocyanin styryl (I) or formula (II) dyes fluorescent dye composition; the second chamber can be provided with reduction of keratin materials and semi-styryl anthocyanin / or of formula (I) or formula (II) disulfide fluorescent dye disulfide reducing agent; third compartment containing an oxidizing agent.

[0339] 或者,染色装置包括装有包含至少一种被保护的m和η为I的式(I)或式(II)半花青苷苯乙烯基硫醇荧光染料的染料组合物的第一室,以及装有能够使被保护的硫醇脱保护以释放出硫醇的试剂的第二室,任选包含氧化剂的第三室。 The first [0339] Alternatively, the apparatus comprising containing dye comprising at least one of m and η is protected as a formula I (I) or formula (II) and a half anthocyanin styryl dye thiol fluorescent dye composition room, and can be fitted with the protected thiol deprotection second chamber to release the thiol reagents, optionally third compartment contains an oxidizing agent.

[0340] 上述每个装置都可配备将所需混合物施用于毛发上的配置,例如法国专利2 586913中所述装置。 [0340] Each of the above devices can be equipped with the required mixture is applied to the configuration on the hair, such as French Patent 2,586,913 in the device.

[0341] 图1是用染料I处理的ΤΗ4发束的反射度曲线, [0341] FIG. 1 is a reflection of the curve ΤΗ4 dye I treated hair bundle,

[0342] 图2是用染料2和4处理的ΤΗ4发束的反射度曲线, [0342] FIG. 2 is ΤΗ4 Dye 2 and 4 deal with the tress of reflectance curves

[0343] 图3是用染料2和4处理的ΤΗ4发束的反射度曲线。 [0343] FIG. 3 is a reflection curve ΤΗ4 dye 2 and 4 deal with the hair bundle.

[0344] 下面的实施例用于说明本发明,本质上并不是限制性的。 [0344] The following examples illustrate the invention, not limiting in nature. 通过常规的分光镜法和光谱测定法对下述实施例的硫醇荧光染料进行了充分表征。 Thiol fluorescent dyes by conventional spectroscopic methods and spectroscopy of the following examples have been well characterized.

[0345] 实施例 [0345] Example

[0346] 合成实施例 [0346] Synthesis Example

[0347] 实施例1:2,2' _{ 二硫烷二基双[乙烷_2,1-二基(甲基亚胺基)-4,1-亚苯基乙烯-2,1-二基]}双(3-乙基-1,3-苯并噻唑-3-鎗)二碘化物[I]的合成: [0347] Example 1: 2,2 '_ {disulfane diyl bis [_2,1- ethane-diyl (methylimino) ethylene 4,1-phenylene-2,1- diyl] bis (3-ethyl-1,3-benzothiazine-3-gun) diiodide [I] Synthesis}:

[0348] [0348]

Figure CN101684204BD00421

[0349] 合成流程: [0349] synthetic scheme:

[0350] [0350]

Figure CN101684204BD00431

[0351]方法: [0351] Method:

[0352] 步骤1:4,4'-{ 二硫烷二基双[乙烷-2,1-二基(甲基亚氨基)]} 二苯甲醛 [0352] Step 1: 4,4 '- {disulfane diyl bis [ethane-2,1-diyl (methylimino)]} dibenzaldehyde

[0353]在 0°C下,将82.3g 氧氯化憐(phosphorous oxychloride)加到500ml DMF 中。 [0353] from 0 ° C, a solution of 82.3g pity oxychloride (phosphorous oxychloride) in 500ml DMF was added. 在0°C下搅拌30分钟后,滴加47 gN,N/ -( 二硫烷二基二乙烷-2,1-二基)双(N-甲基苯胺)的溶液。 After stirring at 0 ° C for 30 minutes, a solution of 47 gN, N / - (disulfane 2,1-ethane-diyl) bis (N- methylaniline) was added. 将混合物在0°C下搅拌90分钟后,在10°C下搅拌75分钟,再于40°C搅拌105分钟。 The mixture was stirred at 0 ° C for 90 minutes, stirring for 75 minutes at 10 ° C and further stirred at 40 ° C 105 min. 然后倒入2.5L冰水中,加入700ml 5N氢氧化钠。 Then poured into ice water and 2.5L, 700ml 5N sodium hydroxide was added. 经硅藻土过滤后得到黄色沉淀物,使之溶于200ml 二氯甲烷,所得溶液用200ml氯化钠饱和水溶液洗涤。 After filtration through celite to give a yellow precipitate was dissolved in 200ml of methylene chloride so that the resulting solution was washed with 200ml of saturated aqueous sodium chloride solution. 经硫酸镁干燥后,蒸发二氯甲烷,黄色残余物(80 g)用硅胶色谱法纯化。 After drying over magnesium sulfate, dichloromethane was evaporated, a yellow residue (80 g) was purified by silica gel chromatography. 干燥后,回收浅黄色粉末。 After drying, recovered as a pale yellow powder. 分析结果显示产物与预期的结构一致。 Analysis showed that the product is consistent with the expected structure.

[0354] 步骤2:2,2'-{ 二硫烷二基双[乙烷-2,1-二基(甲基亚氨基)-4,1-亚苯基乙烯-2,1-二基]}双(3-乙基-1,3-苯并噻唑-3-鎓)二碘化物[1] [0354] Step 2: 2,2 '- {disulfane diyl bis [ethane-2,1-diyl (methylimino) ethylene 4,1-phenylene-2,1-diyl ]} bis (3-ethyl-1,3-benzothiazol-3-ium) diiodide [1]

[0355] 在79°C下,将1.9g N-乙基苯并噻唑鎗碘化物的2ml 二氯甲烷溶液加到1.2g 4,4'-{ 二硫烷二基双[乙烷_2,1-二基(甲基亚氨基)]} 二苯甲醛的9ml乙醇悬浮液中。 [0355] at 79 ° C, a solution of 1.9g N- ethyl 2ml dichloromethane was gun benzothiazole iodide was added 1.2g 4,4 '- {disulfane diyl bis [ethane _2, 1-yl (methylimino)]} 9ml ethanol dibenzaldehyde suspension. 搅拌下将混合物回流72小时。 The mixture was stirred at reflux for 72 hours. 冷却后,将紫色悬浮液过滤。 After cooling, the purple suspension was filtered. 干燥后,回收1.5g黑色粉末。 After drying, the recovered 1.5g of black powder. 分析结果显示产物与化合物[1] 一致,并且是纯的。 The results showed that the product with the compound [1] is consistent and pure.

[0356] 1H NMR(400MHz,Me0H_d4)-l.42(t,6H),3.04(t,4H),3.13(s,6H),3.82(t,4H), [0356] 1H NMR (400MHz, Me0H_d4) -l.42 (t, 6H), 3.04 (t, 4H), 3.13 (s, 6H), 3.82 (t, 4H),

4.84 (q, 4H),6.90 (d, 4H),7.64 (d, 2H),7.68 (dd, 2H),7.78 (dd, 2H),7.95 (d, 4H),8.08 (d,2H),8.15(d,2H),8.30(d,2H)。 4.84 (q, 4H), 6.90 (d, 4H), 7.64 (d, 2H), 7.68 (dd, 2H), 7.78 (dd, 2H), 7.95 (d, 4H), 8.08 (d, 2H), 8.15 (d, 2H), 8.30 (d, 2H).

[0357]实施例 2:2- (2- {4- [ [2- ({2- [ {4- [-2-(1, 3_ 二甲基-1H-苯并咪唑-3- 鎓-2- 基)乙烯基]苯基}(甲基)氣基]乙基} 二硫基)乙基](甲基)氣基]苯基}乙烯基)-1,3-二甲基-1H-3,1-苯并咪唑-3-鎓)二甲基硫酸盐[2]的合成 [0357] Example 2: Preparation of 2- (2- {4- [[2- (2- {[{4- [2- (1, 3_ -1H- benzimidazol-dimethyl-3-ium -2 - yl) ethenyl] phenyl} (methyl) air-yl] ethyl} dithio) ethyl] (methyl) air-yl] ethenyl} phenyl) -1,3-dimethyl--1H- 3,1-benzimidazol-3-ium) dimethyl sulfate [2] Synthesis of

[0358] [0358]

Figure CN101684204BD00441

[0361]方法: [0361] Method:

[0362] 2- (-2- {4- [ [2- ({2_ [ {4_ [2_ (I,3_ 二甲基-1H-苯并咪唑_3_ 鐵_2_ 基)乙烯基]苯基}(甲基)氨基]乙基} 二硫基)乙基](甲基)氨基]苯基}乙烯基)-1,3_ 二甲基-1Η-3,1-苯并咪唑-3-鎗)二甲基硫酸盐[2]的合成 [0362] 2- (-2- {4- [[2- ({2_ [{4_ [2_ (I, 3_ dimethyl -1H- benzimidazol _3_ iron _2_ yl) ethenyl] phenyl} (methyl) amino] ethyl} dithio) ethyl] (methyl) amino] phenyl} vinyl) -1,3_ dimethyl -1Η-3,1- benzimidazol -3- gun) Dimethyl sulfate [2] Synthesis of

[0363] 在79°C下,将0.5g 1,2,3_三甲基_1Η_苯并咪唑_3_鎗甲基硫酸盐的2ml 二氯甲烷溶液加到0.36g 4,4' _{ 二硫烷二基双[乙烷_2,1-二基(甲基亚氨基)]} 二苯甲醛的8ml乙醇悬浮液和0.15ml吡咯烷中。 [0363] at 79 ° C, a solution of 0.5g 1,2,3_ trimethyl _1Η_ benzimidazole gun _3_ 2ml dichloromethane was added methyl sulfate 0.36g 4,4 '_ disulfane diyl bis {[_2,1- ethane-diyl (methylimino)]} 8ml ethanol suspensions and formaldehyde diphenyl 0.15ml pyrrolidine. 将混合物保持在80°C下搅拌7小时。 The mixture was kept under stirring at 80 ° C for 7 hours. 冷却后,将悬浮液倒入25ml冷的乙酸乙酯中。 After cooling, the suspension was poured into 25ml cold ethyl acetate. 将所得沉淀物过滤,用乙酸乙酯洗涤后干燥。 The resulting precipitate was filtered, washed with ethyl acetate and dried. 回收0.3g橙色粉末。 0.3g orange powder was recovered. 分析结果显示产物与化合物[2] —致。 The results showed that the product with the compound [2] - induced.

[0364]实施例 3:3,3' - ( 二硫烧二基二乙烧_2,1- 二基)双(6-氣-2-{-2-[4-( 二甲基氨基)-1-萘基]乙烯基} -1-甲基-1H-苯并咪唑-3-鎗)二溴化物[3]的合成 [0364] Example 3: 3,3 '- (diethyl disulfide burn burn _2,1- diyl) bis (6-gas-2 - {- 2- [4- (dimethylamino) 1-naphthyl] ethenyl} -1-methyl -1H- benzimidazol -3- gun) dibromide [3] Synthesis of

[0365] [0365]

Figure CN101684204BD00451

[0368]方法: [0368] Method:

[0369] 步骤1:3,3' -( 二硫烧二基二乙烧-2,1-二基)双(6-氣-1, 2_ 二甲基-1H-苯并咪唑-3-鎗)二溴化物的合成 [0369] Step 1: 3,3 '- (disulfide burn burn-diyl diacetate 2,1-diyl) bis (6-gas -1, 2_ dimethyl -1H- benzimidazol -3- gun ) Synthesis dibromide

[0370] 将142mg氯-1, 2-二甲基苯并咪唑、IOOmg双(2-溴乙基)二硫化物、54mg碘化钠和0.4ml丙腈在100°C下搅拌17小时。 [0370] The 142mg chloro-1, 2-dimethyl-benzimidazole, IOOmg bis (2-bromoethyl) disulfide, 54mg sodium iodide and 0.4ml propionitrile was stirred at 100 ° C for 17 hours. 冷却后,过滤,用5ml乙腈洗涤5次,回收125mg灰 After cooling, filtration, 5ml of acetonitrile was washed with 5 times, ash recycling 125mg

色粉末。 Colored powder. 分析结果显示产物与预期的结构一致。 Analysis showed that the product is consistent with the expected structure.

[0371]步骤 2:3,3' -( 二硫烧二基二乙烧-2,1-二基)双(6_ 氣_2-{-2-[4-( 二甲基氨基)-1_萘基]乙烯基}-1_甲基-1H-苯并咪唑-3-鎗)二溴化物的合成[0372]将 600mg 3,3, _ ( 二硫烷二基二乙烷_2,1-二基)双(6_ 氯_1,2_ 二甲基_1Η_ 苯并咪唑-3-鎗)二溴化物、370mg 4-二甲氨基萘醛、6ml甲醇和42 μ I哌啶在环境温度下搅拌24小时。 [0371] Step 2: 3,3 '- (disulfide burn burn-diyl diacetate 2,1-diyl) bis (6_ gas _2 - {- 2- [4- (dimethylamino) -1 _ naphthyl] vinyl} -1_ methyl -1H- benzimidazol -3- gun) Synthesis dibromide [0372] The 600mg 3,3, _ (disulfane _2 ethane-diyl, 1-yl) bis (6_ chloro _1,2_ dimethyl _1Η_ benzoimidazol -3- gun) dibromide, 370mg 4- dimethylamino-naphthaldehyde, 6ml of methanol, and 42 μ I piperidine at ambient temperature stirred 24 hours. 将所得混合物滴加到200ml乙醚中。 The resulting mixture was added dropwise 200ml of diethyl ether. 过滤后干燥,回收400mg橙色固体。 After filtration and dried to recover an orange solid 400mg. 分析结果显示产物与预期的结构[3] —致。 The results showed that the product with the expected structure [3] - induced.

[0373] 实施例4:3,3' - ( 二硫烧二基二乙烧-2,1-二基)双(2_ {-2_[4_ ( 二甲氛基)苯基]乙烯基} -1-甲基-1H-苯并咪唑-3-鎗)二溴化物[4]的合成 [0373] Example 4: 3,3 '- (disulfide burn burn-diyl diacetate 2,1-diyl) bis (-2_ 2_ {[4_ (dimethylamino atmosphere yl) phenyl] vinyl} - -1H- benzimidazol-1-methyl -3- gun) dibromide [4] Synthesis of

[0374] [0374]

Figure CN101684204BD00461

[0377]方法: [0377] Method:

[0378] 步骤1:3,3' _( 二硫烷二基二乙烷-2,1-二基)双(1,2-二甲基-1H-苯并咪唑-3-鎗)二溴化物的合成 [0378] Step 1: 3,3 '_ (disulfane 2,1-ethane-diyl) bis (1,2-dimethyl-benzimidazole -3- -1H- gun) dibromo Synthesis of matter

[0379] 在100°C 2.4g 1,2_ 二甲基苯并咪唑、2.1g双(2-溴乙基)二硫化物和6ml丙腈在密封的20ml反应器中搅拌8小时。 [0379] at 100 ° C 2.4g 1,2_-dimethyl-benzimidazole, 2.1g bis (2-bromoethyl) disulfide and propionitrile 6ml 20ml stirred in a sealed reactor for 8 hours. 冷却后,过滤,用IOml洗涤3次后真空干燥,回收 After cooling, filtered, washed and dried in vacuo IOml three times with recovered

2.2g浅褐色固体。 2.2g light brown solid. 分析结果显示产物与预期的结构一致。 Analysis showed that the product is consistent with the expected structure.

[0380] 步骤2:3,3' -( 二硫烧二基二乙烧-2,1-二基)双(2-{-2-[4_( 二甲氛基)苯基]乙烯基} -1-甲基-1H-苯并咪唑-3-鎗)二溴化物的合成 [0380] Step 2: 3,3 '- (disulfide burn burn-diyl diacetate 2,1-diyl) bis (2 - {- 2- [4_ (dimethylamino atmosphere yl) phenyl] vinyl} Synthesis of 1-methyl-benzimidazole -3- -1H- gun) dibromide

[0381] 将L3g3,3, _ ( 二硫烷二基二乙烷_2,1-二基)双(1,2_ 二甲基_1Η_苯并咪唑-3-鐵)二溴化物、Ig 4- 二甲氨基苯甲醒、26ml甲醇和500 μ I哌唳在60°C下搅拌I小时30分钟。 [0381] The L3g3,3, _ (disulfane _2,1- ethane-diyl) bis (dimethyl _1Η_ 1,2_ benzoimidazol -3- iron) dibromide, Ig 4-dimethylamino benzoic awake, 26ml of methanol and 500 μ I piperazine 唳 stirred I hr at 60 ° C for 30 minutes. 加入350 μ I哌啶后,继续搅拌2小时30分钟。 After addition of 350 μ I piperidine, stirring was continued for 2 hours 30 minutes. 冷却后,滤出所得橙色沉淀物,并在4°C下用5ml甲醇洗涤3次。 After cooling, the resulting orange precipitate was filtered off, and at 4 ° C and washed 3 times with 5ml of methanol. 所回收的固体在超声下于热的乙醇中捏合使之软化。 The recovered solid kneaded softened ultrasound in hot ethanol. 将混合物冷却,过滤后干燥。 The mixture was cooled, filtered and dried. 得到450mg橙红色粉末。 To give 450mg orange-red powder. 分析结果显示产物是纯的,并与预期的结构[4] 一致。 Analysis showed that the product was pure and expected structure [4] is consistent.

[0382] 实施例5:2,2' _{ 二硫烷二基双[乙烷-2,1-二基(甲基亚氨基)-4,1-亚苯基乙烯-2,1- 二基]}双(3-乙基-1,3-苯并噁唑-3-鎗)二碘化物[5]的合成 [0382] Example 5: 2,2 '_ {disulfane diyl bis [ethane-2,1-diyl (methylimino) ethylene 4,1-phenylene-2,1-two yl]} bis (3-ethyl-1,3-benzo-3-gun) diiodide [5] Synthesis of

[0383] [0383]

Figure CN101684204BD00471

[0384] 合成流程: [0384] synthetic scheme:

[0385][0386]方法: [0385] [0386] Method:

[0387] 将6.56g 3-乙基_2_甲基-1,3_苯并噁唑_3_鎗碘化物在12ml60: 40异丙醇/N-甲基吡咯烷酮混合物中的溶液加到分散于8ml60: 40异丙醇/N-甲基吡咯烷酮混合物中的4.16g 4,4' _{ 二硫烷二基双[乙烷-2,1-二基(甲基亚氨基)]} 二苯甲醛中。 [0387] The ethyl _2_ 6.56g 3- methyl iodide -1,3_ benzoxazole _3_ gun in 12ml60: 40 isopropanol / N- methylpyrrolidone was added to the dispersion mixture in 8ml60: 40 isopropanol / N- methylpyrrolidone mixture of 4.16g 4,4 '_ {disulfane diyl bis [ethane-2,1-diyl (methylimino)]} dibenz formaldehyde. 将混合物在80°C下搅拌27小时。 The mixture was stirred at 80 ° C at 27 hours. 冷却后,将溶液倒入200ml乙酸乙酯中。 After cooling, the solution was poured into 200ml of ethyl acetate. 滤出沉淀物,用150ml乙酸乙酯洗涤3次后干燥。 The precipitate was filtered off, dried and washed 3 times with 150ml of ethyl acetate. 回收6.83g红色粉末。 Recovering 6.83g red powder. 分析结果显示产物与预期的结构[5] —致。 The results showed that the product with the expected structure [5] - induced.

[0388] 实施例6:2,2' _{ 二硫烷二基双[乙烷-2,1-二基(甲基亚氨基)-4,1-亚苯基乙稀-2,1- 二基]}双(3_甲基-1, 3_喔唑_3_鐵)二甲基硫酸盐[6]的合成 [0388] Example 6: 2,2 '_ {disulfane diyl bis [ethane-2,1-diyl (methylimino) ethylene 4,1-phenylene-2,1- diyl]} bis (3_-1, 3_ Oh azole _3_ iron) dimethyl sulfate [6] Synthesis

[0389] [0389]

Figure CN101684204BD00481

[0392]方法: [0392] Method:

[0393] 2,2' _{ 二硫烷二基双[乙烷-2,1-二基(甲基亚氨基)_4,1-亚苯基乙烯-2, [0393] 2,2 '_ {disulfane diyl bis [ethane-2,1-diyl (methylimino) ethylene -2 _4,1- phenylene,

1- 二基]}双(3-甲基-1,3-噻唑-3-鎗)二甲基硫酸盐[6]的合成 1-yl]} bis (3-methyl-1,3-thiazol-3-gun) dimethyl sulfate [6] Synthesis of

[0394] 将1.66g 2,3-二甲基噻唑鎗甲基硫酸盐在2ml 60: 40异丙醇/N-甲基吡咯烷酮混合物中的溶液加到1.43g 4,4' _{ 二硫烷二基双[乙烷-2,1-二基(甲基亚氨基)]}二苯甲醛在5ml 60: 40异丙醇/N-甲基吡咯烷酮混合物中的悬浮液和0.56ml吡咯烷中。 [0394] The 1.66g 2,3- dimethyl-thiazol-gun methylsulfate in 2ml 60: 40 isopropanol / N- methylpyrrolidone was added to a mixture of 1.43g 4,4 '_ {disulfane diyl bis [ethane-2,1-diyl (methylimino)]} dibenzo formaldehyde in 5ml 60: 40 isopropanol / N- methylpyrrolidone mixture suspension and 0.56ml of pyrrolidine. 在氩气氛、避光下,将混合物保持在50°C下搅拌7小时。 Under an argon atmosphere, dark, the mixture was kept stirred at 50 ° C for 7 hours. 冷却后,将悬浮液倒入25ml冷的乙酸乙酯中。 After cooling, the suspension was poured into 25ml cold ethyl acetate. 滤出所得沉淀物,用乙酸乙酯洗涤后干燥。 The resulting precipitate was filtered off, washed with ethyl acetate and dried. [0395] 实施例7:2-[2- (4- {[2_ (乙酰基硫基)-乙基](甲基)氨基}苯基)乙烯基]-1,3-二甲基-1H-苯并咪唑-3-鎗甲磺酸盐[7]的合成 [0395] Example 7: 2- [2- (4- {[2_ (acetylthio) - ethyl] (methyl) amino} phenyl) ethenyl] -1,3-dimethyl -1H - benzimidazole-gun methanesulfonate -3- [7] Synthesis of

[0396] [0396]

Figure CN101684204BD00491

[0399]方法: [0399] Method:

[0400] 将2_ [2_ {4-[ (2-氣乙基)(甲基)-氛基]苯基}_乙烯基]_1,3_ 二甲基-1H-苯并咪唑-3-鐵甲磺酸盐(1.6g,3.5mmol)和硫代乙酸钾(0.6g, 5.3mmol)在12ml乙醇和4ml水中的混合物加热回流12小时。 [0400] The 2_ [2_ {4- [(2-ethyl-gas) (methyl) - atmosphere-yl] phenyl} _ vinyl] -1H- _1,3_ dimethyl-benzimidazole sulfonic -3- armored salt (1.6g, 3.5mmol) and potassium thioacetate (0.6g, 5.3mmol) in a mixture of 12ml of ethanol and 4ml of water was heated at reflux for 12 hours. 冷却后,真空除去溶剂。 After cooling, the solvent was removed in vacuo. 所得残余物用氧化铝色谱法处理(用二氯甲烷和甲醇(500: 3)的混合物洗脱),得到0.Sg粗产物。 The resulting residue was purified by alumina chromatography (methylene chloride and methanol (500: 3 mixture) elution), to give a crude product 0.Sg. 通过从2-丙醇和乙酸乙酯混合溶剂中重结晶来进行进一步纯化,得到0.7g橙色粉末。 By solvent recrystallization from 2-propanol and further purified by mixing with ethyl acetate, to give 0.7g orange powder.

[0401] 分析结果与预期的结构[7] —致,并表明E/Z比为69: 31。 [0401] The results with the expected structure [7] - consistent, and show E / Z ratio of 69: 31.

[0402] 实施例8:S-{2~r {4-「2-(l,3-二甲基-1H-苯并咪唑-3-鑰-2-基)乙烯基]苯 [0402] Example 8: S- {2 ~ r {4- "2- (l, 3- dimethyl -3- key -1H- benzimidazol-2-yl) ethenyl] benzene

基}(甲基)氨基]-乙基}硫代硫酸盐[8]的合成 } (Methyl) amino] - Synthesis of ethyl} thiosulfate [8]

[0403] [0403]

Figure CN101684204BD00501

[0406]方法: [0406] Method:

[0407] 向2_ [2_ {4-[ (2-氣乙基)(甲基)-氛基]苯基}_乙烯基]_1,3_ 二甲基-1H-苯并咪唑-3-鎗甲磺酸盐(1.0g, 2.2mmol)在IOml乙醇和IOml水的搅拌溶液中加入 [0407] To 2_ [2_ {4- [(2-ethyl-gas) (methyl) - atmosphere-yl] phenyl} _ vinyl] -1H- _1,3_ dimethyl-benzimidazole carboxylic gun -3- salt (1.0g, 2.2mmol) was added to a stirred solution of ethanol and IOml IOml of water

1.4g(8.9mmol)硫代硫酸钠。 1.4g (8.9mmol) sodium thiosulfate. 将混合物加热回流48小时。 The mixture was heated at reflux for 48 hours. 经过滤收集所得固体,用水洗漆3次后用乙醇洗涤2次。 The resulting solid was collected by filtration, washed with water paint washed three times with ethanol twice. 干燥后得到0.Sg黄橙色粉末。 After drying 0.Sg yellow-orange powder.

[0408] 分析结果与化合物[8]的预期的结构一致。 Unanimously [0408] The results with the compound [8] expected structure.

[0409] SML9j.LV _{ 二硫烷二基双[乙烷-2,1-二基亚氨基(2-氧代乙烷-2,1-二基)]}双{2-[2-{4_[双(2-羟乙基)氨基]苯基}乙烯基]-3-甲基-1H-苯并咪唑-3-鎗}氯化物[9]的合成 [0409] SML9j.LV _ {disulfane diyl bis [2,1-ethane two imino (2-oxo-ethane-2,1-diyl)]} bis {2- [2- 4_ {[bis (2-hydroxyethyl) amino] phenyl} ethenyl] -3-methyl} -1H- benzimidazol-gun chloride -3- [9] Synthesis of

[0410] [0410]

Figure CN101684204BD00511

[0411] [9] [0411] [9]

[0412] 反应流程 [0412] Reaction Scheme

[0413] [0413]

Figure CN101684204BD00521

[0414] 步骤1:1,I' -{ 二硫烧二基双[乙烧_2,1- 二基亚氣基(2-氧代乙烧-2,1- _.基)]}双(2,3-二甲基-1H-苯并咪唑-3-鎗)氯化物的合成 [0414] Step 1: 1, I '- {disulfide burn-diyl bis [ethylene bis sulfoxide _2,1- burn gas-yl (2-oxo-2,1-_ yl acetate burn.)]} Bis Synthesis of (2,3-dimethyl-benzimidazole -3- -1H- gun) chloride

[0415] 将化合物1,2_ 二甲基-1H-苯并咪唑(2.93g,20mmol)和N,N' -( 二硫烷二基二乙烷-2,1- 二基)双(2-氯乙酰胺)(1.53g,5mmol)在20ml乙腈中的混合物加热回流24小时。 [0415] Compound 1,2_ -1H- dimethyl-benzimidazole (2.93g, 20mmol) and N, N '- (alkyl disulfide 2,1-ethane-diyl) bis (2- chloroacetamide) (1.53g, 5mmol) in a mixture of 20ml of acetonitrile was heated at reflux for 24 hours. 冷却后,经过滤收集所得白色固体,用乙酸乙酯和二氯甲烷洗涤,得到1.94g白色粉末。 After cooling, the resulting white solid was collected by filtration, washed with ethyl acetate and dichloromethane to give 1.94g of a white powder. 分析结果与预期的结构一致。 Analysis of the results is consistent with the expected structure.

[0416] 步骤2:1,1' - { 二硫烧二基双[乙烧_2,1- 二基亚氣基(2-氧代乙烧-2,1- _.基)]}双{2-[2-{4_[双(2-羟乙基)氨基]苯基}乙烯基]-3-甲基-1H-苯并咪唑-3-鎗}氯化物[9]的合成 [0416] Step 2: 1,1 '- {disulfide burn-diyl bis [ethylene bis sulfoxide _2,1- burn gas-yl (2-oxo-2,1-_ yl acetate burn.)]} Bis {2- [2- {4_ [bis (2-hydroxyethyl) amino] phenyl} ethenyl] -3-methyl} -1H- benzimidazol-gun chloride -3- [9] Synthesis of

[0417] 向4-[双(2-羟乙基)_氨基]苯甲醛(1.7g,8.1mmol)和1,1' _{ 二硫烷二基双[乙烷-2,1-二基亚氨基(2-氧代乙烷-2,1-二基)]}双(2,3_ 二甲基-1H-苯并咪唑-3-鎗)氯化物(1.2g,2mmol)在35ml乙醇的搅拌溶液中加入0.5ml哌啶作为催化剂。 [0417] 4- [bis (2-hydroxyethyl) amino _] benzaldehyde (1.7g, 8.1mmol) and 1,1 '_ {disulfane diyl bis [ethane-2,1-diyl imino (2-oxo-ethane-2,1-diyl)]} bis (2,3_ dimethyl -1H- benzimidazol -3- gun) chloride (1.2g, 2mmol) in 35ml ethanol It was added 0.5ml piperidine as a catalyst. 将反应混合物加热回流7小时。 The reaction mixture was heated at reflux for 7 hours. 冷却后,经过滤收集所得橙色固体后,用二氯甲烷和甲醇洗涤。 After cooling, the resulting orange solid was collected by filtration, washed with dichloromethane and methanol. 干燥后得到1.6g橙色固体。 And dried to give an orange solid 1.6g. 分析结果与预期的结构一致。 Analysis of the results is consistent with the expected structure.

[0418] 实施例10丄1,I, _{二硫烷二基双[乙烷-2,1-二基亚氨基(2-氧代乙烷-2,1-二基)]}双{3-甲基-2-[2-(2,3,6,7-四氢_1Η,5Η_吡啶并[3,2,l_ij]喹啉-9-基)乙烯基]-1H-苯并咪唑-3-鎗}氯化物[10]的 [0418] Example 10 Shang 1, I, _ {disulfane diyl bis [2,1-ethane two imino (2-oxo-ethane-2,1-diyl)]} bis { 3-methyl-2- [2- (2,3,6,7-tetrahydro _1Η, 5Η_ pyrido [3,2, l_ij] quinolin-9-yl) ethenyl] -1H- benzo imidazol-gun} -3- chloride [10]

[0419] [0419]

Figure CN101684204BD00531

[0420] 反应流程 [0420] Reaction Scheme

[0421] [0422] 向2,3,6,7_四氢-1Η,5Η-吡啶并[3,2,l_ij]喹啉_9_甲醛(久洛尼定甲醛,12.01 lOmmol)和1,Ρ -{ 二硫烷-二基双[乙烷-2,1-二基亚氨基(2-氧代乙烷-2,1-二基)]}双(2,3-二甲基-1H-苯并咪唑-3-鎗)氯化物(1.49g,2.5mmol)在15ml乙腈乙醇的搅拌溶液中加入0.2ml哌啶作为催化剂。 [0421] [0422] to 2,3,6,7_ tetrahydro -1Η, 5Η- pyrido [3,2, l_ij] quinoline _9_ formaldehyde (julolidine formaldehyde, 12.01 lOmmol) and 1, Ρ - {disulfane - diyl bis [2,1-ethane two imino (2-oxo-ethane-2,1-diyl)]} bis (2,3-dimethyl -1H - benzoimidazol -3- gun) chloride (1.49g, 2.5mmol) was added to a stirred solution of ethanol in 15ml of acetonitrile 0.2ml piperidine as a catalyst. 将反应混合物加热回流24小时。 The reaction mixture was heated at reflux for 24 hours. 冷却后,经过滤收集所得固体后,用乙腈洗涤3次,得到1.45g红色固体。 After cooling, the resulting solid was collected by filtration, washed 3 times with acetonitrile to give 1.45g of a red solid. 分析结果(1H NMR, 13C NMR和MS)与预期的结构[10] 一致。 The results (1H NMR, 13C NMR and MS) and the expected structure [10] the same.

[0423] 染色实施例 [0423] Dyeing Example

[0424] [0424]

Figure CN101684204BD00541

[0425] 实施例1:染色方法-化合物[I]、[2]或[4] [0425] Example 1: Staining Method - compound [I], [2] or [4]

[0426] 组合物A的制备 Preparation [0426] A composition of

[0427] [0427]

Figure CN101684204BD00542

[0428] 组合物B的制备 Preparation [0428] Composition B

Figure CN101684204BD00543

[0430] 使用时,在环境温度下,将组合物A (22.5ml)和组合物B (2.5ml)混匀后,将所得混合物用于Ig天然白发(NW)两束、1g长效卷发的毛发(PW)两束和1g暗色毛发(色调高度4) 一束达20分钟(10分钟后翻转发束后重新浸泡在混合物中)。 [0430] In use, after at ambient temperature, the composition A (22.5ml) and composition B (2.5ml) mixing the resulting mixture of natural hair for Ig (NW) two beams, 1g permanent wave hair (PW) two beams and 1g dark hair (tone height 4) a bunch of up to 20 minutes (10 minutes after the re-soaked flip tresses mixture).

[0431] 用流水冲洗后,用香波洗发,再次冲洗后干燥,观察由此处理的暗色毛发的亮泽:肉眼观察到色调高度4的发束变得比未处理的对照发束明显有光泽。 [0431] After rinsing with running water, with shampoo shampoo, rinse and dry again observed thus treated glossy dark hair: the naked eye to tone height 4 tress than the untreated control becomes clear and shiny hair bundle . 白发发束被染上较强的色度。 Hair tress was infected with a strong color.

[0432]目测: [0432] Visual:

[0433] 在用实施例[1]、[2]和[4]冲洗和洗发期间,无可见的褪色;洗发泡沫和洗发水基本上无色。 [0433] In Example [1], [2] and during [4] wash and shampoo, no visible discoloration; shampoo foam and shampoo essentially colorless.

[0434] 已观察到的颜色被保持,洗后的毛发保持明显的亮泽效果。 [0434] has been observed that the color is maintained, after washing the hair holding significant glossy effect.

[0435] 反射度结果: [0435] reflection of the results:

[0436] 本发明组合物的亮泽功效表示为毛发反射度的函数。 The composition of the invention glossy effect [0436] as a function of the reflectance of the hair. 这些反射度与色调高度TH4的未处理毛发发束的反射度进行了比较。 These reflections of reflectance and color tone height TH4 untreated hair tress were compared.

[0437] 用波长范围为400-700纳米的可见光照射毛发后,通过KONIKA- MINOLTA®,CM3600d分光光度比色计测得反射度。 [0437] The wavelength range of 400-700 nm visible light hair after by KONIKA- MINOLTA®, CM3600d spectrophotometer colorimeter measured reflectance.

[0438] 用染料I处理的TH4发束的反射度曲线,和用染料2和4处理的TH4发束的反射度曲线见图1-图3。 [0438] reflector curve TH4 dye I treated hair bundle, and dye reflectance curves 2 and 4 TH4 treated tress of Figure 1- Figure 3.

[0439] 首先,用本发明组合物处理的毛发发束的反射度大于未处理毛发的反射度。 [0439] First, the reflectance of the hair with the compositions of the present invention, the treated tresses reflectance than the untreated hair. 更特别地,在560nm以上的波长范围内,用染料[I]处理的发束反射度远远大于对照发束的反射度。 More particularly, in a wavelength range of 560nm or more, with a dye [I] tresses treated reflectance of the reflectance is much larger than the control hair tress. 至于染料[2]和[4],在自500nm以上更大的波长范围内反射度更大。 As dye [2] and [4], in the self-500nm wavelength range greater than greater reflectivity. 用这三种化合物处理的发束看起来更有光泽。 Tress treated with these three compounds look more shiny.

[0440] 系统结果: [0440] System Results:

[0441]用 L*a*b* 系统通过MINOLTA® CM3600D 分光比色计(Illuminant D65)评价了发束的颜色。 [0441] spectrophotometric colorimeter (Illuminant D65) evaluated the color of the hair bundle with L * a * b * system by MINOLTA® CM3600D.

[0442] 在LW系统中,L*表示光亮度,a*表示绿/红色轴,b*为蓝/黄色轴。 [0442] In the LW system, L * represents lightness, a * represents the green / red axis, b * is the blue / yellow axis. L的值越大,颜色越亮或越弱。 The greater the value of L, the lighter or weaker color. 相反地,L的值越小,颜色越暗或越强。 Conversely, the smaller the value of L, the darker or stronger. a*的值越大,色度越红,b*的值越大,则色度越黄。 a * value, the more red color, the greater the value of b *, the more yellow color.

[0443] TH4染色发束与清洗发束之间的色彩差异按照下列公式用(ΛΕ)表示: [0443] tress and clean color difference between the TH4 dyed hair bundles in accordance with the following formula (ΛΕ) said:

[0444] [0444]

Figure CN101684204BD00551

[0445] 在这一公式中,L*,a*和b*表示染色前测得的值,L0*,a0*和b/表示染色(或洗发)前测得的值。 [0445] In this equation, L *, a * and b * represents the value measured before dyeing, L0 *, a0 * and b / a value indicating dye (or hair) before measured.

[0446] Λ E值越大,ΤΗ4发束和染色后的发束之间的颜色差异越大。 [0446] Λ E value, the greater the color ΤΗ4 bundles and dyed hair tresses between differences.

[0447] [0447]

Figure CN101684204BD00552

[0449] 上表所示各值表明,即使对暗色毛发(TH4)都获得了可观察到的着色效果,而对于白发则有非常强的着色。 [0449] The values shown in the above table shows that, even on dark hair (TH4) are given a coloring effect can be observed, but there are very strong for hair coloring.

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WO2006/136617A2 Title not available
WO2007/039527A2 Title not available
Non-Patent Citations
Reference
1Yan Wang et al.Synthesis and fluorescence properties of triad compounds with aromatic sulfur bridges.《Dyes and Pigments》.2001,第51卷第127-136页.
Classifications
International ClassificationC09B49/12, C09K11/06, C09B23/14, A61K8/49, A61Q5/10, C09B49/06
Cooperative ClassificationC09B23/102, A61K8/49, A61Q5/065, A61K8/4946, A61K2800/434, C09B23/145, C09B23/146, A61K8/4933, C09B49/12
Legal Events
DateCodeEventDescription
31 Mar 2010C06Publication
12 May 2010C10Request of examination as to substance
25 Jun 2014C14Granted