CN100349886C - 1,3－二羟基苯衍生物和含有这些化合物的染色剂 - Google Patents

1,3－二羟基苯衍生物和含有这些化合物的染色剂 Download PDF

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CN100349886C
CN100349886C CNB028095456A CN02809545A CN100349886C CN 100349886 C CN100349886 C CN 100349886C CN B028095456 A CNB028095456 A CN B028095456A CN 02809545 A CN02809545 A CN 02809545A CN 100349886 C CN100349886 C CN 100349886C
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amino
benzene
dihydroxyl
diamino
hydroxyethyl
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CN1633426A (zh
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劳伦特·查索特
汉斯-于尔根·布朗
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Procter and Gamble Deutschland GmbH
P&G Hair Care Holding Inc
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P&G Clairol Inc
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Priority claimed from DE20108704U external-priority patent/DE20108704U1/de
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    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract

本发明涉及式(I)或(Ia)的1，3-二羟基苯衍生物或其生理上容许的水溶性盐；其中R′1代表取代的吡啶基、嘧啶基或式(IIa)或式(IIIa)基团。本发明还涉及用于角蛋白纤维上的含有所述化合物的染色剂。

Description

1，3-二羟基苯衍生物和含有这些化合物的染色剂
本发明涉及新的间-二羟基苯衍生物和含有这些化合物的用于角蛋白纤维染色的试剂。
在角蛋白纤维染色领域，尤其是头发染色，氧化染料已具有相当的重要性。本文中，通过让某些显色剂在有适当氧化剂存在的情况下与偶合剂反应，以获得染色效果。尤其地，合适的显色剂是2，5-二氨基甲苯、2，5-二氨基苯乙醇、对-氨基苯酚、1，4-二氨基苯和4，5二氨基-1-(2-羟基乙基)-吡唑；合适的偶合剂是，例如，间苯二酚、2-甲基间苯二酚、1-萘酚、3-氨基苯酚、间-苯二胺、2-氨基-4-(2′-羟基乙氧基)氨基苯甲醚、1，3-二氨基-4-(2′-羟基乙氧基)苯和2，4-二氨基-5-氟代甲苯。
用于染发的氧化染料除了能够产生期望强度的染色效果外，还须满足许多其它要求。例如，这些染料从毒物学和皮肤病学角度上讲必须无害，且所获得的染发效果必须有良好的光不褪色性、抗烫发性、酸不褪色性和揉擦不褪色性。然而，在任何情况下，在不暴露在光、摩擦和化学物质的情况下，染色效果必须在至少4至6周的时间内保持稳定。此外，通过与合适的显色剂和偶合剂结合，必须能够产生大范围的不同色彩明暗效果。
已经尝试通过引入取代基来改进间-二羟基苯的性质。例如，在欧洲未审查的专利申请EP 0 904 774和WO未审查的专利申请99/15148中，已知的在4-位取代的间苯二酚。此外，德国未审查的专利申请DE 30 016-905和DE 198 59 800讲授了取代的间-二羟基苯在氧化染发剂中的使用。然而，就目前已知的染色剂来讲，还不能满足对染色剂的全部要求。因此，仍然需要新的偶合剂，该偶合剂能够高度满足前述要求。
我们已发现，某些如式(I)或(Ia)的1，3-二羟基苯衍生物能够高度地满足对偶合剂的要求，并且它们与大多数已知显色剂一起，能产生强大的色彩明暗效果，该效果具有不寻常的色彩强度、光不褪色性和洗涤不褪色性。
因此，本发明的目标是新的如式(I)的1，3-二羟基-4-杂芳基苯衍生物或其生理上容许的水溶性盐
其中
X代表氧、硫或N-R5；
R1和R2可以是相同的或不同的，且各自独立地代表氢、卤原子(F、CI、Br、I)、羟基、C1-C4-烷氧基、C1-C4-羟基烷氧基、C1-C6-烷基、C1-C4-烷基硫醚基、三氟甲基、-Si(CH3)3基、C1-C4-羟基烷基或C2-C4-二羟基烷基；
R3和R4可以是相同的或不同的，且各自独立地代表氢、羟基、卤原子、氰基、C1-C4-烷氧基、C1-C6-烷基、C1-C4-烷基硫醚基、巯基、硝基、氨基、C1-C4-烷氨基、二(C1-C4)烷氨基、-C(O)H基、-C(O)CH3基、-C(O)CF3基、SI(CH3)3基、C1-C4-羟基烷基或C2-C4-二羟基烷基；和
R5代表氢、C1-C6-烷基、C2-C4-羟基烷基、苯基或乙酰基。
式(I)化合物为，例如，下列物质：
1，3-二羟基-4-(噻吩-2-基)苯、1，3-二羟基-4-(1-甲基-1H-吡咯-2-基)苯、1，3-二羟基-4-(吡咯-2-基)苯、1，3-二羟基-4-(呋喃-2-基)苯、1，3-二羟基-4-(3-氨基噻吩-2-基)苯、1，3-二羟基-4-(3-氯噻吩-2-基)苯、1，3-二羟基-4-(3-甲基噻吩-2-基)苯、1，3-二羟基-4-(3-硝基噻吩-2-基)苯、1，3-二羟基-4-(4-氨基噻吩-2-基)苯、1，3-二羟基-4-(4-氯噻吩-2-基)苯、1，3-二羟基-4-(4-甲基噻吩-2-基)苯、1，3-二羟基-4-(4-硝基噻吩-2-基)苯、1，3-二羟基-4-(5-硝基噻吩-2-基)苯、1，3-二羟基-4-(5-氨基噻吩-2-基)苯、1，3-二羟基-4-(5-氯噻吩-2-基)苯、1，3-二羟基-4-(5-甲基噻吩-2-基)苯、1，3-二羟基-4-(5-硝基噻吩-2-基)苯、1，3，5-三羟基-4-(噻吩-2-基)苯、1，2，3-三羟基-4-(噻吩2-基)苯、1，3，6-三羟基-4-(噻吩-2-基)苯、1，3-二羟基-2-甲基-4-(噻吩2-基)苯、1，3-二羟基-5-甲基-4-(噻吩2-基)苯、1，3-二羟基-6-甲基-4-(噻吩2-基)苯、1，3-二羟基-2-氯-4-(噻吩2-基)苯、1，3-二羟基-5-氯-4-(噻吩2-基)苯、1，3-二羟基-6-氯-4-(噻吩2-基)苯、1，3-二羟基-2-甲氧基-4-(噻吩2-基)苯、1，3-二羟基-5-甲氧基-4-(噻吩2-基)苯和1，3-二羟基-6-甲氧基-4-(噻吩2-基)苯。
优选的式(I)化合物是如下化合物，其中(i)R1、R2、R3和R4基团中的一个或多个基团代表氢且X代表硫或氧，或(ii)R1和R2同时代表氢且X代表硫。
本发明的另一个目标是式(Ia)的1，3-二羟基苯衍生物或其生理上容许的水溶性盐
Figure C0280954500081
其中
R′1代表取代的吡啶基、嘧啶基、下式基团
Figure C0280954500082
或下式基团
Figure C0280954500083
其中R′2、R′3、R′4、R′5和R′6各自独立地代表氢、卤原子(F、CI、Br、I)、氰基、羟基、C1-C4-烷氧基、C1-C4-羟基烷氧基、C1-C6-烷基、C1-C4-烷基硫醚基、巯基、硝基、氨基、C1-C4-烷氨基、羟基(C1-C4)烷氨基、二(C1-C4)烷氨基、二[羟基(C1-C4)-烷基]氨基、[二羟基-(C3-C4)-烷基]氨基、[羟基-(C1-C4)-烷基]-C1-C4-烷氨基、三氟甲基、-C(O)H基、-C(O)CH3基、-C(O)CF3基、-Si(CH3)3基、C1-C4-羟基烷基或C2-C4-二羟基烷基，或两个相邻的R2至R6基团形成一个-O-CH2-O-桥；
X′1代表硫、氮、氧、C-R′9或N-R′8；
X′2代表硫、氮、氧、C-R′10或N-R′8；
X′3代表硫、氮、氧、C-R′11或N-R′8；
R′7、R′9、R′10和R′11各自独立地代表氢、卤原子(F、CI、Br、I)、氰基、C1-C4-烷氧基、C1-C6-烷基、C1-C4-烷基硫醚基、巯基、硝基、氨基、C1-C4-烷氨基、二(C1-C4)烷氨基、二(C1-C4-羟基烷基)氨基、C1-C4-羟基烷氨基、三氟甲基、-C(O)CH3基、-C(O)CF3基、-SI(CH3)3基、C1-C4-羟基烷基或C3-C4-二羟基烷基；和
R′8代表氢、C1-C6-烷基、C2-C4-羟基烷基、苯基或乙酰基，
前提条件为X′1至X′3基团中至少一个和至多两个基团代表C-R′9、C-R′10或C-R′11，和X′1至X′3基团中至多一个基团代表硫、氧或N-R′8，且R′1不代表苯基或羟基苯基。
式(Ia)化合物为，例如：
1，3-二羟基-(噻吩-2-基)苯、1，3-二羟基-5-(1-甲基-1H-吡咯-2-基)苯、1，3-二羟基-5-(吡咯-2-基)苯、1，3-二羟基-5-(呋喃-2-基)苯、1，3-二羟基-5-(3-氨基噻吩-2-基)苯、1，3-二羟基-5-(3-氯噻吩-2-基)苯、1，3-二羟基-5-(3-甲基噻吩-2-基)苯、1，3-二羟基-5-(3-硝基噻吩-2-基)苯、1，3-二羟基-5-(4-氨基噻吩-2-基)苯、1，3-二羟基-5-(4-氯噻吩-2-基)苯、1，3-二羟基-5-(4-甲基噻吩-2-基)苯、1，3-二羟基-5-(4-硝基噻吩-2-基)苯、1，3-二羟基-5-(5-硝基噻吩-2-基)苯、1，3-二羟基-5-(5-氨基噻吩-2-基)苯、1，3-二羟基-5-(5-氯噻吩-2-基)苯、1，3-二羟基-5-(5-甲基噻吩-2-基)苯、1，3-二羟基-5-(5-硝基噻吩-2-基)苯[sic-译者]、1，3，5-三羟基-5-(噻吩-2-基)苯、1，2，3-三羟基-5-(噻吩-2-基)苯、1，3，6-三羟基-5-(噻吩-2-基)苯、1，3-二羟基-2-甲基-5(噻吩-2-基)苯、1，3-二羟基-5-甲基-5-(噻吩-2-基)苯、1，3-二羟基-6-甲基-5-(噻吩-2-基)苯、1，3-二羟基-2-氯-5-(噻吩-2-基)苯、1，3-二羟基-5-氯-5-(噻吩-2-基)苯、1，3-二羟基-6-氯-5-(噻吩-2-基)苯、1，3-二羟基-2-甲氧基-5-(噻吩-2-基)苯、1，3-二羟基-5-甲氧基-5-(噻吩-2-基)苯、1，3-二羟基-6-甲氧基-5-(噻吩-2-基)苯、1，3-二羟基-2-(噻吩-2-基)苯、1，3-二羟基-2-(1-甲基-1H-吡咯-2-基)苯、1，3-二羟基-2-(吡咯-2-基)苯、1，3-二羟基-2-(呋喃-2-基)苯、1，3-二羟基-2-(3-氨基噻吩-2-基)苯、1，3-二羟基-2-(3-氯噻吩-2-基)苯、1，3-二羟基-2-(3-甲基噻吩-2-基)苯、1，3-二羟基-2-(3-硝基噻吩-2-基)苯、1，3-二羟基-2-(4-氨基噻吩-2-基)苯、1，3-二羟基-2-(4-氯噻吩-2-基)苯、1，3-二羟基-2-(4-甲基噻吩-2-基)苯、1，3-二羟基-2-(4-硝基噻吩-2-基)苯、1，3-二羟基-2-(5-硝基噻吩-2-基)苯、1，3-二羟基-2-(5-氨基噻吩-2-基)苯、1，3-二羟基-2-(5-氯噻吩-2-基)苯、1，3-二羟基-2-(5-甲基噻吩-2-基)苯、1，3-二羟基-2-(5-硝基噻吩-2-基)苯[sic-译者]、1，3，5-三羟基-2-(噻吩-2-基)苯、1，2，3-三羟基-2-(噻吩-2-基)苯、1，3，6-三羟基-2-(噻吩-2-基)苯、1，3-二羟基-2-甲基-2-(噻吩-2-基)苯、1，3-二羟基-5-甲基-2-(噻吩-2-基)苯、1，3-二羟基-6-甲基-2-(噻吩-2-基)苯、1，3-二羟基-2-氯-2-(噻吩-2-基)苯、1，3-二羟基-5-氯-2-(噻吩-2-基)苯、1，3-二羟基-6-氯-2-(噻吩-2-基)苯、1，3-二羟基-2-甲氧基-2-(噻吩-2-基)苯、1，3-二羟基-5-甲氧基-2-(噻吩-2-基)苯、1，3-二羟基-6-甲氧基-2-(噻吩-2-基)苯、1，3-二羟基-4-(吡啶-2-基)苯、1，3-二羟基-4-(嘧啶-2-基)苯、1，3-二羟基-4-(5-甲基吡啶-2-基)苯、5-(2，4-二羟基苯基)烟碱腈、1，3-二羟基-4-(5-硝基吡啶-2-基)苯、1，3-二羟基-4-(噻吩-3-基)苯、4′-甲基二苯基-2，4-二酚、4′-氟二苯基-2，4-二酚、1，3-二羟基-4-(4-甲基噻吩-3-基)苯、2′，4′-二羟基二苯基-4-腈、1，3-二羟基-4-(2-氯噻吩-3-基)苯、1-(2′-4′-二羟基二苯基-3-基)、1，3-二羟基-4-苯并[1，3]二茂-5-基苯、4′-硝基二苯基-2，4-二酚、2′-硝基二苯基-2，4-二酚、4-(5-硝基噻吩-2-基)苯、4′-三氟甲基二苯基-2，4-二酚、2′4′-二甲基二苯基-2，4-二酚、3′-甲氧基二苯基-2，4-二酚、4′-氯二苯基-2，4-二酚、1，3-二羟基-5-(吡啶-2-基)苯、1，3-二羟基-5-(嘧啶-2-基)苯、1，3-二羟基-5-(噻吩-3-基)苯、5-噻吩-2-基苯、1，3-二羟基-(5-噻唑-2-基)苯、4′-甲基二苯基-3，5-二酚、1，3-二羟基-5-(5-甲基吡啶-2-基)苯、4′-氟二苯基-3，5-二酚、1，3-二羟基-5-(4-甲基噻吩-3-基)苯、3′，5′-二羟基二苯基-4-腈、1，3-二羟基-5-(2-氯噻吩-3-基)苯、1-(3′，5′-二羟基二苯基-3-基)乙酮、4′-硝基二苯基-3，5-二酚、2′-硝基二苯基-3，5-二酚、4′-三氟甲基二苯基-3，5-二酚、2′，4-′二甲基二苯基-3，5-二酚、3′-甲氧基二苯基-3，5-二酚、4′-氯二苯基-3，5-二酚、1，3-二羟基-5-(5-硝基吡啶-2-基)苯、4′-甲基硫烷基二苯基-3，5-二酚、2′-氯-4′-硝基二苯基-3，5-二酚、4′-甲基硫烷基二苯基-2，4-二酚和1，3-二羟基-4-(噻唑-2-基)苯，
以及其生理上容许的盐。
优选的式(I)化合物是如下化合物，其中：
(i)X′2代表C-R′10和X′1代表硫和X′3代表C-R′11，或X′1代表C-R′9和X′3代表硫或(ii)X′2代表C-R′10和X′1代表硫和X′3代表C-R′11或X′1代表C-R′9和X′3代表硫，且R′9至R′11基团中至少一个基团代表氢。
尤其优选的是下列式(I)和式(Ia)化合物：
1，3-二羟基-4-(噻吩-2-基)苯、1，3-二羟基-4-(5-硝基噻吩-2-基)苯、1，3-二羟基-4-(3-甲基噻吩-2-基)苯、1，3-二羟基-4-(呋喃-2-基)苯、1，3-二羟基-5-(5-氯噻吩-2-基)苯、1，3-二羟基-5-(3-甲基噻吩-2-基)苯、1，3-二羟基-4-(噻吩-3-基)苯和1，3-二羟基-5-(噻吩-3-基)苯
以及其生理上容许的盐。
可通过已知的合成方法制备式(I)和式(Ia)的1，3-二羟基苯衍生物。本发明化合物的合成可通过如下方法完成：在钯(O)催化下偶合(i)式(II)的取代苯和式(III)的杂芳香基化合物或(ii)式(IIa)的取代苯和式R′1-Rd的化合物，紧接着消除保护基团：
Figure C0280954500111
其中
Rb代表卤原子(F、Cl、Br、I)和Rd代表B(OH)2或Rb代表B(OH)2和Rd代表卤原子(F、Cl、Br、I)；Ra代表如“有机合成”(Organic System)，Wiley Interscience，1991中第3章“保护基团”(Protective Groups)中所描述的保护基团，且X、R1、R2、R3、R4和R′1具有与式(I)和式(Ia)中相同的含义。
式(I)和式(Ia)的1，3-二羟基苯衍生物是高度水溶性的，并且染色效果具有极好的色彩强度和稳定性，尤其是光不褪色性、洗不褪色性和揉擦不褪色性。尤其是作为下述的氧化着色剂的组分来讲，它们还具有极好的贮存稳定性。
因此，本发明的另一个目标是用于角蛋白纤维的氧化染色剂，例如，毛发、皮毛、羽毛或羊毛，尤其是人的头发，该目标基于显色剂-偶合剂的组合物，该组合物含有至少一种式(I)或式(Ia)的1，3-二羟基苯衍生物，并且其中在式(Ia)中R′1除具有前述的含义外，还可代表苯基或羟基苯基。
式(I)和式(Ia)化合物可作为游离的苯酚使用，且以其与无机或有机碱(如氢氧化钠、氢氧化钾、碳酸钠或氢氧化四丁基铵)的生理上容许的盐的形式使用。
式(I)和/或式(Ia)的1，3-二羟基苯衍生物在本发明的着色剂中的总存在量，以重量计为约0.005％至20％、约0.01％至5.0％，和尤其优选地0.1％至2.5％。
合适的显色剂为，例如，
1，4-二氨基苯(对-苯二胺)、1，4-二氨基-2-甲苯(对-甲代苯二胺)、1，4-二氨基-2，6-二甲苯、1，4-二氨基-3，5-二乙苯、1，4-二氨基-2，5-二甲苯、1，4-二氨基-2，3-二甲苯、2-氯-1，4-二氨基苯、1，4-二氨基-2-(噻吩-2-基)苯、1，4-二氨基-2-(噻吩-3-基)苯、1，4-二氨基-2-(吡啶-3-基)苯、2，5-二氨基联苯、1，4-二氨基-2-甲氧基甲苯、1，4-二氨基-2-氨基甲苯、1，4-二氨基-2-羟基甲苯、1，4-二氨基-2-(2-羟基乙氧基苯、2-[2-(乙酰胺基)乙氧基]-1，4-二氨基苯、4-苯基氨基苯胺、4-二甲基氨基苯胺、4-二乙基氨基苯胺、4-二丙基氨基苯胺、4-[乙基-(2-羟基乙基)氨基]苯胺、4-[二-(2-羟基乙基)氨基]苯胺、4-[二(2-羟基乙基)氨基]-2-甲基苯胺、4-[(2-甲氧基乙基)氨基]苯胺、4-[(3-羟丙基)氨基]苯胺、4-[(2，3-二羟基丙基)氨基]苯胺、1，4-二氨基-2-(1-羟基乙基)苯、1，4-二氨基-2-(2-羟基乙基)苯、1，4-二氨基-2-(1-甲基乙基)苯、1，3-双-[(4-氨基苯基)-(2-羟基乙基)氨基]-2-丙醇、1，4-双-[(4-氨基苯基)氨基]丁烷、1，8-双(2，5-二氨基苯氧基)-3，6-二氧杂辛烷、4-氨基苯酚、4-氨基-3-甲基苯酚、4-氨基-3-(羟甲基)苯酚、4-氨基-3-氟苯酚、4-甲基氨基苯酚、4-氨基-2-(氨基甲基)苯酚、4-氨基-2-(羟甲基)苯酚、4-氨基-2-氟苯酚、4-氨基-2-[(2-羟基乙基)氨基]甲酚、4-氨基-2-甲酚、4-氨基-2-(甲氧基甲基)苯酚、4-氨基-2-(2-羟基乙基)苯酚、5-氨基水杨酸、2，5-二氨基吡啶、2，4，5，6-四氨基嘧啶、2，5，6-三氨基-4-(1H)-嘧啶酮、4，5-二氨基-1-(2-羟基乙基)-1H-吡唑、4，5-二氨基-1-(1-甲基乙基)-1H-吡唑、4，5-二氨基-1-[4-甲基苯基]甲基]-1H-吡唑、1-[(4-氯苯基)-甲基]-4，5-二氨基-1H-吡唑、4，5-二氨基-1-甲基-1H-吡唑、2-氨基苯酚、2-氨基-6-甲酚、2-氨基-5-甲酚和1，2，4-三羟基苯。
除式(I)和/或式(Ia)化合物外，本发明的着色剂还可含有其他偶合剂，例如
N-(3-二甲基氨苯基)脲、2，6-二氨基吡啶、2-氨基-4-[(2-羟基乙基)-氨基]苯甲醚、2，4-二氨基-1-氟-5-甲苯、2，4-二氨基-1-甲氧基-5-甲苯、2，4-二氨基-1-乙氧基-5-甲苯、2，4-二氨基-1-(2-羟基乙氧基-5-甲苯、2，4-二[2-羟基乙基)氨基]-1，5-二甲氧基苯、2，3-二氨基-6-甲氧基吡啶、3-氨基-6-甲氧基-2-(甲氨基)吡啶、2，6-二氨基-3，5-二甲氧基吡啶、3，5-二氨基-2，6-二甲氧基吡啶、1，3-二氨基苯、2，4-二氨基-1-(2-羟基乙氧基)苯、1，3-二氨基-4-(2，3-二羟基丙氧基)苯、1，3-二氨基-4-(3-羟基丙氧基)苯、1，3-二氨基-4-(2-甲氧基乙氧基)-苯、2，4-二氨基-1，5-二(2-羟基乙氧基)苯、1-(2-氨基乙氧基)-2，4-二氨基苯、2-氨基-1-(2-羟基乙氧基)-4-甲基氨基苯、2，4-二氨基苯氧基乙酸、3-[二(2-羟基乙基)氨基]苯胺、4-氨基-2-二[2-羟基乙基)氨基]-1-乙氧基苯、5-甲基-2-(1-甲基乙基)苯酚、3-[(2-羟基乙基)氨基]苯胺、3-[(2-氨基乙基)氨基]苯胺、1，3-二(2，4-二氨基苯氧基)丙烷、二(2，4-二-氨基苯氧基)甲烷、1，3-二氨基-2，4-二甲氧基苯、2，6-双(羟基乙基)氨基甲苯、4-羟基吲哚、3-二甲基氨基苯酚、3-二乙基氨基苯酚、5-氨基-2-甲酚、5-氨基-4-氟-2-甲酚、5-氨基-4-甲氧基-2-甲酚、5-氨基-4-乙氧基-2-甲酚、3-氨基-2，4-二氯苯酚、5-氨基-2，4-二氯苯酚、3-氨基-2-甲酚、3-氨基-2-氯-6-甲酚、3-氨基苯酚、2-[(3-羟基苯基)氨基]乙酰胺、5-[(2-羟基乙基)氨基]-4-甲氧基-2-甲酚5-[(2-羟基乙基)氨基]-2-甲酚、3-[(2-羟基乙基)氨基]苯酚、3-[(2-甲氧基乙基)氨基]苯酚、5-氨基-2-乙基苯酚、5-氨基-2-甲氧基苯酚、2-(4-氨基-2-羟基苯氧基)乙醇、5-[(3-羟丙基)氨基]-2-甲酚、3-[(2，3-二羟基丙基)氨基]-2-甲酚、3-[(2-羟基乙基)氨基]-2-甲酚、2-氨基-3-羟基吡啶、2，6-二羟基-3，4-二甲基吡啶、5-氨基-4-氯-2-甲酚、1-萘酚、2-甲基-1-萘酚、1，5-二羟基萘、1，7-二羟基萘、2，3-二羟基萘、2，7-二羟基萘、2-甲基-1-萘酚乙酸酯、1，3-二羟基苯、1-氯-2，4-二羟基苯、2-氯-1，3-二羟基苯、1，2-二氯-3，5二羟基-4-甲苯、1，5-二氯-2，4-二羟基苯、1，3-二羟基-2-甲苯、3，4-亚甲基二氧苯酚、3，4-亚甲基二氧苯胺、5-[(2-羟基乙基)氨基]-1，3-苯并间二氧杂环戊烯、6-溴-1-羟基-3，4-亚甲基二氧苯、3，4-二氨基苯甲酸、3，4-二氢-6-羟基-1，4(2H)-苯并嗪、6-氨基-3，4-二氢-1，4[2H]苯并嗪、3-甲基-1-苯基-5-吡唑啉酮、5，6-二羟基吲哚、5，6-二羟基二氢吲哚、5-羟基吲哚、6-羟基吲哚、7-羟基吲哚和2，3-二氢吲哚二酮。
偶合剂和显色剂在本发明的着色剂中可单独存在或者相互混合，本发明的着色剂中的每种偶合剂和显色刺按重量计为约0.005％至20％、优选为约0.01％至5％，和尤其优选为0.1％至2.5％(基于着色剂的总量)。
本发明所述的着色剂含有的显色剂-偶合剂组合物的总量，按重量计优选为约0.01％至20％、约0.02％至10％，和尤其优选为0.2％至6％。通常，显色剂和偶合剂以大约等量使用。但是，从这方面讲，如果显色剂有些过量或不足，都不会不合适。
此外，本发明的着色剂还可含有其他染料组分，例如6-氨基-2-甲酚和2-氨基-5-甲酚，以及来自下列物质的常见直接染料：酸性或碱性染料、三苯基甲烷染料、芳香硝基染料、偶氮染料和分散染料。本发明的着色剂可含有的这些染料组分的量按重量计为约0.1％至4％。
如果附加的偶合剂和显色剂和其他染料组分是碱，其也可以与有机或无机酸(如盐酸或硫酸)的生理上容许的盐的形式使用，或如果它们含芳香OH基则其与例如碱的盐的形式使用。
此外，如果本发明的着色剂用于染发，它们还可包含其他常见的化妆品添加剂，例如抗氧化剂(如抗坏血酸)、巯基乙酸或亚硫酸钠，以及香料油、配合剂、湿润剂、乳化剂、增稠剂和护发剂。
本发明的着色剂可以是，例如溶液的形式，尤其是含水或含水-醇的溶液。但是，尤其优选的制剂形式是霜膏、凝胶或乳液。该组合物由染料组分和用于该组合物的常见添加剂的混合物组成。
溶液、霜膏、乳液或凝胶的常见添加剂为，例如，溶剂(如水)，低级脂肪醇(例如乙醇、丙醇或异丙醇)，甘油或二元醇(如1，2-丙二醇)，还有来自阴离子的、阳离子的、中性的或非离子的表面活性物质的湿润剂或乳化剂，例如，硫酸脂肪酯、乙氧基化的硫酸脂肪酯、烷基磺酸酯、烷基苯磺酸、烷基三甲基铵盐、烷基甜菜碱、乙氧基化的脂肪醇、乙氧基化的壬基苯酚、脂肪酸链烷醇酰胺和乙氧基化的脂肪酯，还有增稠剂如高级脂肪醇、淀粉、纤维素衍生物、凡士林、石蜡油和脂肪酸，以及头发护理剂如阳离子树脂、羊毛脂衍生物、胆固醇、泛酸和甜菜碱。所述组分以通常用于此目的的量使用，例如按重量计，湿润剂和乳化剂的浓度为约0.5％至30％，增稠剂为约0.1％至30％和头发护理剂为约0.1％至5％。
本发明的着色剂根据组合物而定，可以是弱酸性、中性或碱性。尤其，它的pH值为6.5至11.5。优选使用氨水将pH值调至碱性，但也可使用有机胺，例如一乙醇胺和三乙醇胺，或无机碱如氢氧化钠和氢氧化钠。适于调至酸性pH值的为无机或有机酸，例如磷酸、乙酸、柠檬酸或酒石酸。
为了对头发氧化染色，前述着色剂在使用前与氧化剂混合，然后将所得混合物应用到头发上以达到染发效果，应用的量根据头发情况而定，通常为约60至200克。
用于研发染发效果的合适的氧化剂主要为过氧化氢或其加入尿素、三聚氰胺、硼酸钠或碳酸钠的产物，其形式为3％至12％。优选6％的水溶液，大气中的氧也是合适的氧化剂。当使用6％的过氧化氢溶液作为氧化剂时，染发剂与氧化剂的重量比为5∶1至1∶2，但优选为1∶1。主要在染发剂中染料浓度较高或想要获得较强头发漂白效果时，使用较大量的氧化剂。让混合物在15至50C下在头发上作用约10至45分钟，优选30分钟，之后用水冲洗头发并干燥。任选地，冲洗之后用洗发香波漂洗头发，和任选地用弱有机酸漂洗，例如柠檬酸或酒石酸。然后干燥头发。
含式(I)和/或式(Ia)的1，3-二羟基苯衍生物的本发明着色剂，染色效果具有极好的色彩稳定性，尤其是光不褪色性、洗不褪色性和揉擦不褪色性。就其染色特性而言，本发明的染发剂能产生大范围的不同色彩明暗效果，从金黄到棕色、紫色、紫罗兰色以及甚至蓝色和黑色，具体根据染料组分的种类和组合物而定。值得注意的是色彩明暗效果，因为其具有不同寻常的色彩强度。还能证明本专利申请的染发剂具有非常良好的染色特性的是，本着色剂能对灰白头发染色，并且染之前无造成损害的化学处理，不会出现任何问题并且具有良好的覆盖力。
下面的实施例更加详细地举例说明了本发明的目标，而不是限制本发明的范围。
实施例
实施例1 1，3-二羟基苯的合成
        (普通合成方法)
A.2-[2-溴-5-(四氢-2H-吡喃-2-基氧)苯氧基]四氢-2H-吡喃的合成
在氩气下，向在50mL二氯甲烷中溶有9.5g(40mmol)4-溴-1，3-二羟基苯和5g(20mmol)甲苯-4-磺酸吡啶盐的溶液中逐滴加入9g(105mmol)3，4-二氢-2H-吡喃。搅动该反应混合物18小时。然后将反应混合物倒入100mL的乙酸乙酯中，并用稀释的氢氧化钠萃取有机相，然后用硫酸镁进行干燥。在旋转蒸发器中蒸馏掉溶剂，然后在硅胶上用石油醚/乙酸乙酯(7∶1)提纯该残余物。
这生成了9.5g(54％的理论产物)的2-[2-溴-5-(四氢-2H-吡喃-2-基氧)苯氧基]四氢-2H-吡喃。
B.2-{2-(4，4，5，5-四甲基[1，3，2]二氧硼杂环-2-基)-5-(四氢-2H-吡喃-2-基氧)苯氧基}四氢-2H-吡喃的合成
在氩气下，将210mL脱气二烷加入来自步骤A的5.5g(154mmol)2-[2-溴-5-(四氢-2H-吡喃-2-基氧)苯氧基]四氢-2H-吡喃、9g(355mmol)4，4，5，5，4′，4′，5′，5′-八甲基[2，2′]二{[1，3，2]二氧硼杂环基}、1,5g(2.2mmol)二氯-1，1′双(二苯基膦基)二茂铁]钯[PdCl2(dppf)]和6.2g(63.2mmol)乙酸钾的混合物中。在80℃下搅动该混合物24小时，然后倒入水中并用乙酸乙酯萃取。用饱和氯化钠水溶液洗该有机相，经过硫酸钠干燥，然后过滤并蒸发。所得的粗产物在钝化的硅胶上使用己烷(100％)和己烷/乙酸乙酯(9∶1至3∶2)梯度进行提纯。
这生成了4.70g(77％的理论产物)2-{2-(4，4，5，5-四甲基-[1，3，2]二氧硼杂环-2-基)-5-(四氢-2H-吡喃-2-基氧}苯氧基}四氢-2H-吡喃。
C.式(I)的1，3-二羟基苯的合成
在氩气下，将来自步骤B的0.09g(0.2mmol)2-{2-(4，4，5，5-四甲基[1，3，2]二氧硼杂环-2-基)-5(四氢-2H-吡喃-2-基氧)苯氧基}四氢-2H-吡喃和0.04mmol适当的溴衍生物溶解于10mL 1，2-二甲氧基乙烷中。然后，加入0.01g(0.005mmol)四(三苯基膦)钯和0.26mL 2N碳酸钾溶液，并将反应混合物加热至80℃。在反应的末期，将反应混合物倒入10mL乙酸乙酯中，用稀释的氢氧化钠溶液萃取有机相，并用硫酸镁干燥。在旋转蒸发器中蒸馏掉溶剂，然后在硅胶上用石油醚/乙酸乙酯(9∶1)提纯该残余物。
a.1，3-二羟基-4-(苯硫基-2-基)苯[sic-译者]
所用的溴衍生物：2-溴噻吩
质谱：MH+192(100)
b.1，3-二羟基-4-(5-硝基噻吩-2-基)苯
所用的溴衍生物：2-溴-5-硝基噻吩
质谱：MH+237(100)
c.1，3-二羟基-4-(3-甲基噻吩-2-基)苯
所用的溴衍生物：2-溴-3-甲基噻吩
质谱：MH+206(100)
d.1，3-二羟基-4-(吡啶-2-基)苯盐酸盐
所用的溴衍生物：2-溴吡啶
质谱：MH+188(100)
e.1，3-二羟基-4-(吡啶-2-基)苯盐酸盐
所用的溴衍生物：2-溴吡啶
质谱：MH+189(100)
f.1，3-二羟基-4-(5-甲基吡啶-2-基)苯盐酸盐
所用的溴衍生物：2-溴-5-甲基吡啶
质谱：MH+188(100)
g.5-(2，4-二羟基苯基)烟碱腈盐酸盐
所用的溴衍生物：3-溴-5-甲基吡啶
质谱：MH+213(100)
h.1，3-二羟基-4(5-硝基吡啶-2-基)苯盐酸盐
所用的溴衍生物：2-溴-5-硝基吡啶
质谱：MH+233(100)
i.1，3-二羟基-4(噻吩-3-基)苯
所用的溴衍生物：3-溴噻吩
质谱：MH+193(100)
j.4′甲基二苯基-2，4-二酚
所用的溴衍生物：4-溴甲苯
质谱：MH+201(100)
k.二苯基-2，4，4′-三酚
所用的溴衍生物：4-溴苯酚
质谱：MH+203(100)
l.二苯基-2，4，3′-三酚
所用的溴衍生物：3-溴苯酚
质谱：MH+203(100)
m.4′-氟二苯基-2，4-二酚
所用的溴衍生物：4-溴氟苯
质谱：MH+205(100)
n.1，3-二羟基-4-(4-甲基噻吩-3-基)苯
所用的溴衍生物：3-溴-4-甲基噻吩
质谱：MH+207(100)
o.2′，4′-二羟基二苯基-4-腈
所用的溴衍生物：4-溴苯基腈
质谱：MH+206(100)
p.1，3-二羟基-4-(2-氯噻吩-3-基)苯
所用的溴衍生物：3-溴-2-氯噻吩
质谱：MH+227(100)
q.1-(2′，4′-二羟基二苯基-3-基)乙酮
所用的溴衍生物：5-溴苯乙酮
质谱：MH+229(100)
r.1，3-二羟基-4(苯并[1，3]二茂-5-基)苯
所用的溴衍生物：5-溴-1，3-亚甲基二羟苯
质谱：MH+231(100)
s.4′-硝基二苯基-2，4-二酚
所用的溴衍生物：4-溴硝基苯
质谱：MH+232(100)
t.2′-硝基二苯基-2，4-二酚
所用的溴衍生物：2-溴硝基苯
质谱：MH+232(100)
u.4′-三氟甲基二苯基-2，4-二酚
所用的溴衍生物：4-溴三氟甲苯
质谱：MH+255(100)
v.2′，4′-二甲基二苯基-2，4-二酚
所用的溴衍生物：2-溴-5-甲基甲苯
质谱：MH+215(100)
w.3′-甲氧基二苯基-2，4-二酚
所用的溴衍生物：5-溴苯甲醚
质谱：MH+217(100)
x.4′-氯二苯基-2，4-二酚
所用的溴衍生物：4-溴氯苯
质谱：MH+221(100)
y.4′-甲基硫烷基二苯基-2，4-二酚
所用的溴衍生物：4-甲基硫烷基溴苯
质谱：MH+233(100)
z.1，3-二羟基-4-(噻唑-2-基)苯
所用的溴衍生物：2-溴噻唑
质谱：MH+94(100)
实施例2：1，3-二羟基苯的合成
该合成由实施例1中步骤C的方法完成。
a.1，3-二羟基-5-(吡啶-2-基)苯盐酸盐
所用的溴衍生物：3-溴吡啶
质谱：MH+188(100)
b.1，3-二羟基-5-(吡啶-2-基)苯盐酸盐
所用的溴衍生物：2-溴吡啶
质谱：MH+189(100)
c.1，3-二羟基-5-(噻吩-3-基)苯
所用的溴衍生物：3-溴噻吩
质谱：MH+193(100)
d.1，3-二羟基-5-(噻吩-2-基)苯
所用的溴衍生物：2-溴噻吩
质谱：MH+192(100)
e.1，3-二羟基-5-(噻唑-2-基)苯
所用的溴衍生物：2-溴噻唑
质谱：MH+94(100)
f.4′-甲基二苯基-2，4-二酚
所用的溴衍生物：4-溴甲苯
质谱：MH+201(100)
g.1，3-二羟基-4-(5-甲基吡啶-2-基)苯盐酸盐
所用的溴衍生物：2-溴-5-甲基吡啶
质谱：MH+188(100)
h.二苯基-3，5，4′-三酚
所用的溴衍生物：4-溴苯酚
质谱：MH+203(100)
i.二苯基-3，5，3′-三酚
所用的溴衍生物：3-溴苯酚
质谱：MH+203(100)
j.4′-氟二苯基-3，5-二酚
所用的溴衍生物：4-溴氟苯
质谱：MH+205(100)
k.1，3-二羟基-5-(3-甲基噻吩-2-基)苯
所用的溴衍生物：2-溴-3-甲基噻吩
质谱：MH+206(100)
l.1，3-二羟基-5-(4-甲基噻吩-3-基)苯
所用的溴衍生物：3-溴-4-甲基噻吩
质谱：MH+207(100)
m.3′，5′-二羟基-5-(4-甲基噻吩-2-基)苯
所用的溴衍生物：2-溴-3-甲基噻吩
质谱：MH+206(100)
n.1，3-二羟基-5(2-氯噻吩-3-基)苯
所用的溴衍生物：3-溴-2-氯噻吩
质谱：MH+227(100)
o.1，(2′，4′-二羟基二苯基-3-基)乙酮
所用的溴衍生物：3-溴苯乙酮
质谱：MH+229(100)
p.1，3-二羟基-4-(苯并[1，3]二茂-5-基)苯
所用的溴衍生物：5-溴-1，3-亚甲基二羟苯
质谱：MH+231(100)
q.4′-硝基二苯基-2，4-二酚
所用的溴衍生物：4-溴硝基苯
 质谱：MH+232(100)
r.2′-硝基二苯基-2，4-二酚
所用的溴衍生物：2-溴硝基苯
质谱：MH+232(100)
s.1，3-二羟基-5-(5-硝基噻吩-2-基)苯
所用的溴衍生物：2-溴-5-硝基噻吩
质谱：MH+237(100)
t.4′-三氟甲基二苯基-3，5-二酚
所用的溴衍生物：4-溴三氟甲苯
质谱：MH+255(100)
u.2′4′-二甲基二苯基-3，5-二酚
所用的溴衍生物：2-溴-5-甲基甲苯
质谱：MH+215(100)
v.3′-甲氧基二苯基-2，4-二酚
所用的溴衍生物：5-溴苯甲醚
质谱：MH+217(100)
w.4′-氯二苯基-2，4-二酚
所用的溴衍生物：4-溴氯苯
质谱：MH+221(100)
x.4′-甲基硫烷基二苯基-2，4-二酚
所用的溴衍生物：4-甲基硫烷基溴苯
质谱：MH+233(100)
y.2′-氯-4′-硝基二苯基-3，5-二酚
所用的溴衍生物：4-溴-3-氯硝基苯
质谱：MH+266(100)
实施例3至53    染发剂
制备有下列组合物的染发剂溶液：
1.25mmol  式(I)/(Ia)偶合剂，按照表1
1.25mmol  显色剂，按照表1
1.0g      油酸钾(8％水溶液)
1.0g    氨水(22％水溶液)
1.0g    乙醇
0.3g    抗坏血酸
加入100.0g水中
使用之前，将50g前述染色溶液与50g 6％的过氧化氢水溶液混合。然后将该混合物应用到漂白的头发上。在40℃下作用30分钟后，用水冲洗头发，然后用市售洗发香波漂洗并干燥。所得的色彩明暗效果如表1所示。
表1
    实施例序列号 式(I)/(Ia)偶合剂                             偶合剂[sic-译者]
I.1，4-二-氨基-苯   II.2，5-二氨基-甲苯硫酸盐 III.2，5-二氨基-苯乙醇硫酸酯 IV.4，5-二氨基-1-(2′-羟乙基)吡唑硫酸盐
    34567891011121 314 按照实施例1a按照实施例1b按照实施例1c按照实施例1d按照实施例1e按照实施例1f按照实施例1g按照实施例1h按照实施例1i按照实施例1j按照实施例1k按照实施例1l 暗棕色棕色棕色中等金黄色中等金黄色中等金黄色中等金黄色中等金黄色中等金黄色中等金黄色中等金黄色棕色紫色   暗棕色中等金黄色中等金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色金黄色亮金黄色亮金黄色亮棕紫色 暗棕色中等金黄色中等金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色金黄色亮金黄色亮金黄色亮棕紫色 紫色紫色紫色亮紫色亮紫色亮紫色亮紫色亮紫色亮紫色亮紫色亮紫色紫色
表1(续)
    1516171819202122232425262728     按照实施例1m按照实施例1n按照实施例1o按照实施例1p按照实施例1q按照实施例1r按照实施例1s按照实施例1t按照实施例1u按照实施例1v按照实施例1w按照实施例1x按照实施例1y按照实施例1z 中等金黄色中等金黄色中等金黄色中等金黄色中等金黄色中等金黄色中等金黄色中等金黄色中等金黄色中等金黄色中等金黄色中等金黄色中等金黄色灰色 亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮蓝色     亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮蓝色   亮紫色亮紫色亮紫色亮紫色亮紫色亮紫色亮紫色亮紫色亮紫色亮紫色亮紫色亮紫色亮紫色紫罗兰色
表1(续)
    2930313233343536373839404142     按照实施例2a按照实施例2b按照实施例2c按照实施例2d按照实施例2e按照实施例2f按照实施例2g按照实施例2h按照实施例2i按照实施例2j按照实施例2k按照实施例2l按照实施例2m按照实施例2n 金黄色金黄色金黄色金黄色金黄色金黄色金黄色金黄色金黄色金黄色金黄色金黄色金黄色金黄色     亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色     亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色     亮橙色亮橙色亮橙色亮橙色亮橙色亮橙色亮橙色亮橙色亮橙色亮橙色亮橙色亮橙色亮橙色亮橙色
表1(续)
    4344454647484950515253     按照实施例2o按照实施例2p按照实施例2q按照实施例2r按照实施例2s按照实施例2t按照实施例2u按照实施例2v按照实施例2w按照实施例2x按照实施例2y 金黄色金黄色金黄色金黄色金黄色金黄色金黄色金黄色金黄色金黄色金黄色 亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色 亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色亮金黄色     亮橙色亮橙色亮橙色亮橙色亮橙色亮橙色亮橙色亮橙色亮橙色亮橙色亮橙色
实施例54至63染发剂
制备下列组合物的染发剂溶液：
Xg    1，3-二羟基-5-(苯硫基-2-基)苯(偶合剂K1)
[sic-译者]
Ug    显色剂E8至E15，按照表2
Yg    偶合剂K11至K33，按照表3
Zg    直接染料D2或D3，按照表4
10.0g 油酸钾(8％的水溶液)
10.0g 氨水(22％的水溶液)
0.3g  抗坏血酸
加入100.0g水中
使用之前，将30g前述染色溶液与30g 6％的过氧化氢水溶液混合。然后将该混合物应用到漂白的头发上。在40℃下作用30分钟后，用水冲洗头发，然后用市售洗发香波漂洗并干燥。染色效果如表5所示。
表2-显色剂
E8    1，4-二氨基苯
E9    2，5-二氨基苯乙醇硫酸酯
E10   3-甲基-4-氨基苯酚
E11   4-氨基-2-氨基甲酚二盐酸盐
E12   4-氨基苯酚
E13   N，N-双(2′-羟基乙基)-对-苯二胺硫酸盐
E14   4，5-二氨基-1-(2′-羟基乙基)吡唑硫酸盐
E15   2，5-二氨基甲苯硫酸盐
表3-偶合剂
K1    1，3-二羟基-5-(苯硫基-2-基)苯[sic-译者]
K2    1，3-二羟基-4-(苯硫基-2-基)苯[sic-译者]
K12   2-氨基-4-(2′-羟基乙基)氨基苯甲醚硫酸盐
K13   1，3-二氨基-4-(2′-羟基乙氧基)苯硫酸盐
K18   N-(3-二甲基氨基)苯基尿素
K19   1，3-双(2，4-二氨基苯氧基)丙烷四盐酸盐
K21   3-氨基苯酚
K22   5-氨基-2-甲酚
K23   3-氨基-2-氯-6-甲酚
K24   5-氨基-4-氟-2-甲酚硫酸盐
K25   1-萘酚
K26   1-乙酰氧基-2-甲基萘
K31   1，3-二羟基苯
K32   2-甲基-1，3-二羟基苯
K33   1-氯-2，4-二羟基苯
表4-直接染料
D2    6-氯-2-乙基氨基-4-硝基苯酚
D3    2-氨基-6-氯-4-硝基苯酚
表5-染发剂
 实施例序列号     54   55   56   57   58   59
 染料                              染料的量，单位：克
 K1     0.10   0.10   0.13   0.15   0.20   0.10
 E8E9E15K12K12[sic-译者]K13K18K19K13[sic]K31K32K33K21K22K23     0.300.050.050.05 0.250.100.100.050.05 0.300.160.160.100.05 0.250.150.150.050.10 0.250.150.150.10 0.300.150.150.10
 染色效果     金黄色   金黄色   金黄色   金黄色   金黄色   金黄色
表5(续)
  实施例序列号   60     61     62     63
  染料               (染料的量，单位：克)
  K1   0.20     0.20     0.20     0.20
  E8E15E10E11E12E14   0.150.30 0.200.30     0.200.30 0.180.30
  K25K26   0.30     0.30 0.35     0.30
  染色结果   红棕色     红棕色     红棕色     红棕色
实施例64至69染发剂
制备有下列组合物的霜膏形式的染料载体：
Xg    1，3-二羟基-5-(苯硫基-2-基)苯(偶合剂K1)
[sic-译者]
Ug    显色剂E8至E15，按照表2
Yg    偶合剂K11至K33，按照表3
Zg    直接染料D2或D3，按照表4
15.0g 鲸蜡醇
0.3g  抗坏血酸
3.5g  月桂基二亚乙基二醚硫酸钠，28％的水溶液
3.0g  氨水，22％的水溶液
0.3g  无水亚硫酸钠
加入100.0g水中
使用之前，将30g前述染色霜膏与30g 6％的过氧化氢溶液混合。然后将该混合物应用到头发上。在40℃下作用30分钟后，用水冲洗头发，然后用市售洗发香波漂洗并干燥。染色效果如表6所示。
表6-染发剂
 实施例序列号     64     65   66     67     68     69
 染料                                  (染料的量，单位：克)
 K1     1.10     1.10   0.60     0.20     0.40     0.40
 E8E13E15     1.50 1.60 1.80 0.70 0.70 0.70
 K12K13K23K31     0.600.70 1.50 1.250.050.60 0.180.100.20 0.180.10 0.180.10
 D3D2     0.10 0.10 0.10
 染色结果     黑色     黑色   黑色     棕色     棕色     棕色
实施例70至79染发剂
制备下列组合物的染发剂溶液：
Xg    1，3-二羟基-4-(噻吩-2-基)苯(偶合剂K2)
Ug    显色剂E8至E15，按照表2
Yg    偶合剂K11至K33，按照表3
10.0g 油酸钾(8％的水溶液)
10.0g 氨水(22％的水溶液)
10.0g 乙醇
0.3g  抗坏血酸
加入100.0g水中
使用之前，将30g前述染色溶液与30g 6％的过氧化氢水溶液混合。然后将该混合物应用到头发上。在40℃下作用30分钟后，用水冲洗头发，然后用市售洗发香波漂洗并干燥。染色效果如表7所示。
表7-染发剂
  实施例序列号     70     71   72     73   74   75
  染料                                 (染料的量，单位：克)
  K2     0.10     0.10   0.13     0.15   0.20   0.10
  E8E9E15     0.30 0.25 0.30 0.25 0.25 0.30
  K12K13K18K19K21K22K23K24K31K32K33 0.050.05 0.100.050.05   0.160.050.10 0.150.100.05 0.150.10 0.150.10
  染色结果     金黄色     金黄色   金黄色     金黄色   金黄色   金黄色
表7(续)
 实施例序列号  76     77     78     79
 染料              (染料的量，单位：克)
 K1[sic-译者]  0.20     0.20     0.20     0.20
 E8E10E11E12E14E15  0.150.30 0.300.20     0.200.30 0.300.18
 K25K26  0.30     0.30 0.35     0.30
 染色结果  红棕色     红棕色     红棕色     红棕色
实施例80至86  染发剂
制备有下列组合物的霜膏形式的染料载体：
Xg    1，3-二羟基-4-(噻吩-2-基)苯(偶合剂K2)
Ug    显色剂E8至E15，按照表2
Yg    偶合剂K11至K33，按照表3
Zg    直接染料D2或D3，按照表4
15.0g 鲸蜡醇
0.3g  抗坏血酸
3.5g  月桂基二亚乙基二醚硫酸钠，28％的水溶液
3.0g  氨水，22％的水溶液
0.3g  无水亚硫酸钠
加入100.0g水中
使用之前，将30g前述染色霜膏与30g 6％的过氧化氢溶液混合。然后将该混合物应用到头发上。在40℃下作用30分钟后，用水冲洗头发，然后用市售洗发香波漂洗并干燥。染色效果如表8所示。
表8-染发剂
 实施例序列号     80     81     83     84     85     86
 染料                                (染料的量，单位：克)
 K1[sic]     1.10     1.10     0.6     0.20     0.40     0.40
 E8E13E15     1.50 1.60 1.80 0.70 0.70 0.70
 K12K13K23K31     0.600.70 1.50 1.250.050.60 0.180.100.20 0.180.10 0.180.10
 D3D2     0.10 0.10 0.10
 染色结果     黑色     黑色     黑色     黑色     黑色     黑色
除非另外指明，本专利申请中所有百分数均以重量计。

Claims (12)

1.式(I)的1，3-二羟基-4-杂芳基苯衍生物或其生理上容许的水溶性盐
Figure C028095450002C1
其中
X代表氧、硫或N-R5；
R1和R2可以是相同的或不同的，且各自独立地代表氢、卤原子、羟基、C1-C4-烷氧基、C1-C4-羟基烷氧基、C1-C6-烷基、C1-C4-羟基烷基或C2-C4-二羟基烷基；
R3和R4可以是相同的或不同的，且各自独立地代表氢、羟基、卤原子、C1-C4-烷氧基、C1-C6-烷基、C1-C4-烷基硫醚基、巯基、硝基、氨基、C1-C4-烷氨基、二(C1-C4)烷氨基、-C(O)H基、-C(O)CH3基、C1-C4-羟基烷基或C2-C4-二羟基烷基；和
R5代表氢、C1-C6-烷基、C2-C4-羟基烷基、苯基或乙酰基。
2.如权利要求1所述的1，3-二羟基-4-杂芳基苯衍生物，其特征在于它选自式(I)化合物，其中(i)R1、R2、R3和R4基团中的一个或多个基团代表氢，且X代表硫或氧或(ii)R1和R2同时代表氢且X代表硫。
3.如权利要求1或2所述的式(I)的1，3-二羟基-4-杂芳基苯衍生物，其特征在于它选自下列物质：1，3-二羟基-4-(噻吩-2-基)苯、1，3-二羟基-4-(5-硝基噻吩-2-基)苯、1，3-二羟基-4-(3-甲基噻吩-2-基)苯和其生理上容许的盐。
4.试剂，所述试剂基于显色剂-偶合剂组合用于角蛋白纤维的氧化染色，其特征在于它包含至少一种如权利要求1至3中任一项所述的式(I)的1，3-二羟基-4-杂芳基苯衍生物。
5.如权利要求4所述的试剂，其特征在于式(I)化合物选自下列物质：1，3-二羟基-4-(噻吩-2-基)苯、1，3-二羟基-4-(5-硝基噻吩-2-基)苯、1，3-二羟基-4-(3-甲基噻吩-2-基)苯、1，3-二羟基-4-(呋喃-2-基)苯和其生理上容许的盐。
6.如权利要求4或5所述的试剂，其特征在于它包含式(I)的1，3-二羟基-4-杂芳基苯，含量以重量计为0.005％至20％。
7.如权利要求4至6中任一项所述的试剂，其特征在于所述显色剂选自下列物质：
1，4-二氨基苯、1，4-二氨基-2-甲苯、1，4-二氨基-2，6-二甲苯、1，4-二氨基-3，5-二乙苯、1，4-二氨基-2，5-二甲苯、1，4-二氨基-2，3-二甲苯、2-氯-1，4-二氨基苯、1，4-二氨基-2-(噻吩-2-基)苯、1，4-二氨基-2-(噻吩-3-基)苯、1，4-二氨基-2-(吡啶-3-基)苯、2，5-二氨基联苯、1，4-二氨基-2-甲氧基甲苯、1，4-二氨基-2-氨基甲苯、1，4-二氨基-2-羟基甲苯、1，4-二氨基-2-(2-羟基乙氧基)-苯、2-[2-(乙酰胺基)乙氧基]-1，4-二氨基苯、4-苯基氨基苯胺、4-二甲基氨基苯胺、4-二乙基氨基苯胺、4-二丙基氨基苯胺、4-[乙基-(2-羟基乙基)氨基]苯胺、4-[二(2-羟基乙基)氨基]苯胺、4-[二(2-羟基乙基)氨基]-2-甲基苯胺、4-[(2-甲氧基乙基)氨基]苯胺、4-[(3-羟丙基)氨基]苯胺、4-[(2，3-二羟基丙基)氨基]苯胺、1，4-二氨基-2-(1-羟基乙基)苯、1，4-二氨基-2-(2-羟基乙基)苯、1，4-二氨基-2-(1-甲基乙基)苯、1，3-双[(4-氨基苯基)(2-羟基乙基)氨基]-2-丙醇、1，4-双[(4-氨基苯基)氨基]丁烷、1，8-双(2，5-二氨基苯氧基)-3，6-二氧杂辛烷、4-氨基苯酚、4-氨基-3-甲酚、4-氨基-3-(羟甲基)苯酚、4-氨基-3-氟苯酚、4-甲氨基苯酚、4-氨基-2-(氨基甲基)苯酚、4-氨基-2-(羟甲基)苯酚、4-氨基-2-氟苯酚、4-氨基-2-[(2-羟基乙基)氨基]-甲酚、4-氨基-2-甲酚、4-氨基-2-(甲氧基甲基)苯酚、4-氨基-2-(2-羟基乙基)苯酚、5-氨基水杨酸、2，5-二氨基吡啶、2，4，5，6-四氨基-嘧啶、2，5，6-三氨基-4-(1H)-嘧啶酮、4，5-二氨基-1-(2-羟基乙基)-1H-吡唑、4，5-二氨基-1-(1-甲基乙基)-1H-吡唑、4，5-二氨基-1-[(4-甲基苯基)-甲基]-1H-吡唑、1[(4-氯苯基)甲基]-4，5-二氨基-1H-吡唑、4，5-二氨基-1-甲基-1H-吡唑、2-氨基苯酚、2-氨基-6-甲酚、2-氨基-5-甲酚和1，2，4-三羟基苯。
8.如权利要求4至7中任一项所述的试剂，其特征在于除式(I)化合物外，它还包含选自下列物质的其它已知偶合剂：
N-(3-二甲基氨苯基)脲、2，6-二氨基吡啶、2-氨基-4[(2-羟基乙基)-氨基]苯甲醚、2，4-二氨基-1-氟-5-甲苯、2，4-二氨基-1-甲氧基-5-甲苯、2，4-二氨基-1-乙氧基-5-甲苯、2，4-二氨基-1-(2-羟基乙氧基)-5-甲苯、2，4-二[(2-羟基乙基)氨基]-1，5-二甲氧基苯、2，3-二氨基-6-甲氧基吡啶、3-氨基-6-甲氧基-2-(甲氨基)吡啶、2，6-二氨基-3，5-二甲氧基吡啶、3，5-二氨基-2，6-二甲氧基吡啶、1，3-二氨基苯、2，4-二氨基-1-(2-羟基乙氧基)苯、1，3-二氨基-4-(2，3-二羟基丙氧基)苯、1，3-二氨基-4-(3-羟基丙氧基)苯、1，3-二氨基-4-(2-甲氧基乙氧基)苯、2，4-二氨基-1，5-二(2-羟基乙氧基)苯、1-(2-氨基乙氧基)-2，4-二氨基苯、2-氨基-1-(2-羟基乙氧基)-4-甲氨基-苯、2，4-二氨基苯氧基乙酸、3-[二(2-羟基乙基)氨基]苯胺、4-氨基-2-二[(2-羟基乙基)氨基]-1-乙氧基苯、5-甲基-2-(1-甲基乙基)苯酚、3-[(2-羟基乙基)氨基]苯胺、3-[(2-氨基乙基)氨基]苯胺、1，3-二(2，4-二氨基苯氧基)丙烷、二(2，4-二氨基苯氧基)甲烷、1，3-二氨基-2，4-二甲氧基苯、2，6-双(2-羟基乙基)氨基甲苯、4-羟基吲哚、3-二甲基氨基苯酚、3-二乙基氨基苯酚、5-氨基-2-甲酚、5-氨基-4-氟-2-甲酚、5-氨基-4-甲氧基-2-甲酚、5-氨基-4-乙氧基-2-甲酚、3-氨基-2，4-二氯苯酚、5-氨基-2，4-二氯苯酚、3-氨基-2-甲酚、3-氨基-2-氯-6-甲酚、3-氨基苯酚、2-[(3-羟基苯基)氨基]乙酰胺、5-[(2-羟基乙基)氨基]-4-甲氧基-2-甲酚、5-[(2-羟基乙基)氨基]-2-甲酚、3-[(2-羟基乙基)氨基]苯酚、3-[(2-甲氧基乙基)氨基]苯酚、5-氨基-2-乙基苯酚、5-氨基-2-甲氧基苯酚、2-(4-氨基-2-羟基苯氧基)乙醇、5-[(3-羟丙基)氨基]-2-甲酚、3-[(2，3-二羟基丙基)氨基]-2-甲酚、3-[(2-羟基乙基)氨基]-2-甲酚、2-氨基-3-羟基吡啶、2，6-二羟基-3，4-二甲基吡啶、5-氨基-4-氯-2-甲酚、1-萘酚、2-甲基-1-萘酚、1，5-二羟基萘、1，7-二羟基萘、2，3-二羟基萘、2，7-二羟基萘、2-甲基-1-萘酚乙酸盐、1，3-二羟基苯、1-氯-2，4-二羟基苯、2-氯-1，3-二羟基苯、1，2-二氯-3，5-二羟基-4-甲苯、1，5-二氯-2，4-二羟基苯、1，3-二羟基-2-甲苯、3，4-亚甲基二氧苯酚、3，4-亚甲基二氧苯胺、5-[(-羟基乙基)氨基]-1，3-苯并间二氧杂环戊烯、6-溴-1-羟基-3，4-亚甲基二氧苯、3，4-二氨基苯甲酸、3，4-二氢-6-羟基-1，4(2H)苯并嗪、6-氨基-3，4-二氢-1，4[2H]苯并嗪、3-甲基-1-苯基-5-吡唑啉酮、5，6-二羟基吲哚、5，6-二羟基二氢吲哚、5-羟基吲哚、6-羟基吲哚、7-羟基吲哚和2，3-二氢吲哚二酮。
9.如权利要求4至8中任一项所述的试剂，其特征在于它包含显色剂和偶合剂，二者中任一的总含量按所述染色剂的总重量计为0.005％至20％。
10.如权利要求4至9中任一项所述的试剂，其特征在于它还包含至少一种直接染料。
11.如权利要求4至10中任一项所述的试剂，其特征在于它的pH值为6.5至11.5。
12.如权利要求4至11中任一项所述的试剂，其特征在于它为染发剂。
CNB028095456A 2001-05-25 2002-01-28 1,3－二羟基苯衍生物和含有这些化合物的染色剂 Expired - Fee Related CN100349886C (zh)

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