 Use as donor-substituted oxinedi high derivatives and colorants
专利摘要:
The present invention relates to auxindigo derivatives of formulas (1) and (2), methods for their preparation, uses and intermediates thereof. <Formula 1> <Formula 2> In the above formula, 4 to 7 of the radicals described are hydrogen and 1 to 4 of the radicals are carbocyclic aromatic radicals, heterocyclic aromatic radicals, halogens, C 1 -C 18 alkyl, -OR 12 , -CN, -NR 10 R 11 , -COR 9 , -NR 13 COR 9 , -NR 12 COOR 9 , -NR 12 CONR 10 R 11 , -NHSO 2 R 9 , -SO 2 R 9 , -SOR 9 , -SO 2 OR 9 , -CONR 10 R 11 , -SO 2 NR 10 R 11 , -N = NR 14 , -OCOR 9 and -OCONHR 9 wherein two corresponding adjacent radicals may combine to form a fused aromatic ring, R 9 Is a C 1 -C 18 alkyl, C 6 -C 10 aryl, or benzyl, or heterocyclic radical; R 10 and R 11 are each independently hydrogen, C 1 -C 18 alkyl, C 3 to C 24 cycloalkyl, C 6 -C 10 aryl or heteroaryl, or R 10 and R 11 are in each case a different radical R Together with one of 2 to R 4 forms a ring; R 12 is hydrogen, C 1 -C 18 alkyl, C 3 to C 24 cycloalkyl, C 6 -C 10 aryl or heteroaryl; R 13 is hydrogen, C 1 -C 18 alkyl, C 3 to C 24 cycloalkyl, C 1 -C 4 alkylaryl, C 6 -C 10 aryl, or a heterocyclic radical; R 14 is a radical of the coupling component, or C 6 -C 10 aryl. 公开号:KR20000065020A 申请号:KR1019980708558 申请日:1997-04-17 公开日:2000-11-06 发明作者:하인즈 랑갈스；바바라 바그너 申请人:에프. 아. 프라저, 에른스트 알테르 (에. 알테르), 한스 페터 비틀린 (하. 페. 비틀린), 피. 랍 보프, 브이. 스펜글러, 페. 아에글러；시바 스페셜티 케미칼스 홀딩 인크.； IPC主号:
专利说明:
Donor substituted auxindigo derivatives and their use as colorants The present invention relates to auxindigo derivatives of formulas (1) and (2) and mixtures thereof. In the above formula, 4 to 7 of the radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are hydrogen and 1 to 4 of the radicals are unsubstituted or substituted carbosi Click aromatic radicals, unsubstituted or substituted heterocyclic aromatic radicals, halogen, unsubstituted or substituted C 1 -C 18 alkyl, -OR 12 , -CN, -NR 10 R 11 , -COR 9 , -NR 13 COR 9 , -NR 12 COOR 9 , -NR 12 CONR 10 R 11 , -NHSO 2 R 9 , -SO 2 R 9 , -SOR 9 , -SO 2 OR 9 , -CONR 10 R 11 , -SO 2 NR 10 R 11 , -N = NR 14 , -OCOR 9 and -OCONHR 9 wherein two corresponding adjacent radicals may combine to form a fused aromatic ring, wherein R 9 is C 1 -C 18 alkyl, C 6 -C 10 aryl, or benzyl, unsubstituted or substituted with halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, or a 5-7 membered heterocyclic radical; R 10 and R 11 are each independently hydrogen, unsubstituted or substituted with cyano or hydroxy groups C 1 -C 18 alkyl, C 3 to C 24 cycloalkyl, C 6 -C 10 aryl or 5 to 7 membered hetero Aryl or R 10 and R 11 in each case together with one of the other radicals R 2 to R 4 form a 5- or 6-membered carbocyclic or heterocyclic ring; R 12 is hydrogen, C 1 -C 18 alkyl, C 3 to C 24 cycloalkyl, C 6 -C 10 aryl or 5- to 7-membered heteroaryl; R 13 is hydrogen, unsubstituted or substituted with C 1 -C 18 alkyl, C 3 to C 24 cycloalkyl, C 1 -C 4 alkylaryl, unsubstituted with cyano, hydroxy or C 1 -C 4 alkoxycarbonyl groups C 6 -C 10 aryl, or a 5-7 membered heterocyclic radical, or substituted by halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy group; R 14 is a radical of the coupling component or is a radical selected from the group consisting of C 6 -C 10 aryl unsubstituted or substituted with halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy group, Provided that in the auxindigo derivatives of formula 1 (trans form), in each case R 1 and R 2 are not methyl or methoxy at the same time if all remaining radicals of R 1 to R 8 are hydrogen, or R 5 And R 6 is not chlorine at the same time, or R 1 , R 2 , R 3 and R 4 are not methyl at the same time, or R 1 , R 2 , R 5 , R 6 , R 7 and R 8 are methyl at the same time Not In the cis-oxinedigo derivative of formula (2), when R 1 is a dimethylamino group, R 2 is not a hydroxy group at the same time. The invention also relates to a process for the preparation of the auxindigo compounds of the invention for use as colorants and intermediates. Auxindigo as a color development step (see, eg, Ber. Dtsch. Chem. Ges. 44 (1911) 124-128) does not gain any industrial significance as a colorant, in contrast to nitrogen homologue indigo or sulfur homologue thioindigo. I couldn't. The reason for this is that especially auxindigo exhibits absorption at very short wavelengths (413 nm in cyclohexane, see for example J. Chem. Soc. D 1969, 133-134), the absorption coefficient is relatively low (13800, supra) It has no fluorescence, relatively low stability, and is difficult to manufacture. With methyl and methoxy substituted compounds, dichloride compounds, dibenzo substituted compounds and C (O) O (CH 2 ) 2 OMe radicals and two -C 18 H 37 -radicals which may be unbrominated or brominated Derivatives are described in Jutus Liebigs Ann. Chem. 405 (1914) 365, 372; Justus Liebigs Ann. Chem. 442 (1925) 263, 278, 284-300; J. Amer. Chem. Soc. 73 (1951) 4294, 4297; Chem. Ber. 54 (1921) 2933; Org. Mass. Spectrom. 24 (6) (1989) 429-430; Japanese Patent Laid-Open Nos. 61180237, 61179791 and 07150136 (Tokyo Ink). Asymmetrically substituted cis compounds described in Japanese Patent Laid-Open No. 07150136 show only electroluminescence and are not disclosed in terms of their preparation. J. Phys. Chem. 77 (1973) 831-837, describes the results of fluorescence quenching when donor groups are introduced at the 6 and 6 'positions of thioindigo by substitution. Due to the similar nature of oxygen and sulfur, no or very good fluorescence was expected from the corresponding auxindigo compounds. Moreover, the synthesis methods known to date are multistage synthesis and are therefore expensive because they have to isolate each intermediate [Justus Liebigs Ann. Chem. 442 (1925) 284-300, Ber. Dtsch. Chem. Ges. 44 (1911) 124-128 and Ber. Dtsch. Chem. Ges. 42 (1909) 199-202, or Bull. Soc. Chim. France 11 (1944) 82-89 proposed syntheses never yield preferred auxindigo derivatives. It is therefore an object of the present invention to provide an auxindigo derivative which does not have the above disadvantages. In particular, for the visible region, there is provided a colorant which preferably has fluorescence, particularly preferably fluorescence of this solid. Moreover, there is provided an improved method of preparing auxindigo and derivatives thereof without isolating any intermediate. Also provided are auxindigo derivatives having improved absorption coefficients, high yields and good photochemical stability, and colorants based on auxindigo derivatives for use as bat dyes, dye lasers and fluorescent markers. Thus, the auxinigo derivatives of the formulas (1) and (2) of the present invention have been found. In addition, methods of making these materials have been found and found that they can be used to make bat dyes, dye lasers and fluorescent markers. Unless stated otherwise, the following description always relates to trans (Formula 1) and cis (Formula 2) auxindigo derivatives. According to the invention, 4 to 7 of the radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are hydrogen and 1 to 4 of said radicals are unsubstituted or Or substituted carbocyclic aromatic radical, unsubstituted or substituted heterocyclic aromatic radical, halogen, unsubstituted or substituted C 1 -C 18 alkyl, —OR 12 , —CN, —NR 10 R 11 ,- COR 9 , -NR 13 COR 9 , -NR 12 COOR 9 , -NR 12 CONR 10 R 11 , -NHSO 2 R 9 , -SO 2 R 9 , -SOR 9 , -SO 2 OR 9 , -CONR 10 R 11 , -SO 2 NR 10 R 11 , -N = NR 14 , -OCOR 9 and -OCONHR 9 wherein two corresponding adjacent radicals combine to form a fused aromatic ring, and R 9 is C 1 -C 18 alkyl , C 6 -C 10 aryl, or benzyl unsubstituted or substituted with halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, or a 5-7 membered heterocyclic radical; R 10 and R 11 are each independently hydrogen, unsubstituted or substituted with cyano or hydroxy groups C 1 -C 18 alkyl, C 3 to C 24 cycloalkyl, C 6 -C 10 aryl or 5 to 7 membered hetero Aryl or R 10 and R 11 in each case together with one of the other radicals R 2 to R 4 form a 5- or 6-membered carbocyclic or heterocyclic ring; R 12 is hydrogen, C 1 -C 18 alkyl, C 3 to C 24 cycloalkyl, C 6 -C 10 aryl or 5- to 7-membered heteroaryl; R 13 is hydrogen, unsubstituted or substituted with C 1 -C 18 alkyl, C 3 to C 24 cycloalkyl, C 1 -C 4 alkylaryl, unsubstituted with cyano, hydroxy or C 1 -C 4 alkoxycarbonyl groups C 6 -C 10 aryl, or a 5-7 membered heterocyclic radical, or substituted by halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy group; R 14 is a radical of the coupling component or is a radical selected from the group consisting of C 6 -C 10 aryl unsubstituted or substituted with halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy group, With the proviso that in the auxindigo derivatives of formula 1 (trans form), in each case when all remaining radicals of R 1 to R 8 are hydrogen, R 1 and R 2 are not simultaneously methyl or methoxy, or R 5 and R 6 are not chlorine at the same time, or R 1 , R 2 , R 3 and R 4 are not methyl at the same time, or R 1 , R 2 , R 5 , R 6 , R 7 and R 8 are simultaneously Not methyl, When R 1 is a dimethylamino group in the cis-oxinedigo derivative of formula (2), R 2 is not a hydroxy group at the same time. The unsubstituted or substituted carbocyclic aromatic radicals selected are preferably mono to tetracyclic, particularly preferably mono or bicyclic radicals having 5 to 7 carbon atoms per ring, for example phenyl, diphenyl and naph. Til. Unsubstituted or substituted heterocyclic aromatic radicals are preferably mono to tricyclic radicals having 5 to 7 ring atoms. This radical may comprise only one or more heterocyclic rings, or the heterocyclic ring (s) may contain one or more fused benzene rings. Examples include pyridyl, pyrimidyl, pyrazinyl, triazinyl, furanyl, pyrrolyl, thiophenyl, quinolyl, isoquinolyl, coumarinyl, benzofuranyl, benzimidazolyl, benzoxazolyl, dibenzfuranyl, Benzothiophenyl, dibenzothiophenyl, indolyl, carbazolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, indazolyl, benzothiazolyl, pyridazinyl, cynolyl, quinazolyl, Quinoxazolyl, phthalazinyl, phthalazinionyl, phthalimidyl, chromonyl, naphtholactamyl, benzopyridonyl, ortho-sulfobenimidyl, maleinimidyl, naphtharidinyl, benzimidazoloyl, Benzoxazolonyl, benzothiazolonyl, benzothiazolinyl, quinazoloyl, pyrimidyl, quinoxalonyl, phthalazonyl, dioxapyridinyl, pyridonyl, isoquinoloyl, isothiazolyl, benz Soxazolyl, benzisothiazolyl, indazolonyl, acridinyl, acridonyl, quinazolindionyl, benzoxa D. O'Neil, benzoxazolyl Gino carbonyl and there is a phthalimide limiter dill. Two adjacent radicals, such as R 3 and R 5 , R 5 and R 1 , R 1 and R 7, etc., may each be linked to form a carbocyclic or heterocyclic radical, and therefore also claim a fused or condensed ring system. do. Preferably the radicals are selected as fused ring systems. In a preferred embodiment, the carbocyclic and / or heterocyclic aromatic radicals are monosubstituted or polysubstituted by conventional substituents, particularly preferably by substituents which do not dissolve in water. Examples thereof are as follows. Halogen, preferably chlorine, such as fluorine, chlorine, bromine and iodo; Cyano groups (-CN); Unsubstituted or substituted C 1 -C 18 alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert-butyl, tert-amyl, n- Hexyl, 1,1,3,3-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4 -Heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl and 3-undecyl, preferably C 1 -C 12 alkyl, for example methyl, Ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl and 3-undecyl, particularly preferably C 1- C 8 alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3, 3-tetramethylbutyl, n-heptyl, n-octyl, 3-pentyl, 4-heptyl, 3-hexyl and 3- Naphthyl, and particularly preferably C 1 -C 4 alkyl, such as methyl, ethyl, n- propyl, inde isopropyl, n- butyl, i- butyl, sec- butyl and tert- butyl, Here, the alkyl groups are generally substituted by the following groups which do not increase hydrophilicity, for example fluorine, cyano, -OCOR 9 , -OR 10 , -OCOOR 9 , -CON (R 10 ) (R 11 ) -OCONHR 9 Can, Wherein R 9 is C 1 -C 18 alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert-amyl, n-hexyl, 1,1, 3,3-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl , 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl or 3-undecyl, preferably C 1 -C 12 alkyl, for example methyl, ethyl, n-propyl, Isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, 3 -Pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl or 3-undecyl, or C 6 -C 10 aryl, for example phenyl And naphthyl, preferably naphthyl, or benzyl unsubstituted or substituted by halogen, such as chlorine and fluorine, preferably fluorine, C 1 -C 4 alkyl or -OC 1 -C 4 alkyl, or 5 Won to 7 won Teroxycyclic radicals such as pyridyl, pyrimidyl, pyrazinyl, triazinyl, furanyl, pyrrolyl, thiophenyl, quinolyl, isoquinolyl or coumarinyl, R 10 and R 11 are C 1 -C 18 alkyl, preferably C 1 -C 12 alkyl, particularly preferably C 1 -C 8 as defined above which are hydrogen, unsubstituted or substituted by a cyano or hydroxy group Alkyl, particularly preferably C 1 -C 4 alkyl, or C 3 -C 24 cycloalkyl, preferably C 5- , C 6- , C 12- , C 15- , C 16- , C 20 -and C 24 cycloalkyl, aryl or heteroaryl, preferably substituents derived from one of the carbo- and heterocyclic aromatic radicals as defined above, in particular unsubstituted or halogen, C 1 -C 4 alkyl or C 1 -C 4 Or phenyl substituted by alkoxy, or R 10 and R 11 in each case together with one of the other radicals of R 2 to R 4 are 5- to 6-membered rings or hetero rings, for example pyridine, pyrrole, furan or pyran form a ring, and preferred radicals -OR 10 is hydroxy, -O- methyl, ethyl -O-, -Oi- propyl, butyl -Oi-, -O- Fe , -O-2,5- di and -tert- butylphenyl, preferred radicals -CON (R 10) (R 11 ) is -CONH 2, -CONMe 2, -CONEt 2 , -CON (iPr) 2, -CON (i-Bu) 2 , -CONPh 2 , -CON (2,5-di-tert-butylphenyl) 2 . In another preferred embodiment, monoalkylated or dialkylated amino groups, aryl radicals (such as naphthyl or in particular phenyl unsubstituted or substituted by halogen, alkyl or —O-alkyl), or heterocyclic aromatic radicals (such as 2-thienyl, 2-benzoxazolyl, 2-benzothiazolyl, 2-benzimidazolyl, 6-benzimidazoloyl, 2-, 3- or 4-pyridinyl, 2-, 4-, or 6 -Quinolyl, or 1-, 3-, 4-, 6- or 8-isoquinolyl radicals) are used on the alkyl group. If the substituents mentioned again contain alkyl, this alkyl may be branched or unbranched and may have 1 to 18 carbon atoms, in particular 1 to 12, especially 1 to 8, and particularly preferably 1 to 4 carbon atoms. . Examples of unsubstituted alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7- Tridecyl, 3-hexyl, 3-heptyl, 3-nonyl and 3-undecyl, and examples of substituted alkyl groups are hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluoroethyl, cyanomethyl Methoxycarbonylmethyl, acetoxymethyl or benzyl; · -OR 12 [wherein, R 12 is hydrogen, R 9 a, as well as the preferred variant as defined in as defined in R 9 C 1 -C 18 alkyl, C 3 to C 24 cycloalkyl are alkyl, especially preferred C 5 -, C 6- , C 12- , C 15- , C 16- , C 20 -and C 24 cycloalkyl, C 6 -C 10 aryl, for example naphthyl and phenyl, particularly preferably unsubstituted phenyl, and halogen , Phenyl substituted by C 1 -C 4 alkyl or C 1 -C 4 alkoxy, or 5- to 7-membered heteroaryl. Examples of preferred radicals R 12 are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7- Tridecyl, 3-hexyl, 3-heptyl, 3-nonyl, 3-undecyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, Acetoxymethyl, benzyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl , Cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl and pyranylmethyl, with the preferred radicals -OR 12 being hydroxy, methoxy, -O-ethyl, -Oi-propyl, -Oi-butyl, -O-phenyl, -O-2,5-di-tert-butylphenyl; -NR 10 R 11 wherein R 10 and R 11 are as defined above. Examples of preferred radicals include amino, methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, 2-hydroxyethylamino, 2-hydroxypropylamino, N, N-bis (2-hydroxyethyl) Amino, Cyclopentylamino, Cyclohexylamino, Cyclododecylamino, Cyclopentadecylamino, Cyclohexadecylamino, Cycloeicosanylamino, Cyclotetracosanylamino, Phenylamino, N-methylphenylamino, Benzylamino, Dibenzylamino , Piperidyl or morpholinyl; -COR 9 wherein R 9 is as defined above. Examples of preferred radicals R 9 are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7- Tridecyl, 3-hexyl, 3-heptyl, 3-nonyl, 3-undecyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, Acetoxymethyl, benzyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl , Cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl, pyranylmethyl and furfuryl; -NR 13 COR 9 wherein R 9 is as defined above and R 13 is hydrogen, unsubstituted or substituted with C 1 -C 18 alkyl substituted with cyano, hydroxy or a C 1 -C 4 alkoxycarbonyl group , C 3 to C 24 cycloalkyl, C 1 -C 4 alkylaryl, C 6 -C 10 aryl, or 5-membered, unsubstituted or substituted by halogen or C 1 -C 4 alkyl or C 1 -C 4 alkoxy group To 7-membered heterocyclic radicals, and each radical such as alkyl, alkoxy, aryl, etc., is as defined for that radical, including the preferred ranges defined herein. Examples of radicals include acetylamino, propionylamino, butyrylamino, benzoylamino, p-chlorobenzoylamino, p-methylbenzoylamino, N-methylacetamino, N-methylbenzoylamino, N-succinimido, N- Phthalimido or N- (4-amino) phthalimido; -NR 12 COOR 9 wherein R 9 and R 12 are as defined above. Examples of radicals include NHCOOCH 3 , -NHCOOC 2 H 5 and -NHCOOC 6 H 5 ; -NR 12 CONR 10 R 11 wherein R 10 , R 11 and R 12 are as defined above. Examples of radicals include ureido, N-methylureido, N-phenylureido or N ', N'-2', 4'-dimethylphenylureido; -NHSO 2 R 9 , wherein R 9 is as defined above. Examples of radicals are methylsulfonylamino, phenylsulfonylamino, p-tolylsulfonylamino or 2-naphthylsulfonylamino]; -SO 2 R 9 , wherein R 9 is as defined above. Examples of radicals are methylsulfonyl, ethylsulfonyl, phenylsulfonyl or 2-naphthylsulfonyl]; -SOR 9 wherein R 9 is as defined above. Examples of radicals are phenylsulfoxydyl]; -SO 2 OR 9 , wherein R 9 is as defined above. Examples of radicals are methyl, ethyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, or 1 or 2-naphthyl]; -CONR 10 R 11 wherein R 10 and R 11 are as defined above. Examples of radicals include carbamoyl, N-methylcarbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-phenylcarbamoyl, N -1-naphthylcarbamoyl or N-piperidylcarbamoyl; -SO 2 NR 10 R 11 wherein R 10 and R 11 are as defined above. Examples of radicals include sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N-phenylsulfamoyl, N-methyl-N-phenylsulfamoyl or N-morpholisulfamoyl; -N = NR 14 wherein R 14 is a radical of a phenyl radical or a coupling component which is unsubstituted or substituted by halogen, alkyl or -O-alkyl, wherein halogen and alkyl are as defined above. Alkyl in the definition of R 14 may preferably have the number of carbon atoms as defined above. Examples of R 14 are acetoacetarylide, pyrazolyl, pyridonyl, o- or p-hydroxyphenyl, o-hydroxynaphthyl, p-aminophenyl or pN, N-dimethylaminophenyl radicals; -OCOR 9 wherein R 9 is as defined above. Examples of radicals of R 9 are methyl, ethyl, phenyl and o-, m- or p-chlorophenyl]; -OCONHR 9 where R 9 is as defined above. Examples of radicals of R 9 are methyl, ethyl, phenyl and o-, m- or p-chlorophenyl. Halogen is fluorine, chlorine, bromine and iodo, preferably fluorine and chlorine, preferably at least one of the radicals R 1 , R 2 , R 3 , R 4 , R 7 and R 8 is fluorine, chlorine or bromine And particularly preferably R 1 and R 2 are chlorine at the same time. Unsubstituted or substituted C 1 -C 18 alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert-butyl, tert-amyl, n-amyl, n- Hexyl, 1,1,3,3-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4 -Heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl or 3-undecyl, preferably C 1 -C 12 alkyl, for example methyl, Ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl or 3-undecyl, particularly preferably C 1- C 8 alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3, 3-tetramethylbutyl, n-heptyl, n-octyl, 3-pentyl, 4-heptyl, 3-hexyl or 3-heptyl, particularly preferably C 1 -C 4 alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl or tert-butyl, These alkyl groups defined are generally the following groups which do not increase hydrophilicity, for example fluorine, hydroxy, cyano, -OCOR 9 , -OR 10 , -OCOOR 9 , -CON (R 10 ) (R 11 ) -OCONHR 9 may be substituted by Wherein R 9 is C 1 -C 18 alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert-amyl, n-hexyl, 1,1, 3,3-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl , 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl or 3-undecyl, preferably C 1 -C 12 alkyl, for example methyl, ethyl, n-propyl, Isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, 3 -Pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl or 3-undecyl, or C 6 -C 10 aryl, for example phenyl And naphthyl, preferably naphthyl, or benzyl unsubstituted or substituted by halogen, such as chlorine and fluorine, preferably fluorine, C 1 -C 4 alkyl or -OC 1 -C 4 alkyl, or 5 7 to 7 Heterocyclic radical, for example pyridyl, pyrimidyl, pyrazinyl, triazinyl, furanyl, pyrrolyl, thiophenyl, quinolyl, isoquinolinyl, or quinolyl and Kumari carbonyl, R 10 and R 11 are C 1 -C 18 alkyl, preferably C 1 -C 12 alkyl, particularly preferably C 1 -C 8 as defined above which are hydrogen, unsubstituted or substituted by a cyano or hydroxy group Alkyl, particularly preferably C 1 -C 4 alkyl, or C 3 -C 24 cycloalkyl, preferably C 5- , C 6- , C 12- , C 15- , C 16- , C 20 -and C 24 cycloalkyl, aryl or heteroaryl, preferably substituents derived from one of the carbo- and heterocyclic aromatic radicals as defined above, in particular unsubstituted or halogen, C 1 -C 4 alkyl or C 1 -C 4 Or phenyl substituted by alkoxy, or R 10 and R 11 in each case together with one of the other radicals of R 2 to R 4 are 5 to 6 membered rings or other hetero rings, for example pyridine, pyrrole, furan or Form a pyran ring. In another preferred embodiment, monoalkylated or dialkylated amino groups, aryl radicals (eg naphthyl, or in particular phenyl unsubstituted or substituted with halogen, alkyl or —O-alkyl), or heterocyclic aromatic radicals (eg 2-thienyl, 2-benzoxazolyl, 2-benzothiazolyl, 2-benzimidazolyl, 6-benzimidazoloyl, 2-, 3- or 4-pyridinyl, 2-, 4-, or 6 -Quinolyl, or 1-, 3-, 4-, 6- or 8-isoquinolyl radicals) are used on the alkyl group. If the substituents mentioned again contain alkyl, this alkyl may be branched or unbranched and contain 1 to 18 carbon atoms, especially 1 to 12 carbon atoms, especially 1 to 8 carbon atoms, and particularly preferably 1 to 4 carbon atoms. have. Examples of unsubstituted alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7- Tridecyl, 3-hexyl, 3-heptyl, 3-nonyl and 3-undecyl, and examples of substituted alkyl groups are hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluoroethyl, cyano Methyl, methoxycarbonylmethyl, acetoxymethyl or benzyl. In a preferred embodiment, independent of the selection of other radicals within the definition of the radicals R 1 to R 8 , R 1 and R 2 are simultaneously C 4 -C 8 alkyl, eg n-butyl, i-butyl , sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl and 3-undecyl, Preferably C 6 -C 12 alkyl, for example n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, 4-heptyl, 5- Nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl, 3-undecyl, in each case the alkyl radicals can be substituted with such groups which generally do not increase hydrophilicity have. In the radical -OR 12, R 12 is hydrogen, and when the C 1 -C 18 alkyl as defined in R 9, as well as the preferred variant as defined in R 9, in R 1 = R 2 at each occurrence, a radical R 1 to R 8 Independently of the choice of other radicals within the definition of are the same alkoxy radicals, the radicals selected for R 1 and R 2 are preferably C 4 -C 18 alkyl, for example n-butyl, i-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n Dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl and 3-undecyl, particularly preferred Preferably C 6 -C 12 alkyl, for example n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl, 3-undecyl, or, or a C 3 to C 24 cyclo alkyl, particularly preferably C 5 -, C 6 -, C 12 -, C 15 -, C 16 -, C 20 - and C 24 cycloalkyl, C 6 -C 10 aryl, for example naphthyl and phenyl, preferably unsubstituted Phenyl and phenyl substituted by halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, or 5- to 7-membered heteroaryl. Examples of preferred radicals R 12 are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7- Tridecyl, 3-hexyl, 3-heptyl, 3-nonyl, 3-undecyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, Acetoxymethyl, benzyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl , Cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl and pyranylmethyl. Examples of preferred radicals are hydroxyl, methoxy, -O-ethyl, -Oi-propyl, -Oi-butyl, -O-phenyl, -O-2,5-di-tert-butylphenyl. In —NR 10 R 11 , R 10 and R 11 are as defined above. Examples of preferred radicals include amino, methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, 2-hydroxyethylamino, 2-hydroxypropylamino, N, N-bis (2-hydroxyethyl) Amino, Cyclopentylamino, Cyclohexylamino, Cyclododecylamino, Cyclopentadecylamino, Cyclohexadecylamino, Cycloeicosanylamino, Cyclotetracosanylamino, Phenylamino, N-methylphenylamino, Benzylamino, Dibenzylamino , Piperidyl or morpholyl, dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino, di-n-pentylamino, di-n-hexylamino, di-n-heptyl Particular preference is given to amino, di-n-octylamino and di-n-dodecylamino. R 10 and R 11, by themselves or in each case together with at least one of the other free radicals from the list R 1 , R 3 , R 5 , R 7 or R 2 , R 4 , R 6 , R 8 Or six-membered, saturated or unsaturated rings, for example pyridine, pyrrole, piperidine, quinoline or benzoquinolizine derivatives. Examples include Δ11,11 '(2H, 3H, 4H, 6H, 7H, 8H, 10H, 2'H, 3'H, 4'H, 6'H, 7'H, 8'H, 10'H). ) -Bibenzo [i, j] furo [3,2-g] -quinoline-10,10'-dione. In a preferred embodiment, the radicals R 1 to R 8 are those in which the auxindigo derivatives of the formulas (1) and (2) of the invention have at least two, preferably two, three or four, particularly preferably, radicals -NR 10 R 11 . Preferably two and the remainder of the radicals R 1 to R 8 are particularly preferably hydrogen. -COR 9 is a radical wherein R 9 is as defined above. Examples of preferred radicals R 9 are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7- Tridecyl, 3-hexyl, 3-heptyl, 3-nonyl, 3-undecyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, Acetoxymethyl, benzyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl , Cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl, pyranylmethyl and furfuryl. -NR 13 COR 9 is C 1 -C 18 alkyl wherein R 9 is a radical as defined above and R 13 is hydrogen, unsubstituted or substituted by cyano, hydroxy or a C 1 -C 4 alkoxycarbonyl group, C 3 to C 24 cycloalkyl, C 1 -C 4 alkylaryl, C 6 -C 10 aryl, unsubstituted or substituted by halogen or C 1 -C 4 alkyl or C 1 -C 4 alkoxy, or 5-membered to It is a seven-membered heterocyclic radical and each radical, such as alkyl, alkoxy, aryl, etc., is as defined for that radical, including the preferred range defined for that radical. Examples of radicals include acetylamino, propionylamino, butyrylamino, benzoylamino, p-chlorobenzoylamino, p-methylbenzoylamino, N-methylacetamino, N-methylbenzoylamino, N-succinimido, N- Phthalimido or N- (4-amino) phthalimido. -NR 12 COOR 9 is a radical wherein R 9 and R 12 are as defined above. Examples of radicals are -NHCOOCH 3 , -NHCOOC 2 H 5 and -NHCOOC 6 H 5 . —NR 12 CONR 10 R 11 is a radical wherein R 10 , R 11 and R 12 are as defined above. Examples of radicals include ureido, N-methylureido, N-phenylureido or N, N'-2 ', 4'-dimethylphenylureido. -NHSO 2 R 9 is a radical wherein R 9 is as defined above. Examples of this radical are methylsulfonylamino, phenylsulfonylamino, p-tolylsulfonylamino or 2-naphthylsulfonylamino. -SO 2 R 9 is a radical wherein R 9 is as defined above. Examples of this radical are methylsulfonyl, ethylsulfonyl, phenylsulfonyl or 2-naphthylsulfonyl. -SOR 9 is a radical wherein R 9 is as defined above. An example of this radical is phenylsulfoxydyl. -SO 2 OR 9 is a radical wherein R 9 is as defined above. Examples of R 9 radicals are methyl, ethyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, or 1 or 2-naphthyl. -CONR 10 R 11 is a radical wherein R 10 and R 11 are as defined above. Examples of this radical include carbamoyl, N-methylcarbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-phenylcarbamoyl, N-1-naphthylcarbamoyl or N-piperidylcarbamoyl. -SO 2 NR 10 R 11 is a radical wherein R 10 and R 11 are as defined above. Examples of this radical are sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N-phenylsulfamoyl, N-methyl-N-phenylsulfamoyl or N-morpholisulfamoyl. -N = NR 14 is a radical of a phenyl radical or a coupling component, wherein R 14 is unsubstituted or substituted by halogen, alkyl or -O-alkyl, wherein halogen and alkyl are as defined above. Alkyl in the definition of R 14 may preferably have the number of carbon atoms as defined above. Examples of R 14 are acetoacetaryl, pyrazolyl, pyridonyl, o- or p-hydroxyphenyl, o-hydroxynaphthyl, p-aminophenyl or pN, N-dimethylaminophenyl radicals. -OCOR 9 is a radical wherein R 9 is as defined above. Examples of radicals of R 9 are methyl, ethyl, phenyl, o-, m- or p-chlorophenyl. -OCONHR 9 is a radical wherein R 9 is as defined above. Examples of radicals of R 9 are methyl, ethyl, phenyl, o-, m- or p-chlorophenyl. Preferred embodiments relate to oxysindigo derivatives of formulas 1 and 2 which are symmetrically substituted. Here, symmetrically substituted means that (a) the same substituent is present in an even number (e.g. 2, 4, 6 or 8) and (b) a pendant corresponding to the substituent at position X is present at position X '. it means. Examples are auxindigo of formulas 1 and 2 having the same substituents as the radicals R 1 and R 2 and / or R 3 and R 4 and / or R 5 and R 6 and / or R 7 and R 8 Derivatives. Especially preferably symmetrically substituted compounds 1 and 2 have two (identical) substituents. Examples are compounds of formulas 1 and 2 having the same substituents, such as the radicals R 1 and R 2 or R 3 and R 4 or R 5 and R 6 or R 7 and R 8 . Especially preferably the symmetrically substituted compounds of formulas (1) and (2) are substituted by the same substituents at positions 6 and 6 ', ie R 1 = R 2 . An example is an auxindigo compound of formulas (I) and (II) substituted bi- at the 6,6′-position by —NR 10 R 11 . The claimed compounds can be prepared analogously to the processes described in the above-mentioned prior art, or in the preparation of the auxindigo compounds of the formulas (1) and (2) which are disubstituted at the 6- and 6'-positions by -NR 10 R 11 It can be prepared analogously to the method described in detail below. Reference is also made to Barbara Wagner's paper (Munich 1995). Preferred embodiments relate to the auxindigo compounds of Formula 1 and 2 substituted at the 6,6′-position by —NR 10 R 11 , wherein R 10 and R 11 are as defined above, including preferred embodiments. same. Particularly preferred 6,6'-diamino-oxinedigo of formulas (1) and (2) is 6-dimethylamino-2- (6-dimethylamino-3-oxo-2, which in each case is cis and trans or a Z and E configuration. 3H) -Benzofuranilidene) -3 (2H) -benzofuranone, 6-diethylamino-2- (6-diethylamino-3-oxo-2 (3H) -benzofuranilidene) -3 ( 2H) -benzofuranone, 6-di-n-propylamino-2- (6-di-n-propylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofura Non, 6-di-n-butylamino-2- (6-di-n-butylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone, 6-di -n-pentylamino-2- (6-di-n-pentylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone, 6-di-n-hexylamino -2- (6-di-n-hexylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone, 6-di-n-octylamino-2- (6 -Di-n-octylamino-3-oxo-2 (3H) -benzofuranilidene) -3 (2H) -benzofuranone, 6-di-n-dodecylamino-2- (6-di-n Dodecylamino-3-oxo-2 (3H) -benzofura Vinylidene) -3 (2H) - benzofuranone; (E) -6-N-methyl-N '-(2'-methylphenyl) -amino-2- (6-N-methyl-N'-(2'-methylphenyl) amino-3-oxo-2 (3H) -Benzofuranilidene) -3 (2H) -benzofuranone, (Z)-and (E) -6-N- (2'-methylphenyl) -amino-2- (6-N- (2'-methylphenyl) ) Amino-3-oxo-2 (3H) -benzofuranilidene) -3 (2H) -benzofuranone and (Z)-and (E) -Δ11,11 '(2H, 3H, 4H, 6H, 7H, 8H, 10H, 2'H, 3'H, 4'H, 6'H, 7'H, 8'H, 10'H) -bibenzo [i, j] furo [3,2-g] -Quinoline-10,10'-dione. Another preferred embodiment relates to a process for the preparation of the auxindigo compounds of the formulas (1) and (2) substituted di- at the 6- and 6'-positions by the radical -NR 10 R 11 . Especially preferred method (a) alkylating 3-aminophenol of formula (3) with haloacetic acid alkylester, haloacetic acid or haloacid chloride in the presence of a base, (b) treating the alkylation product of step (a) with a base or an acid in the presence of oxygen, and (c) a chemical formula bisubstituted at the 6- and 6'-positions by -NR 10 R 11 , comprising post-treating the reaction mixture produced by a method known per se, preferably by column chromatography. It relates to a method for producing the auxindigo compound of 1 and 2. Compounds of formula (3) are known or described in J. Am. Chem. Soc. 74 (1952) 573, which may be prepared from 3-aminophenol (R 10 and R 11 are hydrogen). In the first reaction step, the phenolic OH group is a haloacetic acid alkylester, preferably a C 1 -C 4 alkylester (eg methylchloroacetate, methylbromoacetate, ethylchloroacetate, ethylbromoacetate, n- or i -Propyl chloroacetate, n- or i-propyl bromoacetate, n-, i-, sec- or tert-butyl chloroacetate or n-, i-, sec- or tert-butyl bromoacetate), haloacetic acid ( Such as chloroacetic acid and bromoacetic acid), its alkali metal salts (especially sodium salts), or halo chlorides (e.g. chloroacetyl chloride, methylchloroacetate are particularly preferred). If desired, Lewis acids, such as FeCl 3 , POCl 3 and PCl 3 or mixtures thereof, can be added to the acetic acid derivative, preferably using chloroacetylchloride. Typically alkylation is carried out in the presence of a base to give a compound of formula 4. Bases used are amides, in particular sterically hindered amides such as lithium piperididyl and lithiumdiisopropylamide (“LDA”), preferably LDA, and alkali metal hydroxides such as NaOH or KOH, preferably Preferably KOH, and may be an alkali metal alcoholate such as NaOMe or NaH, KH, diazabicycloundecene ("DBU") or diazabicyclononene ("DBN"). The reaction of formula (3) to obtain formula (4) is preferably carried out in the presence of an aromatic solvent such as toluene, benzene, xylol, preferably toluene, especially when LDA is used dimethyl sulfoxide ("DMSO" ), Especially where solid KOH is used, HMPA, DEU and DMPU. The molar ratio of alkylating agent to compound of formula 3 is usually selected in the range of 5: 1 to 0.5: 1, preferably 1.5: 1 to 1: 1. The molar ratio of alkylating agent to base is usually selected in the range from 8: 1 to 1: 1, preferably 4: 1 to 1: 1. If a solvent is used, the weight ratio of solvent to base is selected in the range of 50: 1 to 1: 1, preferably 30: 1 to 5: 1. Alkylation is usually carried out at temperatures in the range of -90 to 150 ° C, preferably in the range of -78 to 60 ° C. The pressure is generally selected in the range of 80 to 120 kPa, and atmospheric pressure is preferably used. In addition, the pressure range may be selected outside the usual range depending on the temperature selected. Usually, the reaction time is selected according to the reaction temperature selected, and 0.5 to 100, especially 1 to 20 hours are preferred. The compound of formula 4 may be worked up by conventional methods. However, in a preferred embodiment, the workup step is omitted and the reaction continues. In a second synthesis step, the compound of formula 4 prepared by the described method or by other methods is reacted with a base or an acid in an isolated form or in a reaction mixture to produce the compound of formula 6, wherein the compound of formula 6 is used and the base is used , If desired, an enolate (Formula 5) of a compound of Formula 4 is isolated. Bases used are generally amides, for example nonnucleophilic amides such as lithium piperidinyl and LDA, preferably LDA, alkaline earth metal carbonates such as CaCO 3 , aluminum oxides such as γ-Al 2 O 3 , preferably in the form of a base), and silica gel, preferably in the form of bases treated with alcoholates, for example NaOMe and NaOEt. The acids used are usually inorganic acids, for example sulfuric acid and hydrochloric acid, preferably sulfuric acid, and polyphosphoric acid. The molar ratio of the compound of formula 4 to base or acid is usually selected in the range of 10: 1 to 0.8: 1, preferably 5: 1 to 1: 1. If desired, the cyclic to obtain the coumaranone of formula 6 may be a solvent, for example a polar organic solvent such as 1,2-dichloroethane, 1,2-dichloromethane, nitrobenzene, or concentrated sulfuric acid and hydrofluoric acid (anhydride) Inorganic acids such as carbon dioxide, or carbon disulfide, preferably 1,2-dichloroethane. Cyclicization is usually carried out in the range of 0 to 200 ° C, preferably in the range of 20 to 110 ° C. The pressure is generally selected in the range of 80 to 120 kPa, and atmospheric pressure is preferably used. In addition, the pressure range may be selected outside the usual range depending on the temperature selected. Usually, the reaction time is selected according to the reaction temperature selected, and a range of 1 to 16 hours is preferable. The compound of formula 6 may be worked up by conventional methods. According to conventional studies, the coumaranone of formula (6) is easily dimerized under oxygen atmosphere to produce the auxindigo derivatives of formula (1) and / or (2). Thus, in a preferred embodiment, the reaction which produces the auxindigo derivatives of the formulas (1) and (or) (2) is omitted by post-treatment of the coumaranone of formula (6), or in particular the final reaction In the step, it is carried out in the presence of oxygen, preferably air. Usually, the auxindigo derivatives of formulas (1) and (or) 2 can be isolated from the reaction mixture by methods known per se. This auxindigo derivative is preferably selected from silica gel or aluminum oxide, and particularly preferably silica gel is used and is advantageously separated by chromatography using chloroform as eluent. More preferred synthesis of the auxindigo of formulas (1) and (2) using the reagents defined above starting from the compound of formula (3) is carried out by the following formulated method. (a) reaction of 3-aminophenol of formula (3) with one of the haloacetic acid derivatives defined above and KOH in DMSO, and a predetermined mole of base such as LDA; (b) reaction of 3-aminophenol of formula 3 with chloroacetic acid or sodium chloroacetate and KOH in water, and subsequent reaction in sulfuric acid; (c) first reaction of 3-aminophenol of formula 3 with chloroacetic acid or sodium chloroacetate and KOH in water followed by calcium carbonate; (d) reaction of 3-aminophenol of formula 3 with chloroacetic acid or sodium chloroacetate and γ-aluminum oxide, preferably basic aluminum oxide; (e) reaction of 3-aminophenol of formula 3 with chloroacetic acid or sodium chloroacetate and basic silica gel (sodium ethanol acid); (f) reaction of 3-aminophenol of formula 3 with 1) sodium methanolate, 2) ethylchloroacetate, and 3) polyphosphoric acid under air; (g) the same reaction as in (f) except that no air is present; (h) reaction of 3-aminophenol of formula 3 with chloroacetic acid, silica gel and chloroform or sodium chloroacetate (simple reaction, especially short alkyl chains having 3 atoms); (i) reaction of 3-aminophenol of formula 3 with bromoacetylchloride, FeCl 3 , POCl 3 and PCl 3 or bromoacetylchloride, POCl 3 and PCl 3 ; (j) Reaction of 3-aminophenol of formula 3 with sodium chloroacetate and FeCl 3 , POCl 3 and PCl 3 . In another preferred embodiment, the known 6,6'-dimethoxy-trans-oxinedigo can be prepared in several steps by one of the novel synthetic routes described above starting from 3-methoxyphenol. Another preferred embodiment relates to a process for the preparation of auxindigo 1 and / or 2 starting from coumaranone of formula (6). The reaction conditions typically correspond to the conditions defined in the reaction steps of formulas (6) to (1) and / or (2). In this case, the coumaranone of formula (6) can be synthesized and isolated by a synthetic step as defined above starting from one of the precursors or intermediates of formula (3) or (4), or prepared by other methods. Another preferred embodiment relates to a process for the preparation of the auxindigo derivatives of formulas (1) and / or (2) via coumaranone of formula (6) starting from an ester compound of formula (4). Particularly preferred methods for the preparation of the auxindigo derivatives of formulas (1) and (2) with radicals -NR 10 R 11 as substituents at the 6- and 6'- positions are (a) treating an ester compound of formula 4 with a base or an acid in the presence of oxygen, or <Formula 4> (b) treating by pyrolysis at elevated temperature, preferably in the temperature range of 80 to 200 ° C. for 0.5 to 3 hours, and Subsequently, the resultant reaction mixture in particular comprises post-treatment by methods known per se, preferably by chromatography. The reaction conditions of (a) are typically the conditions defined for the reaction sequence of formula (4)-(6)-(1) and (or) 2, and it is preferred that the coumaranone of formula (6) is not isolated. In this case the ester of formula 4 can be prepared by the synthesis method described above starting from the aminophenol of formula 3, or by other methods. According to variant (b), the auxynedigoes of the formulas (1) and (or) 2 are preferably 3-aminophenoxyacetic acid C 1 -C 6 alkylesters, for example methyl 3-aminophenoxyacetate, ethyl-3 -Aminophenoxyacetate, n-propyl 3-aminophenoxyacetate, n-butyl 3-aminophenoxyacetate, tert-butyl 3-aminophenoxyacetate, n-pentyl 3-aminophenoxyacetate and n-hexyl 3 Aminophenoxyacetates, particularly preferably starting from methyl 3-aminophenoxyacetate, at elevated temperatures, preferably at temperatures in the range from 80 to 200 ° C, particularly preferably at 110 to 150 ° C, especially at 130 ° C. Obtained by thermal decomposition of the compound of formula (4). The residence time here is usually chosen in the range of 0.5 to 3 hours, preferably 0.5 to 1.5 hours, depending on the temperature selected. Usually, in the process for preparing auxindigo of formula (1) substituted with a donor substituted, i.e., auxindigo of formula (1) substituted with a -NR 10 R 11 group, a cis-oxinedigo derivative of formula (2) is also obtained. At high reaction temperatures the content is generally low, but the content of cis-indigo of formula (2) can be up to about 50% even at low reaction temperatures. The cis form of formula (2) can be completely separated from the trans form of formula (1), typically by chromatography (preferably performed carefully). For the preliminary preparation of the (cis-) oxynedigo derivatives of formula (2), in another preferred embodiment the (trans-) oxynedigo derivatives of formula (1), which are more readily accessible, are preferably It can be reduced to leuco form and oxidized again. In general, the two types of mixtures are obtained in molar ratios in the range from 0.8: 1 to 1.2: 1. Auxindigo derivatives of formula (1) are typically reduced herein in polar media such as water or glacial acetic acid. Reducing agents that can be used conventionally are sodium dithionate, zinc in glacial acetic acid or hydrosulfite (sodium formaldehyde sulfoxylate-hydrate), preferably zinc in glacial acetic acid. The molar ratio of the reducing agent to the auxindigo derivative of formula (1) is selected in the range of 500: 1 to 3: 1, preferably 20: 1 to 3: 1. The reduction is preferably carried out in a solvent such as water or glacial acetic acid, particularly preferably glacial acetic acid. The reduction is generally carried out at a temperature in the range of 20 to 150, preferably 50 to 120 ° C. Oxidation of leuco-oxinedigo of formula 7 is usually carried out with air, pure oxygen, hydrogen peroxide or hypochlorous acid. Oxidation of leuco-oxinedigo of formula 7 is usually carried out at a temperature in the range of 0 to 150 ° C, preferably 15 to 40 ° C. Another preferred embodiment of the present invention relates to a leuco-oxinedigo derivative of formula (7) as described above and a process for preparing the same. In another preferred embodiment, the cis-oxyndigo derivative of formula (2) can be thermally or photochemically isomerized to the corresponding trans form. Thermal isomerization is typically carried out in alkanol solvents having 1 to 4 carbon atoms, such as methanol, ethanol, propanol or butanol, and aromatic solvents such as toluene. In general, water increases the reaction rate. Photochemical isomerization is typically carried out using solar or mercury vapor lamps such as Philips HPlc 125 W-lamps. Another embodiment provides a trans-ox of Formula 1 of a cis-oxinedigo derivative of Formula 2 by reaction catalyzed by a Lewis acid such as silica gel, zinc chloride, zinc acetate, iron (III) chloride, an etheride of boron trifluoride. It relates to the conversion to synthigo derivatives and their reverse conversion. Instead of the above-mentioned Lewis acids, other substances with nucleophilic action can be used, for example water-alcohol solutions. The conversion is usually carried out in a mixture such as pyridine / water, 2- or 3- or 4-picoline / water, acetonitrile / water. Usually, Lewis acids use a catalytic amount in the range of 0.1 to 15 mol%, preferably 8 to 12 mol%, particularly preferably 10 mol% per mole of the auxinigo compound. Another preferred embodiment is NR in the 6- and 6'-positions.10R11To an auxindigo derivative of formula 1 di-substituted by a group, wherein R10And R11Is selected such that at least one of these radicals together with the phenyl ring already present forms at least one further ring. Preference is given to fused saturated or unsaturated five- and six-membered rings in which the amine nitrogen atoms are incorporated, for example in the form of carbazole units. In the thus formed rigid derivatives of formula (1), the donor action of the amine nitrogen atom is typically increased, compared to less rigid derivatives, for example the auxindigo derivatives of formula (1) without fused rings, which are usually absorbed and fluorescence This is evidenced by the large long blue shift at. Another preferred embodiment relates to the coumaranone of formula (6) substituted by the NR 10 R 11 group at the 6-position, and to the use thereof for the preparation of the corresponding auxindigo derivatives of the formulas (1) and / or (2). The radicals R 10 and R 11 are defined above including the preferred embodiments. Another embodiment relates to a process for the preparation of the coumaranone of formula (6) by the synthesis as defined above starting from 3-aminophenol of formula (3) or via the ester of formula (4) or directly from the ester of formula (4). Another embodiment relates to esters of formula (4) substituted by NR 10 R 11 groups in the 3-position, and corresponding auxindigo derivatives of formulas (1) and / or (2) and their use for the preparation of coumaranone of formula (6) will be. The radicals R 10 and R 11 are defined above including the preferred embodiments. Another embodiment relates to a process for the preparation of the ester of formula 4 by the synthesis method as defined above starting from 3-aminophenol of formula 3. Another embodiment provides a process for preparing aminophenols of Formula 3 and corresponding auxindigo derivatives of Formulas 1 and / or 2, coumaranone of Formula 6 and esters of Formula 4 at the 3-position substituted by NR 10 R 11 groups It is about. The radicals R 10 and R 11 are defined above including the preferred embodiments. Particularly preferred 3-aminophenols are N, N'-di-n-propyl-3-aminophenol, N, N'-di-n-butyl-3-aminophenol, N, N'-di-n-pentyl- 3-aminophenol, N, N'-di-n-hexyl-3-aminophenol, N, N'-di-n-octyl-3-aminophenol, N, N'-di-n-dodecyl-3 -Aminophenol and N-methyl-N '-(2'-methylphenyl) -3-aminophenol. Other preferred embodiments include (Z)-and (E) -Δ11,11 '(2H, 3H, 4H, 6H, 7H, 8H, 10H, 2'H, 3'H, 4'H, 6'H, 7'H, 8'H, 10'H) -bibenzo [i, j] furo [3,2-g] -quinoline-10,10'-dione and a process for producing the same. This method of preparation is carried out similarly to the reaction of the 3-aminophenol as defined above with a base and an alkylating agent, followed by cyclic and dimerization. J. Am. Chem. Soc. 8-hydroxy-2,3,6,7-tetrahydro-1H, 5H-benzo [i, j] quinoline, obtainable by the process described in 86 (1964), 2533, is preferably Lewis, such as silica gel. In the presence of an acid it is reacted with a C 2 unit (eg methylchloroacetate) as a base and alkylating agent such as sodium methylate. The workup can be carried out by a method known per se, preferably by chromatography. Other preferred embodiments include natural materials such as paper, wood, straw, leather and raw leather, natural fiber materials such as cotton, wool, silk, jute, sisal, hemp, flax, and animal hair (e.g. horse hair), And bat dyeing of viscose fiber, nitrated nitrile or cupricammonium rayon (conversion products such as rayon). The auxindigo derivatives of formula 1 and / or 2 are preferably methods known per se, for example, "Praktischer Leitfaden zum Farben von Textifasern in Laboratorien" [Practical guideline for dyeing textile fibers in laboratories], Julius It can be betted with hydrosulfite by the same method as described in Springer Verlag, 1930 Berlin). In the case of the auxindigo derivatives of the formulas (1) and (or) 2 substituted with -NR 10 R 11 radicals at the 6-, 6'-positions, blue fluorescent, clear yellow bats are typically prepared by the above method. Cotton, for example, can be dyed red using them. Reoxidation can be advantageously assisted by adding hydrogen peroxide in the air. Another preferred embodiment relates to the reduction of auxindigo of formula 1 and / or 2 with zinc in boiling glacial acetic acid. Usually, a blue fluorescing dark yellow solution is obtained using an auxindigo derivative of formula (I) and / or (II) substituted by -NR 10 R 11 radicals at the 6-, 6'-positions. Cotton dyeing typically uses those obtained by atmospheric oxidation. For example, when using trans-6-dimethylamino-2- (6-dimethylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone, the corresponding blue The cis-isomer is preferably obtained in reoxidized form. Advantageously the auxinigo derivatives of formulas (1) and (2) of the present invention have excellent fluorescence. In addition, the auxindigo derivatives of the formulas (1) and (2) of the present invention, particularly the cis-isomers of the formula (2), have high light resistance as solids. The fluorescence of the auxindigo derivatives of formulas 1 and 2 in the solid state also extends to the near infrared (NIR) region, thereby conferring particularly industrial utility. Broad spectral separation between absorbance and fluorescence is particularly important, for example in laser applications. The solubility of the auxindigo derivatives of formulas (1) and (2) positively assists this use. The auxindigo derivatives of the formulas (1) and (2) of the present invention are usually colored agents, in each case by means known per se, including the remaining compounds excluded here and the auxindigo derivatives obtainable by the process of the invention. And especially suitable for use as pigments and dyes, preferably for the following uses. (a) for bulk dyeing polymers, wherein the polymers are polyvinylchloride, cellulose acetate, polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, melamine resins, silicones, polyesters, polyethers, Polystyrene, polymethylmethacrylate, polyethylene, polypropylene, polyvinylacetate, polyacrylonitrile, polybutadiene, polychlorobutadiene or polyisoprene and a copolymer of the aforementioned monomers); (b) natural materials such as paper, wood, straw, leather and rawhide; Or natural fiber materials such as cotton, wool, silk, jute, sisal, hemp, flax and animal hair (eg horse hair); And bat dyes for dyeing their conversion products such as viscose fibers, nitrated nitriles or cupricammonium rayon (rayon); (c) varnishes, paints, in particular automotive finishes, coatings, paper colorants, printing inks, inks (especially for inkjet printers, preferably as fluorescent inks in homogeneous solutions and for painting and substrates, and dry radiometers (Xerox processes)) And for electrophotographic such as laser printers; (d) for security signs (eg, used for checks, check cards, currency notes, coupons, documents, identification cards, etc.) that should be colorless without mistake; (e) additives for colorants (for example, pigments and dyes in which a specific color tone is obtained and in which a luminescent color tone is particularly preferred); (f) Preferred for the marking of objects for the machine reading of objects via fluorescence (eg for machine reading of objects for sorting, including recycling of plastics in which alphanumeric prints or bar codes are preferably used). box); (g) converting optical frequencies to obtain longer wavelengths of visible light from shorter wavelength light or to double and triple the frequency of the laser in nonlinear optics, (h) for the production of passive display devices for various types of displays, postings and signs, for example for manual display devices and bulletin boards and traffic signs, (i) starting materials for superconductivity of the organic material (π-π interactions, and the addition of iodo usually mediates charge delocalization), (j) for labeling using solid state fluorescence, (k) for decorative and artistic purposes, (l) in biochemistry, medicine, engineering and natural sciences, in which the colorants of the invention can be covalently bound to a substrate or can be bound via secondary balance such as hydrogen bonding or hydrophobic action (adsorption). For tracer purposes, (m) Fluorescent dyes in high sensitivity detection methods, in particular fluorescent dyes in scintillators (see C. Aubert, J. Funfschilling, I. Zschokke-Granacher and H. Langhals, Z. Analyt. Chem. 1985, 320, 361) ) (n) In an optical photo collection system, in a fluorescent solar collector (see H. Langhals, Nachr. Chem. Tech. Lab. 1980, 28, 716), in a fluorescent activated display (W. Greubel and G. Baur, Elektronik 1977 , 26, 6), photoinductive polymerization for the production of plastics, testing of materials (eg in the production of semiconductor circuits), in cold light sources for the analysis of the microstructure of the aggregated semiconductor components, in photoconductors, In photographic processes, as dyes or fluorescent dyes in displays, luminescence or image conversion systems (excited by electron, ion or UV irradiation), for example fluorescent displays, cathode ray tubes or fluorescent lamps; In chemiluminescent systems, for example in chemiluminescent flashes, in an immunoassay or other luminescence detection method, an integrated semiconductor circuit containing the dye itself, or together with other semiconductors, for example in the form of epitaxy. As part; Preferably as signal paints for visually emphasizing handwriting and drawings or other graphics, in particular for markings and other objects from which a visual color effect is obtained in a dye laser; Preferably as a fluorescent dye for producing a laser beam, (o) Optical storage medium for obtaining optical sheath-trans conversion. (A) Preparation of Starting Compounds of Formulas 3 and 4 Example 1 N, N'-di-n-propyl-3-aminophenol (3c) 8.0 g (72 mmol) of 3-aminophenol was dissolved in 100 mL of 96% ethanol and 12.2 g (71.8 mmol) of 1-iodopropane were added. The reaction mixture was heated to the boiling point and after 3 hours, additional 12.2 g (71.8 mmol) of 1-iodopropane were added in portions. Boiling was continued for 12 hours under reflux. The light yellow reaction mixture was then poured into 300 mL of water and basified with Na 2 CO 3 . The mixture was then extracted with chloroform. The chloroform phase was washed with H 2 O and finally dried over MgSO 4. After evaporating chloroform, a brown (gradually darkening) high viscosity liquid was obtained. Yield: 5.5 g (40.0%) of crude product, R f (CHCl 3 ) = 0.25 IR (KBr) n = 3354 cm -1 (s, OH), 2961 (s, CH aliphatic), 2934 (s, CH aliphatic), 2874 (s, CH aliphatic), 1618 (s, C = C), 1580 (s), 1468 (m), 1397 (w), 1378 (m), 1378 (m), 1366 (m), 1300 (w), 1258 (w), 1202 (s), 1171 (m), 1146 (m), 1102 (w), 1012 (m), 820 (w), 752 (m), 688 (m). Example 2: N, N'-di-n-butyl-3-aminophenol (3d) 8.3 g (45 mmol) of 1-iodobutane were dissolved in a solution of 5.0 g (45 mmol) of 3-aminophenol in 200 mL of 96% ethanol and the mixture was boiled under reflux. After 3 hours, 8.3 g (45 mmol) of 1-iodobutane were added dropwise to the hot solution. The reaction mixture was boiled for an additional 24 hours under reflux and then incorporated into 300 mL of water. Na 2 CO 3 was added to the solution until the pH reached 8. The mixture was then extracted by shaking three times with 70 ml of chloroform each time. The combined organic phases were shaken twice with 50 mL of 0.02N NaOH each time, followed by extraction twice with 30 mL of water each. The chloroform phase was dried over MgSO 4 . After evaporating the solvent, a dark brown (gradually darkening) highly viscous liquid was obtained. Yield: 2.4 g (19%) crude product, R f (CHCl 3 ) = 0.32 IR (KBr) n = 3399 cm < -1 > (s, OH), 2958 (s, CH aliphatic), 2935 (s, CH aliphatic), 2873 (m, CH aliphatic), 1618 (s, C = C), 1580 (m), 1504 (s), 1467 (m), 1455 (m), 1401 (w), 1367 (m), 1292 (w), 1241 (w), 1194 (m), 1171 (m), 1145 (w), 1111 (w), 1026 (w), 945 (w), 822 (w), 752 (m), 988 (m). Example 3: N, N'-di-n-pentyl-3-aminophenol (3e) 35.8 g (180 mmol) of 1-iodopentane were dissolved in a solution of 20.0 g (180 mmol) of 3-aminophenol in 200 mL of 96% ethanol and the mixture was heated to the boiling point. After 3 hours, 5.8 g (180 mmol) of 1-iodopentane were added in portions to the boiling reaction solution boiling through a reflux condenser. After boiling under reflux for 15 hours, a dark yellow reaction mixture was obtained which was poured into 400 ml of water and Na 2 CO 3 was added until no bubbles occurred. The solution was then extracted three times with 90 mL of chloroform each time. The organic phases were combined, washed twice with 100 ml of 0.02N NaOH and then twice with 70 ml of water each. The chloroform phase was dried over MgSO 4 . After evaporating the solvent on a rotary evaporator, a brown photosensitive high viscosity liquid was obtained. Yield: 18.8 g (41.9%) of crude product, R f (CHCl 3 ) = 0.42 IR (KBr): n = 3338 cm -1 (w, br, OH), 2956 (s, CH aliphatic), 2932 (s, CH aliphatic), 287a (m, CH aliphatic), 2860 (m, CH aliphatic) , 1619 (s, C = C), 1580 (s), 1503 (s), 1467 (m), 1369 (m), 1278 (w), 1230 (m), 1188 (m), 1170 (m), 1144 (m), 752 (m), 689 (m). Molecular weight of C 16 H 27 NO: theoretical 249.2093, found 249.2247 (MS) Example 4: N, N'-di-n-hexyl-3-aminophenol (3f) 5.7 mL (38 mmol) of 1-iodohexane was added to 4.0 g (0.036 mmol) of 3-aminophenol in 80 mL of 96% ethanol and the mixture was boiled under reflux. After 4 hours, additional 5.7 g (38 mmol) of 1-iodohexane was added in portions. After boiling under reflux for 24 h, the reaction mixture was obtained and poured into 250 mL of water and Na 2 CO 3 was added to a pH of 8. Then extracted twice with 60 mL of chloroform each time. The organic phase was washed with water and dried over MgSO 4 . After evaporating the solvent on a rotary evaporator, a light brown photosensitive viscous liquid was obtained. Yield: 4.4 g (45%), R f (CHCl 3 ) = 0.59 IR (KBr): n = 3322 cm -1 (s, br, OH), 2957 (s, CH aliphatic), 2929 (s, CH aliphatic), 2868 (s, CH aliphatic), 2858 (s, CH aliphatic) , 1617 (s, C = C), 1505 (s), 1467 (m), 1378 (w), 1340 (w), 1281 (w), 1218 (m), 1173 (m), 995 (w), 832 (w), 755 (w), 725 (w), 689 (m). Molecular weight of C 18 H 31 NO: theoretical 277.2406, found 277.2232 (MS) Example 5: N, N'-di-n-octyl-3-aminophenol (3 g) 5.0 g (0.05 mmol) of 3-aminophenol were dissolved in 100 mL of 96% ethanol and 10.8 g (44.9 mmol) of 1-iodooctane were added. After boiling under reflux for 4 hours, an additional 10.8 g (44.9 mmol) of 1-iodooctane was added dropwise and the mixture was boiled further under reflux for 24 hours. The light yellow reaction mixture was then incorporated into 300 mL of water and Na 2 CO 3 was added until no bubbles were generated. The reaction mixture was extracted twice with 70 mL of chloroform each time. The organic phase was extracted by shaking twice with 50 mL of 0.02 N NaOH each time and washed twice with water. The chloroform phase was dried over MgSO 4 . After evaporating the solvent on a rotary evaporator, a brown (gradually darkening) viscous liquid was obtained. Yield: 5.69 g (38.0%), R f (CHCl 3 ) = 0.60 IR (KBr) n = 3301 cm < -1 > (m, br, OH), 2952 (s, CH aliphatic), 2926 (s, CH aliphatic), 2854 (s, CH aliphatic), 1615 (s, C = C) , 1580 (m), 1503 (s), 1467 (m), 1405 (w), 1370 (m), 1279 (m), 1244 (m), 1223 (w), 1167 (m), 1142 (w) , 1020 (w), 828 (w), 822 (w), 752 (w), 725 (w), 690 (w). Molecular weight of C 22 H 39 NO: theoretical 333.3032, found 333.3152 (MS) Example 6: N, N'-di-n-dodecyl-3-aminophenol (3h) 5.0 g (45 mmol) of 3-aminophenol were dissolved in 100 mL of 96% ethanol. After addition of 13.3 g (45.0 mmol) of 1-iodododecane, the reaction mixture was boiled under reflux for 3 hours. 13.3 g (45.0 mmol) of 1-iodododecane was added and then boiled under reflux for 12 h. After adding 350 mL of water, the dark yellow reaction mixture was basified with Na 2 CO 3 . The reaction solution was extracted with 150 ml total chloroform. The chloroform phase was extracted by shaking twice with 70 ml of 0.02 N NaOH each time and washed twice with water. The organic phase was dried over MgSO 4 . After evaporating chloroform on a rotary evaporator, a light brown photosensitive viscous liquid was obtained. Yield 7.4 g (37%), R f (CHCl 3 ) = 0.61 IR (KBr) n = 3328 cm < -1 > (m, br, OH), 2956 (s, CH aliphatic), 2923 (s, CH aliphatic), 2854 (s, CH aliphatic), 1615 (s, C = C) , 1580 (m), 1504 (s), 1467 (s), 1455 (m), 1435 (w), 1401 (w), 1370 (m), 1284 (w), 1191 (w), 1163 (m) , 1000 (w), 868 (w), 753 (w), 745 (w), 689 (w). Molecular weight of C 30 H 35 NO: Theoretical 445.4284, Found 445.4388 (MS) Example 7: N-methyl-N '-(2'-methylphenyl) -3-aminophenol (3i) 15.0 g (74.0 mmol) of 3-hydroxy-2'-methyldiphenylamine were dissolved in 200 mL of 96% ethanol. 21.2 g (150 mmol) of iodomethane were added to the dark brown solution. The mixture was boiled under reflux for 24 h, then 500 mL of water was added and Na 2 CO 3 was added to the solution until no bubbles occurred. Then extracted with chloroform. The organic phase was dried over MgSO 4 . After evaporating the solvent on a rotary evaporator, a dark brown highly viscous liquid was obtained. Yield 6.4 g (41%), R f (CHCl 3 ) = 0.45 IR (KBr) n = 3387 cm < -1 > (s, br, OH), 3074 (s, CH aliphatic), 3030 (m, CH aliphatic), 2955 (s, CH aliphatic), 2933 (m, CH aliphatic), 2820 (w, CH aliphatic), 1620 (s, C = C), 1596 (s, C = C), 1582 (s, C = C), 1495 (s), 1471 (m), 1461 (m), 1455 (m), 1351 (m), 1270 (m), 1193 (m), 1164 (m), 1139 (w), 1113 (m), 1044 (w), 995 (w), 965 (w), 835 (w), 761 (m), 729 (m), 690 (m). Example 8: 8-methoxy-2,3,6,7-tetrahydro-1H, 5H-benzo [i, j] quinoline (intermediate for 3I) The reaction was carried out in a three necked flask with reflux condenser. The extractor was connected between the reaction vessel and the reflux cooler. The extractor was equipped with an extraction shell filled with molecular sieve 4 mm 3. 63.6 g (0.600 mole) Na 2 CO 3 , 18.5 g (0.170 mole) m-anisidine and 354.2 g (2.250 mole) 1-bromo-3-chloropropane were mixed in a reaction vessel. The reaction mixture was stirred vigorously while slowly heating at 70 ° C. for 1 hour, 100 ° C. for 2 hours, and 160 ° C. for 12 hours. In the meantime, the color of the reaction mixture changed from pale yellow to yellowish orange. After cooling, 150 ml of concentrated HCl was added dropwise over 15 minutes and cooled with ice. As a result, a yellowish precipitate was isolated. The reaction solution was steam distilled to recover excess 1-bromo-3-chloropropane. 20% NaOH was added to the distillation collector until the pH reached 8. The basic aqueous reaction solution was extracted three times with 90 ml of ether each time. HANDMO was extracted by washing the ether phase with 100 ml of water and shaking twice with 100 ml of 2N HCl, respectively. The acidic aqueous phase was basified with 10% NaOH (pH = 8) and then extracted three times with 3 x 70 mL of ether. Handemo ether phase was washed with 3 x 50 mL of 10% NaOH and dried over Na 2 S0 4 . After the drying agent was filtered off, 32.1 g (95%) of an oily reddish brown crude product was obtained. For purification, the crude product was chromatographed on a column (300 × 40 mm) using chloroform as the mobile phase. After evaporating the solvent, a slightly oily reddish brown liquid was obtained. Yield: 26 g (85%) [theoretical: 56% purified product], R f (CHCl 3 ) = 0.84 IR (KBr): n = 3500 cm -1 (w), 2936 (s, CH aliphatic), 2837 (s, OCH 3 ), 2773 (m, CH aliphatic), 1606 (s, C = C), 1585 ( s, C = C), 1492 (s), 1464 (s), 1444 (s), 1354 (m), 1335 (m), 1308 (s), 1268 (m), 1250 (s), 1198 (s ), 1185 (m), 1161 (s), 1132 (s), 1062 (s), 1042 (m), 773 (s). Example 9: 8-hydroxy-2,3,6,7-tetrahydro-1H, 5H-benzo [i, j] quinoline (3I) 110 mL (602 mmol) of 48% HI was added to 8.12 g (39.9 mmol) of 8-methoxy-2,3,6,7-tetrahydro-1H, 5H-benzo [i, j] quinoline. The reaction mixture was heated with stirring at 110 ° C. for 4 hours under reflux. After cooling, the dark brown transparent reaction solution was poured into 800 mL of water, which resulted in the separation of an yellowish green precipitate which was heated again to dissolve. After filtration, a clear yellow solution was obtained and 2N NH 3 was added to pH 8. As a result, the colorless precipitate was separated. The aqueous phase was extracted with 3 x 80 mL of ether, and the monoethyl ether phase was dried over MgSO 4 . After filtration of the desiccant, the ether was evaporated on a rotary evaporator to give a reddish brown solid. The crude product was chromatographed twice on a column (300 × 40 mm) using chloroform as mobile phase for purification. Chloroform was evaporated on a rotary evaporator to give a reddish brown solid and dried on silica gel in the drier. Yield: 4.2 g (56%), Melting Point: 121-123 ° C., R f (CHCl 3 ) = 0.80. UV (CHCl 3 ): λ max = 365.4 mm, 501.3sh, 617.5 (B) General experimental guidelines for the preparation of 6,6'-donor substituted auxindigo derivatives The entire reaction was carried out by removing moisture in a fully heated apparatus. Example 10: 0.1 mole of N, N'-dialkyl-3-aminophenol was dissolved in 500 ml of toluene and the solution was cooled to -78 deg. 55 ml of 2 mol of lithium diisopropylamide (LDA) solution in cyclohexane / toluene / tetrahydrofuran were added dropwise for 1 hour with vigorous stirring. This phenolization solution was then added dropwise to a solution of 0.11 mol methylchloroacetate in 500 ml of toluene for 1 hour. After stirring for 3 hours, 55 ml of the LDA solution was carefully added dropwise to the reaction solution at -78 ° C. The reaction mixture was kept at this temperature for 3 hours and then slowly heated to 60 ° C. After 12 hours, the reaction mixture was poured into 2 liters of water, brought to pH 6 with 2N HCl and extracted by shaking three times with 200 ml of chloroform each. The organic phase is first washed several times with 100 ml of 2N HCl each, and finally washed with water, where it is noted that the wash water no longer causes a basic reaction and should be colorless. If the wash water still caused a basic reaction, it was treated repeatedly with aqueous HCl. The chloroform phase was then dried over MgSO 4 . The solvent was evaporated on a rotary evaporator to give a crude product comprising two colorant isomers. This isomer mixture could be worked up and separated by column chromatography on silica gel using chloroform and toluene as the mobile phase. Example 11: 6-dimethylamino-2- (6-dimethylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone (1b + 2b) 7.00 g (50.7 mmol) of anhydrous potassium carbonate and 10.00 g (70.70 mmol) of 3-dimethylaminophenol were added to 75 mL of dehydrated dimethylformamide, and the mixture was refluxed for 3 hours. 7.00 g (74.9 mmol) of sodium chloroacetate were added to the dark brown hot reaction mixture in portions with vigorous stirring for 20 minutes. Subsequently, 50 g of anhydrous aluminum oxide was incorporated into the solution. After boiling for 2 days under reflux, the red brown reaction mixture was filtered through frit (G4 frit). The dark red aluminum oxide precipitate was washed with chloroform until the wash solution was colorless. The organic phases were collected together. After evaporation of the solvent, a dark reddish brown viscous residue was obtained, which was chromatographed on silica gel using chloroform as mobile phase and separated into cis and trans products. Example 12: (E) -6-dimethylamino-2- (6-dimethylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzenefuranone (1b) The crude product mixture was first separated by column chromatography to give a strong red solution in the first run, from which the colorant was isolated as a dark reddish brown solid, which was then filtered through G4 frit and the solvent was evaporated. The colorant was dried at 90 ° C. for 7 hours under an oil pump vacuum. Yield: 310 mg (2.5%), Melting Point:> 320 ° C, R f (CHCl 3 ) = 0.66. UV (CHCl 3 ): λ max (ε) = 307.4 mm (28666), 315.9 sh (26169), 511.7 (25364), 542.2 sh (22015). Fluorescence (CDCl3): λ max = 602 nm Example 13: (Z) -6-dimethylamino-2- (6-dimethylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone (2b) The mixture of crude product was purified by column chromatography to give a strong royal blue solution, from which chloroform was evaporated to give a dark blue colorant. The colorant was dried at 90 ° C. for 7 hours under an oil pump vacuum. Yield: 10 mg (0.1%), melting point:> 300 ° C, R f (CHCl 3 ) = 0.67. UV (CHCl 3 ): λ max = 271.0 nm, 307.9, 595.6 sh, 629.1. Example 14 6-diethylamino-2- (6-diethylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone (1a + 2a) 12.1 g (71.0 mmol) of 3-diethylaminophenol were dissolved in 80 mL of absolute ethanol. After adding 7.67 g (142 mmol) of sodium methylate, the dark brown reaction solution was boiled under reflux for 3 hours. 8.4 g (77 mmol) of methylchloroacetate were then added dropwise for 1 hour, and 32.9 g of silica gel were added. After light boiling at reflux for 4 days, the dark red reaction mixture was filtered through frit (glass frit P4). The dark red silica gel precipitate was washed with chloroform until the wash solution was colorless. The Handemo organic phase was washed three times with 50 ml each of water and dried over MgSO 4 . After evaporation of the solvent, 4.9 g (39%) of a dark red crude product was obtained. Example 15: (E) -6-diethylamino-2- (6-diethylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone (1a) The crude mixture was purified by column chromatography on silica gel using chloroform as the mobile phase to give a strong royal red purple solution in the first run. The colorant was obtained from this, filtered through a G4 frit, and then the solvent was evaporated to give a dark red solid which was dried at 90 ° C. for 8 hours under an oil pump vacuum. Yield: 0.98 g (7.0%), Melting point: 292 ° C, R f (CHCl 3 ) = 0.70. UV (CDCl 3 ): λ max (ε) = 311.4 nm (34224), 321.8 (31886), 523.8 (28997), 555.2 sh (25778). Fluorescence (CDCl 3 ): λ max = 610 nm Example 16: (Z) -6-diethylamino-2- (6-diethylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone (2a) The crude mixture was separated by column chromatography on silica gel using chloroform as mobile phase to give a strong royal blue fraction in the first run. After filtration through G4 frit and evaporation of the solvent, the cis colorant was isolated as a dark blue solid and dried for 8 h at 90 ° C. under an oil pump vacuum. Yield: 10 mg (0.1%), melting point: 285 ° C, R f (CHCl 3 ) = 0.73. UV (CDCl 3 ): λ max (ε) = 277.6 nm, 312.5, 609.8sh, 646.9. Fluorescence (CDCl 3 ): λ max = 610 nm Example 17: (E) -6-di-n-propylamino-2- (6-di-n-propylamino-3-oxo-2 (3H) -benzofuranilidene) -3 (2H) -benzo Furanone (1c) Prepared similarly to Example 10. Melting point of dark red solid; 285 ° C., R f (CHCl 3 ) = 0.87. UV (CDCl 3 ): λ max (ε) = 313.1 nm (30 878), 322.9 (29 101), 496.2 sh (18 521), 527.3 (26 787), 557.1 sh (24 098). Fluorescence (CDCl 3 ): λ max = 620.8 nm Example 18: (Z) -6-di-n-propylamino-2- (6-di-n-propylamino-3-oxo-2 (3H) -benzofuranilidene) -3 (2H) -benzo Furanone (2c) Prepared similarly to Example 10. Melting point of dark blue solid; 283 ° C., R f (CHCl 3 ) = 0.90. UV (CDCl 3 ): λ max (ε) = 275.5 nm, 302.4 sh, 613.7 sh, 651.3. Example 19: (E) -6-di-n-butylamino-2- (6-di-n-butylamino-3-oxo-2 (3H) -benzofuranilidene) -3 (2H) -benzo Furanon (1d) Prepared similarly to Example 10. Melting point; 216.1 ° C., R f (CHCl 3 ) = 0.89. UV (CDCl 3 ): λ max (ε) = 312.7 nm (34 125), 325.5 (32 710), 495.5 sh (19967), 527.4 (29 005) Fluorescence (CDCl 3 ): λ max = 619.1 nm Example 20: (Z) -6-di-n-butylamino-2- (6-di-n-butylamino-3-oxo-2 (3H) -benzofuranilidene) -3 (2H) -benzo Furanon (2d) Prepared similarly to Example 10. Melting point; 214.2 ° C., R f (CHCl 3 ) = 0.92. UV (CDCl 3 ): λ max (ε) = 287.7 nm, 306.7 sh, 552.6 sh, 617.8 sh, 652.1 Example 21 6-di-n-pentylamino-2- (6-di-n-pentylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone (1e) + 2e) 29 ml (58 mmol) of a 2-mol LDA solution in cyclohexane / toluene / tetrahydrofuran were added dropwise to a solution of 14.0 g (56.1 mmol) of N, N'-di-n-pentylaminophenol in 100 ml of toluene for 20 minutes. At this time, it was cooled with ice and stirred vigorously. The reaction solution was stirred at room temperature for 1 hour, and then added dropwise to a solution of 5.1 ml (58 mmol) of methylchloroacetate in 100 ml of toluene with water removal for 30 minutes. After stirring at 60 ° C. for 12 hours, an additional 29 ml (58 mmol) of the LDA solution was added dropwise to the reaction solution for 15 minutes. The reaction mixture was further stirred at 60 ° C. for 12 h, then incorporated into 400 mL of water, brought to pH 6 with 2N HCl, and the mixture was extracted by shaking three times with 80 mL of chloroform each. The organic phase was first washed several times with 50 ml 2N HCl each, followed by water, where the wash water should not cause a basic reaction and should be colorless. If the wash water still caused a basic reaction, it was repeated with aqueous HCl. The chloroform phase was then dried over MgSO 4 . After evaporating the solvent, 29.6 g (7.43%) of a dark red brown crude product were obtained. Post-treatment by column chromatography on silica gel using chloroform as mobile phase afforded the colorant isomer mixture as a purple fraction in the first run. Example 22: (E) -6-di-n-pentylamino-2- (6-di-n-pentylamino-3-oxo-2 (3H) -benzofuranilidene) -3 (2H) -benzo Furanon (1e) The colorant isomer mixture was worked up by column chromatography on silica gel using xylene as mobile phase to give a reddish violet fraction in the first run. The dark red colorant was obtained by filtration on G4 frit, the solvent was evaporated, washed with a large amount of n-hexane and dried at 110 ° C. for 8 hours under an oil pump vacuum. Yield: 680 mg (4.86%), melting point: 163.5 ° C., R f (toluene) = 0.84, R f (CHCl 3 ) = 0.91, R f (xylene) = 0.68. UV (CHCl 3 ): λ max (ε) = 315.4 nm (25 407), 508.2 sh (22 646), 524.2 (23 869). UV (EtOH): λ max (ε) = 309.4 nm (30 992), 317.3 sh (29 019), 524.0 (25 657), 540.0 sh (24 892). Fluorescence (CHCl 3 ): λ max (ε) = 608.1 nm. Fluorescence (EtOH): λ max (ε) = 622 nm sh, 631.6. Example 23: (Z) -6-di-n-pentylamino-2- (6-di-n-pentylamino-3-oxo-2 (3H) -benzofuranilidene) -3 (2H) -benzo Furanon (2e) The colorant isomer mixture was separated by column chromatography on silica gel using xylene as the mobile phase to give a strong blue fraction in the first run. Filtration over G4 frit and evaporation of the solvent gave a blue highly viscous residue. It was dissolved in 100 ml of n-hexane. The dark blue colorant was freeze separated from this solution at −17 ° C., then filtered over frit and washed with n-hexane. Yield: 360 mg (2.57%), Melting point: 162.8 ° C., R f (toluene) = 0.91, R f (CHCl 3 ) = 0.95, R f (xylene) = 0.81. UV (CHCl 3 ): λ max (ε) = 276.7 nm (16 284), 309.5 (13 058), 616.4 sh (27 573), 653.1 (32 280). Example 24 6-di-n-hexylamino-2- (6-di-n-hexylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone (1f) + 2f) 4.0 g (0.1 mol) of N, N'-di-n-hexyl-3-aminophenol were dissolved in 50 ml of toluene. 7.4 mL (15 mmol) of a 2 molar LDA solution in cyclohexane / toluene / tetrahydrofuran was removed at −17 ° C. and added dropwise. The reaction mixture was heated to boiling point and boiled for 3 hours. After cooling, the phenolated solution was added dropwise to a solution of 1.6 g (14 mmol) of methylchloroacetate in 10 ml of dehydrated toluene for 30 minutes. The reaction mixture was stirred at 60 ° C. for 1 h and then slowly added dropwise further with 7.4 mL (15 mmol) of 2 moles of LDA solution while cooling with ice. Finally the mixture was heated to boiling point and boiled under reflux for 12 hours. The dark red brown reaction solution was incorporated into 400 mL of water, neutralized with half concentrated HCl, and the mixture was extracted with chloroform. The organic phase was washed several times with water and dried over MgSO 4 . After chloroform was removed on a rotary evaporator, 2.2 g of a dark reddish brown highly viscous residue was obtained. Purple fractions containing cis and trans colorants were isolated from the first run of the crude product by column chromatography on silica gel using chloroform as the mobile phase. After evaporation of the solvent 0.5 g of a reddish violet solid was obtained. Example 25: (E) -6-di-n-hexylamino-2- (6-di-n-hexylamino-3-oxo-2 (3H) -benzofuranilidene) -3 (2H) -benzo Furanon (1f) The isomer mixture was separated by column chromatography on silica gel using toluene as the mobile phase, so that the trans isomer was obtained as a reddish purple fraction in the first run. This solution was filtered and the solvent was evaporated on a rotary evaporator. The resulting dark red precipitate was dried at 100 ° C. for 7 hours under an oil pump vacuum. Yield: 0.40 g (8.8%), Melting point: 117.1 ° C., R f (toluene) = 0.95, R f (CHCl 3 ) = 0.89 UV (CHCl 3 ): λ max (ε) = 311.7 nm (29 5158), 324.9 (27 695), 528.1 (25 111), 55.3 sh (22668). Fluorescence (CHCl 3 ): λ max (ε) = 617.9 nm. Example 26 (Z) -6-di-n-hexylamino-2- (6-di-n-hexylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzo Furanon (2f) The isomer mixture was separated by column chromatography on silica gel using toluene as the mobile phase to give a blue fraction from the first run. This solution was filtered over G4 frit. The solvent was evaporated and the resulting blue highly viscous residue was dissolved in 500 mL of n-hexane, from which the cis-isomer was separated at -17 ° C, which was filtered and washed with n-hexane. R f (toluene) = 0.98, R f (CHCl 3 ) = 0.98 UV (CHCl 3 ): λ max (ε) = 300.6 nm, 612.3 sh, 652.0. Example 27 6-di-n-octylamino-2- (6-di-n-octylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone (1 g + 2g) 7.5 ml (15 mmol) of a 2 molar LDA solution in cyclohexane / toluene / tetrahydrofuran were removed with water at −17 ° C. and stirred vigorously with N, N′-di-n-hexyl-3-aminophenol in 50 ml of toluene. To 5.0 g (0.02 mol) of solution was added. The reaction solution was heated to boiling point and boiled under reflux for 4 hours. The cooled solution was slowly added dropwise to a solution of 1.7 g (15 mmol) of methylchloroacetate in 50 ml of toluene. Finally, 7.5 ml (15 mmol) of an additional 2 mol LDA solution was added dropwise while cooling with ice. The reaction mixture was stirred at 80 ° C. for 48 hours and then 400 ml of water was incorporated. The solution was neutralized with half the concentrated HCl with stirring. The organic phase was separated and the aqueous solution extracted with shaking with chloroform. Handomo washed the organic phase with 2N HCl several times and finally with water. If the wash water still caused an alkali reaction, it was repeatedly treated with 2N HCl. The organic phase was dried over MgSO 4 . After evaporation of the solvent on a rotary evaporator, 4.1 g of dark red brown highly viscous crude product was obtained. Example 28: (E) -6-di-n-octylamino-2- (6-di-n-octylamino-3-oxo-2 (3H) -benzofuranilidene) -3 (2H) -benzo Furanone (1 g) 4.1 g of the crude product was column chromatographed on silicala using toluene as the mobile phase to give a trans colorant as reddish purple fraction in the first run. Filter through G4 frit, evaporate the solvent and dry the dark red product at 90 ° C. under oil pump vacuum for 7 hours. Yield: 0.5 g (9%), Melting point: 110.2 ° C., R f (toluene) = 0.94, R f (CHCl 3 ) = 0.87 UV (CHCl 3 ): λ max (ε) = 311.8 nm (12958), 327.3 (12045), 496.4sh (7763), 528.8 (11666), 558.7sh (10487). Fluorescence (CHCl 3 ): λ max (ε) = 615.5 nm. Example 29: (Z) -6-dioctylamino-2- (6-dioctylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone (2 g) 4.1 g of the crude product was chromatographed on silica gel using toluene as the mobile phase. The blue fraction was separated in the first run and the solvent was evaporated on a rotary evaporator. The resulting blue highly viscous residue was dissolved in 200 ml of n-hexane. The dark colourant was frozen at −17 ° C., filtered, washed with n-nucleic acid and dried at 80 ° C. for 8 hours under oil pump vacuum. R f (toluene) = 0.97, R f (CHCl 3 ) = 0.88 UV (CHCl 3 ): λ max (ε) = 300.6 nm, 613.7 sh, 652.9. Example 30 6-di-n-dodecylamino-2- (6-di-n-dodecylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone (1h + 2h) 6.0 g (0.01 mol) of N, N'-di-n-hexyl-3-aminophenol were dissolved in 50 ml of toluene. 9.0 ml (15 mmol) of a 1.5 mol LDA solution in toluene were stirred for 30 minutes while removing moisture and cooling with ice. The reaction solution was stirred slightly for 30 minutes while boiling. The cooled phenolization solution was added to a solution of 1.6 g (14 mmol) of methylchloroacetate in 50 ml of toluene at 60 ° C. for 30 minutes. 9.0 ml (0.01 mol) of 1.5 mol LDA were added in portions to the dark brown mixture while cooling with ice. After stirring for 48 h at 80 ° C., the dark red brown reaction mixture was poured into 300 mL of water and neutralized with half concentrated HCl. The organic phase was separated and the aqueous phase was extracted by shaking three times with 50 ml of each chloroform. The collected organic phases were washed several times with 2N HCl and finally with water. If the wash water still caused an alkali reaction, 2N HCl was repeated. The organic phase was then dried over MgSO 4 . The solvent mixture was evaporated on a rotary evaporator. 4.9 g of the dark reddish brown high viscosity product contained two product isomers. Example 31: (E) -6-di-n-dodecylamino-2- (6-di-n-dodecylamino-3-oxo-2 (3H) -benzofuranilidene) -3 (2H) -Benzofuranone (1h) The crude product was column chromatographed on silica gel using toluene as the mobile phase to give the trans isomer as reddish violet fraction in the first run. After evaporating the solvent on a rotary evaporator, a dark red high viscosity residue was obtained, which was dissolved in 250 ml of n-hexane. After cooling to −17 ° C., the trans colorant was precipitated, suction filtered through a P5 frit, washed with n-hexane and dried at 70 ° C. for 7 hours under an oil pump vacuum. Yield: 70 mg (1.1%), melting point: 107.2 ° C, R f (toluene) = 0.98, R f (CHCl 3 ) = 0.98 UV (CHCl 3 ): λ max (ε) = 341.0 nm (31150), 322.7 (28879), 497.0sh (20750), 527.5 (29247), 559.0sh (26847). Fluorescence (CHCl 3 ): λ max (ε) = 614.9 nm. Example 32: (Z) -6-di-n-dodecylamino-2- (6-di-n-dodecylamino-3-oxo-2 (3H) -benzofuranilidene) -3 (2H) -Benzofuranone (2h) 4.1 g of the crude product was chromatographed on silica gel using toluene as the mobile phase. The sheath colorant was isolated as blue fraction in the first run. The solvent was evaporated on a rotary evaporator, the blue highly viscous residue was dissolved in 100 ml of n-hexane and the dark blue colorant was frozen at -17 ° C. The precipitate was suction filtered through G5 frit, washed with slightly cold n-hexane and dried at 80 ° C. for 7 hours under oil pump vacuum. Yield: 20 mg (3 × 10 −3 %), Melting Point: 105.1 ° C., R f (toluene) = 0.99, R f (CHCl 3 ) = 0.99. UV (CHCl 3 ): λ max (ε) = 279.0 nm (18853), 311.4 (11691), 619.1 sh (34789), 653.4 (41078). Example 33: 6-N- (2'-Methylphenyl) -amino-2- (6-N- (2'-methylphenyl) -amino-3-oxo-2 (3H) -benzofuranilidene) -3 ( 2H) -benzofuranone (1j + 2j) 10.0 g (44.2 mol) of N- (2'-methylphenyl) -3-aminophenol in 50 ml of toluene while cooling 23.0 ml (11.5 mmol) of a 2-mol LDA solution in cyclohexane / toluene / tetrahydrofuran with ice and removing water ) Was added dropwise and the mixture was stirred at 80 ° C. for 3 hours. The cooled phenolized solution was slowly added dropwise to a solution of 5.0 g (45 mmol) of methylchloroacetate in 50 ml of toluene. An additional 23.0 mL (11.5 mmol) of 2 molar LDA solution was added with cooling on ice and the reaction mixture was stirred at 80 ° C. for 48 h. The cooled dark brown reaction mixture was incorporated into 300 mL of water and neutralized with half concentrated HCl. The organic phase was separated and the aqueous solution was extracted with shaking twice with chloroform, and the handheld organic phase was washed several times with water. After drying over MgSO 4 , the solvent was evaporated on a rotary evaporator. A dark brown high viscosity residue was obtained. Example 34: (E) -6-N- (2'-methylphenyl) -amino-2- (6-N- (2'-methylphenyl) -amino-3-oxo-2 (3H) -benzofuranilidene ) -3 (2H) -benzofuranone (1j) The crude product mixture was purified by column chromatography on silica gel using toluene as the mobile phase to give a yellowish orange fraction in the first run. The solvent was evaporated and the dark red highly viscous residue was dissolved in 250 ml of n-hexane. After cooling at −17 ° C. for 2 days, the dark orange precipitate was isolated. The precipitate was suction filtered, washed with a small amount of n-hexane and dried at 80 ° C. for 6 hours under oil pump vacuum. Yield: 0.2 g (2%), Melting point: 315.1 ° C, R f (toluene) = 0.20, R f (CHCl 3 ) = 0.83. UV (CHCl 3 ): λ max (ε) = 312.7 nm (31211), 488.8 (27034), 514.31 sh (23707). Fluorescence (CHCl 3 ): λ max (ε) = 582.0 nm. Example 35: (Z) -6-N- (2'-methylphenyl) -amino-2- (6-N- (2'-methylphenyl) -amino-3-oxo-2 (3H) -benzofuranilidene ) -3 (2H) -benzofuranone (2j) The crude product was column chromatographed on silica gel using toluene as the mobile phase to give a blue fraction in the first run. The solvent was evaporated on a rotary evaporator, a dark blue colorant was obtained and dried at 80 ° C. for 7 hours under oil pump vacuum. Yield: <10 mg (<9.5 × 10 -5 %), Melting Point: 303-306 ° C, R f (toluene) = 0.4, R f (CHCl 3 ) = 0.84. UV (CHCl 3 ): λ max (ε) = 286.0 nm, 297.9 sh, 362.7 sh, 577.2 sh, 602. Example 36: (E) -6-N-methyl-N '-(2'-methylphenyl) -amino-2- (6-N-methyl-N'-(2'-methylphenyl) -amino-3-oxo -2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone (1i) 6.0 g (0.03 mol) of N-methyl-N '-(2'-methylphenyl) -3-aminophenol are dissolved in 100 ml of toluene and 15.0 ml (30.0 mmol) of a 2-mol LDA solution in cyclohexane / toluene / tetrahydrofuran ) Was added dropwise at -17 ° C while removing moisture. After stirring for 3 hours at 80 ° C., the cooled mixture was added dropwise to a solution of 3.2 g (29 mmol) of methylchloroacetate in 50 ml of toluene for 30 minutes. Finally, 15.0 mL (30.0 mmol) of additional LDA was added in portions at -17 ° C. The dark brown reaction mixture was stirred at 80 ° C. for 48 hours, then incorporated in 300 ml of water and cooled. The dark red brown solution was neutralized with half concentrated HCl. The organic phase was separated and the aqueous phase was extracted with chloroform. Handemo washes the organic phase several times with water and dried over MgSO 4. The solvent mixture was evaporated on a rotary evaporator to give a residue of dark red brown high viscosity product. Purification by column chromatography on silica gel using toluene as the mobile phase gave a reddish orange fraction in the first run. After evaporation of the solvent, the resulting dark red viscous residue was dissolved in 200 ml of n-hexane and the mixture was kept at -17 ° C for 2 days. During this process the dark reddish orange precipitate was separated, filtered over frit, washed with a small amount of n-hexane and dried at 80 ° C. for 6 hours under an oil pump vacuum. Yield: 0.32 g (4.6%), Melting point: 221-247 ° C., R f (toluene) = 0.61, R f (CHCl 3 ) = 0.93. UV (CHCl 3 ): λ max (ε) = 309.1 nm (27251), 318.2 (24989), 472.7 sh (14992), 505.1 (22344), 532.3 sh (19643). Fluorescence (CHCl 3 ): λ max = 591.0 nm. Example 37: Δ11,11 '(2H, 3H, 4H, 6H, 7H, 8H, 10H, 2'H, 3'H, 4'H, 6'H, 7'H, 8'H, 10' H) -bibenzo [i, j] furo [3,2-g] -quinoline-10,10'-dione (1 l + 2 l) 2.39 g (44.2 mmol) of sodium methylate are divided into 4.2 g (22 mmol) of 8-hydroxy-2,3,6,7-tetrahydro-1H, 5H-benzo [i, j] quinoline in 100 mL of absolute ethanol. Was added. After heating to the boiling point, 2.4 ml (27 mmol) of methylchloroacetate were slowly added dropwise. 50 ml of silica gel was added with vigorous stirring and the brown suspension was boiled at 100 ° C. for 12 hours under reflux. The reaction mixture turned red significantly and the pH was 6.5. Silica gel was suction filtered through G4 frit and washed with ethanol. The ethanolic solution mainly comprised unreacted 8-hydroxy-2,3,6,7-tetrahydro-1H, 5H-benzo [i, j] quinoline, which was reacted 2 and 3 times as described above. It was. The product was still absorbed on silica gel. The silica gel was collected from three batches and extracted with toluene for 12 hours. The solvent was evaporated and 0.22 g (4%) of a mixture of cis and trans as dark purple needles was obtained. This isomer was separated on a column (800 × 40 mm) on silica gel using chloroform as the mobile phase. Example 38: (E) -Δ11,11 '(2H, 3H, 4H, 6H, 7H, 8H, 10H, 2'H, 3'H, 4'H, 6'H, 7'H, 8' H, 10'H) -bibenzo [i, j] furo [3,2-g] -quinoline-10,10'-dione (1 l) 0.22 g of the crude product was separated by column chromatography on silica gel using chloroform as the mobile phase to give a dark purple fraction in the first run. After evaporating the solvent, a trans colorant was obtained as a dark purple solid which was dried at 100 ° C. for 6 hours under an oil pump vacuum. Yield: 0.2 g (4%), Melting Point: 360 ° C, R f (CHCl 3 ) = 0.63. UV (CHCl 3 ): λ max (ε) = 324.2 nm (18273), 331.3 sh (17846), 549.3 nm (17770), 580.3 sh (15745). Fluorescence (CHCl 3 ): λ max = 644 nm. Example 39: (Z)-DELTA 11, 11 '(2H, 3H, 4H, 6H, 7H, 8H, 10H, 2'H, 3'H, 4'H, 6'H, 7'H, 8' H, 10'H) -bibenzo [i, j] furo [3,2-g] -quinoline-10,10'-dione (2 l) 0.22 g of the crude product was chromatographed on a silica gel column (800 × 40 nm) using chloroform as the mobile phase. A cyan fraction was obtained in the first run, from which the cis colorant was obtained in the form of a dark blue solid and dried for 6 h at 100 ° C. under an oil pump vacuum. Yield: 10 mg (2 × 10 −3 %), Melting Point: 360 ° C., R f (CHCl 3 ) = 0.71. UV (CHCl 3 ): λ max (ε) = 693.0 nm, 648.8 sh. (C) Preparation of 6,6'-donor substituted auxindigo derivatives with Lewis acid Example 40 6-diethylamino-2- (6-diethylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone (1a) 10.0 g (60.5 mmol) of 3-diethylaminophenol were removed at a reaction temperature of 60 ° C. and mixed with 12.5 g (90.1 mmol) of bromoacetic acid with vigorous stirring with a glass stirrer. 7.0 g (46 mmol) of phosphorus chloride, 6.3 g (46 mmol) of phosphorus trichloride and 24.6 g (152 mmol) of anhydrous iron trichloride were added. After reacting for 24 hours, 3 parts of ice was added to the dark purple mixture, and the solid mixture was dissolved under careful heating and stirring. After adding sodium citrate (as a complex to Fe 3+ ions), the mixture was extracted by shaking three times with 80 ml of chloroform each time. The dark red organic phase was dried over MgSO 4 . The solvent was evaporated on a rotary evaporator to give 55.66 g of a dark purple high viscosity crude product. 0.7 g of the crude product was worked up by column chromatography on silica gel using chloroform as mobile phase. The trans colorant isomers could be separated as reddish purple fractions in the first run. After evaporating the solvent on a rotary evaporator, the resulting dark red solid was dried at 95 ° C. for 7 hours under an oil pump vacuum. Yield: 0.03 g (19%, based on total batch), melting point: 292 ° C., R f (CHCl 3 ) = 0.70. Example 41 6-diethylamino-2- (6-diethylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone (1a + 2a) 1 g (6 mmol) of 3-diethylaminophenol was dissolved in 20 mL of dehydrated chloroform. 1 g (9 mmol) of chloroacetylchloride was added dropwise over 30 minutes. About 10 g of silica gel was incorporated until the entire reaction solution was absorbed and the mixture was heated at 60-70 ° C. for 6 days. Finally, the silica gel was suction filtered through G4 frit and washed with chloroform until the wash solution was colorless. The dark red organic phases were combined and the solvent was evaporated on a rotary evaporator. 0.4 g of a dark red solid was obtained and then separated into isomers by column chromatography on silica gel using chloroform as solvent. The cis isomers were obtained as blue fractions in the first run and the trans isomers as reddish violet fractions. After evaporating the solvent, the resulting colorant isomers were dried for 7 hours at 95 ° C. under an oil pump vacuum. (E) -isomer (1a) (Z) -isomer (2a) Yield: 0.14 g (12%) Yield: 0.01 g (0.84%) Melting Point: 292 ℃ Melting Point: 285 ℃ R f (CHCl 3 ) = 0.70 R f (CHCl 3 ) = 0.73 0.22 g of N, N'-diethylaminophenol was recovered. Example 42 6-dimethylamino-2- (6-dimethylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone (1b) 20 g (15 mmol) of 3-dimethylaminophenol were dissolved in 40 mL of dehydrated dry chloroform. 25 mL (30 mmol) of chloroacetylchloride was added dropwise with vigorous stirring. Then about 40 g of silica gel was incorporated until the reaction solution was absorbed. The reaction mixture was heated to reflux for 2 days under reflux and then left for 2 days. Finally, the silica gel precipitate was filtered off. The precipitate was washed with isopropanol until the wash solution was actually colorless. The dark red organic phase was put together. The solvent mixture was evaporated on a rotary evaporator. The dark red highly viscous residue was worked up by column chromatography on silica gel using chloroform as the mobile phase. The colorant was separated into a red solution in the first run. After evaporating the solvent on a rotary evaporator, the colorant was dried for 5 hours at 60 ° C. under an oil pump vacuum. Yield: 0.11 g (4.2%), Melting Point: 320 ° C, R f (CHCl 3 ) = 0.66. Example 43 6-di-n-butylamino-2- (6-di-n-butylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone (1d ) 1.8 g (8.1 mmol) of 3-di-n-butylaminophenol was dissolved in 20 mL of dehydrated dry chloroform. 0.7 ml (8.8 mmol) of chloroacetyl chloride were added dropwise with vigorous stirring. Then, about 10 g of silica gel was added dropwise until a large amount of the reaction solution was absorbed, and the mixture was boiled under reflux for 15 hours. Finally, the solid was filtered and washed with chloroform until the wash solution was actually colorless. The organic phases were brought together. The solvent was evaporated on a rotary evaporator to give 1.4 g of a dark brown high viscosity crude product. The crude product was worked up by column chromatography on silica gel using chloroform as solvent to give an auxindigo colorant as a reddish violet fraction in the first run. After evaporating the chloroform, the resulting colorant was dried at 75 ° C. for 5 hours under an oil pump vacuum. Yield: 0.04 g (1.9%), Melting point: 2161. DEG C, R f (CHCl 3 ) = 0.89. Example 44 6-diethylamino-2- (6-diethylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone (1a) 1 g (6 mmol) of 3-diethylaminophenol was dissolved in 29 g of dehydrated anhydrous ethanol. 10 g of basic aluminum oxide was added dropwise to the solution with vigorous stirring. 0.7 g (6.0 mmol) of chloroacetyl chloride was added dropwise through a reflux condenser. The dark purple reaction mixture was heated to boiling point under reflux with vigorous stirring. After 2 hours, 1.0 mL (12 mmol) of chloroacetylchloride was added dropwise through a reflux condenser. After another 30 minutes, additional 1.5 mL (18 mmol) of chloroacetylchloride and 2 g of basic aluminum oxide were added. After 10 minutes, the reaction mixture turned dark red. The reaction mixture was left at 60-70 ° C. for 60 hours. Finally, the mixture was suction filtered through a G4 frit and the solid was washed several times with anhydrous alcohol until the wash solution was actually colorless. The dark red organic phases were put together. Ethanol was evaporated on a rotary evaporator. 3 g of a dark red highly viscous residue were obtained, which were purified by column chromatography on silica gel using chloroform as the mobile phase. The colorant was isolated as a reddish purple fraction in the first run. After evaporating the solvent, the resulting dark red solid was dried at 95 ° C. for 5 hours under an oil pump vacuum. Yield: 0.01 g (0.92%), Melting point: 292 ° C, R f (CHCl 3 ) = 0.70. Example 45 6-methoxy-2- (6-methoxy-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone (1k) 20.0 mL (0.185 mol) of 3-methoxyphenol was mixed with 50 mL of toluene. 100 mL (0.200 mole) of a 2-mole LDA solution in cyclohexane / toluene / tetrahydrofuran was added dropwise for 30 minutes with water removal and vigorous stirring. The reaction temperature was slowly increased to 60 ° C. After 48 hours, the reaction solution was added dropwise to a solution of 21.8 g (0.210 mol) of methylchloroacetate for 3 hours with water removal at room temperature. The reaction solution was stirred at 60 ° C. for 1 hour. It was then cooled to −17 ° C. and additional 100 mL (0.200 mole) of 2 molar LDA solution in cyclohexane / toluene / tetrahydrofuran were added dropwise for 1 hour. After heating at 60 ° C. for 24 hours, additional 10.0 ml (0.096 mol) of methylchloroacetate and 30 ml of 2 mol of LDA solution were added. The light brown reaction mixture was stirred at 60 ° C. for 24 hours and then incorporated into 300 mL of water. The basic solution was neutralized with half concentrated HCl and finally extracted by shaking three times with 80 ml of toluene each time. The organic phase was collected, washed with about 50 ml of water and dried over MgSO 4 . After evaporation of the solvent on a rotary evaporator, a tan residue was obtained. After several treatments by column chromatography on silica gel using toluene as the mobile phase, the colorant was obtained as a yellowish fluorescing yellow solution in the first run, and the intermediate methyl (m-methoxyphenoxy) acetate was blue in the main run. Obtained as a fluorescent yellow solution. Example 46: (E) -6-methoxy-2- (6-methoxy-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) -benzofuranone (1k) The yellow fluorescent yellow solution obtained in the first run by workup by column chromatography on silica gel using toluene as the mobile phase was concentrated on a rotary evaporator until a yellow high viscosity residue was obtained. It was dissolved in 150 ml of n-hexane / acetone mixture (10: 1) and the yellow colorant was freeze separated at 17 ° C. The colorant was filtered over frit, washed with n-hexane and dried in the drier. Yield: 0.07 g (2,3 × 10 -3 %), melting point: 309.5 ° C. (theoretical value: 310 ° C.), R f (toluene) = 0.74, R f (CHCl 3 ) = 0.76. UV (CHCl 3 ): λ max (ε) = 272.9 nm, 404.0 (sh), 421.4, 44.9. Fluorescence (CHCl 3 ): λ max (ε) = 475.3 nm, 495.0. Example 47 Methyl (3-methoxyphenoxy) Acetate (4k) In the process for the preparation of 6,6'-dimethoxyoxinedigo (1k), a yellow solution of blue fluorescence was obtained in the so-called main run while the reaction mixture was separated by column chromatography. After evaporation of the solvent, a yellow highly viscous residue was dissolved in 150 ml of an n-hexane / acetone mixture (10: 1) and the mixture was kept at -17 ° C for 12 hours. The intermediate was then worked up by column chromatography on silica gel using toluene as the mobile phase to separate into a blue fluorescence yellow phase. Yield: 8.6 g (23%), n D : 1.5239 (Theoretical: 1.5229) R f (toluene) = 0.65, R f (CHCl 3 ) = 0.73. UV (CHCl 3 ): λ max (ε) = 319.4 nm. Fluorescence (CHCl 3 ): λ max (ε) = 410 nm. Example 48 Methyl (3-methoxyphenoxy) Acetate (4b) 5.0 g (30 mmol) of 3-diethylaminophenol were dissolved in 80 mL of dry toluene and cooled to -78 ° C. Within 15 minutes 15 ml of a 2 molar LDA solution was added. After warming to room temperature, this phenolated solution was added dropwise to a solution of 2.7 ml (30 mmol) of methylchloroacetate in 15 ml of dry toluene. The dark brown reaction mixture was stirred at room temperature for 3 hours and then added to 300 ml of water. A small amount of 2N HCl was then added to acidify the solution. Thereafter, the reaction mixture was extracted three times with 80 ml of chloroform each time. The organic phase was collected and dried over MgSO 4 . After filtration of the desiccant, the solvent was evaporated on a rotary evaporator to give a dark brown high viscosity residue. Fractional distillation under reduced pressure of the oil pump gave analytical pure, slightly yellow viscous liquid product, which quickly turned dark brown under the influence of light and air. n D : 1.5379, R f (CHCl 3 ) = 0.63. UV (CHCl 3 ): λ max (ε) = 304.7 nm., 352.9 sh (br.) Fluorescence (CHCl 3 ): λ max (ε) = 450 nm. Example 49 Betting of 6-diethylamino-2- (6-diethylamino-3-oxo-2 (3H) -benzofuranylidene) -3 (2H) benzofuranone (1a) (a) Hydrosulfite and 70 mg (1.7 mmol) of Compound 1a were stirred with 15 ml of water at 50 ° C. 5 ml of 30% NaOH was added to the dark red suspension (pH = 9). 4 g of sodium aldehyde-sulfoxylate hydrate were interspersed in the suspension with stirring. The concentrated bat thus obtained was diluted with 30 mL and kept at 50 ° C. for 30 minutes. The non-reduced dye was filtered to give a clear yellow solution with blue fluorescence. Staining bats were maintained at 50 ° C. for the entire staining experiment. Staining experiments were carried out in several procedures. Here, cotton fibers were immersed in the bat for about 30 minutes. After removing the fibers, they were suspended for about 30 minutes and the process was repeated. The resulting cotton fibers were dyed red. If desired, reoxidation may use hydrogen peroxide. (b) 0.10 g of Auxindigo (Example 14) of Compound 1a was dissolved in 40 ml of acetic acid. 1.67 g (25.5 mmol) of zinc powder were incorporated into the dark red solution. The solution was heated to the boiling point and then gradually turned yellow. The zinc precipitate was filtered to give a clear dark yellow solution of blue fluorescence. Cotton ribbons were immersed in this solution for 15 minutes. Oxidation in air mainly formed a blue cis form of compound 2a. No color change was observed visually under the air and during the day (during the day) for several months. Optical Spectroscopic Properties of 6,6'-donor Substituted Auxindigo 1a-1k, 2a-2k and 2j numberR a) Sheath / TransFluorescent light c)1a(C 2 H 5 ) 2 N523.8610.0 2a 646.91b(CH 3 ) 2 N511.7602.0 2b 629.11c(nC 3 H 7 ) 2 N527.4620.8 2c 651.31d(nC 4 H 9 ) 2 N527.4619.0 2d 652.11e(nC 5 H 11 ) 2 N524.2608.1 2e 653.11f(nC 6 H 13 ) 2 N528.1617.9 2f 652.01 g(nC 8 H 17 ) 2 N528.8615.5 2 g 652.91h(nC 12 H 25 ) 2 N627.5614.9 2h 653.41i2-CH 3 C 6 H 4 ' CH 3 N505.1591.0 1j2-CH 3 C 6 H 4 ' HN488.8582.0 2j 602.01kCH 3 O421.4475.3a) substitution at positions 6 and 6 'of Formulas 1 and 2 b) maximum absorption in chloroform solution c) maximum fluorescence in chloroform solution; Fluorometer (Perkin Elmer 3000)
权利要求:
Claims (9) [1" claim-type="Currently amended] Auxindigo derivatives of Formula 1 or Formula 2 or mixtures thereof. <Formula 1> <Formula 2> In the above formula, 4 to 7 of the radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are hydrogen and 1 to 4 of the radicals are unsubstituted or substituted carbosi Click aromatic radicals, unsubstituted or substituted heterocyclic aromatic radicals, halogen, unsubstituted or substituted C 1 -C 18 alkyl, -OR 12 , -CN, -NR 10 R 11 , -COR 9 , -NR 13 COR 9 , -NR 12 COOR 9 , -NR 12 CONR 10 R 11 , -NHSO 2 R 9 , -SO 2 R 9 , -SOR 9 , -SO 2 OR 9 , -CONR 10 R 11 , -SO 2 NR 10 R 11 , -N = NR 14 , -OCOR 9 and -OCONHR 9 wherein two corresponding adjacent radicals may combine to form a fused aromatic ring, wherein R 9 is C 1 -C 18 alkyl, C 6 -C 10 aryl, or benzyl, unsubstituted or substituted with halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, or a 5-7 membered heterocyclic radical; R 10 and R 11 are each independently hydrogen, unsubstituted or substituted with cyano or hydroxy groups C 1 -C 18 alkyl, C 3 to C 24 cycloalkyl, C 6 -C 10 aryl or 5 to 7 membered hetero Aryl or R 10 and R 11 in each case together with one of the other radicals R 2 to R 4 form a 5- or 6-membered carbocyclic or heterocyclic ring; R 12 is hydrogen, C 1 -C 18 alkyl, C 3 to C 24 cycloalkyl, C 6 -C 10 aryl or 5- to 7-membered heteroaryl; R 13 is hydrogen, unsubstituted or substituted with C 1 -C 18 alkyl, C 3 to C 24 cycloalkyl, C 1 -C 4 alkylaryl, unsubstituted with cyano, hydroxy or C 1 -C 4 alkoxycarbonyl groups C 6 -C 10 aryl, or a 5-7 membered heterocyclic radical, or substituted by halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy group; R 14 is a radical of the coupling component or is a radical selected from the group consisting of C 6 -C 10 aryl unsubstituted or substituted with halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy group, Provided that in the auxindigo derivatives of formula 1 (trans form), in each case R 1 and R 2 are not methyl or methoxy at the same time if all remaining radicals of R 1 to R 8 are hydrogen, or R 5 And R 6 is not chlorine at the same time, or R 1 , R 2 , R 3 and R 4 are not methyl at the same time, or R 1 , R 2 , R 5 , R 6 , R 7 and R 8 are methyl at the same time Not In the cis-oxinedigo derivative of formula (2), when R 1 is a dimethylamino group, R 2 is not a hydroxy group at the same time. [2" claim-type="Currently amended] (a) alkylating 3-aminophenol of formula (3) with haloacetic acid alkylester, haloacetic acid or haloacid chloride in the presence of a base, <Formula 3> (b) in a second reaction step, treating the alkylation product of step (a) with a base or an acid in the presence of oxygen, and (c) post-treating the reaction mixture produced by a method known per se, preferably by column chromatography, A process for preparing the auxindigo derivative of formula 1 or 2 of claim 1 substituted at the 6- and 6′-positions by —NR 10 R 11 . [3" claim-type="Currently amended] (a) treating an ester compound of formula 4 with an acid or base in the presence of oxygen, or <Formula 4> (b) pyrolyzing at elevated temperatures, preferably at temperatures ranging from 80 to 200 ° C. for 0.5 to 3 hours, and then subjecting the resulting reaction mixture to a process known per se, preferably by column chromatography. Processing, A process for preparing the auxindigo derivative of formula 1 or 2 of claim 1 substituted at the 6- and 6′-positions by —NR 10 R 11 . [4" claim-type="Currently amended] Leuco auxindigo derivatives of formula (7). <Formula 7> [5" claim-type="Currently amended] Coumaranone of formula (6). <Formula 6> [6" claim-type="Currently amended] Esters of formula 4. <Formula 4> [7" claim-type="Currently amended] 3-Aminophenol of Formula 3; <Formula 3> [8" claim-type="Currently amended] (Z)-and / or (E)-DELTA 11, 11 '(2H, 3H, 4H, 6H, 7H, 8H, 10H, 2'H, 3'H, 4'H, 6'H, 7' H, 8'H, 10'H) -bibenzo [i, j] furo [3,2-g] -quinoline-10,10'-dione. [9" claim-type="Currently amended] As colorant for bulk dyeing of polymers; Batches for the production of varnishes, paints, in particular automotive finishes, coatings, paper colorants, printing inks, inks (especially for inkjet printers, painting and substrates, and electrophotographic such as for dry radiography (Xerox processes) and laser printers) As a dye; For security signs; As an additive to colorants such as pigments and dyes from which a particular color tone is obtained; For object marking for machine reading of the object via fluorescence; For switching optical frequencies; For the production of passive display elements for the purposes of various types of displays, publications and signs; As starting material for superconductivity of organic materials; For labeling using solid state fluorescence; Decorative and artistic; Tracer; As a fluorescent dye in a high sensitivity detection method; In optical photo-collecting systems, in fluorescent solar collectors, in fluorescently activated displays, as photoinductive polymerization for the manufacture of plastics, as cold light sources for material testing, in photoconductors, in photophotographic processes, in display, light emitting or image conversion systems As a dye or fluorescent dye in; In chemiluminescent systems, as components of integrated semiconductor circuits containing dyes by themselves or with other semiconductors in luminescence immunoassays or other luminescence detection methods; As signal paint in optical dye lasers or as optical storage media, Use of an auxindigo derivative of formula 1 or 2 according to claim 1 or according to claim 2.
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同族专利:
公开号 | 公开日 AU2387497A|1997-11-19| DE69709343D1|2002-01-31| JP2000510508A|2000-08-15| ES2169382T3|2002-07-01| AU717688B2|2000-03-30| CA2249217A1|1997-11-06| US6156914A|2000-12-05| EP0900255A1|1999-03-10| WO1997041176A1|1997-11-06| EP0900255B1|2001-12-19| DE69709343T2|2002-08-22| DE19616532A1|1998-02-26|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题
法律状态:
1996-04-25|Priority to DE19616532.6 1996-04-25|Priority to DE19616532A 1997-04-17|Application filed by 에프. 아. 프라저, 에른스트 알테르 (에. 알테르), 한스 페터 비틀린 (하. 페. 비틀린), 피. 랍 보프, 브이. 스펜글러, 페. 아에글러, 시바 스페셜티 케미칼스 홀딩 인크. 1997-04-17|Priority to PCT/EP1997/001915 2000-11-06|Publication of KR20000065020A
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申请号 | 申请日 | 专利标题 DE19616532.6|1996-04-25| DE19616532A|DE19616532A1|1996-04-25|1996-04-25|Donor-substituted oxindigo derivatives and their use as dyes| PCT/EP1997/001915|WO1997041176A1|1996-04-25|1997-04-17|Donor-substituted oxindigo derivatives and their use as colourants| 相关专利
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