Xanthene compounds having wavelengths in range of 650 to 1200 nm

Abstract

The present invention relates to a compound of formula (I) (R4 is-SO3-, or a group of formula-SO2NR12R13), to a process for the preparation thereof and to the use thereof as: as a compound that absorbs light emitted from a radiation source and optionally emits light different from the light of the radiation source and having a wavelength in the range of 650 to 1200 nm; in photovoltaic applications; or in bioimaging, or in photodynamic therapy; or as a semiconductor in organic electronic applications; as laser dyes, in inks for machine readability and / or security applications or for laser welding of plastics; or used for trademark protection or used as a liquid marker. Compounds of formula (I) may have a high molar extinction coefficient, high fluorescence quantum yield, high solubility and stability in application media, good storage stability and / or good detectability even in very small amounts in corresponding labeled liquids. # imgabs0 #

Description

[0001] The present invention relates to a

[0002] Compounds of formula (I), methods for their preparation, and their use as compounds that absorb light emitted from a radiation source and optionally emit light having a wavelength in the range of 650 to 1200 nm different from that of the radiation source; in photovoltaic applications; or in bioimaging, or in photodynamic therapy, or as semiconductors in organic electronic applications; as laser dyes, in inks for machine readability and / or security applications, or for laser welding of plastics; or for trademark protection, or as liquid markers. Compounds of formula (I) may have a high molar extinction coefficient, a high fluorescence quantum yield, high solubility and stability in the application medium, good storage stability, and / or good detectability, even in very small amounts in the correspondingly labeled liquid. Background Art

[0003] WO 2009 / 094536 A1 discloses compounds of formula III:

[0004] or a stereoisomer, tautomer, hydrate, solvate or salt thereof; wherein R 1 selected from the group consisting of H, alkyl, and substituted alkyl;

[0005] R 2 、R 4 、R 5 、R 6 、R 7 、R 8 and R 10 each independently selected from the group consisting of H, alkyl, substituted alkyl, alkoxy, substituted alkoxy, acyl, acylamino, acyloxy, amino, substituted amino, aminocarbonyl, aminothiocarbonyl, aminocarbonylamino, aminothiocarbonylamino, aminocarbonyloxy, aminosulfonyl, aminosulfonyloxy, aminosulfonylamino, amidino, carboxyl, carboxyl ester, (carboxyl ester)amino, (carboxyl ester)oxy, cyano, halo, hydroxy, nitro, SO 3 ′, sulfonyl, substituted sulfonyl, sulfonyloxy, thioacyl, thiol, alkylthio, substituted alkylthio, aryl, substituted aryl, heteroaryl, substituted heteroaryl, cycloalkyl, substituted cycloalkyl, heterocyclyl, and substituted heterocyclyl; and

[0006] R 11 Selected from the group consisting of: H, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocyclyl, substituted heterocyclyl, cycloalkyl, and substituted cycloalkyl; and use of the compound for detecting analytes containing aldehyde and ketone groups.

[0007] US20220056335 A1 relates to a near-infrared dye comprising a structure having formula I,

[0008]

[0009] where R 1 Contains substituted or unsubstituted C1-C 10 Straight chain or branched alkyl, substituted or unsubstituted C1-C 10 Straight chain or branched alkoxy, C3-C 10 cycloalkyl, substituted or unsubstituted aryl or heteroaryl, or any combination thereof; and wherein R 2 Including C1-C 10 Straight chain or branched alkyl, C3-C 10 A cycloalkyl group or any combination thereof, a method for preparing the dye, a composition comprising the dye, a method for imaging a biological sample using the composition, and an optoelectronic device using the dye.

[0010] Chathuranga Rathnamalala et al., J.Org.Chem. 2019, 84, 13186-13193 reported the synthesis of NIR II emitting dyes by C-H bond functionalization of 1-methyl-2-phenylindoleazine with 3,6-dibromoxanthene. The rhodindolizine (RhIndz) spironolactone product is non-fluorescent; however, when the lactone ring is opened by the formation of an ethyl ester derivative, The fluorophore absorbs at 920 nm and emits at 1092 nm, which are both in the NIR II region.

[0011] Satadru Chatterjee et al., RSC Adv., 2021, 11, 27832, report two short-wave infrared (SWIR)-emitting xanthene-encoded RosIndolizine dyes. Ph RosIndz and tol Synthesis and characterization of RosIndz They have great potential in high-resolution deep tissue in vivo bioimaging.The emission of these dyes is shown in the SWIR region with a peak emission at 1097 nm.

[0012] Satadru Chatterjee et al., J.Org.Chem. 2022, 87, 11319-11328 reported the synthesis of four novel rhodazole dyes, such as The dyes were characterized photophysically via steady-state absorption and emission spectroscopy to show significant SWIR absorption (λ 最大 吸收 =926-1096nm, where all starting points are >1000nm) and emission (λ 最大 发射 =1082-1256nm).

[0013] WO 00 / 064988 relates to a compound having the formula The compound R 1 and R 6 It is H;

[0014] R 2 、R 3 、R 4 and R 6 are independently H, F, Cl, Br, I, CN; or C1-C 18 Alkyl, or C1-C 18 Alkoxy, wherein each alkyl or alkoxy group is optionally further substituted with F, Cl, Br, I, a carboxylic acid, a salt of a carboxylic acid, or a carboxylic ester of a C1-C6 alcohol; or -SO3X, wherein X is H or a counterion;

[0015] or R 1 With R 2 Combined, or R 6 With R 5 The bond is a fused six-membered aromatic ring;

[0016] R 8 and R 9 is independently H, C1-C6 alkyl, C1-C6 carboxyalkyl, C1-C6 sulfoalkyl, a salt of C1-C6 carboxyalkyl, or a salt of C1-C6 sulfoalkyl, wherein the alkyl portion is optionally substituted with amino, hydroxy, carboxylic acid, a salt of a carboxylic acid, or a C1-C6 alkyl carboxylate; or -LR X ; or -LS C ; or R 8 and R 9 One or more of which are Q moieties; or R 8 With R 9 Combined to form a saturated 6-membered or 6-membered heterocyclic ring, the heterocyclic ring is optionally fused to the Q portion and optionally further substituted by methyl, carboxylic acid, a salt of a carboxylic acid, a C1-C6 alkyl carboxylate, or -LR X , or -LS C replace;

[0017] wherein each Q moiety is 1 to 4 aromatic or heteroaromatic rings, and when 2 to 4 of these rings are present, they are fused to each other and, regardless of the number, are optionally substituted with halogen, cyano, sulfo, alkali or ammonium salts of sulfonamide, carboxyl, alkali or ammonium salts of carboxyl, nitro, alkyl, perfluoroalkyl, alkoxy, alkylthio, amino,

[0018] Monoalkylamino, dialkylamino; alkylamide; or -LR X Replaced by -LS C substituted; wherein each heteroaromatic ring in Q is a 5-membered or 6-membered aromatic heterocyclic ring having 1 to 3 heteroatoms selected from the group consisting of O, N or S in any combination; and

[0019] K is O or N + R 18 R 19 ;

[0020] where R 18 and R 19 is independently H, C1-C6 alkyl, C1-C6 carboxyalkyl, C1-C6 sulfoalkyl, a salt of C1-C6 carboxyalkyl, or a salt of C1-C6 sulfoalkyl, wherein the alkyl portion is optionally substituted with amino, hydroxy, carboxylic acid, a salt of a carboxylic acid, or a C1-C6 alkyl carboxylate; or -LR X ; or -LS C ; or R 18 and R 19 One or more of which are Q moieties; or R 18 With R 19 Combined to form a saturated 5- or 6-membered heterocyclic ring, which is piperidine or pyrrolidine optionally fused to the Q moiety and optionally further substituted with methyl, carboxylic acid, a salt of a carboxylic acid, a C1-C6 alkyl carboxylate; or -LR X ; or -LS C ;

[0021] R 10 is H, CN, a carboxylic acid, a salt of a carboxylic acid, or a carboxylic acid ester of a C1-C6 alcohol; or R 10 Is saturated or unsaturated C1-C 18 Alkyl, which is optionally substituted one or more times with F, Cl, Br, carboxylic acid, a salt of a carboxylic acid, a carboxylic acid ester of a C1-C6 alcohol, -SO3X, amino, alkylamino, or dialkylamino, wherein the alkyl group has 1-6 carbon atoms; or R 10 Has the following formula, where R 12 、R 13 、R 14 、R 15 and R 16are independently H, F, Cl, Br, I, -SO3X, carboxylic acid, carboxylic acid salt, CN, hydroxyl, amino, hydrazine; or C1-C 18 Alkyl, C1-C 18 Alkoxy, C1-C 18 Alkylthio, C1-C 18 Alkanoylamino, C1-C 18 Alkylaminocarbonyl, C2-C 36 Dialkylaminocarbonyl, C1-C 18 Alkoxycarbonyl, or C6-C 18 Arylcarboxamido, the alkyl or aryl portion of which is optionally substituted one or more times with F, Cl, Br, I, hydroxy, carboxylic acid, a salt of a carboxylic acid, a carboxylic ester of a C1-C6 alcohol, -SO3X, amino, alkylamino, dialkylamino, or alkoxy, each alkyl portion having 1-6 carbon atoms; or a pair of adjacent

[0022] Substituent R 13 and R 14 、R 14 and R 15 , or R 15 and R 16 When combined, they form a fused 6-membered aromatic ring, which is optionally further substituted with a carboxylic acid or a carboxylate salt; or R 12 、R 13 、R 14 、R 15 and R 16 One of them is -LR X or -LS C ;

[0023] The condition is R 8 、R 9 、R 18 and R 19 At least one of is a Q moiety or is fused to a Q moiety; and

[0024] A further condition is that R 8 、R 9 、R 12 、R 13 、R 14 、R 15 、R 16 、R 18 or R 19 At least one of them is -LR X or -LS C ; or at least one Q segment is -LR X or -LS C Replace;

[0025] L is a covalent bond; and

[0026] R X is a reactive functional group which is a maleimide, an isocyanate, an isothiocyanate, a phosphoramidite, a reactive platinum complex, a perfluorobenzamido group, a perfluorobenzamido azido group, a succinimide ester, a sulfosuccinimide ester, an alkali metal salt or alkaline earth metal salt of a sulfosuccinimide ester, a symmetrical anhydride, a mixed anhydride of a chloroformatic acid ester having 2 to 8 carbon atoms, a mixed anhydride of a carboxylic acid or a perfluorocarboxylic acid having 2 to 8 carbon atoms, a mixed anhydride of a sulfonic acid or a fluorinated sulfonic acid having 1 to 8 carbon atoms, or an ester of a phenol or naphthol further substituted one or more times with a nitro group, a sulfo group, a carboxyl group, an alkali metal or alkaline earth metal salt of a sulfo group or a carboxyl group, a cyano group, a fluorine group, a chlorine group, or a trifluoromethyl group; or R X is an adduct of a carboxylic acid and a carbodiimide having 2 to 14 carbons; and

[0027] S C is a conjugated substance, such as a substance having the formula Compounds; and their use as luminescence quenching compounds.

[0028] In the field of biomarkers, the interfering effects of the biomarker matrix can be minimized by using NIR II absorbing and emitting markers. There is an unmatched need for chromophores that absorb and emit particularly in the NIR region, and very particularly in the NIR II region. In the field of fluorescence bioimaging applications, the availability of NIR emitting molecules remains an important need.

[0029] It was therefore an object of the present invention to provide compounds which may have a high stability, a high absorption coefficient and / or a fluorescence quantum yield compared to the compounds known in the art, in particular in the NIR region, very particularly in the NIRII region. Summary of the Invention

[0030] Surprisingly, it has been found that these and further objects are achieved by compounds of formula (I) as defined below.

[0031] Therefore, the present invention relates to compounds having the formula

[0032] in,

[0033] R 1 and R 2 Independently of each other are Groups;

[0034] R 3 is hydrogen, -CO2H or -SO3H;

[0035] R 4 Yes-SO3 - , or having the formula -SO2NR 12 R13 group, provided that in R 4 In the absence of a negative charge, the compound of formula (I) comprises an anionic counterion;

[0036] R 5 It is C1-C 24 Alkyl, substituted by one or more R 14 Substituted C3-C 10 -cycloalkyl, C6-C 10 Aryl-C1-C 10 Alkylene - which can be substituted by one or more R 14 Substituted and the alkylene group may be interrupted by one or more selected from O, S and -NR 9 Non-adjacent groups; can be substituted by one or more substituents R 14 Substituted C6-C 10 Aryl, or may be substituted by one or more R 14 Substituted C2-C 14 heteroaryl;

[0037] R 6 is hydrogen, C1-C 24 Alkyl, C1-C 24 Alkoxy, which may be substituted by one or more R 14 Substituted C6-C 10 -aryl, and C1-C 24 -fluoroalkyl, fluorine, chlorine or bromine;

[0038] R 7 It is C1-C 24 Alkyl, C1-C 24 Alkoxy, C1-C 24 Fluoroalkyl, group NR 10 R 11 , fluorine, chlorine or bromine;

[0039] R 8a 、R 8b and R 8c independently selected from C1-C 24 Alkyl, C1-C 24 Alkoxy, C1-C 24 Fluoroalkyl, fluorine, chlorine or bromine;

[0040] R 9 is hydrogen, or C1-C4 alkyl;

[0041] R 10 and R 11 Independently of each other are C1-C 24 Alkyl, hydroxy-C1-C 24Alkyl, which may be substituted by one or more R 14 Substituted C6-C 10 -aryl, or substituted by one or more R 14 Substituted C3-C 10 -cycloalkyl; or

[0042] R 10 and R 11 Together with the nitrogen to which they are bound, they form a five- or six-membered ring system which may be interrupted by -O-, -S- or -NR 12 '- and may be part of a fused ring system which may be substituted by one or more substituents R 14 replace;

[0043] R 12 and R 13 are independently hydrogen, C1-C 24 Alkyl, hydroxy-C1-C 24 Alkyl, substituted by one or more R 14 Substituted C3-C 10 -cycloalkyl, C6-C 10 Aryl-C1-C 10 Alkylene, which may be substituted by one or more R 14 Substituted and the alkylene group may be interrupted by one or more selected from O, S and -NR 12 'non-adjacent groups; may be substituted by one or more substituents R 14 Substituted C6-C 10 Aryl, or may be substituted by one or more R 14 Substituted C2-C 14 heteroaryl; or

[0044] R 12 and R 13 Together with the nitrogen to which they are bound, they form a five- or six-membered ring system which may be interrupted by -O-, -S- or -NR 12 '- and may be part of a fused ring system which may be substituted by one or more substituents R 14' replace;

[0045] R 12 ' is hydrogen, or C1-C4 alkyl;

[0046] R 14 It is C1-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Fluoroalkyl, nitro, cyano, hydroxy, fluorine, chlorine or bromine;

[0047] R 14'It is C1-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Fluoroalkyl, nitro, cyano, hydroxyl, -(CH2) n5 COOH group, -(CH2) n5 COO - radical, fluorine, chlorine or bromine;

[0048] And n1 is 0, 1 or 2; n2 is 0, 1 or 2, n3 is 0 or 1, n4 is 0, 1 or 2, and n5 is 0, or an integer from 1 to 10.

[0049] A further aspect of the invention relates to the use of a compound of formula (I) as defined above as a fluorescent dye that absorbs light emitted from a radiation source and optionally emits light different from the light of the radiation source and having a wavelength in the range of 650 to 1200 nm, in particular 680 to 1200 nm.

[0050] A further aspect of the present invention relates to the use of compounds of formula (I) as defined above as fluorescent dyes in conversion LEDs.

[0051] A further aspect of the invention relates to the use of a compound of formula (I) as defined above in a near infrared spectrometer device.

[0052] A further aspect of the invention relates to the use of a compound of formula (I) as defined above in agricultural films.

[0053] A further aspect of the present invention relates to the use of compounds of formula (I) as defined above in photovoltaic applications.

[0054] A further aspect of the invention relates to the use of a compound of formula (I) as defined above in a fluorescent solar concentrator.

[0055] A further aspect of the present invention relates to the use of compounds of formula (I) as defined above as semiconductors in organic electronic applications.

[0056] A further aspect of the invention relates to the use of compounds of formula (I) as defined above as laser dyes, in inks for machine readability and / or security applications or for laser welding of plastics.

[0057] A further aspect of the invention relates to the use of a compound of formula (I) as defined above for trademark protection or as a marker for liquids, in particular oils.

[0058] Another aspect of the present invention relates to a color converter comprising

[0059] (i) a compound of formula (I) as defined above;

[0060] (ii) a polymer matrix material selected from the group consisting of polystyrene, polycarbonate, polyacrylate, polymethyl methacrylate, polymethacrylate, polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl chloride, polybutylene, polysiloxane, epoxy resin, polyvinyl alcohol, poly(ethylene vinyl alcohol)-copolymer, polyacrylonitrile, polyvinylidene chloride, polystyrene acrylonitrile, polybutylene terephthalate, polyethylene terephthalate, 2,5-furandicarboxylate polyester, polyvinyl butyrate, polyvinyl chloride, polyamide, polyoxymethylene, polyimide, polyetherimide, or mixtures thereof; and

[0061] (iii) optionally a light scattering agent.

[0062] Another aspect of the present invention relates to a near-infrared light source comprising

[0063] (i) a light source selected from a blue LED, a red LED, or a white LED; and

[0064] (ii) A color converter as defined above.

[0065] Compounds of formula (I) as described herein provide several benefits, in particular high solubility and stability in the application medium. In addition, certain compounds of formula (I) are very suitable as fluorescent dyes, due to their good solubility in the application medium and high fluorescence quantum yield, so that they can be used as NIR compounds emitting light having a wavelength of 650 to 1200 nm, in particular 680 to 1200 nm. In addition, compounds of formula (I) are very suitable as markers for liquids, in particular oils, such as mineral oils, due to their advantageous application properties, such as good solubility in liquids, high molar extinction coefficients, good storage stability, and good detectability even in very small amounts in the corresponding labeled liquid.

[0066] Figure 1 : Normalized UV / VIS / NIR absorption spectra of dichlorosulfonylfluorescein in dichloromethane solution

[0067] DETAILED DESCRIPTION

[0068] Here and throughout the specification, the term "near infrared light" refers to light in the range of 680 to 1700 nm, particularly 680 to 1200 nm. As used herein, "NIR I" refers to the region of the electromagnetic spectrum having a wavelength of about 680 nm to about 900 nm, while "NIR II" refers to the region of the electromagnetic spectrum having a wavelength of about 900 nm to about 1200 nm.

[0069] Here and throughout the specification, the term "visible light" refers to light in the range of approximately 380 nm to 740 nm.

[0070] As used herein, "photoluminescent" refers to a molecule that absorbs a photon, thereby exciting an electron in the molecule to a higher electronic excited state, and then radiates the photon as light when the electron returns to a lower energy state. In one aspect, the NIR compounds and compositions disclosed herein are photoluminescent in the NIR region.

[0071] As used herein, "fluorescence quantum yield" (φ) refers to the ratio of absorbed photons to photons emitted through fluorescence.

[0072] As used herein, "Stokes shift" refers to the difference between the position of a maximum in an absorption band of a compound and the position of a maximum in the fluorescence emission of the same compound.

[0073] In one aspect, the NIR compounds disclosed herein have a Stokes shift of 150 nm or greater in the NIR region.

[0074] "Molar absorptivity," "molar absorption coefficient," "extinction coefficient," and "molar attenuation coefficient" (ε) refer to how strongly a chemical compound absorbs light at a given wavelength. Molar absorptivity is an intrinsic property of the compound; however, it varies with wavelength and solvent. Molar absorptivity is usually expressed as the absorption at a specific wavelength, such as the position of a maximum in an absorption band. Units are usually L / mol cm or M -1 cm -1 In one aspect, the disclosed NIR compounds have high ε in the NIR spectral region.

[0075] An “anionic counterion” is an anion, or an anionic group associated with the cationic charge of a compound of formula (I); more particularly, the anionic counterion is selected from i) a halide, such as chloride or bromide; ii) a nitrate; iii) a sulfonate, including a C1-C6 alkylsulfonate: Alk-S(O)2O - , such as methanesulfonate or mesylate and ethanesulfonate; iv) arylsulfonate: ArS(O)2O - , such as benzenesulfonate and toluenesulfonate (toluenesulfonate or tosylate); v) citrate; vi) succinate; vii) tartrate; viiii) lactate; ix) alkyl sulfate: Alk-OS(O)O - Such as methyl sulfate and ethyl sulfate; x) aryl sulfate: Ar-OS(O)O - Such as benzene sulfate and toluene sulfate; xi) alkoxy sulfate: Alk-OS(O)2O- Such as methoxysulfate and ethoxysulfate; xii) aryloxysulfate: Ar-OS(O)2O - -(xiv) phosphate; xiii) phosphate; xiv) acetate; xv) triflate; and xvi) borate, such as tetrafluoroborate.

[0076] Here and throughout the specification, the term "halogen" denotes fluorine, bromine, chlorine or iodine, in particular chlorine, bromine or iodine.

[0077] The term "C1-C n -alkyl" refers to a group of straight-chain or branched saturated hydrocarbon groups having 1 to n carbon atoms. For example, the term C1-C 24 -alkyl designates the group of straight-chain or branched saturated hydrocarbon radicals having 1 to 24 carbon atoms, while the term C1-C4-alkyl designates the group of straight-chain or branched saturated hydrocarbon radicals having 1 to 4 carbon atoms, and the term C5-C 20 Alkyl designates the group of straight-chain or branched saturated hydrocarbon groups having 5 to 20 carbon atoms, and the term C6-C 20 -Alkyl designates the group of straight or branched saturated hydrocarbon radicals having 6 to 20 carbon atoms. Examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylpropyl (isopropyl), 1,1-dimethylethyl (tert-butyl), pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylbutyl, Methylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl (tert-octyl), nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl and, in the case of nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl and their isomers, in particular mixtures of isomers, such as "isononyl" and "isodecyl". Examples of C1-C4-alkyl are, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl.

[0078] As used herein, the term "C1-C 24 "Fluoroalkyl" means a linear or branched C1-C 24 Alkyl, wherein some or all of the hydrogen atoms in these groups may be replaced by fluorine as above. Examples of C1-C2-fluoroalkyl are fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and pentafluoroethyl.

[0079] As used herein, the term "C1-C 24 "Alkoxy" means a straight or branched C1-C12 radical as defined above bonded to the remainder of the molecule via an oxygen radical. 24 Examples of C1-C4-alkoxy are methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy.

[0080] As used herein, the term "C3-C 10 "Cycloalkyl" means a monocyclic, bicyclic or tricyclic cycloalkyl group which is unsubstituted or substituted by one or more groups R 7 (e.g. 1, 2, 3 or 4 R 7 C3-C 10 Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, and norbornyl (=bicyclo[2.2.1]heptyl).

[0081] As used herein, the term "C6-C 10 "-aryl" means phenyl or naphthyl.

[0082] As used herein, the term "heteroaryl", especially C2-C 14Heteroaryl refers to a heteroaromatic monocyclic, bicyclic or tricyclic fused system having 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring members, wherein at least one ring is aromatic and contains 1, 2, 3 or 4 heteroatoms selected from N, S or O. Monocyclic heteroaryl is preferably a 5-membered or 6-membered heteroaryl group containing 1, 2 or 3 heteroatoms selected from O, S or N, such as 2-furyl (furan-2-yl), 3-furyl (furan-3-yl), 2-thienyl (thien-2-yl), 3-thienyl (thien-3-yl), 1H-pyrrol-2-yl, 1H-pyrrol-3-yl, pyrrol-1-yl, imidazol-2-yl, imidazol-1-yl, imidazol-4-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 4H-[1,2,4]-triazol-3-yl, 1,3,4-triazol-2-yl, 1,2,3-triazol-1-yl, 1,2,4-triazol-1-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl. Bicyclic fully aromatic heteroaryl groups are 9- or 10-membered and contain 1, 2, 3 or 4 heteroatoms selected from O, S or N. Examples are quinolyl, isoquinolyl, indolyl, isoindolyl, indolizinyl, benzofuranyl, isobenzofuranyl, benzothiophenyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, benzopyrazolyl, benzimidazolyl, benzotriazolyl, benzotriazinyl.

[0083] As used herein, the term "C6-C 10 Aryl-C1-C 10 Alkylene (also referred to as aralkyl) refers to a C6-C8 group as defined herein having at least one unsubstituted or substituted aryl group. 10 Aryl substituted alkyl. The alkyl group of the aralkyl group may be interrupted by one or more selected from O, S and -NR 12 ' non-adjacent groups, where R 12 ' is as defined below or above. C6-C 10 -Aryl-C1-C 10 -alkylene is preferably phenyl-C1-C 10-alkylene, more preferably phenyl-C1-C4-alkylene, for example benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-1-yl, 2-phenylprop-1-yl, 3-phenylprop-1-yl, 1-phenylbut-1-yl, 2-phenylbut-1-yl, 3-phenylbut-1-yl, 4-phenylbut-1-yl, 1-phenylbut-2-yl, 2-phenylbut-2-yl, 3-phenylbut-2-yl or 4-phenylbut-2-yl; preferably benzyl and 2-phenylethyl.

[0084] In a preferred embodiment, the compound of formula (I) is Compounds, wherein n1, n2, n3, R 1 、R 2 、R 3 、R 8a 、R 8b and R 8c As defined above or below.

[0085] In the embodiment described, n1, n2 and n3 are preferably 0.

[0086] Therefore, the formula Compounds containing : are more preferred.

[0087] R 3 Preferred is hydrogen.

[0088] R 1 and R 2 Preferably, it has the formula groups, especially where R 5 、R 6 and R 7 As defined above or below.

[0089] R 7 Preferably the group -NR 10 R 11 , where R 10 and R 11 Independently of each other are C1-C 24 Alkyl, hydroxy-C1-C 24 Alkyl, which may be substituted by one or more R 14 Substituted C6-C 10 -aryl, or substituted by one or more R 14 Substituted C3-C 10 -cycloalkyl; or R 10 and R 11 Together with the nitrogen to which they are bound, they form a five- or six-membered ring system which may be interrupted by -O-, -S- or -NR 12'- and may be part of a fused ring system which may be substituted by one or more substituents R 14 replace.

[0090] Group -NR 10 R 11 Examples are phenylmethylamino, diphenylamino, dimethylamino, methylethylamino, 2-hydroxyethylmethylamino, 2-hydroxyethylethylamino, di-2-hydroxyethylamino, 2-ethylhexylmethylamino, 2-ethylhexylethylamino, 3-propylheptylmethylamino and 3-propylheptylethylamino.

[0091] Group -NR 10 R 11 An example of R is shown below, where R 10 and R 11 Together with the nitrogen to which they are bound, they form a five- or six-membered ring system:

[0092]

[0093] BOC is tert-butoxycarbonyl. n5 is preferably 0 or an integer from 1 to 5, more preferably 0 or 1.

[0094] R 1 and R 2 More preferably, the formula group.

[0095] R 5 Preferably C6-C 10 Aryl, which may be substituted by one or more substituents R 14 Substituted; such as, for example, phenyl, 4-cyanophenyl, 4-trifluoromethylphenyl, 4-nitrophenyl, 3,5-bis-trifluoromethylphenyl, 4-hydroxyphenyl or 4-methoxyphenyl, especially phenyl.

[0096] R 6 Preferred are C1-C4 alkyl or CF3 groups, especially methyl.

[0097] R 1 and R 2 Even more preferably, a compound having the formula A group in which R 5 is phenyl, 4-cyanophenyl, 4-trifluoromethylphenyl, 4-nitrophenyl, 3,5-bis-trifluoromethylphenyl, 4-hydroxyphenyl or 4-methoxyphenyl, in particular phenyl; and

[0098] R 6 It is a C1-C4 alkyl group, or a CF3 group.

[0099] The most preferred5 is phenyl and R 6 is a methyl group, namely R 1 and R 2 Indicates a formula group.

[0100] The compound of formula (Ia') (wherein R 3 Examples of (being hydrogen) are shown in the following table:

[0101]

[0102] In another preferred embodiment, the compound of formula (I) is A compound wherein n6 is 0 or 1, An - is an anion, and n1, n2, n3, R 1 、R 2 、R 3 、R 8a 、R 8b 、R 8c 、R 12 and R 13 As defined above or below.

[0103] In the embodiment described, n1, n2 and n3 are preferably 0.

[0104] Therefore, the formula The compound is more preferred. n6 is 0 or 1, An - is an anion, and R 1 、R 2 、R 3 、R 12 and R 13 As defined above or below.

[0105] For example, if -NR 12 R 13 Indicates a formula If the group -NR 12 R 13 If it has no negative charge, then n6 is 1.

[0106] The anion is selected from i) halides, such as chloride or bromide; ii) nitrate; iii) sulfonate, including C1-C6 alkylsulfonate: Alk-S(O)2O - , such as methanesulfonate or mesylate and ethanesulfonate; iv) arylsulfonate: ArS(O)2O -, such as benzenesulfonate and toluenesulfonate (toluenesulfonate or tosylate); v) citrate; vi) succinate; vii) tartrate; viiii) lactate; ix) alkyl sulfate: Alk-OS(O)O - Such as methyl sulfate and ethyl sulfate; x) aryl sulfate: Ar-OS(O)O - Such as benzene sulfate and toluene sulfate; xi) alkoxy sulfate: Alk-OS(O)2O - Such as methoxysulfate and ethoxysulfate; xii) aryloxysulfate: Ar-OS(O)2O - -(xiv) phosphate; xiii) phosphate; xiv) acetate; xv) triflate; and xvi) borate, such as tetrafluoroborate.

[0107] R 3 Preferred is hydrogen.

[0108] R 1 and R 2 Preferably, it has the formula groups, especially where R 5 、R 6 and R 7 As defined above or below.

[0109] R 7 Preferably the group -NR 10 R 11 , where R 10 and R 11 Independently of each other are C1-C 24 Alkyl, hydroxy-C1-C 24 Alkyl, which may be substituted by one or more R 14 Substituted C6-C 10 -aryl, or substituted by one or more R 14 Substituted C3-C 10 -cycloalkyl; or R 10 and R 11 Together with the nitrogen to which they are bound, they form a five- or six-membered ring system which may be interrupted by -O-, -S- or -NR 12 '- and may be part of a fused ring system which may be substituted by one or more substituents R 14 replace.

[0110] Group -NR 12 R 13Examples are phenylmethylamino, diphenylamino, dimethylamino, methylethylamino, 2-hydroxyethylmethylamino, 2-hydroxyethylethylamino, di-2-hydroxyethylamino, 2-ethylhexylmethylamino, 2-ethylhexylethylamino, 3-propylheptylmethylamino and 3-propylheptylethylamino.

[0111] Group -NR 12 R 13 An example of R is shown below, where R 12 and R 13 Together with the nitrogen to which they are bound, they form a five- or six-membered ring system:

[0112]

[0113] Especially

[0114] R 1 and R 2 More preferably, the formula group.

[0115] R 5 Preferably C6-C 10 - aryl, which may be substituted by one or more substituents R 14 Substituted; such as, for example, phenyl, 4-cyanophenyl, 4-trifluoromethylphenyl, 4-nitrophenyl, 3,5-bis-trifluoromethylphenyl, 4-hydroxyphenyl or 4-methoxyphenyl, especially phenyl.

[0116] R 6 Preferred are C1-C4 alkyl or CF3 groups, especially methyl.

[0117] R 1 and R 2 Even more preferably, a compound having the formula A group in which R 5 is phenyl, 4-cyanophenyl, 4-trifluoromethylphenyl, 4-nitrophenyl, 3,5-bis-trifluoromethylphenyl, 4-hydroxyphenyl or 4-methoxyphenyl, in particular phenyl; and

[0118] R 6 It is a C1-C4 alkyl group, or a CF3 group.

[0119] The most preferred 5 is phenyl and R 6 is a methyl group, namely R 1 and R 2 Indicates a formula Examples of compounds of formula (Ib') are shown in the table below. of compounds.

[0120]

[0121] A method for producing a A method for producing a compound, the method comprising:

[0122] i) Make it have the formula The compound with formula The compound is reacted in the presence of diisopropylethylamine in a solvent, especially n-butanol, at a temperature from 20°C to the boiling point of the solvent, wherein n1, n2, n3, n4, R 1 、R 2 、R 3 、R 5 、R 6 、R 7 、R 8a 、R 8b and R 8c As defined above.

[0123] With formula The compound can be converted into a compound having the formula of compounds.

[0124] With formula The compound of formula (IV) can be prepared by reacting a compound of formula (IV) with a compound of formula (HNR) 15 -X 1 -X 2 (V) is obtained by reacting the compound, wherein X 2 It is a reactive functional group.

[0125] With formula The compound of formula (IV) can be prepared by reacting a compound of formula (IV) with a compound of formula (HNR) 12 R 13 The compound (VII) is obtained by reaction.

[0126] The compound of formula (VI) (wherein X 2 is a reactive functional group) is converted into a compound having formula (VI) (wherein X 2 is a conjugated substance).

[0127] X 1 is a linking group;

[0128] X 2 is a reactive functional group,

[0129] R 15 is hydrogen, or C1-C4 alkyl; and

[0130] n1, n2, n3, R1 、R 2 、R 3 、R 8a 、R 8b 、R 8c 、R 12 and R 13 As defined above.

[0131] Preferred X 1 The moiety has 1-20 non-hydrogen atoms selected from the group consisting of C, N, O, P, and S; and is composed of any combination of ether, thioether, amine, ester, carboxamide, sulfonamide, hydrazide linkages, and aromatic or heteroaromatic linkages. 1 Preferably, it contains 4 to 10 non-hydrogen atoms, including one or two heteroatoms. 1 Examples of include substituted or unsubstituted polymethylene, arylene, alkylenearylene, arylenealkylene or arylenethio. In one embodiment, X 1 The formula is (CH2) a (CONH(CH2) b ) z - or including the formula wherein a has any value from 0 to 5, b has any value from 1 to 5, and z is 0 or 1.

[0132] X 2 is an acrylamide, an activated ester of a carboxylic acid, an acyl azide, an acyl nitrile, an aldehyde, an alkyl halide, an amine, an anhydride, an aniline, an aryl halide, an azide, an aziridine, a borate, a carboxylic acid, a diazoalkane, a haloacetamide, a halotriazine, a hydrazine (including a hydrazide), an imino ester, an isocyanate, an isothiocyanate, a maleimide, a phosphoramidite, a reactive platinum complex, a sulfonyl halide, or a thiol group. "Reactive platinum complex" means a chemically reactive platinum complex, such as described in US Pat. No. 5,714,327.

[0133] Preferably, X 2 is a phosphoramidite, a succinimidyl ester of a carboxylic acid, a haloacetamide, a hydrazine, an isothiocyanate, a maleimide group, a perfluorobenzamide group, or an azidoperfluorobenzamide group. More preferably, X 2 is a phosphoramidite, a reactive platinum complex, or a succinimidyl ester of a carboxylic acid. 2 When a reactive platinum complex is present, it is typically a haloplatinate.

[0134] If the reactive group is a photoactivatable group, such as an azide, diazirinyl, aryl azide, perfluoroaryl azide, or a psoralen derivative, the compounds of the invention typically become chemically reactive only upon irradiation with light of the appropriate wavelength.

[0135] If X 2If X is an activated ester of a carboxylic acid (such as a succinimidyl ester), the reactive compounds of the present invention are particularly useful for preparing conjugates of proteins, polysaccharides, lipids, nucleotides or amino-modified oligonucleotides or haptens. 2 If X is a maleimide or a haloacetamide, the reactive compounds of the present invention are particularly useful for conjugation with thiol-containing species. 2 If X is a hydrazide, the reactive compounds of the present invention are particularly useful for conjugation to periodate-oxidized carbohydrates and glycoproteins. 2 If the reactive compound is a phosphoramidite, the reactive compound of the present invention is particularly useful for preparing conjugates of oligonucleotides.

[0136] Conjugated substances (S C ) are natural or synthetic amino acids (including those separated by phosphate, carbohydrate, or C1 to C 22 Carboxylic acid protected or substituted amino acids), or natural or synthetic amino acid polymers, such as peptides or proteins optionally derivatized with chemical protecting groups; natural or synthetic nucleic acid bases, nucleosides, nucleotides or nucleic acid polymers, carbohydrates, typically natural or synthetic polysaccharides, lipids (typically having 6-60 carbons), including glycolipids, phospholipids, sphingolipids, glycerides and steroids. Wherein the lipid is a phospholipid.

[0137] Group-SO2NR 12' -X 1 -X 2 Instances of (where X 2 is a reactive functional group) is a Groups such as Or -SO2-N(CH3)(CH2)6OH.

[0138] With formula The compounds are novel and form a further subject of the present invention.

[0139] X 1 is a linking group;

[0140] X 2 is a reactive functional group or conjugated species, and

[0141] R 15 is hydrogen, or C1-C4 alkyl; and

[0142] n1, n2, n3, n5, R 1 、R 2 、R 3 、R 8a 、R 8b and R 8cAs defined above. For n1, n2, n3, n5, R 1 、R 2 、R 3 、R 8a 、R 8b and R 8c , the same preferences apply as for compounds of formula (I).

[0143] Examples of compounds of formula (IV) are compounds of formula (IV) wherein R 1 = n1, n2 and n3 are 0, and R 3 is hydrogen (compound (4)).

[0144] A compound of formula (VI) wherein X 2 is a reactive functional group, n1, n2 and n3 are 0, R 3 Examples of (being hydrogen) are shown in the following table:

[0145]

[0146] The compounds of the formula (I) according to the invention can be incorporated without problems into organic and inorganic materials and are therefore suitable for a whole range of end uses, some of which are listed below by way of example.

[0147] Typically, compounds of formula (I) are fluorescent dyes that absorb light in the wavelength range of 450 to 950 nm. They typically have their absorption maximum within the range of 600 to 880 nm. They typically emit light within the range of 680 to 1200 nm. The fluorescence thus generated is advantageously detected using semiconductor detectors, in particular silicon photodiodes or germanium photodiodes. For these applications, it is important to use high concentrations of compounds of formula (I) to convert as much absorbed light as possible.

[0148] The compounds of the formula (I) are very suitable for uniformly pigmenting high molecular weight organic and inorganic materials, such as, in particular, plastics (especially thermoplastics), coatings and printing inks, and also oxide layer systems.

[0149] NIR spectroscopy is a mature technology for detecting the chemical and physical properties of various materials. For example, NIR spectroscopy can be used for non-destructive food analysis or non-destructive plant analysis in agriculture. Compounds with formula (I) are also particularly useful as fluorescent compounds in near-infrared spectrometer equipment to provide light with a wavelength range of 680 to 950 nm.

[0150] Compounds of formula (I) are also of interest as active components in photovoltaic devices. Therefore, the present invention also relates to the use of compounds of formula (I) in photovoltaic applications, in particular in fluorescent solar concentrators. The solar concentrators are based on solar cells and a polymer matrix material containing the compound of formula (I), with the solar cells being located at the periphery of the polymer material.

[0151] The compounds of formula (I) are also of interest as dyes for laser applications.

[0152] The compounds of formula (I) are also of interest as semiconductors in organic electronic applications, in particular as semiconductors in organic field effect transistors or as semiconductors in organic electroluminescent devices. The compounds of formula (I) can also be used as semiconductors in dye-sensitized solar cells.

[0153] Furthermore, the compounds of formula (I) are suitable as near-infrared absorbers for heat management and as NIR laser beam absorbers in the fusion processing of plastic parts. These applications are described in detail in, for example, DE 102004018547, WO 02 / 77081 and WO 04 / 05427.

[0154] Furthermore, compounds of formula (I) can also be advantageously used for laser marking and laser lettering. In this case, the laser light absorbed by the compound of formula (I) causes heating of the plastic, which leads to foaming thereof or conversion of an additionally present dye, and in this way produces the marking or lettering.

[0155] The compounds of formula (I) are also of interest as labeling groups in detection methods, in particular in diagnostic and analytical methods for biological samples (including living cells).

[0156] Therefore, the present invention relates to a composition comprising a compound of formula (I) and a pharmaceutically acceptable carrier; and a method for imaging a biological sample, the method comprising:

[0157] (a) contacting the biological sample with a composition;

[0158] (b) exposing the biological sample and the composition to VIS / NIR radiation; and

[0159] (c) Observing NIR fluorescence emission in the biological sample.

[0160] The biological sample preferably comprises organelles, cells, tissues, organs or any combination thereof.

[0161] Compounds of formula (I) are also of interest for use in inks for machine readability and / or security applications.

[0162] Due to the significant absorption of compounds of formula (I) in the near infrared region of the electromagnetic spectrum, it is also of interest to use them to obtain marks and inscriptions that absorb near infrared light and are invisible to the human eye. Therefore, the invention also relates to the use of compounds of formula (I) as defined above for trademark protection or as markers for liquids. Useful liquids that can be marked with compounds of formula (I) preferably include oils, such as mineral oils, vegetable and animal fat oils, and ethereal oils.

[0163] The example of this type of oil is a natural oil, such as olive oil, soybean oil or sunflower oil, or natural or synthetic motor oil, hydraulic oil or transmission oil, such as motor vehicle oil or sewing machine oil, or brake fluid and mineral oil, according to the present invention, these mineral oils include gasoline, kerosene, diesel oil and also thermal fuel oil. Particularly preferably mineral oil, such as gasoline, kerosene, diesel oil or thermal fuel oil, particularly gasoline, diesel oil or thermal fuel oil. Particularly advantageously, the above-mentioned compound with formula (I) is used as a marker for mineral oil, wherein for example, for tax reasons, labeling is needed simultaneously. In order to minimize the cost of labeling, and in order to minimize the possible interaction of the mineral oil of labeling with any other composition present such as polyisobutylene amine (PIBA), effort is made to minimize the amount of the marker. Another reason for minimizing the amount of the marker can be to prevent their possible harmful effects, such as harmful effects to the fuel intake and exhaust gas outlet zone of an internal combustion engine.

[0164] The compound of formula (I) used as a marker is added to the liquid in an amount that ensures reliable detection. Typically, the total content of markers (based on weight) in the marked liquid is about 0.1 ppb to 5000 ppb, preferably 1 ppb to 2000 ppb and more preferably 1 ppb to 1000 ppb.

[0165] If appropriate, the compounds of formula (I) can also be used in a mixture with other markers / dyes.

[0166] For marking liquids, these compounds are usually added in the form of solutions. Especially in the case of mineral oils, suitable solvents for providing these stock solutions are preferably aromatic hydrocarbons, such as toluene, xylene or relatively high-boiling aromatic compound mixtures.

[0167] The compound of formula (I) can also be used in the form of a mixture comprising the compound of formula (I) and at least one additional IR absorber different from the compound of formula (I). Suitable additional IR absorbers are, in principle, all known classes of IR absorbers that are compatible with the compound of formula (I). Preferred additional IR absorbers are selected from polymethines, phthalocyanines, naphthalocyanines, quinone-diimmonium salts, ammonium salts, rylenes, inorganic IR absorbers and mixtures thereof. Additional polymethine IR absorbers are preferably selected from cyanines, squarylium cyanines, croconaine and mixtures thereof. Additional inorganic IR absorbers are preferably selected from indium tin oxide, antimony tin oxide, lanthanum hexaboride, tungsten bronze, copper salts and the like.

[0168] IR absorbers can generally be used in concentrations of 10 ppm to 25%, preferably 100 ppm to 10%, depending on the chosen application.

[0169] Mixtures of compounds of formula (I) and IR absorbers are particularly suitable for security printing.

[0170] Security printing is the field that deals with the printing of items such as currency, passports, tamper-evident labels, stock certificates, stamps, identity cards, etc. The main purpose of security printing is to prevent forgery, tampering or counterfeiting.

[0171] In the field of automated banknote processing, IR absorption plays an important role. Most currency in circulation carries not only visible color printing, but also specific features that are detectable only in the infrared portion of the spectrum. These IR features are typically used by automated currency processing equipment in banking and vending applications (ATMs, vending machines, etc.) to identify specific currency notes and verify their authenticity, particularly to distinguish them from copies produced by color copiers.

[0172] Therefore, the present invention also relates to a method for detecting the authenticity of a security document as defined above or below, comprising the following steps:

[0173] a) measuring the absorption, reflection or transmission spectrum of the security document in the VIS / NIR range of the electromagnetic spectrum; and

[0174] b) comparing the spectrum measured under a) and / or information derived therefrom with corresponding spectrum and / or information having an authentic security element.

[0175] All security documents need to have good stability and durability. In the case of banknotes, these requirements are extreme because banknotes are subjected to the roughest conditions of use by the public - they are subjected to material stresses caused by folding, crumpling, etc., subjected to wear and tear, exposed to weather, exposed to body fluids such as sweat, washing, dry cleaning, ironing, etc. - and after being subjected to these, they are expected to be as clear as when they started. In addition, despite being subjected to the above conditions, it is necessary that the documents should have a reasonable lifespan, ideally several years. During this time, the documents and the inks thereon (including invisible security marks) should be resistant to fading or discoloration. Therefore, any ink used for security printing methods should be robust, water-resistant, resistant to various chemicals and flexible when solidified. In addition, since some states are abandoning the use of paper as the base material for banknotes, the printing ink formulations adopted should be available on plastics as well as paper. Compounds with formula (I) are particularly suitable for security printing and are particularly used in printing ink formulations adopted for banknotes, identity cards, passports, tax stamps, stock certificates, credit cards, labels, etc. due to their unique application characteristics.

[0176] In security printing, IR absorbers are added to the printing ink formulation. Suitable printing inks are water-based, oil-based or solvent-based printing inks based on pigments or dyes, used for inkjet printing, gravure printing, flexographic printing, screen printing, gravure engraving, offset printing, laser printing or letterpress printing and for electrophotography. The printing inks used for these printing methods usually contain solvents, binding agents and also various additives, such as plasticizers, antistatic agents or waxes. The printing inks used for offset printing, gravure engraving and letterpress printing are usually formulated into high-viscosity pasty printing inks, while the printing inks used for inkjet printing, flexographic printing and gravure printing are usually formulated into liquid printing inks with relatively low viscosity.

[0177] In the context of the present invention, the expression "printing ink" also encompasses formulations which, in addition to at least one IR absorber of the general formula (I), comprise colorants. The expression "printing ink" also encompasses colorant-free printing lacquers.

[0178] The printing ink formulation for security printing according to the invention preferably comprises

[0179] a) a compound of formula (I) as defined above,

[0180] b) a polymeric binder,

[0181] c) a solvent,

[0182] d) optionally at least one colorant, and

[0183] e) optionally at least one further additive.

[0184] Suitable components of printing inks are conventional and well known to those skilled in the art. Examples of such components are described in "Printing Ink Manual", 4th edition, Leach RH et al. (eds.), Van Nostrand Reinhold, Wokingham (1988). Details of printing inks and their formulations are also disclosed in "Printing Inks" - Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, electronic distribution 1999. The formulation of IR-absorbing gravure ink formulations is described in US20080241492 A1. The disclosure of the above document is incorporated herein by reference.

[0185] The printing ink formulations according to the invention generally contain from 0.0001 to 25% by weight, preferably from 0.001 to 15% by weight, in particular from 0.01 to 5% by weight, of component a), based on the total weight of the printing ink formulation.

[0186] The compound of formula (I) is present in the printing ink formulation in dissolved form or in solid form (in finely dispersed state).

[0187] The printing ink formulations according to the invention generally contain 5 to 74% by weight, preferably 10 to 60% by weight, more preferably 15 to 40% by weight, of component b), based on the total weight of the printing ink formulation.

[0188] Suitable polymeric binders b) for the printing ink formulations according to the invention are, for example, selected from natural resins, phenolic resins, phenol-modified resins, alkyd resins, polystyrene homopolymers and copolymers, terpene resins, silicone resins, polyurethane resins, urea-formaldehyde resins, melamine resins, polyamide resins, polyacrylates, polymethacrylates, chlorinated rubber, vinyl ester resins, acrylic resins, epoxy resins, nitrocellulose, hydrocarbon resins, cellulose acetate, and mixtures thereof.

[0189] The printing ink formulation according to the present invention may also contain a component that forms a polymeric binder through a curing process. Thus, the printing ink formulation according to the present invention may also be formulated to be energy-curable, for example, capable of being cured by UV light or EB (electron beam) radiation. In this embodiment, the binder comprises one or more curable monomers and / or oligomers. Corresponding formulations are known in the art and can be found in standard textbooks such as the series "Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints," published in seven volumes by John Wiley & Sons in association with SITA Technology Limited in 1997-1998.

[0190] Suitable monomers and oligomers (also called prepolymers) include epoxy acrylates, acrylated oils, urethane acrylates, polyester acrylates, silicone acrylates, acrylated amines, and acrylic saturated resins. Further details and examples are given in "Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints," Volume II: Prepolymers & Reactive Diluents (edited by G Webster).

[0191] If a curable polymeric binder is employed, it may contain a reactive diluent, i.e., a monomer that acts as a solvent and is incorporated into the polymeric binder upon curing. Reactive monomers are typically selected from acrylates or methacrylates and may be monofunctional or multifunctional. Examples of multifunctional monomers include polyester acrylates or methacrylates, polyol acrylates or methacrylates, and polyether acrylates or methacrylates.

[0192] In the case of printing ink formulations to be cured by UV radiation, it is generally necessary to include at least one photoinitiator to initiate the curing reaction of the monomers upon exposure to UV radiation. Examples of useful photoinitiators can be found in standard textbooks such as "Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints", Volume III, "Photoinitiators for Free Radical Cationic and Anionic Polymerisation", 2nd edition, J. V. Crivello and K. Dietliker, edited by G. Bradley and published by John Wiley & Sons in association with SITA Technologies Ltd. in 1998. In order to achieve efficient curing, it may also be advantageous to include a sensitizer together with the photoinitiator.

[0193] The printing ink formulations according to the invention generally contain from 1 to 94.9999% by weight, preferably from 5 to 90% by weight, in particular from 10 to 85% by weight, of solvent c), based on the total weight of the printing ink formulation.

[0194] Suitable solvents are selected from water, organic solvents and mixtures thereof.For the purposes of the present invention, reactive monomers which also act as solvent are considered to be part of the above-mentioned binder component b).

[0195] Examples of the solvent include water; alcohols such as ethanol, 1-propanol, 2-propanol, ethylene glycol, propylene glycol, diethylene glycol and ethoxypropanol; esters such as ethyl acetate, isopropyl acetate, n-propyl acetate and n-butyl acetate; hydrocarbons such as toluene, xylene, mineral oil and vegetable oil, and mixtures thereof.

[0196] The printing ink formulation according to the invention may contain additional colorants d). Preferably, the printing ink formulation contains 0 to 25% by weight, more preferably 0.1 to 20% by weight, in particular 1 to 15% by weight, of colorants d), based on the total weight of the printing ink formulation.

[0197] Suitable coloring agents d) are selected from conventional dyes and in particular conventional pigments. The term "pigment" is used comprehensively in the context of the present invention to identify all pigments and fillers, examples being color pigments, white pigments and inorganic fillers. These include inorganic white pigments such as titanium dioxide (preferably in rutile form), barium sulfate, zinc oxide, zinc sulfide, basic lead carbonate, lithopone (zinc sulfide+barium sulfate), or colored pigments, examples being iron oxide, bismuth vanadate, lead chromate, lead molybdate, iron blue, cobalt blue, cobalt green, Ni-rutile yellow, Cr-rutile yellow, zinc yellow, zinc green, ultramarine, manganese black, antimony black, manganese violet, carbon black, graphite. In addition to inorganic pigments, the printing ink formulations of the invention may also contain organic color pigments, examples being monoazo, disazo, β-naphthol, naphthol AS, azo pigment lakes, benzimidazolones, metal complex pigments, isoindolinones, isoindolinones, phthalocyanines, quinacridones, perylenes, perinones, diketopyrrolopyrroles, thioindigos, anthraquinones, anthrapyrimidines, indanthrone, flavanthrones, pyranthrones, dioxazines, triarylcarboniums, quinophthalones. Also suitable are synthetic white pigments with air inclusions to increase light scattering, such as Suitable fillers are, for example, aluminosilicates such as feldspar, silicates such as kaolin, talc, mica, magnesite, alkaline earth metal carbonates such as calcium carbonate, for example in the form of calcite or chalk, magnesium carbonate, dolomite, alkaline earth metal sulfates such as calcium sulfate, silicon dioxide, etc.

[0198] The printing ink formulation according to the invention may contain at least one additive e). Preferably, the printing ink formulation contains 0 to 25% by weight, more preferably 0.1 to 20% by weight, in particular 1 to 15% by weight, of at least one component e), based on the total weight of the printing ink formulation.

[0199] Suitable additives (component e)) are selected from plasticizers, waxes, driers, antistatic agents, chelating agents, antioxidants, stabilizers, adhesion promoters, surfactants, flow control agents, defoamers, biocides, thickeners, etc., and combinations thereof. These additives are used in particular to fine-tune the application-related properties of the printing ink, examples being adhesion, abrasion resistance, drying rate, or slip.

[0200] In particular, the printing ink formulation for security printing according to the present invention preferably contains

[0201] a) 0.0001% to 25% by weight of a compound of formula (I),

[0202] b) 5 to 74% by weight of at least one polymeric binder,

[0203] c) 1 to 94.9999% by weight of at least one solvent,

[0204] d) 0 to 25% by weight of at least one colorant, and

[0205] e) 0 to 25% by weight of at least one further additive,

[0206] The sum of components a) to e) hereby adds up to 100%.

[0207] The printing ink formulation according to the present invention is advantageously prepared in a conventional manner, for example by mixing separate components. As previously mentioned, the compound of formula (I) is present in the printing ink formulation in the form of a dissolved or finely dispersed solid. Additional colorants can be used in the printing ink formulation of the present invention or in a separate ink formulation. When using additional colorants in a separate formulation, the application time of the printing ink formulation according to the present invention is generally insignificant. For example, the printing ink formulation according to the present invention can be applied first, and then overprinted with a conventional printing ink. However, this order can also be reversed, or alternatively, the printing ink formulation according to the present invention can be applied in the form of a mixture with a conventional printing ink. In each case, the printed matter is readable under a suitable light source.

[0208] A primer may be applied before the printing ink formulation according to the present invention. For example, the primer is applied to improve adhesion to the substrate. An additional printing lacquer may also be applied, for example in the form of an overlay, to protect the printed image. Additional printing lacquer may also be applied for aesthetic purposes or to control application-related properties. For example, appropriately formulated additional printing lacquer may be used to influence the roughness, electrical properties, or water vapor condensation properties of the substrate surface. The printing lacquer is typically applied online by a varnishing system on a printing press used to print the printing ink formulation according to the present invention.

[0209] The printing ink formulations according to the invention are also suitable for use in multilayer materials. Multilayer materials consist, for example, of two or more plastic foils, such as polyolefin foils, metal foils, or metallized plastic foils, which are bonded to one another, for example, by lamination or with the aid of a suitable laminating adhesive. These composite materials may also include further functional layers, such as odor barriers or water vapor barriers.

[0210] Furthermore, the present invention relates to a security document comprising a substrate and a compound of formula (I) as defined above, or a security document obtainable by a printing process using a printing ink formulation as defined above.

[0211] Mixtures of compounds of the formula (I) and IR absorbers are also particularly suitable for laser welding of plastics.

[0212] Laser welding is preferably performed using an Nd:YAG laser at 1064 nm or a diode laser at 980 nm or 940 nm. The concentration of the novel form of compound (1) or the IR absorber mixture is, for example, 5 to 500 ppm, preferably 10 to 200 ppm.

[0213] In laser welding, plastic parts are welded to each other. The plastic parts to be melted can have any shape. For example, at least one of the plastic parts can be a film.

[0214] Compounds of formula (I) are suitable for welding transparent or at least translucent plastic materials. The plastic materials used can be colorless or colored. In principle, the plastic parts to be melted can consist of the same polymer or different polymers. Preferably, the plastic parts used for laser welding are selected from thermoplastic polymers. However, it is also possible that none of the plastic parts to be melted consist of thermoplastics; however, at least one component may be coated with a thermoplastic containing the compound of formula (I).

[0215] The plastic parts for laser welding preferably comprise or consist of at least one polymer selected from the group consisting of polyolefins, polyolefin copolymers, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymers, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl esters, polyvinyl alkanal, polyvinyl ketal, polyamides, polyimides, polycarbonates, polycarbonate blends, polyesters, polyester blends, poly(meth)acrylates, poly(meth)acrylate-styrene copolymer blends, poly(meth)acrylate-polyvinylidene fluoride blends, polyurethanes, polystyrene, styrene copolymers, polyethers, polyetherketones and polysulfones, and mixtures thereof.

[0216] Preferred are matrix polymers from the group consisting of polyolefins, polyolefin copolymers, polyvinyl acetals, polyamides, polycarbonates, polycarbonate-polyester blends, polycarbonate-styrene copolymer blends, polyesters, polyester blends, poly(meth)acrylates, poly(meth)acrylate-styrene copolymer blends, poly(meth)acrylate-polyvinylidene fluoride blends, styrene copolymers and polysulfones, and mixtures thereof.

[0217] Particularly preferred polymers are transparent or at least translucent. Examples include: polypropylene, polyvinyl butyral, nylon-[6], nylon-[6,6], polycarbonate, polycarbonate-polyethylene terephthalate blends, polycarbonate-polybutylene terephthalate blends, polycarbonate-acrylonitrile / styrene / acrylonitrile copolymer blends, polycarbonate-acrylonitrile / butadiene / styrene copolymer blends, polymethyl methacrylate-acrylonitrile / butadiene / styrene copolymer blends (MABS), polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, impact-modified polymethyl methacrylate, polybutyl acrylate, polymethyl methacrylate-polyvinylidene fluoride blends, acrylonitrile / butadiene / styrene copolymer (ABS), styrene / acrylonitrile copolymer (SAN), polyphenylsulfone, and mixtures comprising two or more (e.g., two, three, four, five) of the foregoing polymers.

[0218] Suitable polymer formulations for laser welding include

[0219] A) a thermoplastic matrix polymer suitable for forming these plastic parts,

[0220] B) a compound of formula (I) as defined above,

[0221] C) optionally at least one further additive.

[0222] Those polymer formulations for laser welding are likewise according to the invention and are suitable for producing melt-bonded plastic parts by means of laser radiation having a wavelength outside the visible range.

[0223] The polymer formulations for laser welding can advantageously be produced by conventional extrusion or kneading methods. Components B) and, if present, C) can be mixed with the matrix polymer A) from the outset in a weight ratio corresponding to the desired final concentration (direct compounding), or a significantly higher concentration of B) and, if present, C) can be initially selected and the resulting concentrate (masterbatch) subsequently diluted with further matrix polymer A) during the production of the part to be melted.

[0224] Suitable additives C) are UV stabilizers, antioxidants, processing plasticizers and the like.

[0225] Furthermore, the polymer formulations for laser welding may contain at least one colorant as an additive for establishing the desired color tone, in particular transparent organic pigments and in particular dyes, such as CI Pigment Yellow 109, 110, 128, 138, 139, 150, 151, 147, 180, 183, 185, 192 and 196, CI Pigment Orange 70, CI Pigment Red 122, 149, 178 and 179, 181, 202, 263, CI Pigment Violet 19, 23, 37 and 29, CI Pigment Blue 15, 15:1, 15:3 and 15:4, 60 , CI Pigment Green 7 and 36, CI Solvent Yellow 14, 21, 93, 130, 133, 145, 163, CI Solvent Red 52, 135, 195, 213, 214 and 225, CI Solvent Blue 35, 45, 67, 68, 97, 104, 122, 132, CI Solvent Violet 13, 46, 49, CI Solvent Green 3, 5 and 28, CI Solvent Orange 47, 60, 86, 114 and 163, CI Solvent Brown 35, 53, as well as CI Disperse Yellow 54, 87, 201, CI Disperse Orange 30, CI Disperse Red 60 and CI Disperse Violet 57.

[0226] Another possible group of additives is that of additives which likewise modify the visual appearance, the mechanical properties or other tactile properties, for example matting agents such as titanium dioxide, chalk, barium sulfate, zinc sulfide, fillers such as nanoparticulate silica, aluminum hydroxide, clay and other phyllosilicates, glass fibers and glass spheres.

[0227] The present invention further provides a color converter comprising

[0228] (i) a compound of formula (I) as defined above;

[0229] (ii) a polymer matrix material selected from the group consisting of polystyrene, polycarbonate, polyacrylate, polymethyl methacrylate, polymethacrylate, polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl chloride, polybutylene, polysiloxane, epoxy resin, polyvinyl alcohol, poly(ethylene vinyl alcohol)-copolymer, polyacrylonitrile, polyvinylidene chloride, polystyrene acrylonitrile, polybutylene terephthalate, polyethylene terephthalate, 2,5-furandicarboxylate polyester, polyvinyl butyrate, polyvinyl chloride, polyamide, polyoxymethylene, polyimide, polyetherimide, or mixtures thereof; and

[0230] (iii) optionally a light scattering agent.

[0231] The concentration of the compound of formula (I) and, if appropriate, the additional colorant, as defined above, in the polymer matrix is determined as a function of the thickness of the color converter and the type of polymer. If a thin polymer layer is used, the concentration of the compound of formula (I) and, if appropriate, the additional colorant, is generally higher than in the case of a thicker polymer layer. Preferably, the concentration of the compound of formula (I) according to the invention is in the range of 0.001% to 2% by weight, in particular 0.001% to 1% by weight, based on the weight of the polymer matrix material.

[0232] In one embodiment of the invention, the color converter does not contain a light scattering agent.

[0233] In another embodiment of the present invention, the color converter contains a light scattering agent. In a preferred embodiment of the present invention, the polymer matrix material contains the scattering agent. Suitable light scattering agents are inorganic white pigments, such as titanium dioxide, barium sulfate, lithopone, zinc oxide, zinc sulfide, and calcium carbonate, having an average particle size according to DIN 13320 of 0.01 to 10 μm, preferably 0.1 to 1 μm, and more preferably 0.15 to 0.4 μm. These light scattering agents are typically present in amounts of 0.01 to 2.0% by weight, preferably 0.05 to 1.0% by weight, and more preferably 0.1 to 0.6% by weight, in each case based on the polymer of the layer containing the scatterer.

[0234] Examples of suitable organic light scattering agents include scattering polymers, such as those based on poly(acrylates); poly(alkyl methacrylates), such as poly(methyl methacrylate) (PMMA); poly(tetrafluoroethylene) (PTFE); silicone-based scattering agents, such as hydrolyzed poly(alkyltrialkoxysilanes), and mixtures thereof. The size (average diameter - weight average) of these light scattering agents is generally in the range of 0.5 to 50 μm, preferably 1 to 10 μm. These light scattering agents are typically contained in an amount of 1 to 10% by weight, in each case based on the polymer of the layer containing the scatterer. A useful light scattering agent is, for example, a mixture of 3 to 5% by weight of a PMMA-based scattering agent and 1.5 to 2% by weight of a silicone-based scattering agent.

[0235] Light-scattering compositions comprising polymer particles based on vinyl acrylate having a core / shell morphology in combination with TiO2, as described in EP-A 634 445, are also suitable.

[0236] The polymer matrix material may further comprise at least one additional additive selected from UV absorbers, hindered amine light stabilizers, flame retardants, UV stabilizers, heat stabilizers, antioxidants, plasticizers, antifog agents, nucleating agents, antistatic agents, fillers or reinforcing materials or combinations thereof.

[0237] Hindered amine light stabilizers, UV stabilizers and heat stabilizers are known to those skilled in the art. Suitable antioxidants or free radical scavengers are, for example, phenols, especially sterically hindered phenols such as butylated hydroxyanisole (BHA) or butylated hydroxytoluene (BHT) or sterically hindered amines (HALS). Stabilizers of this type are available, for example, from BASF under the trade name In some cases, antioxidants and free radical scavengers may be used, for example, by BASF under the trade name The stabilizer may be supplemented with a secondary stabilizer such as a phosphite or phosphonite sold under the trade name PTFE®.

[0238] Suitable UV absorbers are, for example, benzotriazoles such as 2-(2-hydroxyphenyl)-2H-benzotriazole (BTZ), triazines such as (2-hydroxyphenyl)-s-triazine (HPT), hydroxybenzophenones (BP) or oxalanilides. UV absorbers of this type are marketed, for example, by BASF under the trade name Product name sales.

[0239] Color converters containing compounds of formula (I) can be part of agricultural foils, agricultural nets, greenhouse screens, or lighting devices. The color converter can be supported by glass. Agricultural foils, agricultural nets, or greenhouse screens can also consist of color converters used according to the invention. The color converters according to the invention can also be part of near-infrared light sources.

[0240] Therefore, another object of the present invention relates to a near-infrared light source comprising

[0241] (i) a light source selected from a blue LED, a red LED, or a white LED; and

[0242] (ii) A color converter as defined above.

[0243] The near-infrared light source can be a NIR-LED or part of a near-infrared spectrometer.

[0244] The present invention will be described in detail by way of examples.

[0245] Examples

[0246] Example 1

[0247]

[0248] Under a nitrogen atmosphere, 10.0 parts of dichlorosulfonylfluorescein and 10.2 parts of 1-methyl-2-phenylindoleazine were suspended in 150 parts of methanol. 6.4 parts of N,N-diisopropylethylamine were added, and the mixture was slowly heated and stirred under reflux for 4 hours. After cooling, the precipitate was isolated by filtration and washed with dilute hydrochloric acid and water. Drying in an oven at 80°C under vacuum produced 11.2 parts of a bluish-black solid (Compound 1a; 64% yield).

[0249] Example 2

[0250]

[0251] Under a nitrogen atmosphere, 2.4 parts of compound 1a are stirred with 15 parts of phosphorus oxychloride (V) at 90° C. for 2 hours. The mixture is cooled and poured onto an ice / water mixture so that the temperature does not exceed 5° C. The precipitate is filtered off, washed with cold ice water and dried in an oven under vacuum. The resulting sulfonyl chloride (4) is dissolved in 200 parts of acetonitrile and cooled to 5° C.

[0252] 4 parts of N,N-diisopropylethylamine and 4 parts of ethyl isopentazoline were slowly added over 10 minutes. After stirring for three hours, the resulting precipitate was filtered and washed with 2M hydrochloric acid and water. The precipitate was added to 50 parts of a 1:1 mixture of 5M hydrochloric acid and dioxane and stirred at 90°C for 10 hours. The precipitate was filtered, washed with water, and dried in a vacuum oven at 40°C. Yield: 1.2 parts of compound 2a as a dark powder.

Claims

1. A compound having the formula in, R 1 and R 2 Independently of each other are Groups; R 3 is hydrogen, -CO2H or -SO3H; R 4 Yes-SO3 - , or having the formula -SO2NR 12 R 13 The group, The condition is that R 4 In the absence of a negative charge, the compound of formula (I) comprises an anionic counterion; R 5 It is C1-C 24 Alkyl, substituted by one or more R 14 Substituted C3-C 10 -cycloalkyl, C6-C 10 Aryl-C1-C 10 Alkylene - which can be substituted by one or more R 14 Substituted and the alkylene group may be interrupted by one or more selected from O, S and -NR 9 Non-adjacent groups; can be substituted by one or more substituents R 14 Substituted C6-C 10 Aryl, or may be substituted by one or more R 14 Substituted C2-C 14 heteroaryl; R 6 is hydrogen, C1-C 24 Alkyl, C1-C 24 Alkoxy, which may be substituted by one or more R 14 Substituted C6-C 10 -aryl, and C1-C 24 -fluoroalkyl, fluorine, chlorine or bromine; R 7 It is C1-C 24 Alkyl, C1-C 24 Alkoxy, C1-C 24 Fluoroalkyl, group NR 10 R 11 , fluorine, chlorine or bromine; R 8a 、R 8b and R 8c independently selected from C1-C 24 Alkyl, C1-C 24 Alkoxy, C1-C 24 Fluoroalkyl, fluorine, chlorine or bromine; R 9 is hydrogen, or C1-C4 alkyl; R 10 and R 11 Independently of each other are C1-C 24 Alkyl, hydroxy-C1-C 24 Alkyl, which may be substituted by one or more R 14 Substituted C6-C 10 -aryl, or substituted by one or more R 14 Substituted C3-C 10 -cycloalkyl; or R 10 and R 11 Together with the nitrogen to which they are bound, they form a five- or six-membered ring system which may be interrupted by -O-, -S- or -NR 12 '- and may be part of a fused ring system which may be substituted by one or more substituents R 14 replace; R 12 and R 13 are independently hydrogen, C1-C 24 Alkyl, hydroxy-C1-C 24 Alkyl, substituted by one or more R 14 Substituted C3-C 10 -cycloalkyl, C6-C 10 Aryl-C1-C 10 Alkylene, which may be substituted by one or more R 14 Substituted and the alkylene group may be interrupted by one or more selected from O, S and -NR 12 'non-adjacent groups; may be substituted by one or more substituents R 14 Substituted C6-C 10 Aryl, or may be substituted by one or more R 14 Substituted C2-C 14 heteroaryl; or R 12 and R 13 Together with the nitrogen to which they are bound, they form a five- or six-membered ring system which may be interrupted by -O-, -S- or -NR 12 '- and may be part of a fused ring system which may be substituted by one or more substituents R 14' replace; R 12 ' is hydrogen, or C1-C4 alkyl; R 14 It is C1-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Fluoroalkyl, nitro, cyano, hydroxy, fluorine, chlorine or bromine; R 14' It is C1-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Fluoroalkyl, nitro, cyano, hydroxyl, -(CH2) n5 COOH group, -(CH2) n5 COO - radical, fluorine, chlorine or bromine; And n1 is 0, 1 or 2; n2 is 0, 1 or 2, n3 is 0 or 1, n4 is 0, 1 or 2, and n5 is 0, or an integer from 1 to 10.

2. The compound according to claim 1, which is a compound having the formula where R 1 、R 2 and R 3 As defined in claim 1.

3. The compound according to claim 1, which is a compound having the formula Where n6 is 0 or 1, An - is an anion, and R 1 、R 2 、R 3 、R 12 and R 13 As defined in claim 1.

4. The compound according to claim 3, wherein The group -NR 12 R 13 is selected from the group consisting of phenylmethylamino, diphenylamino, dimethylamino, methylethylamino, 2-hydroxyethylmethylamino, 2-hydroxyethylethylamino, di-2-hydroxyethylamino, 2-ethylhexylmethylamino, 2-ethylhexylethylamino, 3-propylheptylmethylamino and 3-propylheptylethylamino; or R 12 and R 13 Together with the nitrogen to which they are bound, they form a five- or six-membered ring system selected from the group consisting of Especially wherein BOC is tert-butyloxycarbonyl and n5 is 0, or an integer from 1 to 5, more preferably 0 or 1.

5. The compound according to any one of claims 1 to 4, wherein R 1 and R 2 Is a formula A group in which R 5 is phenyl, 4-cyanophenyl, 4-trifluoromethylphenyl, 4-nitrophenyl, 3,5-bis-trifluoromethylphenyl, 4-hydroxyphenyl or 4-methoxyphenyl, in particular phenyl; and R 6 It is a C1-C4 alkyl group, or a CF3 group.

6. The compound according to claim 5, wherein R 5 is phenyl and R 6 It's methyl.

7. The compound according to any one of claims 1 to 6, wherein R 3 It's hydrogen.

8. Use of a compound according to any one of claims 1 to 7 as a compound that absorbs light emitted from a radiation source and optionally emits light having a wavelength in the range of 650 to 1200 nm different from the light of the radiation source; or as a semiconductor in organic electronic applications; as a laser dye for bioimaging, in photodynamic therapy, in inks for machine readability and / or security applications or for laser welding of plastics; or for trademark protection or as a marker for liquids, in particular oils.

9. A printing ink formulation for security printing comprising a) a compound according to any one of claims 1 to 7, b) a polymeric binder, c) a solvent, d) optionally at least one colorant, and e) optionally at least one further additive.

10. A security document comprising a substrate and a compound of formula (I) according to any one of claims 1 to 7, or a security document obtainable by a printing process, wherein Use of the printing ink formulation according to claim 9.

11. A method of detecting the authenticity of a security document according to claim 10, the method comprising the steps of: a) measuring the absorption, reflection or transmission spectrum of the security document in the VIS / NIR range of the electromagnetic spectrum; as well as b) comparing the spectrum measured under a) and / or information derived therefrom with corresponding spectrum and / or information having an authentic security element.

12. A composition comprising a compound according to any one of claims 1 to 7 and a pharmaceutically acceptable carrier.

13. A method for imaging a biological sample, the method comprising: (a) contacting the biological sample with the composition according to claim 12; (b) exposing the biological sample and the composition to VIS / NIR radiation; and (c) Observing NIR fluorescence emission in the biological sample.

14. A method for producing a A method for producing a compound comprising i) Make it have the formula The compound with formula The compound is reacted in the presence of diisopropylethylamine in a solvent, especially n-butanol, wherein n1, n2, n3, n4, R 1 、R 2 、R 3 、R 5 、R 6 、R 7 、R 8a 、R 8b and R 8c As defined in claim 1.

15. The method according to claim 14, comprising: (ii) the compound having the formula The compound is converted into a compound having the formula Compounds; (iii) reacting the compound of formula (IV) with a compound of formula HNR 15 -X 1 -X 2 (V) to obtain a compound having the formula A compound wherein X 2 Is a reactive functional group; or the compound having formula (IV) and having formula HNR 12 R 13 (VII) to obtain a compound having the formula compounds, and (iv) optionally converting the compound of formula (VI) obtained in step (iii) into a compound of formula (VI), wherein X 2 It is a conjugated substance, X 1 is a linking group; R 15 is hydrogen, or C1-C 24 alkyl; and n1, n2, n3, R 1 、R 2 、R 3 、R 8a 、R 8b 、R 8c 、R 12 and R 13 As defined in claim 1.

16. A compound having the formula where X 1 is a linking group; X 2 is a reactive functional group or conjugated species, and R 15 is hydrogen, or C1-C4 alkyl; and n1, n2, n3, n5, R 1 、R 2 、R 3 、R 8a 、R 8b and R 8c As defined in claim 1.

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