Perylene-substituted 3,4: 9,10-tetracarboxydiimides, preparation process and its use as modulable fl

专利摘要:
Perylene-3,4: 9,10-substituted tetracarboxydiimides, preparation process and their use as modulable fluorophores. The present invention relates to perylene-3, 4: 9,10-tetracarboxydiimides substituted at positions 1, 6, 7 and/or 12, of formula I IMAGE its preparation procedure, and its use as modulable fluorophores. (Machine-translation by Google Translate, not legally binding)
公开号:ES2719503A1
申请号:ES201830029
申请日:2018-01-10
公开日:2019-07-10
发明作者:De La Varga Alberto Diez；Pérez Tomás Torroba；Gredilla Patricia Calvo；Velásquez Daisy Carolina Romero
申请人:Universidad de Burgos；
IPC主号:

专利说明:

[0001] Perylene-3,4: 9,10-substituted tetracarboxyidiimides, preparation procedure and its use as modular fluorophores
[0002]
[0003] SECTOR OF THE TECHNIQUE
[0004]
[0005] This invention falls within the technical sector of fluorophores that can be anchored to surfaces or useful in bioconjugation in which their emission can be modulated based on the substituents in said positions.
[0006]
[0007] STATE OF THE TECHNIQUE
[0008]
[0009] Of the different organic molecules useful as fluorophores, the diimides of perylene-3,4: 9,10-tetracarboxylic acid, known as perylene diimides (PDI) or perylene, stand out thanks to their intense absorption in the visible and its great electronic mobility. bisimides (GDP). Its rigid aromatic structure favors intermolecular interactions and imparts semiconductor character type n, very useful for optoelectronic and photovoltaic applications. These derivatives are very stable compounds both chemically and thermally, in addition to being against radiation. They exhibit high quantum yields, which can even reach the unit. Modifications in their substituents alter their solubility, making them versatile in different media, both organic and aqueous. Variations in the substituents of the imide positions do not significantly affect their fluorescent properties, allowing the inclusion of bioconjugable biomolecules, while in the substituents of positions 1, 6, 7 or 12 (bay positions) modify their luminescent properties, allowing modulate , among others, the emission wavelengths of the resulting fluorophore.
[0010]
[0011] These and other characteristics of IDPs are found in various monographs and scientific articles, for example, among the most recent: (a) W. Jiang, L. Ye, X. Li, C. Xiao, F. Tan, W. Zhao, J. Hou and Z. Wang. Chem. Commun. 2014, 50, 1024-1026. (b) R. K. Dubey, N. Westerveld, F. C. Grozema, E. J. Sudholter and W. F. Jager. Org. Lett. 2015, 17, 1882-1885. (c) Y. Fan, K. Ziabrev, S. Zhang, B. Lin, S. Barlow and S. R. Marder. ACS Omega 2017, 2, 377-385. (d) A. J. Payne, S. Li, S. V. Dayneko, C. Risko and G. C. Welch. Chem. Commun. 2017
[0012]
[0013] Two different ways of functionalization of PDI have been explored mainly: substitution in the imidic nitrogens and substitution in positions 1, 6, 7 and 12. The examples of functionalization in these latter positions are limited to inclusion of two or four equal substituents, resulting in almost all symmetric products. Only in some cases asymmetric derivatives have been achieved at positions 1.7, one of the substituents being a halogen.
[0014]
[0015] For the case of substitution in the imida position, see: N. Pasaogullari, H. Icil and M. Demuth. Pigm kings. 2006, 69, 118-127. For the case of substitution in positions 1 and 7, see: (a) S. Shoaee, T. M. Clarke, C. Huang, S. Barlow, S. R. Marder, M. Heeney, I. McCulloch and J. R. Durrant. J. Am. Chem. Soc. 2010, 132, 12919-12926. (b) X. Zhang, S. Pang, Z. Zhang, X. Ding, S. Zhang, S. He and C. Zhan. Tetrahedron Lett.
[0016] 2012, 53, 1094-1097. (c) Q. Zhao, S. Zhang, Y. Liu, J. Mei, S. Chen, P. Lu, A. Quin, Y. Ma, J. Z. Sun and B. Z. Tang. J. Mater. Chem. 2012, 22, 7387-7394. (d) M. Zhu, H. Guo, K. Cai, F. Yang and Z. Wang. Dyes Pigm. 2017, 140, 179-186. For the case of tetrasubstitution in positions 1, 6, 7 and 12, see: (a) G. Seybold and G. Wagenblast. Pigm kings. 1989, 11, 303-317. (b) H. Arms, P. Blaschka, A. Bohm and G. Henning. 2000
[0017] 1,7-Disubstituierte Perylen-3,4,9,10-tetracarbonsauren, Deren Dianhydride und Diimide. Patent, publication number: EP0869956 B1. (c) F. Wurthner. Chem. Commun.
[0018] 2004, 1564-1579. (d) B. Pagoaga, L. Giraudet and N. Hoffmann. Eur. J. Org. Chem. 2014, 2014, 5178-5195.
[0019] Thus, it would be desirable to have a methodology for the asymmetric functionalization of IDPs in the bay positions; as well as batteries of compounds that emit fluorescence depending on their structure at different wavelengths, and that are applicable in areas such as bioconjugation or bioimage, among others.
[0020]
[0021] In the market there are already fluorescent molecules useful for bioconjugation, such as bodipys or even a few examples of perilenes. Some show low photostabilities, are very sensitive to pH or ionic strength, or their fluorescent emission intensities are low.
[0022]
[0023] In other cases, the fluorophores used have low emission wavelengths, so unwanted phenomena such as energy absorption or scattering are frequent. Some general examples are described in the biomarked bibliography: (a) S. l. Niu, C. Massif, G. Ulrich, PY Renard, A. Romieu and R. Ziessel. Chem. Eur. J. 2012, 18, 7229-7242. (b) F. Heisig, S. Gollos, SJ Freudenthal, A. El-Tayeb, J. Iqbal and CE Müller. J. Fluoresc. 2014, 24, 213-230; or bioimage: (a) M. Jurásek, S. Rimpelová, E. Kmonícková, P. Drasar and T. Ruml. J. Med. Chem. 2014, 57, 7947-7954. (b) S. Parisotto, B. Lace, E. Artuso, C. Lombardi, A. Deagostino, R. Scudu, C. Garino, C. Medana and C. Prandi. Org. Biomol Chem. 2017, 15, 884-893; as well as individuals using IDPs in biomarking: (a) M. Chen, Y. Ding, Y. Gao, X. Zhu, P. Wang, Z. Shi and Q. Liu. RSC Adv. 2017, 7, 25220-25228. (b) YL Wu, NE Horwitz, KS Chen, DA Gomez-Gualdron, NS Luu, L. Ma, TC Wang, MC Hersam, JT Hupp, OK Farha, RQ Snurr and MR Wasielewski. Nat. Chem. 2017, 9, 466-472; or bioimage: (a) K. Huth, T. Heek, K. Achazi, C. Kühne, LH Urner, K. Pagel, J. Dernedde and R. Haag. Chem. Eur. J. 2017, 23, 4849-4862. (b) P. Sun, P. Yuan, G. Wang, W. Deng, S. Tian, C. Wang, X. Lu, W. Huang and Q. Fan. Biomacromolecules 2017.
[0024] Regarding the selective substitution in the POI bay positions, few works have been published to date, including those cited in the following paragraph.
[0025]
[0026] The 1,7-diphenoxyperylene diimides have been the most used due to their ease of synthesis by dibromation followed by nucleophilic substitution. The synthesis of derivatives with a single phenoxide moiety is difficult and to date only 1-bromo-7-alkoxy derivatives have been prepared (H. Zhao, YY Zhang, H. Xu, ZM He, ZL Zhang and HQ Zhang. Tetrahedron 2015, 71, 7752-7757). For the symmetric 1,6,7,12-tetraphenoxyperylene diimides, a similar methodology has been used. In the first place, halogenation of the bay positions of the perylene dianhydrides, with subsequent formation of the imide by condensation with amines. Finally, in a nucleophilic substitution process or through reactions catalyzed by transition metals, the corresponding symmetric tetrasubstituted derivatives have been obtained ((a) VI Rogovik, LF Gutnik. Zhurnal Organicheskoi Khimii 1988, 24, 635-639. (B) G Syebold, G. Wagenblast, Dyes. Pigm. 1989, 11, 303-317. (C) C. Huang, S. Barlow and SR Marder. J. Org. Chem. 2011, 76, 2386-2407). Finally, there are no works in which the synthesis of asymmetric POIs in the four bay positions is reported.
[0027]
[0028] A problem in bio-conjugation is the provision of large batteries of anchoring molecules, which requires the development of specific systems for each application with high temporal and economic costs. This tool offers a wide range of possibilities when designing molecules for biomarking, thus expanding the number of available species. IDPs are very attractive fluorophores because they correct the deficiencies of other fluorophores such as fluorescein, rhodamine and ICG (MHY Cheng, H. Savoie, F. Bryden and RW Boyle. Photochem. Photobiol. Sci. 2017, 16, 1260- 1267). The great versatility of the method of the present invention is that it allows to obtain compounds with two functionalization positions, that is to say, it lies in the possibility of substitution with different biological fragments in the imide positions, allowing interaction with different targets and thus controlling the biological specificity (what will be detected and what parts of the cell will go), and in the bay positions select the emission color to modulate fluorescent emission. In addition, substituents in bay positions will condition the final solubility of the system. When replacing them with hydrophobic groups, there is a batochromic shift of the absorption and emission maxima in comparison with unsubstituted IDPs, keeping their high fluorescence in solution (H. Quante and K. Müllen. Angew. Chem. Int. Ed. 1995, 34, 1323-1325). On the other hand, the introduction of hydrophilic groups hardly modifies the displacement of the absorption bands (C. Li and H. Wonneberger. Adv. Mater. 2012, 24, 613-636). In this way, chromophores can be obtained that absorb practically the entire visible spectrum and part of the near IR ((a) AC Grimsdale and K. Müllen. 2006. Polyphenylene-type Emissive Materials: Poly (para-phenylene) s, Polyfluorenes and Ladder Polymers in Emissive Materials Nanomaterials, 1-82. Berlin, Heidelberg: Springer Berlin Heidelberg. (b) C. Li, M. Liu, NG Pschirer, M. Baumgarten and K. Müllen. Chem. Rev. 2010, 110, 6817-6855. (C) TM Figueira-Duarte and K. Müllen. Chem. Rev. 2011, 111, 7260-7314. (D) F. He and L. Yu. J. Phys. Chem. Lett. 2011, 2 , 3102-3113. (E) CJ Brabec, M. Heeney, I. McCulloch and J. Nelson. Chem. Soc. Rev. 2011, 40, 1185-1199).
[0029]
[0030] The present invention provides a methodology for the synthesis of asymmetric PDI derivatives at bay positions, for which there was no existing procedure.
[0031]
[0032] The diimide perylene (PDI) substituted in their bay positions (1, 6, 7 and 12) by different substituents, such as those described in the present invention, possess many desirable characteristics, such as high fluorescence, high chemical and optical stability, different wavelengths of fluorescent emission depending on the substituents in these positions and the possibility of easy functionalization at positions N and N ', which allows their use in different applications such as bioimage or biomarking.
[0033]
[0034] DESCRIPTION OF THE INVENTION
[0035]
[0036] Throughout the present invention:
[0037] - the term "regioisomers" refers to position isomers that have the same functional group or substituent in different positions; that is, the regioisomers have the same molecular formula but different chemical and physical properties;
[0038] - the terms "biomarker" and "fluorophore" have the usual meaning;
[0039] - the term "modulable" means that the emission wavelength (color) can be controlled according to the substituents in the bay positions. That is, each compound of formula I has a unique emission wavelength, which will depend on which substituents it carries. The emission length of the final product can be modulated by selecting the substituents;
[0040] - "C1-C40 alkyl", "C1-C20 alkyl", "C1-C10 alkyl", "C1-C6 alkyl" and "C1-C4 alkyl", as a group or part of a group, independently refer to a group straight or branched chain alkyl containing from 1 to 40, from 1 to 20, from 1 to 10, from 1 to 6 and from 1 to 4 carbon atoms respectively;
[0041] - "C1-C4 alkyl" includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and ferf-butyl groups,
[0042] - "C1-C6 alkyl" includes the groups of "C1-C4 alkyl" and, among others, pentyl, isopentyl , sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, hexyl, iso-hexyl and sec- hexyl, - "C1-C10" includes groups "C1-C6" and, among others, heptyl, iso - heptyl, octyl, iso-octyl, 2-ethylhexyl, nonyl, decyl and 2-propylheptyl,
[0043] - "C1-C20 alkyl" includes the groups of "C1-C10 alkyl" and, among others, dodecyl, 2-butylnonyl, 3-butylnonyl and 2-hexylheptyl,
[0044] - "C1-C40 alkyl" includes the groups "C1-C20 alkyl" and, among others, tridecyl and tetradecyl;
[0045] - Cy1 and Cy3 independently refer to a phenyl or a 5- or 6-membered heteroaryl containing 1 to 3 heteroatoms selected from nitrogen, oxygen and sulfur. Cy1 and Cy3 bind to the rest of the molecule through any carbon or nitrogen atom in the available ring. In addition, Cy ¹ and Cy ³ may be optionally substituted as indicated in the definition of formula I, the substituents may be the same or different and may be located at any available position of the ring system. Examples include, among others, phenyl, thienyl, furyl, pyrrolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, imidazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl, 1,2,4-oxadiazolyl, 1,2,4-thiadiazolyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl;
[0046] - Cy2 refers to a monocyclic ring of 3 to 7 members or bicyclic of 6 to 11 members which can be carbocyclic or heterocyclic. When it is heterocyclic it can contain 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur. The bicyclic rings can be formed by two fused rings through two adjacent carbon or nitrogen atoms, or through two non-adjacent carbon or nitrogen atoms forming a bridge ring, or they can be formed by two rings joined through a single carbon atom forming an espirano type ring. The Cy2 group can be saturated, partially unsaturated or aromatic. Cy2 is attached to the rest of the molecule through any available carbon or nitrogen atom. In Cy2 one or more carbon or sulfur atoms of Cy2 may optionally be oxidized forming CO, SO or SO2 groups. In addition, Cy2 may be optionally substituted as indicated below, in the definition of a compound of formula I, if substituted, the substituents may be the same or different and may be located at any available position of the ring system. Examples include, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, azetidinyl, aziridinyl, oxiranyl, oxetanyl, imidazolidinyl, isothiazolidinyl, isoxazolidinyl, oxazolidinyl, pyrazolidinyl, pyrrolidinyl, thiazolidinyl, dioxanyl, morpholinyl, thiomorpholinyl, 1,1-dioxothiomorpholinyl, piperazinyl, homopiperazinyl, piperidinyl, pyranyl, tetrahydropyranyl, homopiperidinyl, oxazinyl, oxazolinyl, pyrrolinyl, thiazolinyl, pyrazolinyl, imidazolinyl, isoxazolinyl, isothiazolinyl, 2-oxo-pyrrolidinyl, 2-piperazinyl, 2-piperazinyl, 2-piperazinyl, 2-piperazine 2-oxo-1,2-dihydropyridyl, 2-oxo-1,2-dihydropyrazinyl, 2-oxo-1,2-dihydropyrimidinyl, 3-oxo-2,3-dihydropyridazyl, phenyl, naphthyl, thienyl, furyl, pyrrolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, imidazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl, 1,2, 4-oxadiazolyl, 1,2,4-thiadiazolyl, pyridyl, pyrazinyl, piri midinilo, pyridazinyl, benzimidazolyl, benzooxazolyl, benzofuranyl, isobenzofuranyl, indolyl, isoindolyl, benzothiophenyl, benzothiazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, indazolyl, imidazopyridinyl, pyrrolopyridinyl, thienopyridinyl, imidazopyrimidinyl, imidazopirazinilo, imidazopyridazinyl, pirazolopirazinilo, pyrazolopyridinyl, pyrazolopyrimidinyl, benzo [1,3] dioxolyl, phthalimidyl, 1-oxo-1,3-dihydroisobenzofuranyl, 1,3-dioxo-1,3-dihydroisobenzofuranyl, 2-oxo-2,3-dihydro-1 W-indolyl , 1-oxo-2,3-dihydro-1W-isoindolyl, perhydroquinolinyl, 1-oxoperhydroisoquinolinyl, 1-oxo-1,2-dihydroisoquinolinyl, 4-oxo-3,4-dihydroquinazolinyl, 2-aza-bicyclo [2.2.1 ] heptanyl, 5-aza-bicyclo [2.1.1] hexanyl, 2W-spiro [benzofuran-3,4'-piperidinyl], 3W-spiro [isobenzofuran-1,4'-piperidinyl], 1-oxo-2,8 -diazaspiro [4.5] decanyl and 1-oxo-2,7-diazaspiro [4.5] decanyl.
[0047] In the above definition of Cy ² , when the specified examples refer to a bicyclic ring in general terms, all possible arrangements of atoms are included.
[0048]
[0049] - Cy ⁴ represents:
[0050]
[0051] - a saturated, partially unsaturated or aromatic carbocyclic ring of 3 to 7 members, where Cy ⁴ is attached to the rest of the molecule through an available carbon or nitrogen atom. In addition, Cy ⁴ may be optionally substituted as indicated in the definition of formula I, the substituents may be the same or different and may be located at any available position of the ring system,
[0052]
[0053] - or a saturated heterocyclic, partially unsaturated or aromatic ring of 3 to 7 members containing 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, and where Cy ⁴ is attached to the rest of the molecule through a carbon atom or available nitrogen, and where one or more carbon or sulfur atoms of Cy ² may be oxidized forming CO, SO or SO ^{2 groups} . In addition, Cy ⁴ may be optionally substituted as indicated in the definition of formula I, the substituents may be the same or different and may be located at any available position of the ring system.
[0054] Examples include, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, azetidinyl, aziridinyl, oxiranyl, oxetanyl, imidazolidinyl, isothiazolidinyl, isoxazolidinyl, oxazolidinyl, pyrazolidinyl, pyrrolidinyl, thiazolidinyl, dioxanyl, morpholinyl, thiomorpholinyl, 1,1-dioxothiomorpholinyl, piperazinyl, homopiperazinyl, piperidinyl, pyranyl, tetrahydropyranyl, homopiperidinyl, oxazinyl, oxazolinyl, pyrrolinyl, thiazolinyl, pyrazolinyl, imidazolinyl, isoxazolinyl, isothiazolinyl, 2-oxo-pyrrolidinyl, phenyloxylazoyloxylazoyloxylazoyloxylazoyloxylazoyloxylazolezolyl, phenyloxylazolezolyl, phenyloxylazolezolyl, phenyl imidazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl, 1,2,4-oxadiazolyl, 1,2, 4-thiadiazolyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl.
[0055]
[0056] When in the definitions used throughout the present description for cyclic groups the specified examples refer to a ring radical in general terms, for example, pyridyl, thienyl or indolyl, all possible binding positions are included. Thus, for example, in the definitions of Cy ¹ to Cy ⁴ , which do not include any limitation regarding the binding position, the term pyridyl includes 2-pyridyl, 3-pyridyl and 4-pyridyl; and thienyl includes 2- thienyl and 3-thienyl.
[0057] The term "optionally substituted by one or more" means the possibility of a group being substituted by one or more, preferably by 1, 2, 3 or 4 substituents, provided that said group has sufficient available positions that can be substituted. If present, said substituents may be the same or different and may be located over any available position.
[0058]
[0059] When two or more groups with the same numbering appear in a definition of a substituent (for example -NR7R7, -NR11R11, etc.), this does not mean that they have to be identical. Each of them is independently selected from the list of possible meanings given for said group, and therefore they can be the same or different.
[0060]
[0061] When the phrase appears: "In a particular embodiment of the present invention ..:" or "In a preferred embodiment of the present invention ..:" the definition of the embodiments that are included after said phrase, in each case, it refers both to the compounds of formula I , and to the compounds of formula II , and to the compounds of formula III ; provided that the radical groups or substituents mentioned are applicable to the corresponding formula.
[0062]
[0063] The present invention has as its object a compound of structural formula I, as defined in claim 1, or according to particular embodiments, in any of the dependent claims thereof.
[0064]
[0065] The present invention relates first to a compound of formula I :
[0066]
[0067] where:
[0068] - each R ⁱ and R ⁵ independently represent hydrogen, halogen, C ¹ -C ²⁰ alkyl, -CN, -COR ⁷ , -CO ² R ⁷ , -CONR ⁷ R ⁷ , -OR ⁷ , -OCOR ⁷ , -SR ⁷ , -NR ⁷ R ⁷ , -NR ⁷ COR ⁷ , -SO R ⁷ , -SO ² R ⁷ , -SO ² NR ⁷ R ⁷ , -CF ³ or Cy ¹ , where C ¹ -C ²⁰ alkyl can be independently , optionally substituted by one or more R ⁸ , and Cy ¹ may, independently, be optionally substituted by one or more R ⁹ ;
[0069] - each R ⁴ independently represents nitrogen or CR ⁵ ;
[0070] - each R ³ independently represents hydrogen, C ¹ -C ²⁰ alkyl, -CN, -COR ⁷ , -CO ² R ⁷ , -CONR ⁷ R ⁷ , -OR ⁷ , -OCOR ⁷ , -SR ⁷ , -NR ⁷ R ⁷ , -NR ⁷ COR ⁷ , -SO R ⁷ , -SO ² R ⁷ , -SO ² NR ⁷ R ⁷ or Cy ¹ , where C ¹ -C ²⁰ alkyl can be, independently, optionally substituted by one or more R ⁸ , and Cy ¹ may, independently, be optionally substituted by one or more R ⁹ ;
[0071]
[0072] - each R ² independently represents R ¹⁰ , -COR ¹⁰ , -CO ² R ¹⁰ , -SO ² R ¹⁰ , Cy ² , -COCy ² , -CO ² Cy ² , -SO ² Cy ² or Y, where R ¹⁰ can be independently, optionally substituted by one or more R ⁸ , Cy ² may, independently, be optionally substituted by one or more R ¹⁰ , and Y is:
[0073]
[0074] - each R6 independently represents oxygen or sulfur;
[0075] - R7 each independently represent hydrogen, C1-C20 or C and 4, where alkyl C ¹ -C ²⁰ may be independently optionally substituted by one or more R13 alkyl, and C and 4 may be optionally substituted by one or more R14;
[0076] or two R7 groups are united forming a saturated 5-7 membered heterocycle with the nitrogen atom:
[0077] - not substituted;
[0078] - or replaced by one or more R14,
[0079] - or unsubstituted, which contains an additional heteroatom selected from oxygen, sulfur or unsubstituted nitrogen,
[0080] - or unsubstituted, which additionally contains a heteroatom selected from oxygen, sulfur or nitrogen substituted by one or more R ¹⁴ ,
[0081] - or substituted by one or more R14; which additionally contains a heteroatom selected from oxygen, sulfur or unsubstituted nitrogen,
[0082] - or substituted by one or more R14; which additionally contains a heteroatom selected from oxygen, sulfur or nitrogen substituted by one or more R ¹⁴ ;
[0083]
[0084] - each R8 independently represents Cy3, -OR11, -SR11 or -NR11R11, where Cy3 can be, independently, optionally substituted by one or more R9;
[0085] - each R10 independently represents hydrogen, C1-C40 alkyl, Cy4, -OR ¹¹ , -SR ¹¹ , -NR ¹¹ R ¹¹ - (CH2CH ₂ O) 2- (CH2) 2-NH- (CO) - (CH2) 4 -T or - (CH2) 5-NH- (CO) - (CH2) 4-T where C1-C40 alkyl can be, independently, optionally substituted by one or more R12 or SiR19, Cy4 can be, independently, optionally substituted by one or more R ⁹ , and T is:
[0086]
[0087]
[0088]
[0089] - each R ¹¹ independently represents hydrogen, C ¹ -C ⁶ or Cy ³ alkyl, where C ¹ -C ⁶ alkyl can be, independently, optionally substituted by one or plus -OH or -OC rC 4 alkyl, wherein C1-C4 alkyl can be independently substituted by one or more -OH, and Cy3 can be independently substituted by one or more C1-C6 alkyl;
[0090] - or two R11 groups are united forming with the nitrogen atom forming a 5- to 7-membered heterocycle, saturated:
[0091] - not replaced,
[0092] - or substituted by one or more C1-C6 alkyl groups,
[0093] - or unsubstituted, which additionally contains a heteroatom selected from unsubstituted nitrogen, oxygen and sulfur,
[0094] - or unsubstituted, which additionally contains a heteroatom selected from oxygen, sulfur or nitrogen substituted by one or more C1-C6 alkyl groups,
[0095] - or substituted by one or more C1-C6 alkyl groups, which additionally contains a heteroatom selected from unsubstituted nitrogen, oxygen and sulfur,
[0096] - or substituted by one or more C1-C6 alkyl groups, which additionally contains a heteroatom selected from oxygen, sulfur or nitrogen substituted by one or more C1-C6 alkyl groups;
[0097] - each R9 and R14 independently represent R11, -OR11, -SR11 or -NR11R11;
[0098] - each R12 and R13 independently represent -OR11, -SR11, -NR11R11 or Cy3, where Cy ³ can be, independently, optionally substituted by one or more C1-C6 alkyl;
[0099] - each R19 independently represents C1-C20 alkyl, -OC1-C20 alkyl, Cy4 or -OCy4, where Cy4 may be optionally substituted by one or more R14;
[0100] - each Cy1 and Cy3 independently represent phenyl or a 5- or 6-membered aromatic heterocycle containing 1 to 3 heteroatoms selected from nitrogen, oxygen and sulfur, and where each Cy1 and Cy3 is independently linked to the rest of the molecule through any available carbon or nitrogen atom. In addition, they may be optionally substituted by R ⁹ substituents, which may be the same or different and may be located in any available position of the ring system;
[0101] - each Cy2 independently represents a saturated ring, partially unsaturated or aromatic, monocyclic of 3 to 7 members or bicyclic of 6 to 11 members, which is carbocyclic or heterocyclic; when Cy ² is heterocyclic it contains 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur; the bicyclic rings are formed by two rings fused through two adjacent carbon or nitrogen atoms, or through two non-adjacent carbon or nitrogen atoms forming a bridge ring, or is formed by two rings joined through a single carbon atom forming a ring of the spiral type, and in Cy2 one or more carbon or sulfur atoms of Cy2 are not oxidized or are oxidized forming groups CO, SO or SO2, and where Cy2 is not substituted or substituted with R10 substituents that are not equal or equal, and are located in any available position of the ring system; and where. Cy2 is attached to the rest of the molecule through any available carbon or nitrogen atom; Y
[0102] - each Cy4 independently represents a saturated, partially unsaturated or aromatic ring of 3 to 7 members:
[0103] - carbocyclic, where Cy4 is attached to the rest of the molecule through an available carbon or nitrogen atom, and can be substituted with R ¹⁴ substituents that may be the same or not, and are located at any available position of the ring system,
[0104] - or heterocyclic, containing 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, and where Cy4 is attached to the rest of the molecule through an available carbon or nitrogen atom, and where one or more carbon or sulfur atoms of Cy2 may be oxidized forming CO, SO or SO2 groups and may be substituted with R14 substituents that may be the same or not, and are located in any available position of the ring system;
[0105] as well as its regioisomers, and mixtures of two or more compounds of formula I, regioisomers or combinations thereof.
[0106]
[0107] In formula I, when m = 0, the ring becomes a five-member ring.
[0108]
[0109] For the embodiments mentioned below, the definition refers to both the compounds of formula I , and the compounds of formula II , and the compounds of formula III mentioned below; provided that the radical groups or substituents mentioned are applicable to the corresponding formula.
[0110]
[0111] In a particular embodiment of the present invention, in the compound of formula I , each X independently represents chlorine.
[0112]
[0113] In another particular embodiment of the present invention, in the compound of formula I, each X independently represents R ¹⁵
[0114] In another particular embodiment of the present invention, in the compound of formula I, each X independently represents R ¹⁵
[0115]
[0116]
[0117]
[0118] In another particular embodiment of the present invention, in the compound of formula I, each R ⁴ independently represents CR ⁵ .
[0119]
[0120] In another particular embodiment of the present invention, in the compound of formula I, each R ⁵ independently represents hydrogen, halogen, C ¹ -C ²⁰ alkyl, -CN, -COR ⁷ , -CO ² R ⁷ , -CONR ⁷ R ⁷ , -OR ⁷ , -OCOR ⁷ , -SR ⁷ , -NR ⁷ R ⁷ , -NR ⁷ COR ⁷ , -SO R ⁷ , -SO ² R ⁷ , -SO ² NR ⁷ R ⁷ , -CF ³ or Cy ¹ , where C ¹ -C ²⁰ alkyl can be, independently, optionally substituted by one or more R 8, Cy ¹ can, independently, be optionally substituted by one or more R ⁹ , and where R ¹ , R ² , R ³ , R6, R ⁷ , R8, R ⁹ and Cy ¹ have the meaning given above.
[0121]
[0122] In a preferred embodiment of the present invention, each R ⁵ is hydrogen.
[0123] In another preferred embodiment of the present invention, each R ⁵ is -CO ² CH ³ .
[0124] In another preferred embodiment of the present invention, each R ⁵ is -CF ³ .
[0125] In a particular embodiment of the present invention, each R ³ independently represents hydrogen, C ¹ -C ²⁰ alkyl, -CN, -COR ⁷ , -CO ² R ⁷ , -CONR ⁷ R ⁷ , -OR ⁷ , -SR ^7, -NR ⁷ R ^7, -SOR ^7, -SO ² R ⁷ or Cy ¹ wherein C ¹ -C ²⁰ may be independently optionally substituted by one or more R8, Cy ¹ may be independently optionally substituted by one or more R ⁹ , and where R ¹ , R ² , R ⁵ , R6, R ⁷ , R8, R ⁹ and Cy ¹ have the meaning given above.
[0126]
[0127] In a preferred embodiment of the present invention, each R ³ is hydrogen. In a particular embodiment of the present invention, each R ¹ independently represents hydrogen, halogen, C ¹ -C ²⁰ alkyl, -CN, -COR ⁷ , -CO ² R ⁷ , -CONR ⁷ R ⁷ , -OR ⁷ , -OCOR ⁷ , -SR ⁷ , -NR ⁷ R ⁷ , -NR ⁷ COR ⁷ , -SO In a preferred embodiment of the present invention, each R1 is hydrogen.
[0128] In a particular embodiment of the present invention, each R6 independently represents oxygen or sulfur, and where R ^ R2, R3 and R5 have the meaning given above.
[0129]
[0130] In a preferred embodiment of the present invention, each R6 is an oxygen.
[0131]
[0132] In a particular embodiment of the present invention, each R ² independently represents R10, -COR10, -CO2R10, -SO2R10, Cy2, -COCy2, -CO2Cy2, -SO2Cy2 or Y, where R10 can be, independently, optionally substituted by one or more R8, Cy2 may, independently, be optionally substituted by one or more R10, and is:
[0133]
[0134]
[0135]
[0136]
[0137] and where R1, R3, R5, R6, R8, R10 and Cy1 have the meaning given above.
[0138]
[0139] In a preferred embodiment of the present invention, each R ² is hydrogen.
[0140] In another preferred embodiment of the present invention, each R2 is a -CO2C (CH3) 3 chain.
[0141]
[0142] In another preferred embodiment of the present invention, each R2 is a Y chain, where Y is:
[0143]
[0144]
[0145]
[0146]
[0147] In a particular embodiment of the present invention, each R7 independently represents hydrogen, C1-C20 alkyl or Cy4.
[0148] In another particular embodiment of the present invention, two R7 groups can be joined by forming with the nitrogen atom a saturated 5- to 7-membered heterocycle that may additionally contain a heteroatom selected from nitrogen, oxygen and sulfur, and which may be, independently, optionally substituted by one or two R14.
[0149]
[0150] In another particular embodiment of the present invention, each R9 independently represents R11.
[0151]
[0152] In another particular embodiment of the present invention, each R10 independently represents hydrogen, C1-C40 alkyl, Cy4, -OR ¹¹ , -SR ¹¹ , -NR ¹¹ R ¹¹ - (CH2CH ₂ O) 2- (CH2) 2- NH- (CO) - (CH2) 4-T or - (CH2) 5-NH- (CO) - (CH2) 4-T where C1-C40 alkyl can be, independently, optionally substituted by one or more R ¹² or SiR ¹⁹ , Cy ⁴ may, independently, be optionally substituted by one or more R ⁹ , and T is:
[0153]
[0154]
[0155]
[0156]
[0157] In a preferred embodiment of the present invention, each R ¹⁰ independently represents hydrogen or C ¹ -C ¹⁰ alkyl, where C ¹ -C ¹⁰ alkyl can be, independently, optionally substituted by one or more -OH or -OC1-C4 I rent.
[0158]
[0159] In another preferred embodiment of the present invention, each R ¹⁰ independently represents Cy3, where Cy3 can be, independently, optionally substituted by one or more C1-C6 alkyl.
[0160]
[0161] In another preferred embodiment of the present invention, each R ¹⁰ independently represents - (CH2CH ₂ O) 2- (CH2) 2-NH- (CO) - (CH2) 4-T or - (CH ² ) ⁵ -NH - (CO) - (CH ² ) ⁴ -T and T is:
[0162]
[0163]
[0164]
[0165]
[0166] In another preferred embodiment of the present invention, each R ¹⁰ independently represents SiR ¹⁹ .
[0167] In a particular embodiment of the present invention, each R11 independently represents C1-C6 or Cy3 alkyl, where C1-C6 alkyl can be, independently, optionally substituted by one or more -OH or -OC1-C4 alkyl, where C1 alkyl -C4 may be, independently, optionally substituted by one or more -OH, and Cy3 may, independently, be optionally substituted by one or more C1-C6 alkyl.
[0168]
[0169] In another particular embodiment of the present invention, two R11 groups are linked to form a 5- to 7-membered heterocycle with the nitrogen atom:
[0170]
[0171] - not replaced,
[0172]
[0173] - or substituted by one or more C1-C6 alkyl groups,
[0174]
[0175] - or unsubstituted, which additionally contains a heteroatom selected from unsubstituted nitrogen, oxygen and sulfur,
[0176]
[0177] - or unsubstituted, which additionally contains a heteroatom selected from oxygen, sulfur or nitrogen substituted by one or more C1-C6 alkyl groups,
[0178]
[0179] - or substituted by one or more C1-C6 alkyl groups, which additionally contains a heteroatom selected from unsubstituted nitrogen, oxygen and sulfur,
[0180]
[0181] - or substituted by one or more groups C1-C6 ,, additionally containing a heteroatom selected from oxygen, sulfur or nitrogen substituted by one or more alkyl ^C1 - ^C6.
[0182]
[0183] In another particular embodiment of the present invention, each R ¹² independently represents -OR11 or Cy3, where Cy3 can be, independently, optionally substituted by one or more C1-C6 alkyl.
[0184]
[0185] In another particular embodiment of the present invention, each R ¹³ independently represents -OR11 or Cy3, where Cy3 can be, independently, optionally substituted by one or more C ¹ -C ⁶ alkyl.
[0186]
[0187] In another particular embodiment of the present invention, each R ¹⁴ independently represents R11.
[0188] In a particular embodiment of the present invention, each R19 independently represents C1-C20 alkyl, -OC1-C20 alkyl, Cy4 or -OCy4, where Cy ⁴ may be optionally substituted by one or more R ¹⁴ .
[0189]
[0190] In a preferred embodiment of the present invention, each R ¹⁹ independently represents C1-C20 alkyl.
[0191]
[0192] In a preferred embodiment of the present invention, each Cy1 is phenyl.
[0193] In a particular embodiment of the present invention, each Cy ² independently represents a carbocyclic or heterocyclic 3 to 7 membered monocyclic saturated ring, where Cy2 is attached to the rest of the molecule through any available carbon or nitrogen atom, and where Cy2 contains 1 to 3 heteroatoms selected from nitrogen, oxygen and sulfur.
[0194]
[0195] In a preferred embodiment of the present invention, each Cy3 is phenyl.
[0196] In another preferred embodiment of the present invention, each Cy3 independently represents a 5 or 6 membered aromatic heterocycle containing from 1 or 2 heteroatoms selected from nitrogen, oxygen and sulfur, and where Cy ³ is attached to the rest of the molecule a through any available carbon or nitrogen atom.
[0197]
[0198] In a particular embodiment of the present invention, each Cy ⁴ independently represents a saturated 3- to 7-membered carbocyclic or heterocyclic ring, optionally containing 1 to 3 heteroatoms selected from nitrogen, oxygen and sulfur, and where Cy ⁴ is attached to the rest of the molecule through any available carbon or nitrogen atom.
[0199]
[0200] In a particular embodiment of the present invention, the compound of formula I is selected from:
[0201]
[0202]
[0203]
[0204]
[0205]
[0206]
[0207]
[0208] The present invention also has as its object a process for preparing a compound of structural formula I, as defined in claim 26, or according to particular embodiments, in any of the dependent claims thereof.
[0209]
[0210] In a second aspect, the present invention relates to a process for the preparation of a compound of structural formula I, its regioisomers, or mixtures thereof, which comprises reacting a compound of structural formula II:
[0211]
[0212]
[0213] where:
[0214] - each R1, R2, R3, and R ¹⁵ independently have the same meaning as in the case
[0215] of the formula I;
[0216] - each R ¹⁶ independently represents halogen, -OSO ² R ¹⁸ or R15, with the condition
[0217] that in structure I resulting from this reaction, the substituents X (R16) do not
[0218] they can be neither the four equal, nor the same two to two (asymmetric structures result);
[0219] - each R ¹⁸ represents C ¹ -C10 alkyl, -CF3, -C ⁴ F9, -CH ² CF ³ or Cy5, where Cy ⁵ can be, independently, optionally substituted by one or more halogens, alkyl
[0220] C ¹ -C ⁴ or -NO ² ; Y
[0221] - each Cy ⁵ represents phenyl;
[0222] its regioisomers or mixtures thereof, with a compound of structural formula
[0223] III,
[0224]
[0225]
[0226] where:
[0227] - each R ⁴ , R ⁵ independently have the same meaning as in the case of formula I;
[0228] - each R ¹⁷ independently represents -OH or -SH;
[0229] their regioisomers or mixtures thereof
[0230]
[0231] in the case of compounds of formula I with m = 1, or
[0232]
[0233] The process comprises a decarbonylation reaction of a compound of formula II, in the case of compounds of formula I with m = 0.
[0234]
[0235] Structure I with the 5-membered ring (m = 0) can be obtained from a compound of formula II with a 6-membered ring (there is a decarbonylation during the reaction).
[0236]
[0237] As indicated above, particular embodiments of the process of the invention refer to all those in which the substituent groups of the formula II and III have the meanings given above for the formula I, provided that the substituents are appropriate in the case of formula II or formula III.
[0238]
[0239] In a particular embodiment of the present invention, in the compound of formula II, each R ² independently represents R ¹⁰ , -COR ¹⁰ , -CO ² R ¹⁰ , -SO ² R ¹⁰ , Cy ² , -COCy ² , - CO ² Cy ² , -SO ² Cy ² or Y, where R ¹⁰ can be, independently, optionally substituted by one or more R ⁸ , Cy ² can be, independently, optionally substituted by one or more R ¹⁰ , Y is:
[0240]
[0241]
[0242] and where R1, R3, R8, R10 and Cy2 have the same meaning as for the compound of formula I.
[0243] In a preferred embodiment of the present invention, in the compound of formula II, each R2 represents -CO2C (CH3) 3.
[0244]
[0245] In a preferred embodiment of the present invention, in the compound of formula II, each R1 represents hydrogen.
[0246]
[0247] In a preferred embodiment of the present invention, in the compound of formula II, each R ³ represents hydrogen.
[0248]
[0249] In a particular embodiment of the present invention, in the compound of formula III, each R4 independently represents C-R5.
[0250]
[0251] In another particular embodiment of the present invention, in the compound of formula III, each R ⁵ independently represents hydrogen, halogen, C ¹ -C ²⁰ alkyl, -CN, -COR ⁷ , -CO ² R ⁷ , -CONR ⁷ R ⁷ , -OR ⁷ , -OCOR ⁷ , -SR ⁷ , -NR ⁷ R ⁷ , -NR ⁷ COR ⁷ , -SO R7, -SO2R7, -SO2NR7R7, -CF3 or Cy1, where C1-C20 alkyl can be, independently, optionally substituted by one or more R8, Cy ¹ may be, independently, optionally substituted by one or more R9, and where R7, R8, R9 and Cy ¹ have the same meaning as for the compound of formula I.
[0252]
[0253] In a preferred embodiment of the present invention, in the compound of formula III, each R5 represents hydrogen.
[0254]
[0255] In another preferred embodiment of the present invention, in the compound of formula III, each R5 represents -CO2CH3.
[0256]
[0257] In another preferred embodiment of the present invention, in the compound of formula III, each R5 represents -CF3.
[0258]
[0259] In a particular embodiment of the present invention, in the compound of formula III, each R17 represents -OH or -SH.
[0260] In a preferred embodiment of the present invention, in the compound of formula III, each R17 represents -OH.
[0261]
[0262] The present invention also has as its object a material consisting of a compound of formula I, or a mixture of regioisomers of formula I, or a mixture comprising any of the compounds of formula I in any proportion, as defined above, anchored by a chemical bond to a solid surface.
[0263]
[0264] In a preferred embodiment of the present invention, the solid surface is silica (SiO2). For example, compounds called PDI 17 or PDI 18 can be used for anchoring on solid surfaces.
[0265]
[0266] Additionally, the present invention aims at the use of a compound of structural formula I, or of a mixture of regioisomers of formula I, or of a mixture comprising any of the compounds of formula I, regioisomers or combinations thereof in any proportion , as biomarkers or fluorophores in bioimaging.
[0267]
[0268] In a particular embodiment, the present invention has as its object the use of the compounds mentioned in the preceding paragraph, of formula I, or their regioisomers, or a mixture comprising any of the compounds of formula I in any proportion, in bioimage applications mobile.
[0269]
[0270] In a preferred embodiment of the present invention, the cells to be studied are epithelial. As an illustrative example of the use of the compounds in cell biomagen techniques, the compound called PDI 19 can be used.
[0271]
[0272] In a particular embodiment of the present invention, the compound of structural formula I, as previously defined, or a mixture of regioisomers of formula I, or a mixture comprising any of the compounds of formula I in any proportion is employed in detection of biological compounds (biomarked).
[0273]
[0274] As an illustrative example of the use of compounds in biological biomarking, the species to be detected is avidin, and compounds called PDI 20, PDI 21 or PDI 24 can be used as an example.
[0275]
[0276] The method of the present invention provides alternatives for the construction of particular molecules or structures for bioconjugation, specifically markers. fluorescent In a fast, simple and effective way, sets of biomolecule anchoring nanostructures are obtained, with different and modulable optical properties (as illustrative examples are shown the PDI examples 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 22 and 23 ). It is proposed not a specific solution to the problem, but a technology that can be used to improve traditional applications or explore new ones.
[0277]
[0278] In addition, the applied methodology offers the possibility of joining groups of siloxane in one or both positions (as examples illustrating PDI 17 and PDI 18 ), useful for chemically immobilizing fluorescent markers to solid surfaces such as silica, and over the other imide position, biomolecules. This would allow the construction of devices such as dosimeters, useful in the detection of biological contaminant species such as enterotoxins.
[0279] Possible specific applications of these products as fluorophores in microscopy are, for example, the detection of avidin or the study of epithelial cells; being useful for the former, compounds of formula I in which at least one R ¹⁰ represents - (CH2CH ₂ O) 2- (CH2) 2-NH- (CO) - (CH2) 4- T or - (CH2) -NH- (CO) - (CH2) 4- T where T is:
[0280]
[0281]
[0282]
[0283]
[0284] such as examples PDI 20 , 21 and 24 ; or for the latter, compounds of formula I in which at least one R2 represents Y , Y being:
[0285]
[0286]
[0287]
[0288]
[0289] such as example PDI 19 .
[0290]
[0291] A further object of the invention is the use of a compound of structural formula I composed of structural formula I, or a mixture of regioisomers of formula I, or a mixing of any of the compounds of formula I in any proportion, with the proviso that R2 is not H or -CO2C (CH3) 3, in the detection of biological compounds.
[0292]
[0293] A further object of the invention is a material consisting of a compound of formula I , such that said compound of formula I is a compound:
[0294] - a) that contains a SiR19 group,
[0295] - b) or a compound of structural formula I in which at least one R2 is H,
[0296] - or regioisomers of a) or b)
[0297] - or mixtures of them in any proportion
[0298] anchored by a chemical bond on solid surfaces, for example, silica, as shown by way of example in the following two schemes:
[0299]
[0300]
[0301]
[0302]
[0303] A further object of the invention is the use of a material as defined above, anchored by a chemical bond to a solid surface, for example, silica, as a biomarker or fluorophore in bioimage.
[0304]
[0305] BRIEF DESCRIPTION OF THE FIGURES
[0306] Figure 1. Absorption and emission graphs, and photographs of compound PDI 3 (in solution) in which the marked solvatochromic effect is illustrated by way of example of this type of products. Above: Photographs under white and 366 nm lights. Medium: Absorption spectra (left) and normalized absorption (right). Bottom: Emission spectra (left) and normalized emission (right). The arrows indicate the hypsochromic displacement of maximum emission with the decrease of the polarity of the medium. Solvents: 1: Water, 2: Methanol (MeOH), 3: Dimethylsulfoxide (DMSO), 4: W, W-Dimethylformamide (DMF), 5: Acetonitrile (MeCN), 6: Acetone, 7: Ethyl acetate (AcOEt) , 8: Tetrahydrofuran (THF), 9: Chloroform (CHCl3), 10: Dichloromethane (DCM), 11: Toluene, 12: Diethyl ether (Et2O), 13: n-Hexane (Hx), 14: Cyclohexane (MCH). For simplicity, only eight solvents have been represented.
[0307]
[0308] EXAMPLES
[0309]
[0310] The present invention is further illustrated by the following examples, which cannot be considered as limiting its scope.
[0311]
[0312] Example 1. W, W-Bis (ferc-butylpiperidine-1-carboxylate) -1,6,7,12-tetrachloroperylene-3,4: 9,10-tetracarboxy diimide (PDI 1) .
[0313]
[0314] In a microwave vial and under an inert atmosphere, 1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic dianhydride (0.50 g, 0.95 mmol) and 1,4-diaza bicycles are dried [2.2.2] octane (0.26 g, 2.41 mmol). 20 ml of anhydrous DMF and 4-amino-1- (ferc-butylpiperidin-1-carboxylate) -piperidine (0.47 g, 2.30 mmol) are added, sealed with a septum and irradiated for 110 hours at 110 ° C in the microwave . The reaction crude is poured onto 15 ml of 1M aqueous HCl solution, kept under stirring for one hour. Finally, filter and wash with distilled water. The resulting product is purified by flash column chromatography (silica gel, DCM: CH3CN, 20: 3), obtaining the diimide perylene as an orange solid (0.79 g, 0.89 mmol, 95%).
[0315]
[0316] • PF (° C): > 350 ° C.
[0317] • Rf (DCM: MeOH, 50: 2): 0.60.
[0318] • FT-IR (KBr, cm-1): 2977, 2931, 2852, 1701, 1661, 1590, 1420, 1366, 1337, 1275, 1243, 1150, 1005, 951, 908, 749, 684, 547.
[0319] • 1H NMR (300 MHz, CDCh) δ: 8.66 (s, 4H), 5.24 -5.15 (m, 2H), 4.31 (s, 4H), 2.88 -2.66 (m, 8H), 1.69 (d, J = 11 Hz, 4H), 1.51 (s, 18H).
[0320] • 13C NMR (75 MHz, CDCl3) δ : 162.7, 154.8, 135.5, 133.2, 131.5, 128.6, 123.6, 123.4, 79.9, 52.6, 44.2, 43.9, 29.8, 28.6, 28.4.
[0321] • MS (MALDI +, DCTB): m / z calc. for C39H33Cl4N4O6 ([M + 2H- (COOC (CH3) 3)] +): 793.1149; exp .: 793.1142.
[0322] • UV-VIS (DCM) λmax / nm (ε / M ^-1 cm ^-1 ): 515 (37900).
[0323] • Emission (DCM) λmax / nm: 548.
[0324] • τ / ns (DCM, x2): 5.26 (1.06).
[0325] • Φ (DCM): 0.44 ± 0.01.
[0326]
[0327] Example 2. MM, -Bis (te / 'c-butylpiperidin-1-carboxylate) -1- (dimethyl-5-oxyisophthalate) -6,7,12-trichloroperylene-3,4: 9,10-tetracarboxy d¡¡ mda (POI 2).
[0328]
[0329] NaH (17.6 mg, 0.44 mmol) and dimethyl 5-hydroxyisophthalate (104.2 mg, 0.49 mmol) are dried in a microwave vial and under an inert atmosphere. 20 ml of anhydrous DMF are added and allowed to stir for 10 minutes. CuI (6.0 mg, 0.03 mmol), o-phenanthroline monohydrate (12.6 mg, 0.06 mmol), cesium carbonate (430.0 mg, 1.32 mmol) and W, W-bis (tert-butylpiperidine-1-carboxylate) are added - 1,6,7,12-tetrachloroperylene-3,4: 9,10-tetracarboxy diimide (100 mg, 0.10 mmol), sealed with a septum and irradiated for one hour at 110 ° C in the microwave. The solvent is removed under reduced pressure and the resulting product is purified by flash column chromatography (silica gel, DCM: CH3CN, 7: 3), obtaining the diimide perylene as a pink solid (8.2 mg, 0.01 mmol, 7%).
[0330]
[0331] • PF (° C):> 350 ° C.
[0332] • Rf (DCM: MeOH, 50: 2): 0.50.
[0333] • 1H-NMR (300 MHz, CDCU) δ: 8.72-8.52 (m, 4H), 8.35 (dt, J = 11.2 and 1.4 Hz, 1H), 8.17 (s, 1H), 7.76 (d, J = 1.4 Hz , 1H), 5.16-5.08 (m, 2H), 4.31 (s, 4H), 3.94-3.95 (d, J = 14.4 Hz, 6H), 2.86-2.65 (m, 8H), 1.69-1.63 (m, 4H ), 1.48 (s, 18H).
[0334] • MS (MALDI-, DCTB): m / z calc. for C54H49Cl3N4O13 ([M] -): 1066.2356; exp .: 1066.0.
[0335] • UV-VIS (DCM) λmax / nm (s / M‘1-cm'1): 528 (40800).
[0336] • Emission (DCM) λmax / nm: 574.
[0337] • τ / ns (DCM, x2): 6.02 (1.19).
[0338] • Φ (DCM): 0.82 ± 0.01.
[0339] Example 3. N, N'-B is (ferc-butylp iperid in-1-carboxylate) -1,7-b is (d im ethyl-5-oxyisophthalate) -6,12-dichloroperylene-3,4: 9 , 10-tetracarboxy diimide (PDI 3).
[0340]
[0341] NaH (17.6 mg, 0.44 mmol) and dimethyl 5-hydroxyisophthalate (104.2 mg, 0.49 mmol) are dried in a microwave vial and under an inert atmosphere. 20 ml of anhydrous DMF are added and allowed to stir for 10 minutes. CuI (6.0 mg, 0.03 mmol), o-phenanthroline monohydrate (12.6 mg, 0.06 mmol), cesium carbonate (430.0 mg, 1.32 mmol) and W, W-bis (tert-butylpiperidine-1-carboxylate) are added - 1,6,7,12-tetrachloroperylene-3,4: 9,10-tetracarboxy diimide (100 mg, 0.10 mmol), sealed with a septum and irradiated for one hour at 110 ° C in the microwave. The solvent is removed under reduced pressure and the resulting product is purified by flash column chromatography (silica gel, DCM: CH3CN, 7: 3), obtaining the diimide perylene as a pink solid (27.3 mg, 0.02 mmol, 20%).
[0342]
[0343] • PF (° C):> 350 ° C.
[0344] • Rf (DCM: MeOH, 50: 2): 0.30.
[0345] • FT-IR (KBr, cm ^-1 ): 2951, 2928, 2854, 1732, 1701, 1667, 1587, 1502, 1459, 1431, 1408, 1402, 1366, 1323, 1292, 1249, 1170, 1135, 1107, 1032, 1002, 905, 755, 721, 669.
[0346] • 1H-NMR (400 MHz, CDCl3) δ: 8.65 (d, J = 1.2 Hz, 2H), 8.33 (t, J = 1.3 Hz, 2H), 8.17 (s, 2H), 7.70 (d, J = 1.2 Hz, 1H), 7.65 (d, J = 1.3 Hz, 3H), 5.17-5.09 (m, 2H), 4.29 (s, 4H), 3.88 (s, 12H), 2.90-2.60 (m, 9H), 1.66 (d, J = 12.7 Hz, 3H), 1.53 (s, 18H).
[0347] • 13C-NMR (101 MHz, CDCl ³ ) δ: 166.2, 165.0, 162.9, 162.9, 156.2, 155.8, 154.9, 154.8, 135.4, 132.7, 132.5, 132.4, 132.1, 129.7, 126.6, 124.4, 124.2, 123.5, 123.1 , 122.2, 121.7, 120.9, 120.2, 79.9, 52.8, 52.6, 52.5, 44.3, 43.9, 29.9, 28.6, 28.4.
[0348] • MS (MALDI-, DCTB): m / z calc. for C6 ⁴ H58Cl ² N4O18 ([M] "): 1240.3118 exp .:
[0349] 1239.9431.
[0350] • UV-VIS (DCM) λmax / nm (s / M‘1-cm'1): 535 (38100).
[0351] • Em ision (DCM) λmax / nm: 575.
[0352] • τ / ns (DCM, x 2): 5.25 (1.06).
[0353] • Φ (DCM): 0.90 ± 0.01.
[0354]
[0355] Example 4.MM, -B is (fe / 'c-butylp iperid in-1-carboxylate) -1,6,7-tris (dim ethyl-5-oxyisophthalate) -12-chloroperylene-3,4: 9, 10-tetracarboxy diimide (PDI 4).
[0356] NaH (17.6 mg, 0.44 mmol) and dimethyl 5-hydroxyisophthalate (104.2 mg, 0.49 mmol) are dried in a microwave vial and under an inert atmosphere. 20 ml of anhydrous DMF are added and allowed to stir for 10 minutes. CuI (6.0 mg, 0.03 mmol), o-phenanthroline monohydrate (12.6 mg, 0.06 mmol), cesium carbonate (430.0 mg, 1.32 mmol) and W, W-bis (tert-butylpiperidine-1-carboxylate) are added - 1,6,7,12-tetrachloroperylene-3,4: 9,10-tetracarboxy diimide (100 mg, 0.10 mmol), sealed with a septum and irradiated for one hour at 110 ° C in the microwave. The solvent is removed under reduced pressure and the resulting product is purified by flash column chromatography (silica gel, DCM: CH3CN, 7: 3), obtaining the diimide perylene as a pink solid (15.5 mg, 0.01 mmol, 10%).
[0357]
[0358] • PF (° C): > 350 ° C.
[0359] • Rf (DCM: MeOH, 50: 2): 0.40.
[0360] • 1 H-NMR (300 MHz, CDCl 3 ) δ: 8.57 (d, J = 1.5 Hz, 2H), 8.32 (d, J = 1.4 Hz, 2H), 8.16 (d, J = 2.4 Hz, 2H), 8.13 (s, 1H), 8.02 (d, J = 1.4 Hz, 2H), 7.69-7.62 (m, 4H), 5.11-5.03 (m, 2H), 4.26 (s, 4H), 3.90 (d, J = 22.4 Hz, 18H), 2.86-2.53 (m, 9H), 1.66-1.61 (m, 3H), 1.42 (d, J = 1.4 Hz, 18H).
[0361] • MS (MALDI-, DCTB): m / z calc. for C74H67ClN4O ² 3 ([M] "): 1414.3879; exp .:
[0362] 1414.4285.
[0363] • UV-VIS (DCM) λmax / nm ( ε / M ^-1 cm ^-1 ): 544 (49900).
[0364] • Emission (DCM) λmax / nm: 589.
[0365] • τ / ns (DCM, X2): 6.29 (1.26).
[0366] • Φ (DCM): 0.84 ± 0.01.
[0367]
[0368] Example 5. N, N'-Bis (ferc-butylpiperidin-1-carboxylate) -1,6,7,12-tetrakis (dimethyl-5-oxyisophthalate) perilen-3,4: 9,10-tetracarboxy diimide (PDI 5 ) .
[0369]
[0370] NaH (17.6 mg, 0.44 mmol) and dimethyl 5-hydroxyisophthalate (104.2 mg, 0.49 mmol) are dried in a microwave vial and under an inert atmosphere. 20 ml of anhydrous DMF are added and allowed to stir for 10 minutes. CuI (6.0 mg, 0.03 mmol), o-phenanthroline monohydrate (12.6 mg, 0.06 mmol), cesium carbonate (430.0 mg, 1.32 mmol) and W, W-bis (tert-butylpiperidine-1-carboxylate) are added - 1,6,7,12-tetrachloroperylene-3,4: 9,10-tetracarboxy diimide (100 mg, 0.10 mmol), sealed with a septum and irradiated for one hour at 110 ° C in the microwave. The solvent is removed under reduced pressure and the resulting product is purified by flash column chromatography (silica gel, DCM: CH3CN, 7: 3), obtaining the diimide perylene as a pink solid (69.7 mg, 0.04 mmol, 40%).
[0371] • PF (° C):> 350 ° C.
[0372] • Rf (DCM: MeOH, 50: 2): 0.20.
[0373] • FT-IR (KBr, cm '1): 2951, 2925, 2849, 1735, 1698, 1664, 1587, 1505, 1454, 1431,
[0374] • ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 8.31 (t, J = 1.4 Hz, 4H), 8.13 (s, 4H), 7.67 (d, J = 1.4 Hz, 8H), 5.08-5.00 (m , 2H), 4.21 (s, 4H), 3.86 (s, 24H), 2.75-2.52 (m, 9H), 1.60 (d, J = 11.6 Hz, 3H), 1.40 (s, 18H).
[0375] • ¹³ C-NMR (101 MHz, CDCI3) δ: 165.1, 163.1, 155.9, 154.9, 154.7, 133.1, 132.7, 132.0, 126.5, 124.5, 124.0, 121.2, 121.1, 120.9, 120.9, 79.8, 52.7, 52.6, 52.4 , 44.1, 43.6, 29.9, 28.6, 28.4.
[0376] • MS (MALDI-, DCTB): m / z calc. for C ⁸⁴ H ⁷⁶ N ⁴ O ²⁸ ([M] -): 1588.4641; exp .:
[0377] 1588.0849.
[0378] • UV-VIS (DCM) λmax / nm (ε / M ^-1 cm ^-1 ): 545 (43600).
[0379] • Em ision (DCM) λmax / nm: 584.
[0380] • τ / ns (DCM, X2): 6.15 (1.22).
[0381] • Φ (DCM): 0.91 ± 0.01.
[0382]
[0383] Example 6. N, N'-Bis (ferc-butylpiperid in-1-carboxylate) -1,6,7,12-tetrakis (dim ethyl-5-oxyisophtate Iato) perilen-3,4: 9-tricarboxy diimide (PDI 6).
[0384]
[0385] NaH (17.6 mg, 0.44 mmol) and dimethyl 5-hydroxyisophthalate (104.2 mg, 0.49 mmol) are dried in a microwave vial and under an inert atmosphere. 20 ml of anhydrous DMF are added and allowed to stir for 10 minutes. CuI (6.0 mg, 0.03 mmol), o-phenanthroline monohydrate (12.6 mg, 0.06 mmol), cesium carbonate (430.0 mg, 1.32 mmol) and W, W-bis (tert-butylpiperidine-1-carboxylate) are added - 1,6,7,12-tetrachloroperylene-3,4: 9,10-tetracarboxy diimide (100 mg, 0.10 mmol), sealed with a septum and irradiated for one hour at 110 ° C in the microwave. The solvent is removed under reduced pressure and the resulting product is purified by flash column chromatography (silica gel, DCM: CH ³ CN, 7: 3), obtaining the diimide perylene as a purple solid (8.6 mg, 0.02 mmol, 5%).
[0386] • PF (° C):> 350 ° C.
[0387] • Rf (DCM: MeOH, 50: 2): 0.20.
[0388] • FT-IR (KBr, cm-1): 2954, 2926, 2852, 1735, 1698, 1665, 1590, 1496, 1454, 1428, 1391, 1363, 1323, 1243, 1175, 1005, 1002, 914, 803, 757, 721.
[0389] • ¹ H-NMR (400 MHz, CDCl ³ ) 5 : 8.33 (t, J = 1.4 Hz, 1H), 8.31 (t, J = 1 .4 Hz, 1H), 8.30 (t, J = 1.4 Hz, 1H ), 8.27 (t, J = 1.4 Hz, 1H), 8.16 (d, J = 3.4 Hz, 2H), 7.75 (s, 1H), 7.67 (d, J = 1.4 Hz, 4H), 7.61 (t, J = 1.5 Hz, 4H), 6.81 (s, 1H), 5.07 (tt, J = 12.0 and 3.7 Hz, 1H), 4.47 (tt, J = 12.1 and 3.7 Hz, 1H), 4.21 (s, 4H), 3.90 (dd, J = 3.8 and 1.1 Hz, 24H), 2.80-2.57 (m, 7H), 1.82 (d, J = 11.1 Hz, 2H), 1.63 (m, 2H), 1.43 (s, 9H), 1.34 ( s, 9H).
[0390] • ¹³ C-NMR (101 MHz, CDCl ₃ ) δ: 166.6, 165.2, 165.2, 165.2, 165.1, 163.3, 156.9, 156.8, 156.7, 156.6, 156.3, 155.8, 154.7, 154.6, 154.2, 152.6, 139.9, 132.6, 132.6, 132.5, 132.4, 132.2, 129.6, 126.3, 126.2, 126.2, 125.9, 125.6, 124.5, 124.3, 123.9, 123.9, 123.3, 123.1, 122.3, 122.2, 122.1, 122.0, 121.5, 121.4, 118.5, 116.5, 111.2, 102.5, 80.0, 79.7, 52.7, 52.3, 50.5, 44.5, 44.4, 29.9, 28.6, 28.4.
[0391] • MS (MALDI-, DCTB): m / z calc. for C ⁸³ H ⁷⁶ N ⁴ O ²⁷ ([M] +): 1560.4691; exp .: 1560.4898.
[0392] • UV-VIS (DCM) λmax / nm ( ε / M ^-1 cm ^-1 ): 548 (11800).
[0393] • Emission (DCM) λmax / nm: 590.
[0394] • τ / ns (DCM, X2): 5.93 (1.27).
[0395] • Φ (DCM): 0.78 ± 0.01.
[0396]
[0397] Example 7. N, N'-Bis (ferc-butylpiperidin-1-carboxylate) -1,7-bis (3,5-bis (trifIuoromethyl) phenoxy) -6,12-dicIoroperilen-3,4: 9,10- tetracarboxy diimide (PDI 7) .
[0398] NaH (4.7 mg, 0.11 mmol) and 3,5-bis (trifluoromethyl) phenol (119.5 mg, 0.52 mmol) are dried in a microwave vial and under an inert atmosphere. 20 ml of anhydrous DMF are added and allowed to stir for 10 minutes. CuI ( ^6.6 mg, 34.6 mmol), o-phenanthroline monohydrate (12.5 mg, 0.07 mmol), cesium carbonate (451.1 mg, 1.38 mmol) and W, W-bis (tert-butylpiperidine-1-carboxylate) are added ) -1,6,7,12-tetracloroperilen-3,4: 9,10-tetracarboxi diimide ^{(1 0 0 0} mg, ^{0 1 1} mmol), sealed with a septum and irradiated for one hour at 110 ° C in microwave. The solvent is removed under reduced pressure and the resulting product is purified by flash column chromatography (silica gel, DCM: CH ³ CN, 5: 1), obtaining the diimide perylene as a red solid with orange fluorescent emission in solid state (42.9 mg, 0.03 mmol, 29%).
[0399]
[0400] • PF (° C): > 350 ° C.
[0401] • Rf (DCM: MeOH, 50: 1): 0.40.
[0402] • FT-IR (KBr, cm ^-1 ): 3069, 2975, 2933, 2864, 1703, 1668, 1595, 1511, 1462, 1410, 1372, 1334, 1295, 1278, 1180, 1138, 1104, 1027, 989, 947, 887, 807, 703, 682.
[0403] • ¹ H-NMR (300 MHz, CDCl ₃ ) δ: ^{8 .6 8} (s, 2H), 8.16 (s, 2H), 7.58 (s, 2H), 7.25 (s, 4H), 5.18-5.10 (m , 2H), 4.31 (s, 4H), 2.74-2.66 (m, 8H), 1.69 (d, 3H), 1.48 (s, 18H).
[0404] • ¹⁹ F-NMR (300 MHz, CDCl ³ ) δ: -63.71.
[0405] • ¹³ C-NMR (101 MHz, CDCl ³ ) δ: 162.7, 162.7, 156.5, 154.8, 154.4, 135.8, 134.3, 133.9, 132.9, 132.4, 129.7, 124.7, 123.8, 123.7, 122.5, 121.6, 121.0, 120.1, 119.6, 118.6, 79.9, 52.6, 28.6, 28.4.
[0406] • MS (MALDI-, DIT): m / z calc. for C ⁶⁰ H ⁴⁶ Cl ² F i ² N ⁴ O i ⁰ ([M] -): 1280.2394; exp .: 1280.2533.
[0407] • UV-VIS (DCM) λmax / nm (ε / M ^-1 cm ^-1 ): 525 (52600).
[0408] • Emission (DCM) λmax / nm: 569.
[0409] • τ / ns (DCM, X2): 5.59 (1.08).
[0410] • Φ (DCM): 0.83 ± 0.01.
[0411]
[0412] Example 8. N, N'-Bis (ferc-butylpiperidin-1-carboxylate) -1,6,7,12-tetrakis (3,5-bis (trifluoroomethyl) phenoxy) perilen-3,4: 9,10-tetracarboxy diimide (POI 8).
[0413]
[0414] NaH (4.7 mg, 0.11 mmol) and 3,5-bis (trifluoromethyl) phenol (119.5 mg, 0.52 mmol) are dried in a microwave vial and under an inert atmosphere. 20 ml of anhydrous DMF are added and allowed to stir for 10 minutes. CuI (6.6 mg, 34.6 mmol), o-phenanthroline monohydrate (12.5 mg, 0.07 mmol), cesium carbonate (451.1 mg, 1.38 mmol) and W, W-bis (tert-butylpiperidine-1-carboxylate) are added - 1,6,7,12-tetrachloroperylene-3,4: 9,10-tetracarboxy diimide (100.0 mg, 0.11 mmol), sealed with a septum and irradiated for one hour at 110 ° C in the microwave. The solvent is removed under reduced pressure and the resulting product is purified by flash column chromatography (silica gel, DCM: CH3CN, 5: 1), obtaining the diimide perylene as a red solid with orange solid state fluorescent emission (98.0 mg, 0.06 mmol, 51%).
[0415]
[0416] • PF (° C):> 350 ° C.
[0417] • Rf (DCM: MeOH, 50: 1): 0.60.
[0418] • FT-IR (KBr, cm ^-1 ): 3069, 2979, 2933, 2857, 1706, 1668, 1595, 1508, 1459, 1414, 1372, 1337, 1299, 1278, 1177, 1131, 1104, 1030, 989, 947, 894, 807, 703, 682.
[0419] • ¹ H NMR (300 MHz, CDCl ₃ ) δ: 8.19 (s, 4H), 7.61 (s, 4H), 7.29 (s, 8H), 5.11-5.05 (m, 2H), 4.27 (s, 4H), 2.78 (s, 4H), 2.69-2.55 (m, 4H), 1.67 (d, J = 9.1 Hz, 4H), 1.45 (s, 18H).
[0420] • ¹⁹ F NMR (300 MHz, CDCl ₃ ) δ: -63.70.
[0421] • ¹³ C NMR (101 MHz, CDCl ₃ ) δ: 162.7, 156.5, 154.7, 154.6, 134.6, 134.3, 133.9, 133.6, 133.1, 126.5, 124.7, 123.8, 121.5, 121.3, 121.1, 119.6,
[0422] • MS (MALDI-, DIT): m / z calc. for C76H52F24N4O12 ([M] -): 1668.3193; exp .:
[0423] 1668.3053.
[0424] • UV-VIS (DCM) λmax / nm (ε / M ^-1 cm ^-1 ): 534 (45000).
[0425] • Emission (DCM) λmax / nm: 577.
[0426] • τ / ns (DCM, x2): 5.49 (1.04).
[0427] • Φ (DCM): 0.98 ± 0.01.
[0428]
[0429] Example 9. N, N'-Bis (ferc-butylpiperidin-1-carboxylate) -1,7-bis (3,5-bis (trifIuoromethyl) phenoxy) -6- (dimethyl-5-oxyisophtharate) -12-cIoroperylene- 3,4: 9,10-tetracarboxy diimide (PDI 9).
[0430]
[0431] NaH (1.7 mg, 0.07 mmol) and dimethyl 5-hydroxyisophthalate (29.5 mg, 0.14 mmol) are dried in a microwave vial and under an inert atmosphere. 20 ml of anhydrous DMF are added and allowed to stir for 10 minutes. CuI (4.0 mg, 0.02 mmol), 4,4-dimethoxy-2,2-bipyridine (9.1 mg, 0.04 mmol), cesium carbonate (274.5 mg, 0.84 mmol) and N, N'-bis (ferc- are added) Butylpiperidin-1-carboxylate) -1,7-bis (3,5-bis (trifluoromethyl) phenoxy) -6,12-dichloroperylene-3,4: 9,10-tetracarboxy diimide (90.0 mg, 0.07 mmol), sealed with a septum and irradiate for one hour at 110 ° C in microwave. The solvent is removed under reduced pressure and the resulting product is purified by flash column chromatography (silica gel, DCM: CH3CN, 5: 1), yielding the diimide perylene as a red solid with solid-state orange fluorescent emission (8.2 mg, 0.006 mmol, 38%).
[0432] • PF (° C):> 350 ° C.
[0433] • Rf (DCM: MeOH, 50: 1): 0.41.
[0434] • FT-IR (KBr, cm '1): 3066, 2954, 2926, 2853, 1731, 1703, 1661, 1591, 1518, 1462, 1428, 1396, 1365, 1323, 1295, 1274, 1250, 1173, 1138, 1002, 933, 905, 846, 804, 758,724.
[0435] • 1H NMR (400 MHz, CDCl ₃ ) δ: ^{8 .6 8} (s, 1H), 8.65 (s, 2H), 8.36 (s, 1H), 8.21 (s, 1H), 8.12 (s, 1H), 7.63 (s, 2H), 7.48 (s, 1H), 7.32 (s, 2H), 7.26 (s, 2H), 5.15-5.12 (m, 2H), 4.29 (s, 4H), 3.90 (s, ⁶ H ), 2.84 (s, 4H), 2.70-2.65 (m, 4H), 1.69-1.64 (m, 4H), 1.48 (s, 18H).
[0436] • 19F NMR (300 MHz, CDCl ₃ ) δ: -63.63.
[0437] • 13C NMR (101 MHz, CDCl3) δ: 164.9, 162.8, 155.5, 155.4, 154.8, 154.5, 135.6, 133.0, 132.6, 132.4, 128.4, 124.6, 124.4, 123.4, 122.5, 121.3, 120.7, 119.5,
[0438] • MS (MALDI-, DCTB) m / z: calc. for C ⁷⁰ H ⁵⁵ CIF ¹² N ⁴ O ¹⁵ ([M] -): 1454.3165; exp .:
[0439] 1454.3166.
[0440] • UV-VIS (DCM) λmax / nm (ε / M ^-1 cm ^-1 ): 531 (56100).
[0441] • Em ision (DCM) λmax / nm: 578.
[0442] • τ / ns (DCM, x2): 6.00 (1.03).
[0443] • Φ (DCM): 0.92 ± 0.01.
[0444]
[0445] Example 10. N, N'-Bis (ferc-butylp iperid in-1-carboxylate) -1,7-bis (3,5-bis (trifluoro ethyl) phenoxy) -6,12-bis (d im ethyl-5 -oxyisophtharate) perilen-3,4: 9,10-tetracarboxy diimide (PDI 10).
[0446]
[0447] NaH (1.7 mg, 0.07 mmol) and dimethyl 5-hydroxyisophthalate (29.5 mg, 0.14 mmol) are dried in a microwave vial and under an inert atmosphere. 20 ml of anhydrous DMF are added and allowed to stir for 10 minutes. CuI (4.0 mg, 0.02 mmol), 4,4-dimethoxy-2,2-bipyridine (9.1 mg, 0.04 mmol), cesium carbonate (274.5 mg, 0.84 mmol) and N, N'-bis (tert) are added Butylpiperidin-1-carboxylate) -1,7-bis (3,5-bis (trifluoromethyl) phenoxy) -6,12-dichloroperylene-3,4: 9,10-tetracarboxy diimide (90.0 mg, 0.07 mmol), sealed with a septum and irradiate for one hour at 110 ° C in microwave. The solvent is removed under reduced pressure and the resulting product is purified by flash column chromatography (silica gel, DCM: CH3CN, 5: 1), obtaining the diimide perylene as a red solid with orange fluorescent emission in solid state (3.9 mg, 0.006 mmol, 16%).
[0448]
[0449] • PF (° C):> 350 ° C.
[0450] • Rf (DCM: MeOH, 50: 1): 0.37.
[0451] • FT-IR (KBr, cm '1): 2954, 2926, 2853, 1731, 1703, 1664, 1591, 151, 1459, 1428, 1407, 1365, 1320, 1278, 1246, 1177, 1135, 1107, 1027, 999, 936, 804, 755, 724, 699.
[0452] • 1H NMR (300 MHz, CDCl ₃ ) δ: 8.65 (s, 2H), 8.37-8.32 (m, 3H), 8.23-8.11 (m, 3H), 7.69 (s, 3H), 7.64 (s, 3H) , 7.49 (s, 1H), 7.36 (s, 1H), 5.17-5.05 (m, 2H), 4.27 (s, 4H), 3.88 (d, J1 = 3.8Hz, 12H), 2.82 (s, 4H), 2.72-2.62 (m, 4H), 1.68-1.65 (m, 4H), 1.47 (s, 18H).
[0453] • 19F NMR (300 MHz, CDCl ₃ ) δ: -63.62.
[0454] • 13C NMR (101 MHz, CDCl3) δ: 165.3, 163.1, 158.9, 158.7, 157.5, 156.6, 152.1, 136.5, 125.1, 124.4, 122.5, 120.7, 119.7, 119.5, 97.5, 97.2, 95.7, 79.8, 66.9, 52.8 , 52.8, 52.5, 38.9, 34.2, 32.2, 31.9, 29.9, 29.5, 29.1, 28.6, 24.6, 25.0, 23.1, 22.9, 14.2.
[0455] • MS (MALDI-, DCTB) m / z: calc. for C ⁸⁰ H ⁶⁴ F ¹² N ⁴ O ²⁰ ([M] -): 1628.3928; exp .: 1628.3965.
[0456] • UV-VIS (DCM) λmax / nm (s / M ' ¹ -cm'1): 536 (30100).
[0457] • Em ision (DCM) λmax / nm: 583.
[0458] • τ / ns (DCM, x2): 5.88 (1.08).
[0459] • Φ (DCM): 0.87 ± 0.01.
[0460]
[0461] Example 11. N, N'-Bis (ferc-butylp iperid in-1-carboxylate) -1- (3,5-bis (trifIuorom ethyl) phenoxy) -6,7,12-tris (dim ethyl-5-oxyisophtate) ) perilen-3,4: 9,10-tetracarboxy diimide (PDI 11).
[0462]
[0463] NaH (1.7 mg, 0.07 mmol) and dimethyl 5-hydroxyisophthalate (29.5 mg, 0.14 mmol) are dried in a microwave vial and under an inert atmosphere. 20 ml of anhydrous DMF are added and allowed to stir for 10 minutes. CuI (4.0 mg, 0.02 mmol), 4,4-dimethoxy-2,2-bipyridine (9.1 mg, 0.04 mmol), cesium carbonate (274.5 mg, 0.84 mmol) and N, N'-bis (tert) are added Butylpiperidin-1-carboxylate) -1,7-bis (3,5-bis (trifluoromethyl) phenoxy) -6,12-dichloroperylene-3,4: 9,10-tetracarboxy diimide (90.0 mg, 0.07 mmol), sealed with a septum and irradiate for one hour at 110 ° C in microwave. The solvent is removed under reduced pressure and the resulting product is purified by flash column chromatography (silica gel, DCM: CH ³ CN, 5: 1), obtaining the diimide perylene as a red solid with orange fluorescent emission in solid state (6.4 mg, 0.004 mmol, 27%).
[0464]
[0465] • PF (° C):> 350 ° C.
[0466] • Rf (DCM: MeOH, 50: 1): 0.33.
[0467] • FT-IR (KBr, cm ^-1 ): 2954, 2926, 2853, 1734, 1696, 1661, 1588, 1504, 1459, 1431, 1365, 1316, 1292, 1278, 1274, 1246, 1170, 1135, 1107, 1034, 1002, 943, 908, 807, 755, 724, 699.
[0468] • ¹ H NMR (400 MHz, CDCl ₃ ) δ: 8.65 (s, 2H), 8.35-8.32 (m, 3H), 8.17 (s, 3H), 7.70-7.68 (m, 3H), 7.65 (s, 1H ), 7.65 (s, 2H), 7.37 (s, 2H), 5.16-5.11 (m, 2H), 4.30 (s, 4H), 3.88 (s, 18H), 2.83 (s, 4H), 2.73-2.66 ( m, 4H), 1.68-1.66 (m, 4H), 1.55 (s, 18H).
[0469] • ¹⁹ F NMR (300 MHz, CDCl ₃ ) δ: -63.60.
[0470] • ¹³ C NMR (101 MHz, CDCl ₃ ) δ: 164.9, 163.0, 163.0, 162.0, 160.7, 160.5, 160.4, 160.2, 159.9, 159.4, 132.8, 132.4, 129.8, 126.7, 124.4, 121.7, 120.2, 120.1, 57.4 , 57.3, 52.7, 52.5, 28.6.
[0471] • MS (MALDI-, DCTB) m / z: calc. for C ⁸² H ⁷⁰ F ⁶ N ⁴ O ²⁴ ([M] -): 1608.4279;
[0472] exp .: 1608.3923.
[0473] • UV-VIS (DCM) λmax / nm (ε / M ^-1 cm ^-1 ): 538 (33600).
[0474] • Em ision (DCM) λmax / nm: 583.
[0475] • τ / ns (DCM, x2): 6.07 (0.98).
[0476] • Φ (DCM): 0.95 ± 0.01.
[0477]
[0478] Example 12. N, N'-B is (ferc-butylp iperid in-1-carboxylate) -1,6,7,12-tetrakis (dicarboxy-5-oxyisophtharate) perilen-3,4: 9,10-tetracarboxy diimide (POI 12).
[0479]
[0480] On an agitated solution of N, N'bis (tert-butylpiperidin-1-carboxylate) -1,6,7,12-tetrakis (dimethyl-5-oxyisophthalate) perylene-3,4: 9,10-tetracarboxy diimide (20.0 mg, 0.01 mmol) in THF (8 ml) another LiOH (38.0 mg, 0.96 mmol) in water ⁽² ml) is added. The reaction mixture is allowed to stir overnight at 45 ° C. After that time, the solvent is removed under reduced pressure, obtaining the diimide perylene as a brown solid (17.6 mg, 0.01 mmol, 99%).
[0481]
[0482] • PF (° C):> 350 ° C.
[0483] • Rf (MeOH): 0.00.
[0484] • FT-IR (KBr, cm ^-1 ): 3445, 2067, 1638, 1380, 1252, 993, 624.
[0485] • ¹ H-NMR (300 MHz, D ₂ O) δ : 8.42 (s, 2H), 7.87-7.82 (m, 5H), 7.51-7.47 (m, 14H), 7.27 (d, J = 7.2 Hz, 2H ), 7.16 (s, 1H), 3.93-3.87 (m, 7H), 2.99-2.90 (m,
[0486] 6H), 1.98-1.88 (m, 5H), 1.39 (s, 18H).
[0487] • MS (MALDI-, DCTB) m / z: calc. for C ⁷⁶ H ⁶⁰ N ⁴ O ²⁸ ([M] -): 1476.3389; exp .:
[0488] 1476.3358.
[0489] • UV-VIS (H ₂ O) λmax / nm (ε / M ^-1 cm ^-1 ): 464 (41100).
[0490] • Emission (H ₂ O) λmax / nm: 509.
[0491] • τ / ns (H ₂ O, X2): 5.97 (1.06).
[0492] • Φ (H ₂ O): 0.92 ± 0.01.
[0493]
[0494] Example 13. W, W-Bis (piperidin-4-yl) -1,6,7,12-tetracyloroperylene-3,4: 9,10-tetracarboxy diimide (PDI 13).
[0495]
[0496] On a stirred solution of N, N-bis (ferc-butylpiperidine-1-carboxylate) -1,6,7,12-tetrachloroperylene-3,4: 9,10-tetracarboxy diimide (0.10 g, 0.11 mmol) in DCM ( 15 ml) trifluoroacetic acid (2.5 ml) is added dropwise. The reaction mixture is allowed to stir for two hours. After that time, an aqueous solution of 1M NaOH is added to basic pH (8-9). The mixture is extracted with DCM, washed with water and the solvent is removed under reduced pressure, obtaining the diimide perylene as a red solid (70.0 mg, 0.09 mmol, 90%).
[0497]
[0498] • PF (° C):> 350 ° C.
[0499] • Rf (DCM: MeOH, 50: 4): 0.00.
[0500] • FT-IR (KBr, cm ^-1 ): 2921, 2851, 1700, 1651, 1586, 1366, 1316, 1261, 1236, 1001, 804, 745.
[0501] • ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 8.65 (s, 4H), 5.24-5.15 (m, 2H), 4.32 (s, 2H), 2.88-2.72 (m, 8H), 1.96-1.70 ( m, 8H).
[0502] • MS (ESI +): m / z: calc. for C ³⁴ H ²⁵ CLN ⁴ O ⁴ ([M + H] +): 693.0624; exp .: 693.0618. • UV-VIS (DCM) λmax / nm (ε / M ^-1 cm ^-1 ): 513 (37800).
[0503] • Emission (DCM) λmax / nm: 548.
[0504] • τ / ns (DCM, X2): 6.73 (1.30).
[0505] • Φ (DCM): 0.88 ± 0.01.
[0506] Example 14. N, N'-B is (piperid in-4-yl) -1,6,7,12-tetrakis (d im ethyl-5-oxyisophthalate) perilen-3,4: 9,10-tetracarboxy diimide ( POI 14).
[0507]
[0508] On a stirred solution of N, N-bis (tert-butylpiperidine-1-carboxylate) -1,6,7,12-tetrakis (dimethyl-5-oxyphysophthalate) perilen-3,4: 9,10-tetracarboxy diimide (170.0 mg, 0.10 mmol) in DCM (6.5 ml) trifluoroacetic acid (4.4 ml) is added dropwise. The reaction mixture is allowed to stir for two hours. After that time, an aqueous solution of 1M NaOH is added to basic pH (8-9). The mixture is extracted with DCM, washed with water and the solvent is removed under reduced pressure, obtaining the diimide perylene as a dark pink solid (144.0 mg, 0.11 mmol, 97%).
[0509]
[0510] • PF (° C):> 350 ° C.
[0511] • Rf (DCM: MeOH, 50: 4): 0.00.
[0512] • FT-IR (KBr, cm '1): 3437, 2951, 2923, 2849, 1732, 1695, 1661, 1587, 1508, 1459, 1431, 1411, 1385, 1320, 1300, 1286, 1252, 1181, 1007, 999, 903, 803, 752, 721.
[0513] • ¹ H-NMR (400 MHz, CDCl3) δ: 8.34 (t, J = 1.4 Hz, 4H), 8.17 (s, 4H), 7.70 (d, J = 2.1 Hz, 8H), 5.08-5.02 (m, 2H), 3.89 (s, 24H), 3.20 (d, J = 12.5 Hz, 4H), 2.74 2.55 (m, 9H), 1.64 (s, 3H).
[0514] • ¹³ C-NMR (101 MHz, CDCU) δ: 165.1, 163.1, 155.9, 154.9, 133.1, 132.7, 126.5,
[0515] • MS (MALDI +, DCTB): m / z calcd for C ⁷⁴ H ⁶¹ N ⁴ O ²⁴ ([M + H] +): 1389.3670; exp .:
[0516] 1389.3803.
[0517] • UV-VIS (DCM) λmax / nm (ε / M ^-1 cm ^-1 ): 548 (18600).
[0518] • Em ision (DCM) λmax / nm: 582.
[0519] • τ / ns (DCM, X2): 5.64 (1.11).
[0520] • Φ (DCM): 0.95 ± 0.01.
[0521]
[0522] Example 15. N, N'-Bis (piperidin-4-yl) -1,6,7,12-tetrakis (3,5-b is (trifluorom ethyl) phenoxy) perilen-3,4: 9,10-tetracarboxy diimide (PDI 15).
[0523]
[0524] On a stirred solution of N, N-bis (tert-butylpiperidin-1-carboxylate) -1,6,7,12-tetrakis (3,5-bis (trifluoromethyl) phenoxy) perilen-3,4: 9,10- Tetracarboxy diimide (0.10 g, 0.06 mmol) in DCM (900 pl) is added dropwise trifluoroacetic acid (600 pl). The reaction mixture is allowed to stir for 2 hours. After that time, an aqueous solution of 1M NaOH is added to basic pH (8-9). The mixture is extracted with DCM, it is washed with water and the solvent is removed under reduced pressure, obtaining the diimide perylene as a fuchsia solid (86.0, 0.06, 98%).
[0525]
[0526] • PF (° C):> 350 ° C.
[0527] • Rf (DCM: MeOH, 50: 2): 0.00.
[0528] • FT-IR (KBr, cm ^-1 ): 3435, 3069, 2933, 2867, 1703, 1664, 1598, 1501, 1459, 1414, 1372, 1341, 1302, 1281, 1177, 1135, 1044, 992, 954, 887, 849, 804, 703, 685.
[0529] • ¹ H NMR (300 MHz, CDCl ₃ ) δ: 8.19 (s, 2H), 8.19 (s, 1H), 7.75 (s, 1H), 7.61 (s, 2H), 7.56 (s, 2H), 7.29 ( s, ⁶ H), 7.16 (s, 1H), 7.01 (s, 1H), 5.10 5.04 (m, 2H), 3.23 (d, J = 12.4 Hz, 4H), 2.78-2.72 (m, 4H), 2.65 -2.56 (m, 4H), 2.03-2.01 (m, 2H), 1.69 (d, J = 10.6 Hz, 4H).
[0530] • 19F NMR (300 MHz, CDCI3) δ: -63.58.
[0531] • ¹³ C NMR (101 MHz, CDCl ₃ ) δ: 162.9, 162.7, 157.9, 157.3, 156.6, 155.6, 154.6, 134.3, 134.0, 133.8, 133.1, 126.8, 126.6, 124.8, 123.9, 123.0,
[0532] • MS (MALDI +, DCTB) m / z: calc. for C ⁶⁶ H ³⁷ F ²⁴ N ⁴ O ⁸ ([M + H] +): 1469.2223;
[0533] exp .: 1469.2139.
[0534] • UV-VIS (DCM) λmax / nm (ε / M ^-1 cm ^-1 ): 533 (22300).
[0535] • Emission (DCM) λmax / nm: 577.
[0536] • τ / ns (DCM, X2): 3.03 (0.99).
[0537] • Φ (DCM): 0.32 ± 0.01.
[0538]
[0539] Example 16. N, N'-Bis (piperidin-4-yl) -1- (3,5-bis (trifluoromethyl) phenoxy) -6,7,12-tris (dimethyl-5-oxyisophtharate) perilen-3,4 : 9,10-tetracarboxy diimide (PDI 16).
[0540]
[0541] On a stirred solution of W, W-bis (tert-butylpiperidin-1-carboxylate) -1- (3,5-bis (trifluoromethyl) phenoxy) -6,7,12-tris (dimethyl-5-oxyisophthalate) perilen- 3,4: 9,10-tetracarboxy diimide (50.0 mg, 0.03 mmol) in DCM (450 pl) trifluoroacetic acid (300 pl) is added dropwise. The reaction mixture is allowed to stir for two hours. After that time, an aqueous solution of 1M NaOH is added to basic pH (8-9). The mixture is extracted with DCM, washed with water and the solvent is removed under reduced pressure, obtaining the diimide perylene as red solid with orange fluorescent emission in solid state (40.8 mg, 0.03 mmol, 93%).
[0542] • PF (° C):> 350 ° C.
[0543] • Rf (DCM: MeOH, 50: 2): 0.00.
[0544] • FT-IR (KBr, cm ^-1 ): 3452, 2954, 2923, 2853, 1730, 1703, 1665, 1591, 1505, 1459, 1431, 1375, 1320, 1278, 1246, 1173, 1134, 1107, 1037, 999, 940, 905, 793, 755, 720.
[0545] • 1H-NMR (300 MHz, MeOD) δ: 8.52 (s, 2H), 8.11 (s, 2H), 8.07 (s, 2H), 8.02 (d, J = 6.2 Hz, 1H), 7.95 (s, 1H ), 7.66 (s, 1H), 7.61 (s, 1H), 7.54 (s, 5H), 7.47 (s, 1H), 5.29-5.20 (m, 2H), 3.83 (s, 18H), 3.51 (d, J = 12.2 Hz, 4H), 3.19-3.07 (m, 5H), 3.03-2.87 (m, 5H), 2.01 (s, 4H).
[0546] • ¹⁹ F-NMR (300 MHz, CDCl ₃ ) δ: -63.75.
[0547] • ¹³ C-NMR (101 MHz, CDCl ₃ ) δ: 169.5, 161.9, 160.6, 158.4, 124.4, 124.2, 116.8, 116.5, 116.1, 115.9, 114.4, 112.1, 112.0, 110.7, 109.6, 108.3, 107.5, 106.5, 104.9, 52.5, 49.3, 49.1.48.9, 48.7, 48.5, 46.2, 45.6, 44.0, 38.7, 30.3, 29.6, 22.5.
[0548] • MS (MALDI +, DIT) m / z: calc. for C ⁷² H ⁵⁵ F ⁶ N ⁴ O ²⁰ ([M + H] +): 1409.3308; exp .:
[0549] 1409.3330.
[0550] • UV-VIS (DCM) λmax / nm (ε / M ^-1 cm ^-1 ): 540 (17500).
[0551] • Emission (DCM) λmax / nm: 584.
[0552] • τ / ns (DCM, X2): 5.88 (1.08).
[0553] • Φ (DCM): 0.81 ± 0.01.
[0554]
[0555] Example 17. W- (Piperidin-4-yl) -N '- ((3- (triethoxysilyl) propyl) piperidin-1-carboxamide) -1,6,7,12-tetrakis (3,5-bis (trifIuoromethyl) phenoxy) perilen-3,4: 9,10-tetracarboxy diimide (PDI 17).
[0556]
[0557] W, W-bis (piperidin-4-yl) -1,6,7,12-tetrakis (3,5-bis (trifluoromethyl) phenoxy is dried in a round bottom flask equipped with a stirring core and under an inert atmosphere. ) Perilen-3,4: 9,10-tetracarboxy diimide (80.0 mg, 0.05 mmol), chloroform (100 ml) is added and placed in a sand bath at 120 ° C with stirring. 13 pl of 3- (triethoxysilyl) propylisocyanate dissolved in chloroform (50 ml) are added by an automatic injection system (70 ml with a flow of 0.2 ml / min). The reaction is allowed to stir for 24 hours at reflux (61 C). The solvent is removed under reduced pressure and the resulting product is purified by flash column chromatography (silica gel, DCM: CH ³ CN: MeOH, 50: 3: 1.5), obtaining the diimide perylene as a brown solid with orange fluorescent emission in solid state (15.0 mg, 0.01 mmol, 16%).
[0558]
[0559] • PF (° C):> 350 ° C.
[0560] • Rf (DCM: MeOH, 50: 2): 0.14.
[0561] • FT-IR (KBr, cm ^-1 ): 3426, 3072, 2976, 2928, 1701, 1668, 1596, 1512, 1458, 1413, 1386, 1374, 1335, 1299, 1278, 1179, 1137, 1107, 1086, 990, 951,888, 852, 804, 728, 701,680.
[0562] • ¹ H NMR (400 MHz, CDCl ₃ ) δ: 8.19 (d, J = 6.5 Hz, 4H), 7.60 (d, J = 5.1 Hz, 4H), 7.28 (d, J = 2.4 Hz, 8H), 5.14 -5.09 (m, 2H), 4.78-4.75 (m, 1H), 4.09 (d, J = 12.5 Hz, 2H), 3.83-3.78 (m, ⁶ H), 3.62 (d, J = 9.1 Hz, 2H) , 3.25-3.20 (m, 2H), 3.11-3.00 (m, 4H), 2.92-2.85 (m, 2H), 2.70-2.60 (m, 2H), 1.83 (d, J = 10.7 Hz, 2H), 1.69 (s, 1H), 1.67-1.58 (m, 4H), 1.22-1.18 (m, 9H), 0.65-0.61 (m, 2H).
[0563] • ¹⁹ F NMR (300 MHz, CDCl ₃ ) δ: -63.58.
[0564] • ¹³ C NMR (101 MHz, CDCl ₃ ) δ: 162.6, 162.4, 157.4, 156.5, 156.4, 154.7, 154.5, 134.6, 134.3, 133.9, 133.6, 133.1, 126.5, 124.7, 124.2, 123.8, 121.6, 121.5, 121.3 , 121.3, 121.1, 120.9, 119.6, 118.6, 118.3, 58.6, 53.6, 52.5, 49.6, 44.8, 44.3, 43.4, 32.1, 30.4, 29.8, 29.7, 29.5, 29.3, 29.1, 28.2, 25.8, 23.5, 22.8, 18.4 , 14.3, 7.8.
[0565] • MS (MALDI +, DCTB) m / z: calc. for C ⁷⁶ H ⁵ sF ²⁴ N ⁵ O ¹² Si ([M + H] +):
[0566] 1716.3463; exp .: 1716.3628.
[0567]
[0568] Example 18. N, N'-Bis ((3- (triethoxysilyl) propyl) piperidin-1-carboxamide) -1,6,7,12-tetrakis (3,5-bis (trifluoroomethyl) phenoxy) perilen-3,4 : 9,10-tetracarboxy diimide (PDI 18).
[0569] W, W-bis (piperidin-4-yl) -1,6,7,12-tetrakis (3,5-bis (trifluoromethyl) phenoxy is dried in a round bottom flask equipped with a stirring core and under an inert atmosphere. ) Perilen-3,4: 9,10-tetracarboxy diimide (80.0 mg, 0.05 mmol), chloroform (100 ml) is added and placed in a sand bath at 120 ° C with stirring. 13 pl of 3- (triethoxysilyl) propylisocyanate dissolved in chloroform (50 ml) are added by an automatic injection system (70 ml with a flow of 0.2 ml / min). The reaction is allowed to stir for 24 hours at reflux (61 C). The solvent is removed under reduced pressure and the resulting product is purified by flash column chromatography (silica gel, DCM: CH3CN: MeOH, 50: 3: 1.5), the diimide perylene being obtained as a brown solid with a solid-state orange fluorescent emission (30.0 mg, 0.015 mmol, 28%).
[0570]
[0571] • PF (° C):> 350 ° C.
[0572] • Rf (DCM: MeOH, 50: 2): 0.26.
[0573] • FT-IR (KBr, cm ^-1 ): 2979, 2926, 2854, 1702, 1666, 1594, 1511, 1455, 1413, 1370, 1307, 1300, 1281, 1182, 1133, 1106, 1073, 991, 952, ^{8 8 6} , 846, 804, 754, 731, 701,682.
[0574] • ¹ H NMR (400 MHz, CDCl ₃ ) δ: 8.18 (s, 4H), 7.61 (s, 3H), 7.56 (s, 2H), 7.29 (s, 7H), 5.14-5.18 (m, 2H), 4.75-4.73 (m, 2H), 4.10 (d, J = 13.0 Hz, 4H), 3.84-3.78 (m, 12H), 3.26-3.21 (m, 4H), 2.91-2.85 (m, 4H), 2.71 2.61 (m, 4H), 1.69-1.59 (m, 8H), 1.23-1.19 (m, 18H), 0.66-0.62 (m, 4H).
[0575] • ¹⁹ F NMR (300 MHz, CDCl ₃ ) 5: -63.59.
[0576] • ¹³ C NMR (101 MHz, CDCl ₃ ) δ: 162.6, 157.4, 156.5, 154.6, 134.6, 134.3, 134.0, 133.6, 133.1, 126.5, 124.7, 123.8, 121.5, 121.3, 121.1, 119.6,
[0577] • MS (MALDI +, DCTB) m / z: calc. for Cs ⁴ H ⁷³ F ²⁴ N ⁶ O ¹⁵ Si ² ([M-OEt] +):
[0578] 1917.4284; exp .: 1917.4368.
[0579]
[0580] Example 19. N, N'-Bis ((mupirocin) piperidin-1-carboxamide) -1- (3,5-bis (trifIuoromethyl) phenoxy) -6,7,12-tris (dimethyl-5-oxyisophtharate) perilene- 3,4: 9,10-tetracarboxy diimide (PDI 19).
[0581]
[0582] On a stirred solution of 92% mupirocin (13.6 mg, 0.03 mmol) in DCM (700 pl), N, N'-diisopropylethylamine (10 pl, 0.05 mmol), W, W-bis (piperidin-4-yl) are added -1,6,7,12-tetrakis (3,5-bis (trifluoromethyl) phenoxy) perilen-3,4: 9,10-tetracarboxy diimide (20.0 mg, 0.01 mmol) dissolved in DCM (1 ml) and PyBOP ( 14.2 mg, 0.03 mmol). The reaction mixture is allowed to stir for two hours at 25 ° C. The solvent is removed under reduced pressure and the resulting product is purified by flash column chromatography (silica gel, DCM: CH3CN: MeOH, 50: 3: 3), obtaining the diimide perylene as a fuchsia solid (18.6 mg, 0.01 mmol, 56 %).
[0583]
[0584] • PF (° C):> 350 ° C.
[0585] • Rf (DCM: MeOH, 50: 4): 0.27.
[0586] • FT-IR (KBr, cm '1): 3690, 3675, 3647, 3627, 3567, 2954, 2919, 2850, 1730, 1699, 1668, 1650, 1637, 1591, 1557, 1508, 1455, 1400, 1372, 1337, 1278, 1180, 1132, 1089, 1051, 957, 890797, 755, 727, 702.
[0587] • ¹ H-NMR (400 MHz, CDCl ₃ ) 5 : 8.19 (s, 4H), 7.61 (s, 4H), 7.29 (s, 8H), 5.72 (d, J = 13.4 Hz, 2H), 5.17 (s , 2H), 4.80 (d, J = 10.4 Hz, 2H), 4.07-4.03 (m, ⁶ H), 3.84 (d, J = 2.6 Hz, 1H), 3.82 (s, 1H), 3.80 (s, 1H ), 3.78 (s, 1H), 3.74 (d, J = 3.4 Hz, 2H), 3.65 (s, 1H), 3.54 (dd, J = 11.7 and 2.9 Hz, 2H), 3.44 (t, J = ^{8. 6} Hz, 2H), 3.35 3.26 (m, 1H), 3.14 (t, J = 12.6 Hz, 3H), 2.79 (td, J = 5.6 and 2.4 Hz, 2H), 2.69 (dd, J = 7.9 and 2.3 Hz , 2H), 2.62-2.53 (m, ⁶ H), 2.35-2.26 (m, ⁶ H), 2.19 (s, 9H), 2.02 (s, 6 H), 1.71 (t, J = 6.5 Hz, 9H) , 1.47 (d, J = 6.9 Hz, 2H), 1.41 (d, J = 6.7 Hz, 2H), 1.31 (s, 18H), 1.20 (d, J = 6.2 Hz, 9H), 0.95 (dd, J = 14.1 and 7.1 Hz, ⁶ H). • ¹⁹ F-NMR (300 MHz, CDCl3) δ : -63.74.
[0588] • MS (MALDI +, DCTB) m / z: calc. for Cm H ¹²⁰ F ²⁴ N ⁴ O ²⁴ Na ([M + Na] +): 2455.7801;
[0589] exp .: 2455.7965.
[0590] • UV-VIS (DCM) λmax / nm (ε / M ^-1 cm ^-1 ): 535 (25700).
[0591] • Em ision (DCM) λmax / nm: 580.
[0592] • τ / ns (DCM, x2): 5.35 (1.07).
[0593] • Φ (DCM): 0.62 ± 0.01.
[0594]
[0595] Example 20. N, N'-B is ((6-biotinam idohexanyl) piperidin-1-carboxam ida) -1,6,7,12-tetrakis (dim ethyl-5-oxyisophtharate) perilen-3,4: 9, 10-tetracarboxy diimide (PDI 20).
[0596]
[0597] On a stirred solution of W-succinimidyl 6-biotinamidohexanoate (12.7 mg, 0.03 mmol) in DCM (700 pl), N, N'-diisopropylethylamine (10 pl, 0.06 mmol), W, W-bis (piperidine-) are added 4-yl) -1,6,7,12-tetrakis (dimethyl-5-oxyisophthalate) perilen-3,4: 9,10-tetracarboxy diimide (20.0 mg, 0.01 mmol) dissolved in DCM (1.1 ml) and PyBOP ( 14.6 mg, 0.03 mmol). The reaction mixture is allowed to stir for two hours at 25 ° C. The solvent is removed under reduced pressure and the resulting product is purified by flash column chromatography (silica gel, DCM: MeOH, 4: 1), obtaining the diimide perylene as a pink solid (18.1 mg, 0.009 mmol, 63%).
[0598]
[0599] • PF (ºC):> 350ºC.
[0600] • Rf (DCM: MeOH, 50: 4): 0.41.
[0601] • FT-IR (KBr, cm ^-1 ): 2957, 2925, 2854, 1732, 1701, 1647, 1590, 1462, 1428, 1326, 1300, 1286, 1258, 1107, 996, 758.
[0602] • ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 8.31 (t, J = 1.5 Hz, 4H), 8.13 (s, 4H), 7.67 (d, J = 1.5 Hz, 8H), ^{6 .66} (s , 1H), 6.07 (d, J = 6.0 Hz, 1H), 5.18-5.10 (m, 2H), 4.72 (d, J = 9.6 Hz, 3H), 4.47-4.43 (m, 2H), 4.32-4.22 ( m, 2H), 3.86 (m, 25H), 3.70-3.61 (m, 2H), 3.17-3.04 (m, ⁶ H, CH ² ), 2.85 (dd, J = 12.9 and 4.9 Hz, 2H), 2.68 ( d, J = 12.9 Hz, 2H), 2.63-2.55 (m, 7H), 2.37-2.30 (m, 4H), 2.13 (t, J = 7.3 Hz, 4H), 1.79-1.51 (m, 15H), 1.48 -1.34 (m, 9H).
[0603] • ¹³ C-NMR (101 MHz, CDCl ³ : MeOD) δ: 174.1, 171.9, 165.1, 163.1, 162.9, 155.8, 154.7, 132.9, 132.5, 126.3, 124.3, 123.8, 123.7, 123.6, 120.9, 120.8, 61.9, 60.1, 55.3, 54.2, 52.5, 43.8, 43.7, 40.3, 38.9, 36.3, 35.6, 30.7, 29.6, 28.5, 28.1,27.8, 26.4, 25.4, 25.1.
[0604] • HRMS (MALDI +, DCTB): m / z calc. for C ¹⁰⁶ H ¹¹¹ N ¹⁰ O ³⁰ S ² [(M + H) +]:
[0605] 2067.6904; exp .: 2067.6920.
[0606] • UV-VIS (DCM) λmax / nm (ε / M ^-1 cm ^-1 ): 550 (33700).
[0607] • Emission (DCM) λmax / nm: 585.
[0608] • τ / ns (DCM, x2): 5.71 (1.24).
[0609] • Φ (DCM): 0.94 ± 0.01.
[0610]
[0611] Example 21. N, N'-Bis ((6-biotinamidohexanyl) piperidin-1-carboxamide) -1,6,7,12-tetrakis (dicarboxy-5-oxyisophtharate) perilen-3,4: 9,10-tetracarboxy diimide (POI 21). On an agitated solution of N, N'-bis ((6-biotinamidohexanil) piperidin-1-carboxamide) -1,6,7,12-tetrakis (dimethyl-5-oxyisophthalate) perilen-3,4: 9,10- Tetracarboxy diimide (24.0 mg, 0.01 mmol) in THF (8 ml) is added another LiOH (21.0 mg, 0.92 mmol) in water (2 ml). The reaction mixture is allowed to stir overnight at 45 ° C. After that time, the solvent is removed under reduced pressure, obtaining the diimide perylene as a brown oily solid (23.5 mg, 0.01 mmol, 99%).
[0612]
[0613] • PF (° C):> 350 ° C.
[0614] • Rf (MeOH): 0.00.
[0615] • FT-IR (KBr, cm ^-1 ): 3431, 2940, 2857, 2781, 1976, 1635, 1567, 1454, 1408, 1385, 1320, 1260, 1206, 1152, 1124, 1104, 1022, 968, 871, 596
[0616] • ¹ H-NMR (300 MHz, D ² O) δ: 7.88 (s, 2H), 7.77 (d, J = 8.7 Hz, 2H), 7.64 (d, J = 6.8 Hz, 2H), 7.53 (s, 4H), 7.43-7.32 (m, ⁶ H), 4.56-4.53 (m, 2H), 4.36-4.32 (m, 2H), 3.62-3.50 (m, 2H), 3.32-3.22 (m, 4H), 3.13 (t, J = ^{6 .8} Hz, 3H), 2.93 (dd, J = 18.1 and 5.3 Hz, 4H), 2.73 (d, J = 13.1 Hz, 2H), 2.57 2.61 (m, 3H), 2.42-2.28 (m, 4H), 2.14 (m, 5H), 2.01 (s, 5H), 1.57-1.45 (m, 15H), 1.35-1.29 (m, 10H).
[0617] • ¹³ C-NMR (101 MHz, D ² O) 5: 176.8, 165.5, 143.4, 127.4, 125.3, 125.3, 117.9, 111.5, 62.2, 60.4, 55.5, 39.9, 39.4, 37.7, 35.7, 28.3, 28.0, 27.8 , 27.3, 26.3, 25.7, 25.4.
[0618] • MS (MALDI-, DCTB): m / z calc. for C98H94N10O30S2 [(M) "]: 1954.5573; exp .:
[0619] 1954.5641.
[0620] • UV-VIS (H ₂ O) λmax / nm (ε / M ^-1 cm ^-1 ): 468 (46100).
[0621] • Emission (H ₂ O) λmax / nm: 512.
[0622] • τ / ns (H ₂ O, X2): 6.73 (1.24).
[0623] • O (H ₂ O): 0.81 ± 0.01.
[0624]
[0625] Example 22. N, N'-Bis ((hex-5-in) piperidin-1-carboxylate) -1,6,7,12-tetrakis (dimethyl-5-oxyisophthalate) perilen-3,4: 9,10- tetracarboxy diimide (PDI 22).
[0626]
[0627] On a stirred solution of N, N'-diisopropylethylamine (16.7 mg, 0.13 mmol) and N, N-bis (piperidin-4-yl) -1,6,7,12-tetrakis (dimethyl-5-oxyisophthalate) perilen- 3,4: 9,10-tetracarboxy diimide (45 mg, 0.032 mmol) in DCM (10 ml) under inert atmosphere, hex-5-stainlessyl chloride (9.0 mg, 0.07 mmol) is added dropwise. The reaction mixture is allowed to stir for 1.5 hours at 25 ° C. The solvent is removed under reduced pressure and the resulting product is purified by flash column chromatography (silica gel, DCM: MeOH, 25: 1), obtaining the diimide perylene as a pink solid (20.0 mg, 0.01 mmol, 40%).
[0628]
[0629] • PF (° C):> 350 ° C.
[0630] • Rf (DCM: MeOH, 50: 2): 0.50.
[0631] • ¹ H-NMR (400 MHz, CDCh) δ: 8.33 (t, J = 1.4 Hz, 4H), 8.15 (s, 4H), 7.69 (d, J = 1.4 Hz, 8 H), 5.18-5.12 (m , 2H), 4.78 (d, J = 8.4 Hz, 2H), 4.02 (d, J = 12.3 Hz, 2H), 3.88 (s, 24H), 3.10 (t, J = 12.8 Hz, 2H), 2.72-2.55 (m, 6 H), 2.45 (t, J = 7.4 Hz, 4H), 2.27 (td, J = 6.7 and 2.6 Hz, 4H), 1.94 (t, J = 2.6 Hz, 2H), 1.85-1.82 (m, 4H) , 1.75-1.67 (m, 4H).
[0632] • ¹³ C-NMR (101 MHz, CDCl ₃ ) δ: 170.6, 165.0, 163.1, 155.8, 154.8, 133.0, 132.6, 126.4, 124.4, 123.9, 121.2, 121.1, 120.9, 83.9, 69.1, 52.7, 51.9, 45.6, 41.9, 31.7, 29.7, 28.8, 28.1,23.9, 18.1.
[0633] • HRMS (MALDI +, DCTB): m / z calc. for C ⁸⁶ H ⁷³ N ⁴ O ²⁶ [(M + H) +]: 1577.4508;
[0634] exp .: 1577.4524.
[0635] • UV-VIS (DCM) λmax / nm (e / M ^ -cm’1): 550 (29700).
[0636] • Emission (DCM) λmax / nm: 589.
[0637] • τ / ns (DCM, x2): 6.03 (1.23).
[0638] • Φ (DCM): 0.95 ± 0.01.
[0639]
[0640] Example 23. W - ((Hex-5-in) piperidin-1-carboxylate) -W- (piperidin-4-yl) -1,6,7,12-tetrakis (dimethyl-5-oxyisophtharate) perilen-3, 4: 9,10-tetracarboxy diimide (PDI 23).
[0641]
[0642] On a stirred solution of N, N-diisopropylethylamine (18.6 mg, 0.14 mmol) and N, N-bis (piperidin-4-yl) -1,6,7,12-tetrakis (dimethyl-5-oxNsophthalate) perilen-3 , 4: 9,10-tetracarboxy diimide (100.0 mg, 0.07 mmol) in DCM (50 ml) under inert atmosphere, hex-5-stainlessyl chloride (9.4 mg, 0.07 mmol) is added dropwise. The reaction mixture is allowed to stir for 5 hours at 25 ° C. The solvent is removed under reduced pressure and the resulting product is purified by flash column chromatography (silica gel, DCM: MeOH, 50: 1), obtaining the diimide perylene as a pink solid (22.3 mg, 0.015 mmol, 21%).
[0643]
[0644] • PF (° C):> 350 ° C.
[0645] • Rf (DCM: MeOH, 50: 2): 0.70.
[0646] • ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 8.35 (q, J = 1.2 Hz, 4H), 8.16 (d, J = 12.2 Hz, 4H), 7.68 (dd, J = 3.8 and 1.4 Hz, 8H ), 5.19-5.12 (m, 2H), 4.79 (d, J = 8.5 Hz, 1H), 4.02 (d, J = 12.9 Hz, 1H), 3.88 (s, 24H), 3.17-3.04 (m, ⁶ H ), 2.76-2.53 (m, 4H), 2.47 (t, J = 7.4 Hz, 2H), 2.27 (td, J = 6.7 and 2.6 Hz, 2H), 1.94 (t, J = 2.6 Hz, 1H), 1.87 -1.83 (m, 4H), 1.74 (d, J = 14.8 Hz, 2H). • ¹³ C-NMR (101 MHz, CDCl ₃ : MeOD) δ: 171.2, 165.9, 165.0, 163.0, 155.7, 154.8, 154.7, 154.6, 136.7, 132.8, 132.4, 132.2, 126.3, 124.5, 124.3, 124.1, 123.6, 121.2, 121.1, 121.0, 120.7, 97.5, 53.8, 52.6, 52.4, 52.3, 29.5, 24.0, 23.8, 17.8.
[0647] • HRMS (MALDI, DCTB +): m / z calc. for C ⁸⁰ H ⁶⁷ N ⁴ O ²⁵ [(M + H) + j: 1483.4089;
[0648] exp .: 1483.4134.
[0649] • UV-VIS (DCM) λmax / nm (e / M ^ -cm'1): 575 (22700).
[0650] • Emission (DCM) λmax / nm: 590.
[0651] • τ / ns (DCM, x2): 5.62 (1.28).
[0652] • Φ (DCM): 0.84 ± 0.01.
[0653]
[0654] Example 24. W - ((Hex-5-in) piperidin-1-carboxylate) -W - ((9-biotinamido-4,7-dioxanoniol) piperidin-1-carboxamide) -1,6,7,12-tetrakis (dimethyl-5-oxyisophthalate) perilen-3,4: 9,10-tetracarboxy diimide (PDI 24).
[0655]
[0656] On a stirred solution of W-succinimidyl 6-biotinamide-4,7-dioxanonanoate (6.5 mg, 0.013 mmol) in DCM (700 pl), W, W-diisopropylethylamine (4.5 pl, 0.026 mmol), W- ( (hex-5-in) piperidin-1-carboxylate) -W- (piperidin-4-yl) -1,6,7,12-tetrakis (dimethyl-5-oxyisophthalate) perilen-3,4: 9,10- tetracarboxy diimide (20.0 mg, 0.013 mmol) dissolved in DCM (4 ml) and PyBOP (6.8 mg, 0.013 mmol). The reaction mixture is allowed to stir for three hours at 25 ° C. The solvent is removed under reduced pressure and the resulting product is purified by flash column chromatography (silica gel, DCM: MeOH, 100: 1), obtaining the diimide perylene as a pink solid (13.0 mg, 0.012 mmol, 54%).
[0657]
[0658] • PF (° C):> 350 ° C.
[0659] • Rf (DCM: MeOH, 50: 2): 0.80.
[0660] • ¹ H-NMR (400 MHz, CDCh) δ: 8.34-8.33 (m, 4H), 8.15 (d, J = 3.1 Hz, 4H), 7.69 (t, J = 12.2 Hz, 8H), 6.82 (s, 1H), 5.99 (s, 1H), 5.21-5.10 (m, 2H), 4.79 4.75 (m, 2H), 4.48-4.45 (m, 1H), 4.30-4.27 (m, 1H), 4.03-3.97 (m , 1H), 3.88 (s, 24H), 3.67 (dt, J = 6.7 and 3.4 Hz, 2H), 3.60 (s, 2H), 3.53 (t, J = 4.3 Hz, 2H), 3.40 (s, 2H) , 3.10 (tq, J = 7.4 and 4.3 Hz, 4H), 2.84 (d, J = 11.1 Hz, 1H), 2.72-2.54 (m, 9H), 2.46 (t, J = 7.4 Hz, 2H), 2.26 ( td, J = 6.8 and 2.7 Hz, 2H), 2.21 (d, J = 7.8 Hz, 1H), 1.94 (t, J = 2.6 Hz, 1H), 1.85 (q, J = 7.2 Hz, 2H), 1.75- 1.68 (m, 4H), 1.50 (d, J = 4.5 Hz, 6H), 1.42 (d, J = 6.7 Hz, 4H).
[0661] • ¹³ C-NMR (101 MHz, CDCisiMeOD) δ: 173.7, 170.6, 169.5, 165.1, 163.7, 163.1, 155.9, 154.9, 133.1, 132.7, 126.6, 124.5, 123.9, 121.2, 121.2, 121.1, 121.1, 120.9, 120.9 , 83.9, 70.3, 69.1, 67.3, 61.9, 60.4, 53.9, 53.6, 52.7, 52.0, 51.8, 45.6, 42.2, 41.9, 39.2, 35.8, 33.5, 31.7, 29.8, 25.6, 23.9, 17.8, 18.2, 18.6.
[0662] • HRMS (MALDI, DCTB +): m / z calc. for CgyHgsNyOsüSNa [(M + Na) +]:
[0663] 1890.5580; exp .: 1890.5542.
[0664] • UV-VIS (DCM) λmax / nm (ε / M ^-1 cm ^-1 ): 550 (31100).
[0665] • Emission (DCM) λmax / nm: 589.
[0666] • τ / ns (DCM, x2): 6.78 (1.22).
[0667] • Φ (DCM): 0.87 ± 0.01.
[0668]
[0669] Optical properties of the compounds of the invention
[0670] Table 1 shows a summary of the optical properties of the PDI compounds specified herein. The following are indicated: the solvent in which they are measured; Aabs wavelength of maximum absorption; s molar absorptivity coefficient, ^ em: wavelength of maximum emission; ⁰ : quantum yield (measured using the integrating sphere method); ^t . half-life of fluorescence (measured by exciting at 404 nm with a PS laser); X: chi-square value (measure of the quality of the adjustment of the experimental half-life to a sum of two exponentials).
[0671]

权利要求:
Claims (44)
[1]
1. A compound of formula I,

[2]
2. A compound according to claim 1, wherein at least one X is chlorine or where at least one X is R ¹⁵

[3]
3. A compound according to any one of claims 1 or 2, wherein at least one group R4 is C-R5.
[4]
4. A compound according to any one of claims 1 to 3, wherein each R5 independently represents hydrogen, halogen, C ¹ -C ²⁰ alkyl, -CN, -COR ⁷ , -CO ² R ⁷ , -CONR ⁷ R ⁷ , -OR ⁷ , -OCOR ⁷ , -SR ⁷ , -NR ⁷ R ⁷ , -NR ⁷ COR ⁷ , -SO R7, -SO2R7, -SO2NR7R7, -CF3 or Cy1, where the C1-C20 alkyl group is not substituted, or is, independently, substituted by one or more R8, Cy1 is not substituted, or is, independently, substituted by one or more R9, and where R1, R2, R3, R6, R7, R8, R9 and Cy1 have the same meaning than in claim 1.
[5]
5. A compound according to any one of claims 1 to 3, wherein at least one R5 is hydrogen, or at least one R5 is -CO2CH3, or at least one R5 is -CF3.
[6]
6. Compound according to any one of claims 1 to 5, wherein each R3 independently represents hydrogen, C ¹ -C ²⁰ alkyl, -CN, -COR ⁷ , -CO ² R ⁷ , -CONR ⁷ R ⁷ , -OR ⁷ , -SR ^7, -NR ⁷ R ^7, -SOR ^7, -SO ² R ⁷ or Cy ^1, where C1-C20 alkyl is unsubstituted or is independently substituted by one or more R8, Cy1 is unsubstituted, or is independently substituted by one or more R9, and wherein R1, R2, R5, R6, R7, R8, R9 and Cy1 have the same meaning as in claim 1.
[7]
7. A compound according to any one of claims 1 to 4, wherein at least one R ³ is hydrogen.
[8]
8. A compound according to any one of claims 1 to 7, wherein each R1 independently represents hydrogen, halogen, C ¹ -C ²⁰ alkyl, -CN, -COR ⁷ , -CO ² R ⁷ , -CONR ⁷ R ⁷ , - OR ⁷ , -OCOR ⁷ , -SR ⁷ , -NR ⁷ R ⁷ , -NR ⁷ COR ⁷ , -SO R7, -SO2R7, -SO2NR7R7, -CF3 or Cy1, where the C1-C20 alkyl group is not substituted, or is, independently, substituted by one or more R8, Cy1 is not substituted, or is, independently, substituted by one or more R9, and where R1, R3, R5, R6, R7, R8, R9 and Cy1 have the same meaning as in claim 1.
[9]
9. - Compound according to any one of claims 1 to 7, wherein at least one R1 is hydrogen.
[10]
10. - Compound according to any one of claims 1 to 9, wherein each R6 independently represents oxygen or sulfur, and wherein R1, R2, R3 and R5 have the same meaning as in claim 1.
[11]
11. - Compound according to any one of claims 1 to 9, wherein at least one R6 is an oxygen.
[12]
12. - Compound according to any one of claims 1 to 11, wherein each R ² independently represents R10, -COR10, -CO2R10, -SO2R10, Cy2, -COCy2, -CO2Cy2 or Y, where R10 is unsubstituted, or is, independently, substituted by one or more R8, Cy2 is not substituted, or is, independently, substituted by one or more R10, Y is:

[13]
13. A compound according to any one of claims 1 to 14, wherein at least one R2 is hydrogen, or where at least one R2 is -CO2C (CH3) 3 or where at least one R2 is Y , where Y is:

[14]
14. - Compound according to any one of claims 1 to 13, wherein each R7 independently represents hydrogen, C1-C20 or Cy4 alkyl, or where two R7 groups are linked to form a 5- to 7-membered heterocycle, saturated with the nitrogen atom :
- not replaced,
- or replaced by one or more R14,
- or unsubstituted, which contains an additional heteroatom selected from oxygen, sulfur or unsubstituted nitrogen,
- or unsubstituted, which additionally contains a heteroatom selected from oxygen, sulfur or nitrogen substituted by one or more R ¹⁴ ,
- or substituted by one or more R14; which additionally contains a heteroatom selected from oxygen, sulfur or unsubstituted nitrogen,
- or substituted by one or more R14; which additionally contains a heteroatom selected from oxygen, sulfur or nitrogen substituted by one or more R ¹⁴ .
[15]
15. - Compound according to any one of claims 1 to 14, wherein each R9 independently represents R11.
[16]
16. - Compound according to any one of claims 1 to 15, wherein each R10 independently represents hydrogen, C1-C40 alkyl, Cy4, -OR ¹¹ , -SR ¹¹ -NR ¹¹ R ¹¹ - (CH2CH ₂ O) 2) - ( CH2) 2-NH- (CO) - (CH2) 4-T or - (CH2) 5-NH- (CO) - (CH2) 4-T, where the C1-C40 alkyl group is not substituted or is independently , substituted by one or more R12 or SiR19, Cy4 is not substituted or is independently substituted by one or more R ⁹ , and T is:

[17]
17. - Compound according to any one of claims 1 to 16, wherein each R11 independently represents:
- C1-C6 alkyl unsubstituted, or substituted by one or more -OH or -OC1-C4 alkyl, where C1-C4 alkyl is not substituted or is substituted by one or more -OH,
- or Cy3 not substituted, or substituted by one or more C1-C6 alkyl groups,
- or where two R11 groups are attached forming a 5- to 7-membered heterocycle with the nitrogen atom:
- not replaced,
- or substituted by one or more C1-C6 alkyl groups,
- or unsubstituted, which additionally contains a heteroatom selected from unsubstituted nitrogen, oxygen and sulfur,
- or unsubstituted, which additionally contains a heteroatom selected from oxygen, sulfur or nitrogen substituted by one or more C1-C6 alkyl groups,
- or substituted by one or more C1-C6 alkyl groups, which additionally contains a heteroatom selected from unsubstituted nitrogen, oxygen and sulfur,
- or substituted by one or more C1-C6 alkyl groups, which additionally contains a heteroatom selected from oxygen, sulfur or nitrogen substituted by one or more C1-C6 alkyl groups.
[18]
18. - Compound according to any one of claims 1 to 17, wherein each R12 independently represents -OR11 or Cy3, where Cy3 is not substituted or is independently substituted by one or more C1-C6 alkyl groups.
[19]
19. - Compound according to any one of claims 1 to 18, wherein each R13 independently represents -OR11 or Cy3, wherein Cy3 is not substituted, or is, independently, substituted by one or more C1-C6 alkyl groups.
[20]
20- Compound according to any one of claims 1 to 19, wherein each R14 independently represents R ¹¹ .
[21]
21. Compound according to any one of claims 1 to 20, wherein each R19 independently represents C1-C20 alkyl, -OC1-C20 alkyl, Cy4 or -OCy4, where Cy ⁴ is not substituted, or is independently substituted by one or more R ¹⁴ .
[22]
22. - Compound according to any one of claims 1 to 20, wherein each Cy1 independently represents phenyl.
[23]
23. - Compound according to any one of claims 1 to 22, wherein each Cy2 independently represents a monocyclic saturated ring of 3 to 7 carbocyclic or heterocyclic members, where Cy2 is attached to the rest of the molecule through any carbon or nitrogen atom available, and where Cy2 contains 1 to 3 heteroatoms selected from nitrogen, oxygen and sulfur.
[24]
24. A compound according to any one of claims 1 to 23, wherein each Cy3 independently represents phenyl, or where each Cy3 independently represents a 5- or 6-membered aromatic heterocycle containing 1 or 2 heteroatoms selected from nitrogen, oxygen and sulfur, and where Cy3 is attached to the rest of the molecule through any available carbon or nitrogen atom.
[25]
25. - Compound according to any one of claims 1 to 24, wherein each Cy4 independently represents a ring:
- saturated carbocyclic, 3 to 7 members and where Cy4 is attached to the rest of the molecule through any available carbon atom, or
- saturated 3 to 7 membered heterocyclic containing 1 to 3 heteroatoms selected from nitrogen, oxygen and sulfur, and where Cy ⁴ is attached to the rest of the molecule through any available carbon or nitrogen atom.
[26]
26.
[27]
27.- Method according to claim 26, wherein at least one R4 is C-R5.
[28]
28. The method according to any one of claims 26 to 27, wherein R5 independently represents hydrogen, halogen, C1-C20 alkyl, -CN, -COR7, -CO2R7, -CONR7R7, -OR7, -OCOR7, -SR7, -NR7R7 , -NR7COR7, -SO R7, -SO2R7, -SO2NR7R7, -CF3 or Cy1, where the C1-C20 alkyl group is not substituted, or is, independently, substituted by one or more R8, Cy ¹ is not substituted, or is , independently, substituted by one or more R9, and wherein R1, R2, R3, R6, R7, R8, R9 and Cy1 have the same meaning as in claim 1.
[29]
29. The method according to any one of claims 26 to 27, wherein at least one R5 is -CO2CH3.
[30]
30. - Method according to any one of claims 26 to 29, wherein at least one R ¹⁷ is -OH or -SH.
[31]
31. - Method according to any one of claims 26 to 30, wherein each R2 independently represents hydrogen, R10, -COR10, -CO2R10, -SO2R10, Cy2, -COCy2, -CO2Cy2, -SO2Cy2 or Y, where R10 is not substituted or is independently substituted by one or more R8, Cy ² is not substituted or is independently substituted by one or more R10, where Y is:

[32]
32. - Method according to any one of claims 26 to 30, wherein at least one R2 is -CO2C (CH3) 3.
[33]
33. - Method according to any one of claims 26 to 32, wherein at least one R ¹ is hydrogen.
[34]
34. The method according to any one of claims 26 to 33, wherein at least one R ³ is hydrogen.
[35]
35. - Method according to any one of claims 26 to 34, wherein each R10 independently represents hydrogen, C1-C40 alkyl, Cy4, -OR11, -SR11 or -NR11R11, wherein the C1-C40 alkyl group is unsubstituted or is, independently, substituted by one or more R12, and Cy4 is not substituted or is, independently, substituted by one or more R9.
[36]
36. - A compound according to claim 1, selected from:

[37]
37.- Use of a compound of structural formula I, or of a mixture of regioisomers of formula I, or of a mixture of any of the compounds of formula I in any proportion as fluorophores, in which the emission wavelength is modular, in bioimage or biomarked applications.
[38]
38. Use according to claim 37, wherein the compound of structural formula I, or a mixture of regioisomers of formula I, or a mixture of any of the compounds of formula I in any proportion, is used in cellular bioimaging.
[39]
39. Use according to any one of claims 37 to 38, wherein the compound of structural formula I is a compound in which at least one R10 independently represents - (CH2CH ₂ O) 2) - (CH2) 2-NH- ( CO) - (CH2) 4-T or - (CH2) 5-NH- (CO) - (CH2) 4-T where T is:

[40]
40. Use according to any one of claims 37 to 38, wherein the compound of formula I has at least one R2 which is Y, Y being:

[41]
41. - Use according to claim 38, wherein the compound of structural formula I, or a mixture of regioisomers of formula I, or a mixture of any of the compounds of formula I in any proportion, with the proviso that R ² is not H or -CO2C (CH3) 3, is used in the detection of biological compounds.
[42]
42. - A material consisting of a compound of formula I, as defined in one of claims 1 to 25, with the proviso that said compound of formula I is a compound:
- a) that contains a SiR19 group,
- b) or a compound of structural formula I in which at least one R2 is H,
- or regioisomers of a) or b)
- or mixtures of them in any proportion
anchored by a chemical bond on solid surfaces.
[43]
43. - A material according to claim 42, wherein the solid surface is silica.
[44]
44. Use of the material defined in claim 42 as a biomarker or fluorophore in bioimage.

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