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    • 专利摘要:
    1- (piperazin-N-ilaril) - and 1,7-di (piperazin-N-ilaryl) perylene-3,4: 9,10-tetracarboximides, preparation process thereof and their use as detectors of oxidizing explosives. The present invention relates to perylene-3,4: 9,10-tetracarboximide derivatives of formula i, where the meaning for x, r1, r2, r3, r4, r5, r6 is that indicated in the description, a procedure for preparing said derivatives and their use as detectors of oxidizing agents, including oxidizing explosives. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2619109A1
    申请号:ES201500934
    申请日:2015-12-23
    公开日:2017-06-23
    发明作者:Fernando FERNANDEZ LAZARO；Nathalie ZINK LORRE；Angela SASTRE SANTOS；Tomás TORROBA PEREZ；Patricia CALVO GREDILLA；José GARCIA CALVO
    申请人:Universidad Miguel Hernandez de Elche；Universidad de Burgos；
    IPC主号:
    专利说明:

    1- (PIPERAZIN-N-ILARIL) -Y 1,7-DI (PIPERAZIN-N-ILARIL) PERILENE-3,4: 9,10-TETRACARBOXIDIIMIDAS, PROCEDURE FOR PREPARATION OF THE SAME AND ITS USE AS DETECTORS OF OXIDIZING EXPLOSIVES
    TECHNICAL FIELD The present invention relates to perilenediimide derivatives of formula 1. characterized by being substituted in position 1 or positions 1 and 7, a process for preparing them and their use as oxidizing agent sensors , including oxidizing explosives.
    State of the art Triacetone tri peroxide (triacetone triperoxide, TATP) is a powerful explosive without military utility due to its sensitivity to mechanical impact, being, however, widely used by terrorists due to its easy preparation and its difficult tracking by explosive detector dogs, which are trained for the identification of nitrogen explosives. The possibility of being prepared in the same place of use is the origin of restrictions on the transport of liquids inside hand luggage at airports. All this gives an idea of the enormous impact that TATP has on the lives of millions of people every day.
    TATP traces can be detected using infrared spectroscopy, mass spectrometry or ionic mobility spectrometry, but the TATP characteristic signals are only clearly visible using large mass spectrometry equipment. The use of chemically modified nanosensor chains based on nanoelectric devices has meant an advance in the discriminated detection of explosive species, although it is a complex methodology. As for simpler methodologies, there are portable optical methods based on chains of calorimetric sensors that detect hydrogen peroxide from the decomposition of TATP. Chemical systems have also been developed for the indirect detection of TATP, which employ hydrogen peroxide to oxidize some chemical species giving rise either to the appearance of a fluorescent species or to the quenching of the fluorescence of the initial molecule. It is evident that the search for a specific portable fluorogenic probe for the easy and direct detection of TATP, and not the indirect detection of its decomposition products, without the use of large and expensive equipment is an unsolved problem.
    These and other properties and characteristics of TATP and their detection methods are found in monographs and scientific articles, such as (a) http://thefutureofthings.com/3035-tatp-countering-the-motherof-satan/, accessed in August, 14,2015. (b) Faina Dubnikova, Ronnie Kosloff, Joseph Almog, Yehuda Zeiri, Roland Boese, Harel Itzhaky, Aaron Alt, and Ehud Keinan, J. Am. Chem. Soco 2005, 127, 1146-1159. (e) EU Aviation Security Regulations and Screening of Liquids, Aerosols and Gels (LAGS), Rapiscan Systems, OSI Systems, Ine., www.rapiscansystems.com. accessed in August, 14, 2015. (d) Magnus Ranstorp and Magnus Normark, Eds .: Understanding Terrorism Innovation and Learning: AI-Qaeda and Beyond, 2015 -Routledge, Taylor & Francis Group LLC, 7625 Empire Drive, Florence, Kentucky 41042 -2919, USA, Chapter 1, pp. 1-15 and references therein. (e) Leonardo C. Pacheco-Londoño, John R. Castro-Suarez, and Samuel P. Hernández-Rivera, Detection of Nitroaromatic and Peroxide Explosives in Air Using Infrared Spectroscopy: QCL and FTIR, Advances in Optical Technologies, Volume 2013, Article ID 532670, 8 pages, http://dx.doi.org/10.1155/2013/532670. (f) Marko Makinen, Marjaana Nousiainen, and Mika Sillanpaa, ion spectrometric detection technologies for ultra-traces of explosives: a review, Mass Spectrometry Reviews, 2011, 30, 940-973. (g) Amir Lichtenstein, Ehud Havivi, Ronen Shacham, Ehud Hahamy, Ronit Leibovich, Alexander Pevzner, Vadim Krivitsky, Guy Davivi, Igor Presman, Roey Elnathan, Yoni Engel, EIi Flaxer, Fernando Patolsky, Supersensitive fingerprinting of explosives by chemically arrays, Nature Communications 5, Article number: 4195, doi: 10.1038 / ncomms5195, 09 July 2014. (h) Hengwei Lin and Kenneth S. Suslick, A Colorimetric Sensor Array for Detection of Triacetone Triperoxide Vapor, J. Am. Chem. Soco 2010, 132, 15519-15521. (i) Miao Xu, Ji-Min Han, Chen Wang, Xiaomei Yang, Jian Pei, and Ling Zang, Fluorescence
    Ratiometric Sensor for Trace Vapor Oetection of Hydrogen Peroxide, ACS Appl. Mater. Interfaces 2014, 6, 8708-8714.
    Among the organic molecules that can be used as active elements in the preparation of fluorogenic sensors, the perimene-3,4,9,10-tetracarboxylic acid diimides, also known as perylenediimides (POI) or as perylene bisimides (PBI), begin to have a role relevant. POIs are very stable compounds both chemically and thermally, and also against electromagnetic radiation. POIs are highly fluorescent, with quantum fluorescence yields that can reach the unit; However, the presence of certain substituents (for example nitrogenous substituents) on the ring suppresses (quenching) their fluorescence, which can be recovered if there are ions or molecules in the medium that can interact with the nitrogen substituents, so that said POI is it becomes a fluorogenic sensor of said ion or molecule.
    These and other properties and characteristics of POIs are found in many monographs and scientific articles, such as (a) F. Würthner. Chem. Commun. 2004, 1564-1579. (b) H. Langhals. He / v. Chim. Minutes 2005,88,1309-1343. (c) A. Herrmann, K. Müllen. Chem. Lett. 2006,35, 978-985. (d) T. Fu, X.-H. lhao, H.-R. Bai, l.-L. Zhao, R. Hu, R.-M. Kong, X.
    B. lhang, W. Tan, R.-Q. Yu Chem. Commun. 2013, 49, 6644-6646. (e) L. Zhang, Y. Wang, J. Yu, G. Zhang, X. Cai, Y. Wu, L. Wang. Tetrahedron Lett. 2013, 54, 4019-4022.
    Thus, it would be desirable to have a specific method for the easy and direct detection of TATP. It would also be desirable that the method be simple and portable for rapid implementation in any enclosure.
    DETAILED DESCRIPTION OF THE INVENTION The authors of the present invention have found that perilenediimides (POIs), substituted in their 1 or 1 and 7 positions by nitrogenous substituents, such as those described below, possess many of the desirable characteristics, such as a fluorescence suppressed that is recovered in the presence of oxidizing molecules (including TATP) and high qUlmlca and optical stability. which allows its use in the detection of said molecules (including TATP).
    So. In a first aspect the present invention relates to a compound of formula 1:
    where:
    RJ X = H ~
    , quot; 'quot; )! ~! 4 Rs Rs RJ R¡ quot; -NJZfRs
    Rs ~ .... N ~
    R ~ l'R R6
    Rs s each R1 and R3 independently represent hydrogen. halogen C, -C20 alkyl. -CN. -COR7. -C02R7. -CONR7R7. -OR7. -OCOR7. -SR7 • -NR7R7. -NR7
    10 COR7, -SOR7, -S02R7, -S02NR7R7 or CY1. wherein C1-C20 alkyl is independently optionally substituted by one or more Ra and CY1 is optionally substituted by one or more Rg; each R2 independently represents C1-C40 alkyl or CY2; where C1-C40 alkyl is optionally substituted by one or more Re Y where CY2 is
    15 optionally substituted by one or more R10; each R4 independently represents nitrogen or C-R3; each R5 independently represents hydrogen. C1-C20 alkyl, -CN. -COR7. -C02R7, -CONR7R7 • -OR7. -OCOR7. -SR7 • -NR7R7. -NR7 COR7, -SOR7 • -S02R7. -S02NR7R7 or CY1. where C1-C20 alkyl is
    20 optionally substituted by one or more Ra and CY1 is optionally substituted by one or more Rg; each R6 independently represents -R11, -COR11, -C02R11, -S02R11; each R7 independently represents hydrogen, C1-C20 alkyl or CY4. where C1-C20 alkyl is optionally substituted by one or more R14 and where CY4 is optionally substituted by one or more R15;
    or two R7 groups can be joined by forming with the N atom a saturated 5- to 7-membered heterocycle that may additionally contain a heteroatom selected from N, O and S, Y that may be optionally substituted by one or two R15; Each RB independently represents CY3. -OR12, -SR12 or -NR12R12, where CY3 is optionally substituted by one or more Rg; each R10 independently represents C1-C40 alkyl, CY4, -OR12, -SR'2 or -NR12R12, where C, -C40 alkyl is optionally substituted by one or more R'3 and where CY4 is optionally substituted by one or more Rg; each R11 independently represents H, C1-C1Q alkyl or CY3, where C1-C10 alkyl is optionally substituted by one or more -OH, -OC1-C4 alkyl and where CY3 is optionally substituted by one or more C, -C alkyl: each R'2 independently represents hydrogen, C1-C6 alkyl or CY3, where C1-C6 alkyl is optionally substituted by one or more -OH, -OC1-C4 alkyl. where C1-C4 alkyl is optionally substituted by one or more -OH and where CY3 is optionally substituted by one or more C1-Cs alkyl: each Rg and R15 independently represent R12, -OR12, -SR12 or -NR12R12: each R13 and R14 independently represent -OR12, -SR12, -NR12R12 or CY3, where CY3 is optionally substituted by one or more C1-C6 alkyl; each CY1 and CY3 independently represent phenyl or a 5- or 6-membered aromatic heterocycle containing 1 to 3 heteroatoms selected from N, OYS, and where each CY1 and CY3 can be independently linked to the rest of the molecule through any atom of C or N available; each CY2 independently represents a saturated, partially unsaturated or aromatic, monocyclic 3- to 7-membered or bicyclic 6 to 11-membered ring that can be carbocyclic or heterocyclic, where CY2 can be attached to the rest of the molecule through any C atom or N available, where CY2 contains 1 to 4 heteroatoms selected from N, OYS, and where one or more C or S atoms of CY2 may optionally be oxidized to form CO groups. SO or S02; and each CY4 independently represents a saturated carboxylic or heterocyclic ring, partially unsaturated or aromatic with 3 to 7 members, optionally containing from 1 to 4 heteroatoms selected from N, O and S, where CY4 is attached to the rest of the molecule through
    5 any available C or N atom, and where one or more C or S atoms of CY4 may optionally be oxidized forming CO, SO or S02 groups: as well as their regioisomers, and mixtures of two or more compounds of formula
    one.
    In a second aspect, the present invention relates to a process for the preparation of a compound of structural formula 1, its regioisomers and mixtures thereof, comprising reacting a compound of structural formula 11, its regioisomers and mixtures thereof. , with a compound of structural formula 111, its
    15 regioisomers and mixtures thereof,
    111 where: each R1, R2, R3, R4, R5 and R6 independently have the same meaning as in claim 1;
    Each R16 independently represents hydrogen, halogen or OS02R1B with the proviso that the two R16 cannot be hydrogen at the same time; R17 represents -B (OR19) (OR19), -SnR19R19R19: R16 represents C1-C10 alkyl, -CF3, -C4Fg, -CH2CF3 or CY5, where CY5 is
    Optionally substituted by one or more halogens, C1-C4 alkyl or N02; each R19 independently represents hydrogen, C1-C10 alkyl or phenyl, where C1-C10 alkyl is optionally substituted by one or more R11 or two R19 groups can be joined to form a heterocycle of 5 to 7 with the atom of B and the atoms of O saturated members that may additionally contain a heteroatom selected from N, OYS, Y that may be optionally substituted by one or more R11; Each CY5 represents phenyl.
    Additionally, the present invention relates to the use of a compound of structural formula 1, or of a mixture of regioisomers of formula 1, or of a mixture comprising any of the compounds of formula I in any proportion as oxidizing agent detectors.
    In the context of the present invention, the term "regioisomersquot"; 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.
    Throughout the present invention "C1-C40 alkyl"; "C1-C20 alkyl"; "C1-C 1 alkyl"; "C 1-CS alkyl"; and "Cl-C4 alkyl" as a group or part of a group, independently refer to a straight or branched chain alkyl group containing from 1 to 40, from 1 to 20, from 1 to 10, from 1 to 6 and from 1 to 4 atoms of C respectively. quot; Cl-C4 alkylquot; It includes methyl groups. ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl; quot; alkylCot CrCs; includes the groups of "Cl-C4 alkyl"; and, among others, pentyl, iso-pentyl, secpentyl, neo-pentyl, 1,2-dimethylpropyl, hexyl, iso-hexyl and sec-hexyl; "Cl-C20 alkyl"; includes the groups of "Cl -CS alkyl"; and, among others, heptyl, iso-heptyl, octyl, iso-odyl, 2-ethylhexyl, nonyl, decyl and dodecyl, 2-propylheptyl, 2-butylnonyl, 3-butylnonyl and 2-hexylheptyl; "C1-C40 alkyl"; includes the groups "C1-C20 alkyl"; and, among others, tridecyl and tetradecyl.
    CY1 and CY3 independently refer to a phenyl or a 5- or 6-membered heteroaryl containing 1 to 3 heteroatoms selected from N, O Y
    S. CY1 AND CY3 bind to the rest of the molecule through any atom of C
    or N of the available ring. In addition, CY1 and CY3 may be optionally substituted as indicated in the definition of formula 1, 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.
    CY2 refers to a 3- to 7-membered monocyclic or 6 to 11-membered bicyclic ring that can be carbocyclic or heterocyclic. When it is heterocyclic it can contain from 1 to 4 heteroatoms selected from N, O Y
    S. The bicyclic rings can be formed by two fused rings through two adjacent C or N atoms, or through two non-adjacent C or N atoms forming a bridge ring, or they can be formed by two rings attached to through a single C atom forming an Spiranus ring. The CY2 group can be saturated, partially unsaturated or aromatic. CY2 can be attached to the rest of the molecule through any available C or N atom. In CY2 one or more C or S atoms of CY2 may optionally be oxidized forming ca, so
    or S02. In addition, CY2 may be optionally substituted as indicated in the definition of a compound of formula 1, 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, ciciobutilo, 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-oxo-piperidinyl, 4-oxo-piperidinyl, 2-oxo-piperazinyl, 2oxo-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, pyrimi dinilo, 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-dioxo1,3-dihydroisobenzofuranyl, 2-oxo-2,3-dihydro-1 H-indolyl, 1 -oxo-2,3-dihydro1 H-isoindolyl, perhydroquinolinyl, 1-oxo-perhydroisoquinolinyl, 1-oxo-1,2-dihydroisoquinolinyl, 4-oxo-3,4-dihydroquinazolinyl, 2-azabicyclo [2.2.1] heptanyl, 5- aza-bicyclo [2.1.1] hexanyl, 2H-spiro [benzofuran3,4'-piperidinyl], 3H-spiro [isobenzofuran-1,4'-piperidinyl]. 1-oxo-2,8 diazaspiro [4.5] decanyl and 1-oxo-2, 7 -diazaspiro [4.5] decanyl.
    In the above definition of CY2, when the specified examples refer to a bicyclic ring in general terms, all possible arrangements of atoms are included.
    CY4 represents a 3 to 7 member ring, saturated, partially unsaturated or aromatic, which can be carbocyclic or heterocyclic. If it is heterocyclic, it contains 1 to 4 heteroatoms selected from N, O, and S that can be optionally oxidized to form CO, SO or S02 groups. CY4 binds to the rest of the molecule through any available C or N atom. In addition, CY4 may be optionally substituted as indicated in the definition of a compound of formula 1, if substituted, the substituents may be the same or different and may be located at any available position of the ring system. Examples include among others, 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, 2oxo-pyrrolidinyl, phenyloxylazolezolyl, phenylazolezolyl, phenyl 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.
    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 CY1 to CY4, 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.
    The expression "optionally substituted by one or more"; means the possibility
    5 of a group being substituted by one or more, preferably by 1, 2, 3 or 4 substituents, more preferably by 1, 2 or 3 substituents and even more preferably by 1 or 2 substituents, provided that said group has sufficient positions available that can be replaced. If present, said substituents may be the same or different and may
    10 be located over any available position.
    When two or more groups with the same numbering appear in a definition of a substituent (for example -NR7R7, -NR12R12, etc.), this does not mean that they have to be identical. Each of them is selected
    15 regardless of the list of possible meanings given for said group, and therefore may be the same or different.
    In one aspect, the present invention relates to a compound of structural formula 1, as previously defined, as well as its regioisomers and mixtures of two or more compounds of formula 1.
    In a particular embodiment, in the compound of formula 1, X is hydrogen.
    In another particular embodiment, in the compound of formula 1, X is
    In a particular embodiment, in the compound of formula 1, R4 is CR3.
    In another particular embodiment, in the compound of formula 1, R4 is nitrogen.
    In another particular embodiment. in the compound of formula l. one R4 of the aromatic ring is C-R3 and the other R4 is nitrogen.
    In a particular embodiment. in the compound of formula l. R3 independently represents hydrogen. halogen C1-C20 alkyl. -OR7 • -SR7. -NR7R7. -SOR7. -S02R7 or CY1. where C1-C20 alkyl is independently optionally substituted by one or more Re and CY1 is optionally substituted by one or more R9. and where R1. R2. R5 Rs. R7 Rs. R9 and CY1 have the same meaning as for the compound of formula l.
    In a preferred embodiment, R3 is hydrogen.
    In another particular embodiment, each R5 independently represents hydrogen. C1-C20 alkyl, -CN. -COR7, -C02R7 • -CONR7R7, -OR7, -SR7, -NR7Rr. -SOR7, -S02Rr
    or CY1, where C1-C20 alkyl is independently optionally substituted by one or more Re and CY1 is optionally substituted by one or more R9, and where R1, R2, Rs, R7, Re, R9, R10, R11, R12, R13, R14, R15, CY1, CY2. CY3 and CY4 have the same meaning as for the compound of formula l.
    In a preferred embodiment, R5 is hydrogen.
    In a particular embodiment of the present invention, R1 is hydrogen, halogen, C1-C20 alkyl, -OR7, -SR7, -NR7R7, -SOR7, -S02Rr or CY1, where C1-C20 alkyl is optionally substituted by one or more Ra and CY1 is optionally substituted by one or more R9, and where R2, Rs, R7, Rs. R9 and CY1 have the same meaning as for the compound of formula l.
    In another particular embodiment, each R2 independently represents C1-C40 alkyl or CY2; where C1-C40 alkyl is optionally substituted by one or more Re Y where CY2 is optionally substituted by one or more R10.
    In a preferred embodiment, each R2 is a 1-hexylheptyl chain.
    In another preferred embodiment, each R2 is a 2,5-di-t-butylphenyl ring.
    In another preferred embodiment, each R2 is a cyclohexyl ring.
    In a particular embodiment of the present invention, Rs independently represents H, -R11, -COR11, -C02R11 • -S02R11.
    In another particular embodiment, R7 independently represents hydrogen, C1-C20 alkyl or CY4.
    In another particular embodiment, two R7 groups can be joined by forming with the N atom a saturated 5- to 7-membered heterocycle that may additionally contain a heteroatom selected from N, OYS, Y which may be optionally substituted by one or two R15 .
    In a particular embodiment, each Rg independently represents R12.
    In another particular embodiment, each R10 independently represents C1-C40 alkyl optionally substituted by one or more R13.
    In a preferred embodiment, each R11 independently represents H or C1-C1O alkyl, where C1-C10 alkyl is optionally substituted by one or more -OH or -OC1-C4 alkyl.
    In another preferred embodiment, each R11 independently represents CY3 optionally substituted by one or more C1-Cs alkyl.
    In a particular embodiment, each R12 independently represents C1-Cs alkyl optionally substituted by one or more -OH, -OC1-C4 alkyl, and where C1-C4 alkyl is optionally substituted by one or more -OH.
    In another particular embodiment, each R13 independently represents -OR12 or CY3, where CY3 is optionally substituted by one or more C1-Cs alkyl.
    In another particular embodiment, each R14 independently represents -OR12 or CY3, where CY3 is optionally substituted by one or more Cl -CS alkyl.
    In another particular embodiment, each R15 independently represents R12.
    In a preferred embodiment, each CY1 independently represents phenyl.
    In a particular embodiment, each CY2 independently represents a 3 to 7-membered carbocyclic or heterocyclic monocyclic saturated ring, where CY2 can be attached to the rest of the molecule through any available C or N atom, and where CY2 contains 1 to 3 heteroatoms selected from N, OY S.
    In a preferred embodiment, each CY3 independently represents phenyl.
    In another preferred embodiment, each CY3 independently represents a 5- or 6-membered aromatic heterocycle containing 1 or 2 heteroatoms selected from N, OYS, and where CY3 can be attached to the rest of the molecule through any C atom or N available.
    In a particular embodiment, each CY4 independently represents a saturated 3- to 7-membered carbocyclic or heterocyclic ring, optionally containing 1 to 3 heteroatoms selected from N, OYS, and where CY4 is attached to the rest of the molecule through of any available C or N atom.
    In another aspect, the present invention relates to a process for preparing the compounds of structural formula 1, as previously defined, their regal isomers and mixtures thereof,
    comprising reacting a compound of structural formula 11, its regioisomers and mixtures thereof, with a compound of structural formula 111, its regioisomers and mixtures thereof,
    5 where: each R1, R2, R3, R4, Rs and R6 independently have the same meaning as for compound 1; each R16 independently represents hydrogen, halogen or OS02R18 with the proviso that the two R16 cannot be hydrogen at the same
    10 time; R17 represents -B (OR19) (OR19), -SnR19R19R19; R18 represents C1-C1Q alkyl, -CF3, -C4F9, -CH2CF3 or CYs, where CYs is optionally substituted by one or more halogen, C1-C4 alkyl or N02; each R19 independently represents hydrogen, C1-C10 alkyl or phenyl,
    Where C1-C10 alkyl is optionally substituted by one or more R11
    or two R19 groups can be joined together with the atom of B and the atoms of O a saturated 5- to 7-membered heterocycle that may additionally contain a heteroatom selected from N, O and S, Y that may be optionally substituted by one or more R11:
    20 each CYs represents phenyl.
    In a particular embodiment, in the compound of formula 111, R4 is C-R3.
    In another particular embodiment, in the compound of formula 111, R4 is nitrogen.
    In another particular embodiment, in the compound of formula 111, one R4 of the aromatic ring is C-R3 and the other R4 is nitrogen.
    In a preferred embodiment, in the compound of formula 111, R3 is hydrogen.
    In a preferred embodiment, in the compound of formula 111, Rs is hydrogen.
    In one preferred embodiment, in the compound of formula 11, each R2 is a 1-hexylheptyl chain.
    In another preferred embodiment, in the compound of formula 11, each R2 is a 2,5-di-t-butylphenyl ring.
    In another preferred embodiment, in the compound of formula 11, each R2 is a cyclohexyl ring.
    In a particular embodiment of the present invention, in the compound of formula 111, R6 independently represents H, -R11, -COR11, -C02R11, -S02R11.
    In a preferred embodiment, in the compound of formula 11, R1 is H.
    In a particular embodiment of the present invention, each R11 independently represents H or Cl-C1Q alkyl, where Cl-Cl0 alkyl is optionally substituted by one or more -OH or -OC1-C4 alkyl.
    In another particular embodiment of the present invention, in the compound of formula 11, one R16 is an atom selected from chlorine, bromine or iodine, and the other R16 is an atom selected from hydrogen, chlorine, bromine or iodine.
    In a preferred embodiment, in the compound of formula 11, one R16 is a bromine atom, and the other R16 is an atom selected from hydrogen or bromine.
    In another particular embodiment of the present invention, in the compound of formula 111, R17 is -B (OR'9) (OR'9).
    In a preferred embodiment, R'9 independently represents hydrogen, C, -C1Q alkyl or phenyl, where C, -C, or alkyl is optionally substituted by one or more Rquot;
    or two R'9 groups can be joined to form a saturated 5- to 7-membered heterocycle with the B atom and the O atoms, and which may be optionally substituted by one or more R ,,;
    In a particular embodiment of the present invention, the compound of formula I is selected from
    V
    N
    jo
    e & Y
    ...i5
    or..
    : 1: zJ
    (~ zJ: r
    CD
    i5
    or..
    .0: -1quot; ~ ::
    ~
    or
    ~
    POI 14
    POI 13 PDI20PDI19
    A further aspect of the present invention relates to the use of a compound of structural formula 1, as previously defined, or of
    5 a mixture of regioisomers of formula 1, or of a mixture comprising any of the compounds of formula I in any proportion as oxidizing agent detectors.
    In a particular embodiment, the oxidizing agent is an oxidizing explosive.
    In a preferred embodiment, the oxidizing explosive agent is tri acetone peroxide (TA TP).
    Embodiment of the invention
    The present invention is further illustrated by the following examples, which cannot be considered as limiting its scope.
    Eiemolo 1. N, N'-di (1'-hexylheptyl) -1- [- (Nquot; '- tert-butoxycarbonylpiperazinNquot; -yl) phenyl] -3.4: 9,10-perilenetetracarboxyidiimide (POI 1)
    POl1 Pd (PPh3) 4 (27 mg, 0.024 mmol) is added under argon
    10 a mixture of N, N'-di (1'-hexylheptyl) -1-bromo-3,4: 9,1-O-perylenetetracarboxyidiimide (200 mg, 0.24 mmol), p- (N'-tert) pinacolate -butyloxycarbonylpiperazinN-yl) phenylboro (110 mg, 0.28 mmol), sodium carbonate (73 mg, 0.7 mmol), THF (20 mL) and water (2.5 mL). It is heated to 70 · e overnight. The crude is dissolved in CH2Cb and washed with water. The organic phase dries
    15 with Na2S04, filter and remove the solvent under reduced pressure. It is purified by column chromatography with silica gel and Ct-I2Cb / methanol (97: 3) as eluent to obtain compound POI 1 as a red solid (190 mg, 78%).
    • 1H-NMR (COCI3) 00.75 (t, 12H), 1.15 (br, 32H), 1.44 (s, 9H), 1.76 (m,
    20 4H), 2.15 (m, 4H), 3.22 (t, 4H), 3.57 (t, 4H), 5.09 (m, 2H), 6.98 (d, 2H), 7 , 34 (d, 2H), 7.96 (d, 1H), 8.08 (br, 1 H), 8.52 (m, 5H)
    • 13C-NMR (COCI3) 014.02, 22.56, 26.88, 28.44, 29.20, 31.74, 32.35, 48.69, 54.62, 54.69, 80.07 , 117.41, 122.43, 123.44, 127.60, 128.15, 128.29, 129.18, 129.44, 129.59, 134.55, 141.71, 151.04, 154 , 66, 25 163,75,164.69
    • MALDI-TOF MS miz: [M +] calculated for C6sHB2N40s 1014.62, found 1014.20
    • IR (KBr): 2920, 2856,1695,1660,1590,1403,1333,1228,1170,808 cm-1
    • UV Vis (CH2Cb), Amaxlnm (Iog E): 490 (4.4)
    5 Eiemolo 2. N, N'-Di (1'-hexylheptyl) -1- (p-piperazin-Nquot; -ylphenyl) -3.4: 9,10 perileneotetracarboxyidiimide (POI 2)
    v
    POl2
    On a solution of POI 1 (80 mg, 0.078 mmol) in dichloromethane (0.5
    mL) trifluoacetic acid (0.33 mL, 4.6 mmol) is added. After stirring for 15
    10 minutes at room temperature, the reaction is stopped by adding water and extracted with dichloromethane. The organic phase is dried with Na2S04, filtered and the solvent is removed under reduced pressure. It is purified by column chromatography with silica gel and CH2 Cb / methanol (6: 0.5) as eluent to obtain the POI 2 compound as a red solid (65 mg, 90%).
    15 • 1H-NMR (COCb) () 0.82 (t, 12H), 1.22 (br, 32H), 1.85 (m, 4H), 2.22 (m, 4H), 3.33 ( br, 4H), 3.50 (br, 4H), 5.18 (m, 2H), 7.06 (d, 2H), 7.44 (d, 2H), 8.02 (d, 1 H) , 8.17 (br, 1 H), 8.60 (m, 5H)
    • 13C-NMR (CDCI3) () 13.90, 22.44, 26.77, 29.08, 31.62, 32.24, 44.55,
    47.71, 54.51, 117.51, 122.37, 123.38, 127.50, 128.04, 128.22, 129.08, 20 129.56,133.95,134,60,141.44,150.69,163,58,164 , 62
    • MALDI-TOF mIz MS: [M +] calculated for CaoH74N404 914.57, experimental 914.55
    • IR (KBr): 3416, 2926,2844,1695,1648,1590,1461,1327,1246,1100,
    1018, 814 cm-1 25 • UV Vis (CH2CI2), Amax / nm (lag e): 489 (4.3)
    Eiemolo 3. N, N'-Di (1 '-hexylheptyl) -1, 7 -di [P- (Nquot;' - tert
    butoxycarbonylpiperazin-NIJ-yl) phenyl] -3.4: 9,10-perylenetetracarboxyidiimide (POI 3)
    POI3
    5 Pd (PPh3) 4 (25 mg, 0.022 mmol) is added over a mixture of N, N'-di (1'hexylheptyl) -1, 7 (6) -dibromo-3,4: 9, 1 O-perylenetetracarboxy diimide (200 mg of the mixture of isomers in which the isomer 1.7, 0.22 mmol) predominates, p- (N'-tert-butoxycarbonylpiperazin-N-yl) phenylboro pinacolate (170 mg, 0.44 mmol) , sodium carbonate (73 mg, 0.7 mmol), THF (20 mL) and water (2.5 mL)
    10 under argon atmosphere. It is heated at 70 ° C overnight. The crude is dissolved in CH2Cb and washed with water. The organic phase is dried with Na2S04, filtered and the solvent is removed under reduced pressure. It is purified by column chromatography with silica gel and CH2Cb / methanol
    (100: 1) as eluent obtaining compound PDI 3 (pure 1.7 isomer)] 5 as a black solid (163 mg, 60%).
    • 1H-NMR (COCb) ii 0.82 (t, 12H), 1.25 (br, 32H), 1.51 (s, 18H), 1.82 (m, 4H), 2.22 (m, 4H ), 3.28 (t, 4H), 3.65 (t, 4H), 5.15 (m, 2H), 7.01 (m, 4H), 7.31 (d, 1 H), 7, 46 (d, 3H), 7.91 (m, 2H), 8.12 (m, 2H), 8.59 (m, 2H)
    • 13C_RMN (COCb) ii 14.01, 22.56, 26.87, 28.43, 29.20, 31.73, 32.37,
    20 48.51, 54.57, 80.03, 117.05, 127.72, 128.84, 129.47, 129.61, 129.84, 130.13, 133.02, 133.54, 135 , 26, 140.77, 141.99, 151.05, 154.68, 163.76, 164.83
    • MALDI-TOF MS miz: [M +] theoretical for CaoH102N60a 1274.77, experimental 1274.60
    25 • IR (KBr): 2932, 2850, 1699, 1654, 1596, 1409, 1327, 1228, 1158, 815 cm-1
    • UV Vis (CH2CI2), A.maxlnm (Iog E): 457 (4.3), 582 (4.2)
    EiernDlo 4. N, N'-Di (1 '-hexylheptyl) -1.7 -di (p-piperazin-Nquot; -ylphenyl) -3.4: 9.1 0
    perilenotetracarboxidiimide (POI 4)
    POl4 On a solution of POI 3 (30 mg, 0.02 mmol) in dichloromethane (0.5 mL)
    5 Trifluoacetic acid (0.1 mL, 1.3 mmol) is added. After stirring for 15 minutes at room temperature, the reaction is stopped by adding water and extracted with dichloromethane. The organic phase is dried with Na2S04, filtered and the solvent is removed under reduced pressure. It is purified by column chromatography with silica gel and CH2Cb / methanol (5: 0.5) as eluent
    10 obtaining the POI 4 compound as a black solid (23 mg, 90%).
    • 1H-NMR (COCb) () 0.81 (t, 12H), 1.21 (br, 32H), 1.82 (br, 4H), 2.22 (br, 4H), 2.40 (br, 2H), 3.48 (br, 8H), 3.65 (br, 8H), 5.15 (br, 2H), 7.02 (d, 4H), 7.50 (d, 4H), 7, 90 (d, 2H), 8.15 (m, 2H), 8.58 (m, 2H)
    • 13C_RMN (COCb) () 14.01, 22.55, 26.88, 29.20, 31.73, 32.36, 43.41,
    15 46.28quot; 54.66, 70.48, 117.95, 121.61, 122.34, 122.84, 127.83, 129.39, 130.33,132.36,134.77,140.37,149.99,163.65,164.68
    • EM MALOI-TOF mIz: [M +] theoretical for C7oH86N606 1074.67, experimental 1074.98
    • IR (KBr): 3427, 2929, 2843, 2504,1695,1653,1576,1519,1446,1409, 20 1327, 1254, 1196, 1139, 927, 808, 718 cm-1
    • UV Vis (CH2CI2), Amax / nm (Iog E): 450 (4.3), 581 (4.3)
    EiernDlo s. N, N'-bis (2 ', S'-di-tert-butylphenyl) -1- [- (N' '' - tert-butoxycarboni Ipi perazi n-Nquot; -yl) feni1] -3.4: 9, 1 O-peri lenotetracarboxidi im ida (POI S)
    POI S
    5 Pd (PPh3) 4 (6.75 mg, 0.006 mmol) is added over a mixture of N, N'bis (2 ', 5' -di-tert-butylphenyl) -1-bromo-3,4: 9, 1 O-perylenetetracarboxyidiimide (50 mg, 0.06 mmol), p- (N ~ tert-butoxycarbonylpiperazin-N-yl) phenylboro pinacolate (31 mg, 0.08 mmol), sodium carbonate (35 mg, 0.34 mmol), THF (5 mL) and water (0.5 mL) under argon. Heats up to 70DC throughout the
    10 night The crude is dissolved in CH2CI2 and washed with water. The organic phase is dried with Na2S04, filtered and the solvent is removed under reduced pressure. It is purified by column chromatography with silica gel and CH2Cl2 / methanol (5: 0.2) as eluent to obtain the POI S compound as a purple solid (58 mg, 96%).
    15 • 1H-NMR (COCI3) OR 1.24-1.28 (m, 36H), 1.45 (s, 9H), 3.24 (m, 4H), 3.59 (m, 4H), 6 , 92 (d, 1H), 6.97 (d, 2H), 7.42 (m, 4H), 7.56 (m, 2H), 8.10 (d, 1 H) 8.22 (d, 1 H), 8.63 (m, 3H), 8.70 (d, 2H)
    • 13C-NMR (COCb) OR 28.39, 29.63, 31.16, 31.71, 31.73, 34.18, 34.20, 35.49, 35.50, 48.42, 49, 38, 80.02, 116.57, 117.29, 122.24, 122.51,
    20 123.41, 123.42, 123.72, 129.54, 132.56, 132.59, 132.60, 133.11, 135.08, 142.03, 143.76, 143.77, 150 , 07, 150.10, 151.21, 154.64, 164.40, 164.44, 164.57
    •. EM MALOI-TOF miz: [M + j theoretical for C67H70N204 1026.53,
    Experimental 1026.56 25 • IR (KBr): 2949, 1706, 1660, 1601, 1403, 1339, 1246, 1181,825 cm-1
    • UV Vis (CH2CI2), Amax / nm (lag E): 493 (4.4), 549 (4.3)
    EiemDlo 6. N-Nquot; -bis (2 ', S'-di-tert-butylphenyl) -1- (p-piperazin-Nquot; -ylphenyl)
    3,4: 9,10-perilenotetracarboxidiimide (POI 6)
    POl6 On a solution of POI 5 (30 mg, 0.029 mmol) in dichloromethane (0.5
    5 mL) trifluoacetic acid (0.15 mL, 1.9 mmol) is added. After stirring for 15 minutes at room temperature, the reaction is stopped by adding water and extracted with dichloromethane. The organic phase is dried with Na2S04, filtered and the solvent is removed under reduced pressure. It is purified by column chromatography with silica gel and CH2Cb / methanol (2: 0.2) as eluent
    10 obtaining the POI 6 compound as a purple solid (23 mg, 88%).
    • 1 H-NMR (COCb) at 1.29-1.33 (m, 36H), 3.29 (m, 4H), 3.47 (m, 4H), 6.97 (d, 1 H), 7.02 (d, 2H), 7.47 (m, 4H), 7.58 (m, 2H), 8.13 (d, 1 H) 8.27 (d, 1 H), 8.68 (m, 3H ), 8.74 (d, 2H)
    • 13C_RMN (COCb) Ú 31.20, 31.74, 34.22, 34.24, 35.52, 35.54, 44.56,
    15 47.63,117,70,122.36,12260,123.50,126.36, 127.68, 127.95, 128.50, 128.60, 128.82, 129.51, 129.67, 130.89, 132 , 58, 132.62, 132.68, 133.95, 135.08, 135.21, 135.62, 141.83, 143.79, 150.11, 150.15, 150.78, 164.40 , 164.44, 164.59
    •. MS MALOI-TOF mIz: [M + H +] theoretical for C62H62N404 927.48, experimental 20 927.45
    • IR (KBr): 3439,2961,1706,1660,1584,1403, 1333, 1251,802 cm-1
    • UV Vis (CH2CI2), Amax / nm (Iog E): 493 (4.4), 540 (4.2)
    Eiemolo 7. N, N'-dicyclohexyl-1- [- (NJJJ-tert-butoxycarbonylpiperazin-Nquot;
    il) phenyl] -3.4: 9,10-perylenetetracarboxyidiimide (POI 7)
    POl7 THF: H20 (20: 2 mL) is added over a mixture of N, N'-dicyclohexyl-1-bromine
    5 3,4: 9,10-perilenotetracarboxyidiimide (100 mg, 0.16 mmol) and Pd (PPh3) 4 (two spatula tips). The mixture is stirred 5 minutes and p (N'-tert-butoxycarbonylpiperazin-N-yl) phenylboro pinacolate (68 mg, 0.17 mmol) and cesium carbonate (156 mg, 0.48 mmol) are added. After 24 hours at reflux, the mixture is extracted with dichloromethane and dried with Na2S04. The product is purified by
    10 column chromatography (silica gel, CH2CI2: CH3CN), obtaining POI 7 as a dark violet solid (84 mg, 65%).
    • 1H-NMR (COCI3) or 1.37 (dd, J = 28.5, 15, .0 Hz, 5H), 1.52 (s, 9H), 1.58 (s, 1 H), 1.99 -1.67 (m, 10H), 2.67-2.44 (m, 4H), 3.33-3.22 (m, 4H), 3.70-3.59 (m, 4H), 5 , 02 (d, J = 10.1 Hz, 2H), 6.99 (d, J = 8.7 Hz, 2H),
    15 7.30 (d, J = 8.7 Hz, 2H), 7.88 (d, J = 8.2 Hz, 1 H), 8.09 (d, J = 8.3 Hz, 1 H) , 8.47-8.41 (m, 1 H), 8.49 (s, 1H), 8.56 (d, J = 8.0 Hz, 1 H), 8.60 (d, J = 8 , 0 Hz, 1H)
    • 13C_RMN (COCI3) or 25.60, 26.70, 28.61, 29.26, 48.67, 54.05, 54.15, 117.38, 122.47, 122.53, 122.81, 123 , 49, 123.68, 127.58, 128.15,
    20 129.53, 129.67, 130.19, 130.56, 131.01, 132.11, 133.36, 134.62, 135.10,136.26,141.81,163.94,164.07,164.12
    •. MALOl-TOF MS miz: [M +] theoretical for C51H50N406 814.3725, experimental 814.3798
    • IR (KBr): 3471,2928,2854,1698,1655,1590,1519,1454,1405,1331, 25 1235,1170,1039,982,914,811,752 cm-1
    • UV Vis (CH2CI2), Amax / nm (lag E): 485 (4.3), 530 (sh, 4.2)
    Example 8. N, Nquot; -dicyclohexyl-1,7-bislP- (Nquot; '- tert-butoxycarbonylpiperazinNquot; -yl) phenyl] -3.4: 9.1 O-perilenotetracarboxyidiimide (POI 8)
    POl8 THF: H20 (40: 4 mL) is added over a mixture of N, N ~ dicyclohexyl-1, 7 (6)
    5 dibromo-3,4: 9,10-perilenotetracarboxyidiimide (220 mg, 0.31 mmol) and Pd (PPh3) 4 (two spatula tips). The mixture is stirred 5 minutes and p- (N'-tert-butoxycarbonylpiperazin-N-yl) phenylboro pinacholate (250 mg, 0.65 mmol) and cesium carbonate (300 mg, 0.93 mmol) are added. After 24 hours at reflux, the mixture is extracted with dichloromethane and dried with Na2S04. The oil is
    10 purified by column chromatography (silica gel, CH2CI2: CH3CN), obtaining a mixture of the 1.6 and 1.7 isomers (200 mg, 60%). Pure 1.7 isomer (POI 8) can be obtained by repeated chromatography as a dark violet solid (33 mg, 10%).
    • 1H-NMR (COCb) B 1.25 (s, 4H), 1.51 (s, 9H), 1.81 (dd, J = 49.3, 11.9
    15 Hz, 7H), 2.54 (d, J = 13.6 Hz, 3H), 3.27 (d, J = 5.3 Hz, 5H), 3.64 (t, J = 5.1 Hz , 5H), 5.01 (s, 2H), 6.98 (d, J = 8.7 Hz, 2H), 7.43 (d, J = 8.6 Hz, 2H), 7.90 (d , J = 8.2 Hz, 1 H), 8.12 (d, J = 8.2 Hz, 1 H), 8.55 (d, J = 10.6 Hz, 1 H)
    • 13C_RMN (COCI3) B 25.59, 26.69, 28.59, 29.26, 43.54, 48.63, 48.74,
    20 53.55, 53.90, 54.02, 80.20, 117.12, 117.23, 122.12, 122.69, 122.85, 127.53, 129.19, 129.40, 129 , 52, 129.67, 130.00, 130.23, 132.12, 132.46,133.08,134,80,135.07,135,21,135.32, 140.76, 142.04, 151.23,154.82,164.01,164,10,164 , 12,164.16
    •. EM MALOI-TOF mIz: [M +] theoretical for C66H7oN60a 1074,5250, experimental 1074,6237
    • IR (KBr): 3453, 2976, 2931, 2851, 1700, 1658, 1582, 1513, 1409, 1326, 1233, 1167, 1122, 1046, 994, 915, 863, 808, 759 cm-1
    • UV Vis (CH2CI2), Amax / nm (Iog E): 457 (4.3), 583 (4.2)
    EiernDlo 9. N. N'-di (1'-hexylheptyl) -1- [2 '- (4 "; -terc-butoxycarbonylpiperazin1quot; -yl) pyridin-5'-yl] -3.4: 9,1O-perilenotetracarboxidiimide (POI 9)
    v
    POl9 Pd (PPh3) 4 (27 mg, 0.024 mmol) is added on a suspension of N, N '
    5 di (1'-hexylheptyl) -1-bromo-3,4: 9, 1O-perylenetetracarboxyidiimide (200 mg, 0.24 mmol), 2- (4'-tert-butoxycarbonylpiperazin-1 '-yl) pyridine pinacolate -5-ilboro (108 mg, 0.28 mmol) and sodium carbonate (73 mg, 0.7 mmol) in a mixture of THF (20 mL) and water (2.5 mL) under argon. Heats up to 70 "C overnight. The crude is dissolved in CH2Cb and washed with water. The
    The organic phase is dried with Na2S04, filtered and the solvent is removed under reduced pressure. It is purified by column chromatography with silica gel and CH2Cb / methanol (100: 1) as eluent to obtain compound POI 9 as a red solid (220 mg, 90%).
    • 1H-NMR (COCb) OR 0.82 (t, 12H), 1.22 (br, 32H), 1.52 (s, 9H), 1.82 (m,
    15 4H), 2.22 (m, 4H), 3.64 (br, 8H), 5.16 (m, 2H), 6.75 (d, 1H), 7.59 (d, 1H), 8 , 09 (d, 1 H), 8.38 (br, 2H), 8.62 (m, 5H)
    • 13C_RMN (COCI3) OR 14.01, 22.55, 22.56, 26.87, 26.89, 28.44, 29.18, 29.20.31.73.32.35.44.75, 54.68.54.75.80.11, 107.63, 114.52, 122.56, 123.58, 127.17, 127.53, 127.59, 128.23, 128.40, 129, 25,
    20 134.66,138.05,138,60,147.73,154.79,158.52, 163.56, 164.51
    • MALOI-TOF MS miz: [M +] calculated C64Hs1NsOs 1015.6181, experimental 1015.6987
    • IR (KBr): 2920, 2850,1689,1654,1584,1409,1316,1246,1158,814
    cm-1 25 • UV Vis (CH2Cb), Amax / nm (lag E): 485 (4.5), 545 (4.4)
    EiemDlo 10. N, N'-di (1'-hexylheptyl) -1- [2 '- (piperazin-1 "; -yl) pyridin-S'-yl] 3,4: 9,10-perylenetetracarboxyidiimide (POI 10 )
    v
    POl10 On a solution of POI 9 (80 mg, 0.078 mmol) in dichloromethane (0.5
    5 mL) trifluoacetic acid (0.33 mL, 4.6 mmol) is added. After stirring for 15 minutes at room temperature, the reaction is stopped by adding water and extracted with dichloromethane. The organic phase is dried with Na2S04, filtered and the solvent is removed under reduced pressure. It is purified by column chromatography with silica gel and CH2Cl2 / methanol (6: 0.5) as eluent
    10 obtaining the compound POl10 in the form of a red solid (66 mg, 93%).
    • 1H_ NMR (COCI3) b 0.75 (t, 12H), 1.15 (br, 32H), 1.77 (br, 4H), 2.16 (br, 4H), 3.58 (s, 4H) , 3.83 (s, 4H), 5.12 (m, 2H), 6.67 (d, 1 H), 7.54 (d, 1 H), 8.05 (d, 1H), 8, 16 (br, 1H), 8.30 (s, 1H), 8.52 (m, 5H)
    • 13C-NMR (CDCI3) or 13.97, 13.98, 22.50, 22.51, 26.83, 26.84, 29.14,
    15 31.68, 32.29, 45.22, 54.61, 54.69, 66.60, 107.38, 122.50, 123.51, 127.50, 127.65, 128.14, 128 , 32, 129.17, 129.20, 130.34, 131.17, 131.56, 134.38, 134.57. 136.40. 137.95, 138.52. 147.63, 158.75, 163.57,164.51
    • EM MALOI-TOF mIz: [M + 2Ht calculated C59H73N504 917,5735, experimental 20 917,5800
    • IR (KBr): 3416, 2920, 2856,1695,1654,1578,1491,1403,1333,1251, 1117, 808 cm-1
    • UV Vis (CH2CI2), Amaxlnm (lag E): 485 (4.5), 535 (4.4)
    EiernDlo 11. N, N'-di (1 '-hexylheptyl) -1, 7-di [2' - (4 "; -terc-butoxycarbonylpiperazin-1"; -yl) pyridin-5'-iI1-3.4: 9, 1 O-perilenotetracarboxyidiirnide (POI 11)
    POl11 Pd (PPh3) 4 (25 mg, 0.022 mmol) is added on a suspension of N, N '
    5 di (1 '-hexylheptyl) -1, 7 (6) -bromo-3,4: 9, 10-perilenotetracarboxyidiimide (200 mg of the mixture of isomers in which the 1,7, 0.22 mmol isomer predominates) , 2- (4'-tert-butoxycarbonylpiperazin-1'-yl) pyridin-5-ylboro pinacholate (175 mg, 0.45 mmol) and sodium carbonate (146 mg, 1.4 mmol) in a mixture of THF (20 mL) water (2.5 mL) under argon atmosphere. Heats at 70C for
    10 all night. The crude is dissolved in CH2CI2 and washed with water. The organic phase is dried with Na2S04, filtered and the solvent is removed under reduced pressure. It is purified by column chromatography with silica gel and CH2Cb / methanol (100: 0.5) as eluent to obtain compound PDI 11 (pure 1.7 isomer) as a black solid (87 mg, 30%).
    15 • 1H_ NMR (COCb) () 0.82 (t, 12H), 1.22 (br, 32H), 1.51 (s, 18H) 1.82 (br, 4H), 2.24 (br, 4H), 3.65 (d, 16H), 5.15 (m, 2H), 6.73 (d, 2H), 7.65 (d, 2H), 8.02 (d, 2H), 8, 20 (br, 2H), 8.42 (s, 2H), 8.56 (br, 2H)
    • 13C-NMR (COCb) 8 13.98, 22.51, 22.52, 22.55, 26.83, 28.39, 29.16, 31.69, 32.32, 44.70, 54, 63, 70.50, 80.05, 107.43, 127.12, 127.57, 20 127.87, 129.27, 129.46, 132.30, 134.96, 137.71, 138.40, 148.12, 154.73, 158.41, 163.49, 164.67
    • MALDI-TOF MS miz: [Mt calculated C7sH1ooNaOa 1276,7658, experimental 1276,7770
    • IR (KBr): 2926,2850,1695,1648,1584,1491,1409,1234,814 cm-1 25 • UV Vis (CH2CI2), Amaxlnm (Iog E): 453 (4.4), 595 (4 ,3)
    EiemDlo 12. N, N'-di (1'-hexylheptyl) -1.7 -di [2 '- (piperazin-1 quot; -il) pyridin-S'-yl] 3.4: 9.1 O- perilenotetracarboxidiimide (POI 12)
    POl12 On a solution of POI 11 (30 mg, 0.023 mmol) in dichloromethane (0.5
    5 mL) trifluoacetic acid (0.1 mL, 1.3 mmol) is added. After stirring for 15 minutes at room temperature, the reaction is stopped by adding water and extracted with dichloromethane. The organic phase is dried with Na2S04, filtered and the solvent is removed under reduced pressure. It is purified by column chromatography with silica gel and CH2Cl2 / methanol (5: 0.5) as eluent
    10 obtaining the compound POl12 in the form of a black solid (25 mg, 86%).
    • 1H_ NMR (CDCI3) () 0.82 (t, 12H), 1.22 (br, 32H), 1.83 (br, 4H), 2.24 (br, 4H), 3.64 (d, 8H ), 3.89 (s, 8H), 5.16 (m, 2H), 6.72 (d, 2H), 7.66 (d, 2H), 8.02 (d, 2H), 8.21 (br, 2H), 8.43 (s, 2H), 8.60 (br, 2H)
    • 13C_RMN (CDCb) () 14.03, 22.58, 22.60, 26.89, 29.22, 29.68, 31.75,
    15 32.38, 45.25, 53.40, 54.70, 66.68, 107.25, 122.35, 127.35, 127.80, 127.93, 129.35, 129.51, 135 , 03, 137.78, 138.16, 138.98, 148.18, 158.73, 158.79, 163.61, 164.67
    • MALDI-TOF MS miz: [Mquot; Ht calculated C68HB4N804 1077.6688, experimental 1077.6453
    20 • IR (KBr): 3434, 2914,2844,1689,1660,1584,1485,1403,1316,1240, 1123, 948, 808 cm-1
    • UV Vis (CH2CI2), Amax / nm (Iog E): 451 (4.3), 595 (4.2)
    EiemDlo 13. N, N'-dicyclohexyl-1- [2 '- (4 "; -terc-butoxycarbonylpiperazin-1"; i) pyridin-5'-yl] -3.4: 9.1 O-perilenotetracarboxyidiimide (POI 13)
    POl13 THF: H20 (20: 2 mL) is added over a mixture of N, N'-dicyclohexyl-1-bromine
    5 3,4: 9,1 O-perilenotetracarboxidiimide (100 mg. 0.16 mmol) and Pd (PPh3) 4 (two spatula tips). The mixture is stirred for 5 minutes and 2 (4'-tert-butoxycarbonylpiperazin-1'-yl) pyridin-5-ylboro pinacolate (67 mg, 0.17 mmol) and cesium carbonate (168 mg, 0 , 47 mmol). After 24 hours at reflux, the mixture is extracted with dichloromethane and dried with Na2S04. The crude is purified by
    JO column chromatography (silica gel, CH2CI2: CH3CN), obtaining POI 13 as a dark violet solid (78 mg, 60%).
    • 1H_ NMR (COCI3) OR 1.50 -1.29 (m, 7H), 1.52 (s, 9H), 1.98 -1.68 (m. 11 H), 2.69 -2.43 (m. 5H), 3.76 -3.53 (m, 8H) , 5.13 -4.93 (m, 3H), 6.72 (d, J = 8.9 Hz, 1 H), 7.52 (dd, J = 8.8, 2.5 Hz, 1 H), 8.06 (d, J = 8.2
    15 Hz, 1 H), 8.20 (d, J = 8.2 Hz, 1 H), 8.31 (d, J = 2.5 Hz, 1 H), 8.66 -8.50 (m, 5H), 8.49 (s, 1 H)
    • 13C-NMR (CDCb) OR 25.59, 26.70, 26.73, 28.61, 29.24, 29.27, 44.87, 54.11, 54.23, 80.26, 107.69, 122.53, 122.73, 122.90, 123.07, 123.55, 123.70, 127.46, 127.55, 128.13, 128.20, 129.04, 129.27, 130.17,
    20 130.63, 131.04, 131.15, 132.21, 134.28, 134.49, 134.81, 136.01, 138.07, 138.63, 147.77, 154.92, 158.62, 163.74, 163.77, 163.82, 163.92, 163.96
    • MALOI-TOF MS miz: [Mt calculated C50H49N506 815.3683, experimental 815.3683
    25 • IR (KBr): 3464,2953,2851,1623,1559,1523,1326,1401,1356,1232, 1177,1191,995,901,823 cm1
    • UV Vis (CH2CI2), Amax / nm (Iog E): 484 (4.4), 521 (4.4) Eiemolo 14. N, N'-dicyclohexyl-1, 7 -di [2 '- (4quot; -terc-butoxycarbonylpiperazin1quot; -yl) pyridin-5'-yl] -3.4: 9.1 O-perilenotetracarboxidiimide (POI 14)
    POl14 THF: H20 (12: 1.2 mL) was added on a mixture of N, N'-dicyclohexyl-1,7
    5 dibromo-3,4: 9,10-perylenetetracarboxyidiimide (89 mg, 0.11 mmol) and Pd (PPh3) 4 (two spatula tips). The mixture is stirred 5 minutes and 2- (4'-tert-butoxycarbonylpiperazin-1'-yl) pyridin-5-ylboro pinacholate (89.5 mg, 0.23 mmol) and cesium carbonate (0.11 mg, 0.34 mmol). After 24 hours at reflux, the mixture is extracted with dichloromethane and dried with Na2S04. The crude is purified by
    10 column chromatography (silica gel, CH2Cb: CH3CN), obtaining POI 14 as a dark green solid (71 mg, 60%).
    • 1H-NMR (COCI3) or 1.39 (d, J = 37.9 Hz, 6H), 1.51 (s, 14H), 1.74 (d, J = 11.3 Hz, 5H), 1.90 (d, J = 12.4 Hz, 4H), 2.62 -2.45 (m, 5H), 3.75 3.51 (m, 15H), 5.07 -4.95 (m, 3H), 6.69 (d, J = 8.8 Hz, 2H), 7.59 (d, J
    15 = 8.6 Hz, 2H), 7.98 (d, J = 8.1 Hz, 2H), 8.18 (d, J = 8.1 Hz, 2H), 8.39 (s, 2H), 8.53 (s, 2H)
    • 13C-NMR (COCb) or 25.58, 26.69, 28.61, 29.28, 29.85, 44.87, 54.12, 80.28,107.53,122.44,123.08,127.28,127.86, 129.44, 129.56, 132.34, 135.01,135.23,137.86,138.55,148.32, 154.94, 158.63, 163.95
    twenty •. MALDI-TOF MS miz: [M +] theoretical for C64H6aNaOa 1076.5155, experimental 1076.5156
    • IR (KBr): 3446, 2924, 2851, 1696, 1658, 1589, 1492, 1409, 1319, 1236, 1167, 1122, 998, 929, 859, 811 cm-1
    • UV Vis (CH2CI2), Amax / nm (Iog e): 445 (4.1), 590 (4.0) 25
    EiemDlo 15. N, N '~ i (1'-hexylheptyl) -1- [2' - (4 "; -terc-butoxycarbonylpiperazin1quot; -yl) pyrimidin-5'-II] -3.4: 9.1 O- perilenotetracarboxidiimide (POI 15)
    v
    POl15 Pd (PPh3) 4 (13 mg, 0.012 mmol) is added on a suspension of N, N '
    5 di (1'-hexylheptyl) -1-bromo-3,4: 9, 1O-perylenetetracarboxyidiimide (100 mg, 0.12 mmol), 2- (4'-tert-butoxycarbonylpiperazin-1'-yl) pyrimidine pinacolate -5-iboro (55 mg, 0.14 mmol) and sodium carbonate (35 mg, 0.35 mmol) in a mixture of THF (10 mL) and water (1.25 mL) under argon. It is heated at 70c C overnight. The crude is dissolved in CH2Cb and washed with water. The
    The organic phase is dried with Na2S04, filtered and the solvent is removed under reduced pressure. It is purified by column chromatography with silica gel and CH2Cb / methanol (97: 3) as eluent to obtain compound POI 15 as a red solid (110 mg, 90%).
    • 1 H-NMR (COCI3) B 0.85 (t, 12H), 1.29 (br, 32H), 1.60 (s, 9H), 2.07 (br,
    15 4H), 2.36 (br, 4H), 3.58 (s, 1 H), 3.78 (s, 3H), 3.92 (s, 1 H), 4.22 (s, 3H) , 5.26 (m, 2H), 8.19 -8.29 (m, 1H), 8.47 -8.91 (m, 5H), 9.47 (s, 1H), 9.79 (s , 1 H), 9.88 (s, 1 H)
    • 13C-NMR (COCb) B 14.01, 14.06, 22.55, 22.57, 22.63, 27.19, 28.44, 28.51, 29.31, 29.36, 31, 73, 31.83, 43.75, 44.03, 54.75, 55.26, 80.15,
    20 80.22,112,13,120,39,122,38,122,72,123.27, 123.57, 124.87, 125.95, 126.37, 126.96, 127.83, 128.14, 129.02, 129.28 , 132.28, 133.45, 150.03,154.85,156.63,157.65,159.52,160.71, 163.57, 164.46
    • MALOI-TOF MS miz: [Mt calculated C63HaoN606 1016.6133, experimental 1016.6272
    25 • IR (KBr): 2920, 1695, 1654, 1590, 1520, 1421, 1321, 1246, 1164,808 cm-1
    • UV Vis (CH2CI2), Amax / nm (lag E): 438 (4.3), 466 (4.5), 543 (4.3)
    Eiemelo 16. N, N'-di (1 '-hexylheptyl) -1- [2' - (piperazin-1 '; -yl) pyrimidin-5'-yl] 3,4: 9,10-perylenetetracarboxyidiimide (POI 16 )
    v
    or not
    5 PDI16 On a solution of POI 15 (80 mg, 0.078 mmol) in dichloromethane (0.5 mL) trifluoacetic acid (0.33 mL, 4.6 mmol) is added. After stirring for 15 minutes at room temperature, the reaction is stopped by adding water and extracted with dichloromethane. The organic phase is dried with Na2S04, filtered and
    10 removes the solvent under reduced pressure. It is purified by column chromatography with silica gel and CH2Cl2 / methanol (6: 0.5) as eluent to obtain compound PDI16 as a red solid (65 mg, 92%).
    • 1H_ NMR (COCh) 00.81 (t, 12H), 1.25 (br, 32H), 1.82 (br, 4H), 2.20 (br,
    4H), 3.62 (s, 2H), 3.87 (s, 2H), 4.14 (s, 2H), 4.36 (s, 2H), 5.15 (m, 2H), 15 8 , 19 -8.29 (m, 1 H), 8.48 (m, 7H)
    • 13C-NMR (COCI3) B 14.02, 22.55, 26.88, 29.18, 29.68, 31.73, 32.33, 54.85,122.81,123.69,129.32,134,76,157.74, 160 , 54,163,44,164.45
    • EM MALOI-TOF miz: [Mt calculated CSSH72NS04 910,5609,
    Experimental 916,5546 20 • IR (KBr): 3434, 2932, 2844,1695,1654,1596,1321,1100,814 cm-1
    • UV Vis (CH2CI2), Amax / nm (lag E): 464 (4.3), 503 (4.3), 535 (4.4)
    Eiernolo 17. N, N'-di (1'-hexylheptyl) -1,7-di [2 '- (4 "; -terc-butoxycarboni1piperazin-1"; -yl) pyrirnidin-5'-yl] -3.4: 9.1 O-perilenotetracarboxidiirnide (POI 17)
    POI17
    5 Pd (PPh3) 4 (13 mg, 0.01 mmol) is added on a suspension of N, N'-di (1'hexylheptyl) -1.7 (6) -bromo-3,4: 9, 1 O -perilenotetracarboxidiimide (100 mg of the mixture of isomers in which the isomer 1,7, 0.10 mmol) predominates, 2- (4'-tert-butoxycarbonylpiperazin-1'-yl) pyrimidin-5-iIboro (100 mg, 0.25 mmol) and sodium carbonate (70 mg, 0.7 mmol) in a mixture of THF
    10 (10 mL) water (1.25 mL) under argon atmosphere. It is heated at 70 ° C overnight. The crude is dissolved in CH2CI2 and washed with water. The organic phase is dried with Na2S04, filtered and the solvent is removed under reduced pressure. It is purified by column chromatography with silica gel and CH2CI2 / methanol (100: 1) as eluent to obtain the compound
    15 POI 17 (pure 1.7 isomer) in the form of a red solid (40 mg, 30%).
    • 1H-NMR (CDCI3) () 0.82 (t, 12H), 1.22 (br, 32H), 1.51 (s, 18H), 1.82 (br, 4H), 2.23 (br, 4H), 3.58 (s, 8H), 3.92 (s, 8H), 5.15 (m, 2H), 8.09 (d, 2H), 8.12 (br, 2H), 8, 28 (s, 1 H), 8.53 (s, 5H)
    • 13C_RMN (CDCb) b 14.03, 22.58, 26.89, 28.44, 29.21, 31.74, 31.76,
    20 32.35, 43.74, 54.83, 80.15, 124.36, 124.80, 128.16, 128.83, 129.19, 129.49, 130.32, 132.26, 134 , 76, 135.92, 154.79, 157.97, 160.69, 163.31,164.34
    • MALOI-TOF MS miz: [M + Ht calculated C7sH9SN100S 1278,7563, experimental 1278,7936
    25 • IR (KBr): 2926, 2856,1706,1660,1596,1508,1321,1240,1164,1000 cm-1
    • UV Vis (CH2CI2), Amax / nm (Iog E): 438 (4.4), 570 (4.3)
    Eiemolo 18. N, N'-di (1'-hexylheptyl) -1,7-di [2 '- (piperazin-1 "; -yl) pyrimidin-5'-yl] 3,4: 9,10-perilenotetracarboxidiimide (POI 18)
    5 PDI18 On a solution of POI 17 (30 mg, 0.02 mmol) in dichloromethane (0.5 mL), trifluoacetic acid (0.1 mL, 1.3 mmol) is added. After stirring for 15 minutes at room temperature, the reaction is stopped by adding water and extracted with dichloromethane. The organic phase is dried with Na2S04, filtered and
    JO removes the solvent under reduced pressure. It is purified by column chromatography with silica gel and CH2Cb / methanol (5: 0.5) as eluent to obtain compound PDI18 as a red solid (22 mg, 80%).
    • 1H_ NMR (CDCI3) 00.82 (t, 12H), 1.26 (br, 32H), 1.89 (br, 4H), 2.20 (br,
    4H), 3.74 (br, 12H), 4.47 (s, 4H), 5.17 (m, 2H), 8.14 (s, 2H), 8.48 (s, 15 2H), 8 , 76 (s, 2H), 8.93 (s, 4H)
    • 13C-NMR (CDCI3) or 14.12, 22.67, 22.69, 26.96, 29.31, 29.77, 31.84, 32.47, 45.34, 53.49, 54, 79, 66.77, 107.34, 122.41, 127.44, 127.89, 128.02, 129.44, 129.60, 132.43, 135.12, 137.87, 138.28, 138.49, 139.07,148.00,148.27,158.82,158.88,163,70,164.76
    20 • MALOI-TOF MS miz: [M + Ht calculated C66Hs2N1004 1078.6515, experimental 1078.6745
    • IR (KBr): 3429, 2932, 2858, 1746, 1656, 1594, 1525, 1485, 1320, 1240, 1164, 1000, 808 cm-1
    • UV Vis (CH2Cb), Amax / nm (Iog E): 451 (4.4), 470 (4.4), 530 (4.4) 25 EiernDlo 19. N, N'-dicyclohexyl-1- [2 '- (4 "; -terc-butoxycarbonylpiperazin-1"; i) pyrirnidin-5'-yl] -3.4: 9, 1 O-perilenotetracarboxyidiirnide (POI 19)
    POl19 THF: H20 (20: 2 mL) is added over a mixture of N, N'-dicyclohexyl-1-bromine
    5 3,4: 9,1 O-perilenotetracarboxidiimide (100 mg, 0.16 mmol) and Pd (PPh3) 4 (two spatula tips). The mixture is stirred 5 minutes and 2 (4'-tert-butoxycarbonylpiperazin-1'-yl) pyrimidin-5-ylboro pinacholate (68 mg, 0.17 mmol) and cesium carbonate (168 mg, 0.47) are added mmol). After 24 hours at reflux, the mixture is extracted with dichloromethane and dried with Na2S04. The crude is purified by
    10 Column chromatography (silica gel, CH2CI2: CH3CN), obtaining POI 19 as a dark violet solid (81 mg, 60%).
    • 1H_ NMR (COCb) or 1.52 (s, 9H), 1.93-1.73 (m, 11H), 2.56-2.51 (m, 4H), 3.57 (s, 4H), 3.91 (s, 4H), 5.03-5.01 ( m, 2H), 8.08 (d, J = 8.2 Hz, 1H), 8.24 (d, J = 8.2 Hz, 1 H), 8.67 -8.32 (m, 7H)
    15 • 13C-NMR (COCI3) or 25.58, 26.69, 28.62, 29.27, 43.89, 54.16, 54.27, 122.85, 123.09, 123.46, 123.83, 123.91, 125.02, 127.64, 128.31, 129.21,129.28,130.40,131.04,131.38, 132.61, 134.38, 134.77, 135.45,135.74,154.96,157.77,160.84,163.99
    • EM MALOI-TOF mIz: [Mt calculated C49H48N606 816.3640, experimental 20 816.376
    • IR (KBr): 3496, 2925, 2867,1644,1567,1494,1312,1445,1325,1283, 1168, 1200, 983, 895, 816 cm1
    • UV Vis (CH2CI2), Amax / nm (Iog E): 459 (4.6), 537 (4.7)
    EiemDlo 20. N, N'-dicyclohexyl-1,7-di [2 '- (4 "-terc-butoxycarbonylpiperazin
    1 "-yl) pyrimidin-5'-yl] -3.4: 9.1 O-perylenetetracarboxyidiimide (POI 20)
    POI 20 THF: H20 (50: 5 mL) is added over a mixture of N, N'-dicyclohexyl-1.7
    5 dibromo-3,4: 9,1 O-perilenotetracarboxyidiimide (250 mg, 0.35 mmol) and Pd (PPh3) 4 (two spatula tips). The mixture is stirred 5 minutes and 2- (4'-tert-butoxycarbonylpiperazin-1'-yl) pyrimidin-5-iI boron pinacholate (289 mg, 0.74 mmol) and cesium carbonate (342 mg, 1 , 05 mmol). After 24 hours at reflux, the mixture is extracted with dichloromethane and dried with Na2S04. The crude
    10 is purified by column chromatography (silica gel, CH2Cb: CH3CN), obtaining POI 20 as a dark green solid (226 mg, 60%).
    • 1 H-NMR (COCb) or 1.46 -1.33 (m, 5H), 1.51 (s, 15H), 1.98 -1.66 (m, 13H), 2.53 (d, J = 12.0 Hz, 5H), 3.57 (s , 8H), 3.90 (d, J = 3.5 Hz, 9H),
    5.01 (s, 3H), 8.06 (d, J = 8.1 Hz, 2H), 8.27 (d, J = 8.2 Hz, 2H), 8.49 (d, 15 J = 2.4 Hz, 5H), 8.59 (s, 1H)
    • 13C-NMR (COCI3) or 24.94, 25.55, 26.67, 28.61, 29.26, 43.62, 43.87, 54.23,80.31,122.75,123.48,124.46,128.10, 129.33, 129.90, 132.28, 134.79,134.87,134.91,154.95,158.09, 160.84, 163.72, 163.80,
    •. EM MALOI-TOF miz: [M +] theoretical for C62H66N100B 1078.5065, experimental 20 1078.5060
    • IR (KBr): 3449, 2976,2931,2851,1700,1658,1586,1513,1413,1319, 1243, 1167, 1129,994,949,859,763 cm-1
    • UV Vis (CH2CI2), Amax / nm (lag e): 430 (4.2), 575 (4.3)
    Description of the figures
    Figure 1 - Fluorescence titration curves of compound POI 1 (concentration 5 x 10-6 M, CHCI3: MeOH 9: 1 v / v) with TATP (from O to 104 equivalents of T ATP)
    Figure 2 - Representation of the intensity of fluorescent emlslon of the compound POI 1 (concentration 5 x 10-6 M, CHCI3: MeOH 9: 1 v / v) as a function of the concentration of TATP (from O to 104 equivalents of TATP)
    Figure 3 - Fluorescence of compound POI 1 (concentration 5 x 10-5 M, CHCI3: MeOH 9: 1 v / v, 0.5 mL) before (left) and after the addition of 1.5 mg of TATP ( right)
    权利要求:
    Claims (32)
    [1]
    1.-A compound of structural formula I
    5 where:
    R3
    X = H ~
    , ~ J! ~ I4 Rs Rs R3 R¡quot; J (: Rs
    N ~ quot; 'fRs
    RS ~ N, R ~ l'R Rs
    Rs s each R1 and R3 independently represent hydrogen, halogen. C1-C20 alkyl. -CN. -COR7, -C02R7, -CONR7R7, -OR7 • -OCOR7, -SR7 • -NR7R7, -NR7 COR7, -SOR7 • -S02R7, -S02NR7R7 or CY1, where C1-C20 alkyl is independently optionally substituted by one or more Re And CY1 is
    10 optionally substituted by one or more Rg; each R2 independently represents C1-C40 alkyl or CY2; where C1-C40 alkyl is optionally substituted by one or more Re Y where CY2 is optionally substituted by one or more R1Q; Each R4 independently represents nitrogen or C-R3:
    Each Rs independently represents hydrogen, C1-C20 alkyl, -CN. -COR7, -C02R7 • -CONR7R7, -OR7. -OCOR7, -SR7, -NR7R7, -NR7 COR7, -SOR7 • -S02R7, -S02NR7R7 or CY1. where C1-C20 alkyl is independently optionally substituted by one or more Re and CY1 is optionally substituted by one or more Rg:
    20 each Rs independently represents -R11, -COR11 • -C02R11 • -S02R11; each R7 independently represents hydrogen, C1-C20 alkyl or CY4, where C1-C20 alkyl is optionally substituted by one or more R14 and where CY4 is optionally substituted by one or more R15;
    or two R7 groups can be joined to form a heterocycle with the N atom
    5 to 5 to 7 saturated members which may additionally contain a heteroatom selected from N, O and S, Y which may be optionally substituted by one or two R15; each R8 independently represents CY3, -OR12, -SR12 or -NR12R12, where CY3 is optionally substituted by one or more Rg;
    Each R10 independently represents C1-C40 alkyl, CY4, -OR12, -SR12 or -NR12R12, where C1-C40 alkyl is optionally substituted by one or more R13 and where CY4 is optionally substituted by one or more Rg; each R11 independently represents H, C1-C10 alkyl or CY3, where C1-C10 alkyl is optionally substituted by one or more -OH, -OC1-C4 alkyl
    15 and where CY3 is optionally substituted by one or more C1-C6 alkyl; each R12 independently represents hydrogen, C1-C6 alkyl or CY3, where C1-C6 alkyl is optionally substituted by one or more -OH, -OC1-C4 alkyl, where C1-C4 alkyl is optionally substituted by one or more -OH and where CY3 is optionally substituted by one or more
    C1-C6 alkyl; each Rg and R15 independently represent R12, -OR12, -SR12 or -NR12R12; each R13 and R14 independently represent -OR12, -SR12, -NR12R12 or CY3, where CY3 is optionally substituted by one or more C1-C6 alkyl; each CY1 and CY3 independently represent phenyl or a heterocycle
    A 5 or 6 membered aromatic containing 1 to 3 heteroatoms selected from N, O, and S, where each CY1 and CY3 can be independently linked to the rest of the molecule through any available C or N atom; each CY2 independently represents a partially saturated ring
    30 unsaturated or aromatic, monocyclic of 3 to 7 members or bicyclic of 6 to 11 members that can be carbocyclic or heterocyclic, where CY2 can be attached to the rest of the molecule through any available C or N atom, where CY2 contains 1 to 4 heteroatoms selected from N, OYS, Y where one or more C or S atoms of CY2 may optionally be
    Oxidized forming CO, SO or S02 groups; and each CY4 independently represents a saturated carboxylic or heterocyclic ring, partially unsaturated or aromatic with 3 to 7 members, optionally containing 1 to 4 heteroatoms selected from N, OYS, where CY4 is attached to the rest of the molecule through any atom of available C or N, and where one or more C or S atoms of CY4 may optionally be oxidized forming ca, SO or S02 groups;
    5 ace! as its regioisomers, and mixtures of two or more compounds of formula
    one.
    [2]
    2.-Compound according to claim 1, wherein X is hydrogen.
    3. 3. Compound according to claim 1, wherein X is
    R3
    Xi4
    RsRs R3 R4quot; quot; quot; J (: Rs
    N- ~ Rs
     Rs ~ N,
    ROs l'R Rs Rs s
    [4]
    4.-Compound according to claim 1 to 3, wherein R4 is C-R3.
    [5]
    5.-Compound according to claim 1 to 3, wherein R4 is nitrogen.
    [6]
    6.-Compound according to claim 1 to 3, wherein one R4 of the aromatic ring is C-R3 and the other R4 is nitrogen.
    [7]
    7.-Compound according to any of claims 1 to 6, wherein each R3
    20 independently represents hydrogen, halogen, C, -C20 alkyl, -OR7, -SR7, -NR7R7, -SOR7, -S02R7 or Cy1. where C, -C2o alkyl is independently optionally substituted by one or more Ra Y Cy, is optionally substituted by one or more Rg, and where R1, R2, R5, R6, R7, Ra, Rg and CY1 have the same meaning as in claim 1
    8. A compound according to any one of claims 1 to 6, wherein R3 is hydrogen.
    [9]
    9.-Compound according to any of claims 1 to 8, wherein each R5
    30 independently represents hydrogen, C, -C20 alkyl, -CN, -COR7, -C02R7, -CONR7R7, -OR7, -SR7, -NR7R7, -SOR7, -S02R7
    5 or Cy. where C, -C20 alkyl is independently optionally substituted by one or more Ra and Cy, is optionally substituted by one or more Rg, and where R1, R2 • Re, R7, Ra, R9, R1o, R11, R12 • R13 • R14 • R15, CY1, CY2, CY3 and CY4 have the same meaning as in claim 1. 10.-Compound according to any of claims 1 to 8. wherein R5 is hydrogen.
    10 11.-Compound according to any of claims 1 to 10, wherein R1 is hydrogen, halogen, C1-C20 alkyl. -OR7. -SR7, -NR7R7, -SOR7 • -S02R7 or Cyquot; where C1-C20 alkyl is optionally substituted by one or more Ra and CY1 is optionally substituted by one or more Rg, and where R2. R6, R7. Ra, Rg and CY1 have the same meaning as in claim 1.
    fifteen 12.-Compound according to any of claims 1 to 11, wherein each R2 independently represents C1-C40 alkyl or CY2; where C1-C40 alkyl is optionally substituted by one or more Re Y where CY2 is optionally substituted by one or more R1o.
    twenty 13.-Compound according to any of claims 1 to 11, wherein each R2 is a 1-hexylheptyl chain.
    25 14. A compound according to any one of claims 1 to 11. wherein each R2 is a 2,5-di-t-butylphenyl ring. 15.-Compound according to any of claims 1 to 11. wherein R2 is a cyclohexyl ring.
    3 o 16.-Compound according to any of claims 1 to 15, wherein Rs independently represents H, -R11 • -COR11, -C02R11. -S02R11.
    [17]
    17.-Compound according to any of claims 1 to 16, wherein each R7 independently represents hydrogen. C1-C20 alkyl or CY4.
    35 18. Compound according to any one of claims 1 to 16, wherein two R7 groups can be joined to form a saturated 5- to 7-membered heterocycle with the N atom which additionally can contain a heteroatom
    selected from N, O Y S, Y which may be optionally substituted by
    one or two R15.
    [19]
    19.-Compound according to any of claims 1 to 18, wherein each Rg independently represents R12.
    [20]
    20.-Compound according to any one of claims 1 to 19, wherein each R10 independently represents Cl-C40 alkyl optionally substituted by one or more R13.
    [21]
    21.-Compound according to any of claims 1 to 20, wherein each Rll independently represents H or Cl-ClO alkyl, wherein Cl-Cl0 alkyl is optionally substituted by one or more -OH or -OC1-C4alkyl.
    [22]
    22.-Compound according to any one of claims 1 to 20, wherein each Rll independently represents CY3 optionally substituted by one or more Cl-CS alkyl.
    [23]
    23.-Compound according to any of claims 1 to 22, wherein each R12 independently represents Cl-C6 alkyl optionally substituted by one or more -OH, -OC1-C4 alkyl, and wherein Cl-C4 alkyl is optionally substituted by one or more -OH.
    [24]
    24.-Compound according to any of claims 1 to 23, wherein each R13 independently represents -OR12 or CY3, wherein CY3 is optionally substituted by one or more Cl-CS alkyl.
    [25]
    25.-Compound according to any of claims 1 to 24, wherein each R14 independently represents -OR12 or CY3, wherein CY3 is optionally substituted by one or more Cl-C6 alkyl.
    [26]
    26. A compound according to any one of claims 1 to 25, wherein each R15 independently represents R12.
    [27]
    27. A compound according to any one of claims 1 to 26, wherein each CYl independently represents phenyl.
    [28]
    28. A compound according to any one of claims 1 to 27, wherein each CY2 independently represents a saturated carbocyclic or heterocyclic 3 to 7 monocyclic ring, where CY2 can be attached to the rest of the molecule through any C or N atom available, and where CY2
    5 contains 1 to 3 heteroatoms selected from N, O and S.
    [29]
    29.-Compound according to any of claims 1 to 28, wherein each
    CY3 independently represents phenyl.
    30. A compound according to any one of claims 1 to 28, wherein each CY3 independently represents a 5- or 6-membered aromatic heterocycle containing 1 or 2 heteroatoms selected from N, OYS, and where CY3 can be attached to the rest of the molecule through any available C or N atom.
    31. A compound according to any of claims 1 to 3D, wherein each CY4 independently represents a saturated carbocyclic or heterocyclic ring, of 3 to 7 members, optionally containing 1 to 3 heteroatoms selected from N, OYS, and where CY4 is attached to the rest of
    20 the molecule through any available C or N atom.
    [32]
    32. A method of preparing the compounds of structural formula 1, their regioisomers and mixtures thereof, comprising reacting a compound of structural formula 11, their
    25 regioisomers and mixtures thereof, with a compound of structural formula 111, its regioisomers and mixtures thereof,
    R2
    I
    N
    where:
    every R1. R2, R3, R4, Rs and R6 independently have the same meaning
    than in claim 1;each R16 independently represents hydrogen, halogen or OS02R18with the proviso that the two R16 cannot be hydrogen at the same timeR17 represents -B (OR19) (OR19), -SnR19R19R19;R18 represents C1-C10 alkyl, -CF3, -C4F9, -CH2 CF3 or CYs, where CYs isoptionally substituted by one or more halogens, C1-C4 alkyl or N02;each R19 independently represents hydrogen, C1-C10 alkyl or phenyl,where C1-C1O alkyl is optionally substituted by one or more R11
    or two R19 groups can be joined to form a saturated 5- to 7-membered heterocycle with the atom of B and the atoms of O which may additionally contain a heteroatom selected from N, O and S, Y which may be optionally substituted by one or more R11; Each CY5 represents phenyl.
    [33]
    33. Method according to claim 32, wherein R4 is C-R3.
    [34]
    34. Method according to claim 32, wherein R4 is nitrogen.
    [35]
    35. Method according to claim 32, wherein one R4 of each aromatic ring is C-R3 and the other R4 is nitrogen.
    [36]
    36. Method of any of claims 32 to 35, wherein R3 is hydrogen.
    [37]
    37. Method according to any of claims 32 to 36, wherein Rs is hydrogen.
    [38]
    38. Method according to any of claims 32 to 37, wherein each R2 is a 1-hexylheptyl chain.
    [39]
    39. Method according to any of claims 32 to 37, wherein each R2 is a 2,5-di-t-butylphenyl ring.
    [40]
    40. Method according to any of claims 32 to 37, wherein R2 is a cyclohexyl ring.
    [41]
    41. Method according to any of claims 32 to 40, wherein R6 independently represents H, -R11, -COR11, -C02R11, -S02R11.
    5 42. Method according to any of claims 32 to 41, wherein R1 is H.
    10 43. Method according to any of claims 32 to 42, wherein each R11 independently represents H or C1-C1O alkyl, wherein C1-C10 alkyl is optionally substituted by one or more -OH or -OC1-C4 alkyl. 44. Method according to any of claims 32 to 43, wherein one R16 is an atom selected from chlorine, bromine or iodine, and the other R16 is an atom selected from hydrogen, chlorine, bromine or iodine.
    ] 5 45. Method according to any of claims 32 to 43, wherein one R16 is a bromine atom, and the other R16 is an atom selected from hydrogen or bromine.
    twenty 46. Method according to any of claims 32 to 45, wherein R17 is -B (OR19) (OR19).
    25 47. The method according to any of claims 32 to 46, wherein R19 independently represents hydrogen, C1-C1O alkyl or phenyl, wherein C1-C1O alkyl is optionally substituted by one or more R11 or two R19 groups can be joined forming the atom of B and the atoms of O a saturated 5- to 7-membered heterocycle, and which may be optionally substituted by one or more R11.
    (~
     And ri
    or
    Q) quot; 'C
    o ~% (h
    z ~
    or
    quot; 'C
    (Il
    and
    Or V ~
    quot; 6
    () (z
    Q)
    Q)
    z ~
    Vl
    gt;
    Vl
    - O (2
    Q) :::: l
    z ~
    C.
    AND
    O ~
    ()
    e =: J
    CX)
    -q-
    POI 14
    POI 13
    POI 20POI 19
    [49]
    49.-Use of a compound of structural formula 1, or of a mixture of regioisomers of formula 1, or of a mixture comprising any of the compounds of formula I in any proportion as oxidizing agent detectors.
    [50]
    50. Use according to claim 49, wherein the oxidizing agent is an oxidizing explosive.
    [51]
    51. Use according to any of claims 49 to 50, wherein the oxidizing explosive agent is acetone triperoxide (TATP).
    160 140
    120:; ca
    ~ 1oo
    UJ
    ~
    .5 80
    .¡¡¡ 60
    ~
    40twenty
    525 550 575 600 625 650 675 700
    Wavelenglh (nm)
    Figure 1
    11 m
    ~ o, o.'quot; or ...
    ~ 'quot; ~ 'quot;
    [TAWJ. M
    Figure 2
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    公开号 | 公开日
    WO2017109264A1|2017-06-29|
    ES2619109B2|2017-10-04|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20130078731A1|2011-09-23|2013-03-28|Jawaharlal Nehru Centre For Advanced Scientific Research|Chromophores for the detection of volatile organic compounds|
    CN103159764A|2011-12-16|2013-06-19|宁波大学|Photo-electricity function material-perylene bisimide type derivative and preparation method thereof|
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