ES2619109B2 - 1 - (Piperazin-n-ylaryl) - and 1, 7-Di (Piperazin-n-ylaryl) Perylene -3, 4: 9, 10-Tetracarboxyidiimides, their preparation procedure and their use as oxidizing explosive detectors - Google Patents

Abstract

1- (Piperazin-N-ylaryl) - and 1,7-di (piperazin-N-ylaryl) perylene-3,4: 9,10-tetracarboximides, preparation process thereof and their use as oxidizing explosive detectors. #The present invention relates to perylene-3,4: 9,10-tetracarboximide derivatives of formula I, wherein the meaning for X, R {sub, 1}, R {sub, 2}, R {sub, 3} , R {sub, 4}, R {sub, 5}, R {sub, 6} is the one indicated in the description, a procedure for preparing said derivatives and their use as detectors of oxidizing agents, including oxidizing explosives.

Description

1- (PIPERAZIN-N ~ LARIL) AND 1,7-DI (PIPERAZIN-N-ILARIL) PERYLENE

3,4: 9,10-TETRACARBOXIDIIMIDAS, PROCEDURE OF

PREPARATION OF THE SAME AND ITS USE AS DETECTORS OF

OXIDIZING EXPLOSIVES

5

Technical Sector

The present invention relates to perilenediimide derivatives of

10

formula l. characterized by being substituted in position 1 or in the

positions 1 and 7, to a procedure for preparing them and their

use as sensors of oxidizing agents, including explosives

oxidizers

fifteen

State of the hf! Cnlca

Triacetone Iriperoxide (triacetone triperoxide, TATP) is a powerful

explosive without military utility due to its sensitivity to mechanical impact,

being, however, widely used by terrorists because of its fictile

twenty

preparation and its difficult tracking by explosive detector dogs, which

They are trained to identify 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 it has

2S

TAMP day in the lives of millions of people.

TATP traces can be detected using infrared spectroscopy,

mass spectrometry or ionic mobility spectrometry, but the

TATP characteristic signals are only clearly visible using

30

Large mass spectrometry equipment. The use of chains of

device-based chemically modified nanosensors

nanoelectric has meant an advance in the discriminated detection of

explosive species, although it is a complex methodology. In

As for simpler methodologies, there are portable optical methods

35

based on chains of calorimetric sensors that detect peroxide from

hydrogen from the decomposition of TATP. Also they have been

developed chemical systems for indirect TATP detection, which

they use hydrogen peroxide to oxidize some chemical species giving

origin either to the appearance of a fluorescent species or to the suppression

(quenching) of the fluorescence of the initial molecule. It is evident that the

search for a specific portable fluorogenic probe for easy detection

5

And direct from TATP, and not the indirect detection of its products from

decomposition. without the use of large and expensive equipment is a

Unsolved problem.

These and other properties and characteristics of TATP and its methods of

JO

detection are collected in monographs and scientific articles,

such as (a) http://thefutureofthings.com/3035-tatp-countering-the-mother

of-satan /, accessed in August, 14.2015. (b) Faina Oubnikava, Ronnie Kosloff,

Joseph Almog, Yehuda Zeiri, Ro land Boese, Harel Itzhaky, Aaran Alt, and

Ehud Kainan, J. Am. Chem Soe. 2005, 127, 1146-1159. (e) EU Avial ion

fifteen

Security Regulations and Screening of Uquids, Aerosols and Gels (LAGS),

Rapiscan Systems, OSI Systems, Inc., www.rapiscansystems.com. accessed

in Augusl, 14, 2015. (d) Magnus Ranslorp and Magnus Normark, Eds .:

Understanding Terrorism Innovation and Leaming: AI-Qaeda and Beyand,

2015 -Routledge, Taylor & Francis Group LLC, 7625 Empire Orive, Florence,

twenty

Kenlueky 41042-2919, USA, Chapler 1, pp. 1-15 and retain Iherein. (and)

Leonardo C. Pacheco-Londoño, John R. Castro-Suarez, and Samuel P.

Hernandez-Rivera Detection of Nitroaromatic and Peroxide Explosives in Air

Using Infrared Spectroscopy: QCL and FTIR, Advances in Oplical

Technalogies, Volume 2013, Article ID 532670, 8 pages,

25

http://dx.doi.org/10.1 155/2013/532670. (t) Marko Makinen, Marjaana

Nousiainen, and Mika Sillanpaa, ion spectrometric detectian technologies tor

ultra-traces of explosives: a review. Mass Spectrometry Reviews, 2011, 30,

940973. (g) Amir Liehlenslein, Ehud Havivi, Ronen Shaeham, Ehud

Hahamy, Ronit Leibovich, Alexander Pevzner, Vadim Krivitsky, Guy Davivi,

30

Igor Presman, Roey Elnathan, Yoni Engel, EH Flaxer, Fernando Patolsky,

Supersensitive fingerprinting of explosives by ehemiealiy moditied

nanosensors arrays, Nature Communications 5, Article number: 4195,

doi: 10.1038 / ncomms5195, 09 July 2014. (h) Hengwei Lin and Kennelh S.

Suslick, A Colorimetric Sensor Array for Detection of Triacetone Triperoxide

35

Steam, J. Am. Chem. Soe. 2010, 132, 15519-15521. (i) Miao Xu, Ji-Min Han,

Chen Wang, Xiaomei Yang, Jian Pei, and Ung Zang, Fluorescence

Ratiometric Sensor for Trace Vapor Detection 01 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 diimides of the perylene-3,4,9,10-tetracarboxylic acid, also known as perylenediimides (PDI) or as perylene bisimides (PSI), begin to have A relevant role. 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 substitutes, so that said POI 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. (e) A. Herrmann, K. Müllen. Chem, Lett. 2006,35, 978-985. (d) T, Fu, x'-H, Zhao, H, -R Bai, Z.-L. Zhao, R. Hu, R, -M. Kong, X, B, Zhang, W, Tan, R.-O. 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 (PDI), substituted in their positions 1 or 1 and 7 by nitrogen substitutes, 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 stability

chemical and optical, which allows its use in the detection of these molecules (including TATP).

Thus, in a first aspect the present invention relates to a compound of

Formula 1:

where:

R,

X = H ~

. J! ~~ 4 R, R,

R, R. '-) (: R,

N-quot; fR, R, ..., l ... N, R ~ 1'-R R. R, '

each R, and RJ independently represent hydrogen, halogen, e, -e20

alkyl, -CN, -CORquot; -CO, Rquot; -CONR, Rquot; -ORquot; -OCORquot; -Srquot; -NR, Rquot; -NR,

10 COR7, -SOR -S02R7. -S02NR7R7 or Cy ,. where e, -e20 alkyl is quot;

independently optionally substituted by one or more Re and Cy, is optionally substituted by one or more Rg; each R2 independently represents C1-C40 alkyl or CY2: where e, -c.m alkyl is optionally substituted by one or more Re and where CY2 is

15 optionally substituted by one or more RlO: each R4 independently represents nitrogen or C-R3: each Rs independently represents hydrogen, C1-C20

alkyl, -CN, -CORquot; -CO, Rquot; -CONR, Rquot; -ORquot; -OCORquot; -Srquot; -NR, Rquot; -NR,

COR7, -SOR7 • -S02R7. -S02NR7R1 or CY1, where C1-C20 alkyl is independently optionally substituted by one or more Rs and CY1 is optionally substituted by one or more Rg:

each R6 independently represents -R11o -COR'l. -C02R, 1. -S02R ,,; each R7 independently represents hydrogen, el-e20 alkyl or CY-4. where l-e20 alkyl is optionally substituted by one or more R'4 and where CY4 is optionally substituted by one or more R, s;

or two R7 groups can be joined to form a saturated 5- to 7-membered helerocycle with the alomo of N which may additionally contain a heleroalomo selected from N, O, and S, Y which may be optionally substituted by one or two R, s; Each Re independently represents CY3. -OR12, -SR12 or -NR12R12, where CY3 is optionally substituted by one or more Rg; each RlO independently represents C, -C40 alkyl, CY4, -OR'2. -SR'2 0NR, 2R12, where Cl ~ C40 alkyl is optionally substituted by one or more R13 and where CY4 is optionally substituted by one or more Rg; each Rll independently represents H, C1-C, Oalkyl or CY3, where Cl ~ CIO alkyl is optionally substituted by one or more -OH, -OC1-C4 alkyl and where CY3 is optionally substituted by one or more C, -C6 alkyl; each R1.2 independently represents hydrogen, C1-C6 alkyl or CY3, where C, -C6 alkyl is optionally substituted by one or more -OH I -OC, -C4 alkyl. where C1 · C4 alkyl is optionally substituted by one or more -OH and where CY3 is optionally substituted by one or more C'-C6 alkyl; each Rg and R'5 independently represent R12, -OR'21 -SR'2 or -NR, 2R12: each R13 and R'4 independently represent -OR'2, -SR12, -NR, 2R12 or CY3, where CY3 is optionally substituted by one or more e, -ce alkyl; each Cy, and Cy, independently represent phenyl or a 5- or 6-membered aromatic heterocycle containing 1 to 3 heteroatoms selected from N, ° YS, 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 ring, partially 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, where CY2 contains 1 to 4 heteroatoms selected from N, OYS, and where one or more C or S bundles of CY2 can be optionally oxidized forming CO, SO or 802 groups: and each CY4 independently represents a ring saturated carbocyclic or heterocyclic, partially saturated 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

5 any available e or N atom, and where one or more CY4 e or S atoms may optionally be oxidized forming CO, SO or 502 groups: as well as their regioisomers, and mixtures of two or more compounds of formula

l.

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. which comprises 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 R ,. R2. R3 "Rs and R6 independently have the same meaning as in claim 1;

20 each R'6 independently represents hydrogen, halogen or OS02R'8 with the proviso that the two R'6 cannot be hydrogen at the same time; R17 represents -B (OR 9) (OR 9), -SnR19R 9R'9:

''

'

R'6 represents C, -C'0 alkyl. -CF3 • -Cquot; F9 • -CH2CF3 or CYs, where CYs is optionally substituted by one or more halogens. C, -Cquot; alkyl or N02: each R9 independently represents hydrogen, C, -C'0 alkyl or tenUo,

'where C, -C'0 alkyl is optionally substituted by one or more Rl1

or two R19 groups can be joined forming with the atom of B and the atoms of

Or a saturated 5- to 7-membered heterocycle that can additionally

contain a heteroatom selected from N, O, and S, and that may be

optionally substituted by one or more R11;

5

Each CYs 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 a mixture comprising any of the compounds of

10

Formula I in any proportion as oxidizing agent detectors.

In the context of the present invention, the term ~ regioisomers ~ refers to

to position isomers that have the same functional group or substituent

in different positions; that is, the regioisomers have the same formula

fifteen

molecular but different chemical and physical properties.

Throughout the present invention ~ Cl · C40 alkyl ~, uC1-C20 alkylquot ;, uC1-C10

rent, quot; C I-C6 rent and ~ C1-C4 alkyl ~, as a group apart from a group,

independently refer to a straight chain alkyl group or

twenty

branched containing 1 to 40, 1 to 20, 1 to 10, 1 to 6 and 1 to 4

We tie C respectively. quot; C, -C4 alkyl; includes methyl, etyl groups,

propyl, isopropyl, butyl, isobutyl, sec-butyl and teft-bulyl; quot; Cl-C6 alkyl;

includes the groups of uC, _C4alkyl ~ and, among others, pentyl, iso-pentyl, sec

pentyl, neo-penyl, 1,2-dimethylpropyl, hexyl, iso-hexyl and sec-hexyl: quot; C1-C20

2S

alkyl · includes the groups of "C, -C, alkyl"; and, among others, heptyl, iso-heptyl,

octyl, iso-octyl, 2-etiJhexyl, nonyl, decyl and dodecyl, 2-propylheptyl, 2

butylnonyl, 3-butylnonyl and 2-hexylheptyl; quot; C, -C40 alkyl; includes groups

quot; C, -C20 alkyl; and, among others, trideci lo and tetradecilo.

30

CYl and CY3 independently refer to a phenyl or a heteroaryl of

5 or 6 members containing 1 to 3 heteroatoms selected from N, O Y

S. Cy, and CY3 bind to the rest of the molecule through any C atom

or N of the available ring. In addition, CYl and CY3 can be optionally

substituted as indicated in the definition of formula 1, the

35

substituents may be the same or different and may be located in

any available position of the ring system. Examples include, between

others, phenyl, thienyl, furyl, pyrrolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl,

imidazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,3,4-oxadiazolyl, 1,3,4thiadiazolyl, 1,2,4-oxadiazolyl, 1,2,4-liadiazolyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl.

CY2 refers to a monocyclic ring of 3 to 7 members or bicyclic of 6 to 11 members 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 rings fused through two adjacent atoms of eo N, or through two non-adjacent atoms of eo N forming a bridge ring, or they can be formed by two rings joined through a single atom of e forming an espirano type 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 bundles of CY2 may optionally be oxidized forming groups CO, SO

or S02_ In addition, CY2 may be optionally substituted as indicated in the definition of a compound of formula I. if substituted, the substituents may be the same or different and may be located in any available position of the ring system. Examples include, among others, cyclopropyl, cyclolabyl, cyclopenyl, cyclohexyl, cycloheptyl, azetidinyl, aziridinyl, oxyranyl, oxetanyl. imidazolidinil0, isothiazolidinyl, isoxazolidinyl, oxazolidinyl, pyrazolidinyl, pyrrolidinyl, thiazolidinyl, dioxanila, morpholinyl, tiomarfoli nila, 1,1-dioxotiomorfalinilo, piperazinyl, homopiperazin yl, piperidinyl, pyranyl, tefrahidropiranilo, homopiperidin yl, oxazinyl, oxazolinila, pyrrolinyl, thiazolinyl, pyrazolinyl , imidazolinyl, isoxazolinyl, isothiazolinyl, 2oxo-pyrrolidinyl, 2-oxo-piperidinyl, 4-oxo-piperidinyl, 2-oxo-piperazinyl, 2oxa-1,2-dihydropyridyl, 2-oxo-1,2-dihydropyrazinyl, 2-oxo -1,2-dihydropyrimidinyl, 3-oxo-2,3-dihydropyridazyl, phenyl, naflyl, thienyl, furyl. pyrrolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, imidazolyl, pyrazolyl0, 1,2,3-triazolyl. 1,2,4-triazolyl, tetrazolyl0, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl, 1,2,4-oxadiazolyl, 1,2,4-thiadiazolyl, pyridyl. pyrazinyl, pyrimidinyl, pyridazinyl, benzimidazolyl, benzooxazolyl, benzofuranyl, isobenzofuranyl. indolyl, isoindolyl, benzothiophenyl, benzothiazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, cinolinyl, naphthyridinyl. indazolyl, imidazopyridinyl, pyrrolopyridinyl, thienopyridinyl, imidazopyrimidinyl, imidazopirazinilo, imidazopyridazinyl, pirazolopirazinilo, pyrazolopyridinyl, pyrazolopyrimidinyl, benzo [1,3] dioxolyl, phthalimidyl, 1-oxo-1,3-dihidroisobenzofuranil0, 1,3-dioxo1, 3-d ih idroisobenzofurani lo, 2-oxo-2,3-dihydro-1 H-indolyl, 1-oxo-2,3-dihydro1 H-isoindolyl, perhydroquinolinyl, 1-oxo-perhydroisoquinolinyl, 1-QXQ-1,2-dihydroisoquinolinyl, 4-oxo -3,4-dihydroquinazolinyl, 2-8zabicyclo (2.2.1] heplanyl, 5-aza-bicyclo (2.1.1] hexanyl, 2H-spiro (benzofuran3,4'-piperidinyl], 3H-spiro [isobenzofuran-1,4 '-piperidinyl], 1-oxo-2, Bdiazapiro [4.5] decanyl and 1-oxo-2, 7-diazaspiro [4.5] decanyl.

In the previous 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 saturated or aromaticQ, which can be carbocyclic or heterocyclic. If it is heterocyclic, it contains 1 to 4 heteroatoms selected from N, O, and S that may be optionally oxidized to form ca, so or S02 groups. CY4 binds to the rest of the molecule through any available e 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, oxyranyl, oxetanyl, imidazolidinyl, isothiazolidinyl. isoxazolidinyl, oxazolidinyl, pyrazolidinyl, pyrrolidinyl, thiazolidinyl, dioxanyl, morpholinyl, thiomorpholinyl, 1, 1-dioxothiomorpholinyl, piperazinyl, homopiperazin yl, piperidinyl, pyranyl, tetrahydropyranyl, homopiperidinyl, oxazinyl, oxazolinyl, pyrrolinyl, thiazolinyl, pyrazolinyl, imidazolinyl, isoxazolinyl, isothiazolinyl , 2oxo-pyrrolidinyl, phenyl, lienyl, 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, pyrimidinyl and pyridazinyl.

When the specified examples refer to a ring radical in general terms, for example pyridyl, thienyl or indolyl, in the definitions used throughout the present description for clinical groups, all possible binding positions are included. Thus, for example, in the definitions of Cy, to CY4, which do not include any limitation regarding the binding position, the

Pyridyl term includes 2-pyridyl, 3-pyridyl and 4-pyridyl: and lienyl includes 2-lienyl and 3-lienyl.

5 10

The expression quot; optionally substituted by one or masquot; means the possibility 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 02 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.

I S

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 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.

twenty

In one aspect, the present invention relates to a compound of formula structure 1, as previously defined, as well as its regioisomers and mixtures of two or more compounds of formula 1.

In a particular embodiment, hydrogen.

in the compound of formula 1, X is

2S

In another particular embodiment, in the compound of formula 1, X is R,: -: eJ 'R'R, R, R4 ";"; -NX, fRs R, -J ..... N ': R', 1'-RR, R, '

In a particular embodiment, in the compound of formula 1, R, is CR ,.

30

In another particular embodiment, in the compound of formula 1, R4 nitrogen. is

In another particular embodiment, in the compound of formula 1, the aromatic ring is C-R3 and the other R4 is nitrogen.

a R, s

5 10

In a particular embodiment, in the compound of formula 1, RJ independently represents hydrogen, halogen, e1-e20 alkyl, -ORT, -SR7, -NR7 R7, -SOR7, -S02R7 or CY1, where C1-C20 alkyl is independently optionally substituted by one or more Ra and CYl is optionally substituted by one or more R g, and where R l. R2, Rs. Rs. R7 Ra. Rg and CYl have the same meaning as for the compound of formula l.

In a preferred embodiment, R3 is hydrogen.

15 20

In another particular embodiment, each Rs independently represents hydrogen, C1-C20 alkyl, -eN, -COR7. -C02R7, -CONR7R7. -OR7, -SR7, -NR7R7, -SOR7, -S02R7 or Cyl, where C1-C20 alkyl is independently optionally substituted by one or more Re and CY1 is optionally substituted by one or more Rg, and where Rquot; R2, R6. R7 Ra. Rg, RlO, R11, R12 • R13 • R14 • R15, CY1, CY2. CY3 and CY4 have the same meaning as for the compound of formula 1.

In a preferred embodiment, Rs is hydrogen.

2S

In a particular embodiment of the present invention, R, is hydrogen, halogen, C, -C20 alkyl, -ORquot; -Srquot; -NR, Rquot; -SORquot; -SO, R, or Cyquot; where C1-C20 alkyl is optionally substituted by one or more Rs and CYl is optionally substituted by one or more Rg, and where R2 • Rs, R7. Ra. Rg and CYl have the same meaning as for the compound of formula l.

30

In another particular embodiment, each R2 independently represents C, -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.

35

In a preferred embodiment, each R2 is a 1-hexylheptyl chain.

In another form butylphenyl.

of preferred embodiment, each R2 is a 2,5-di-l ring

5

In another preferred embodiment. Each R2 is a cyclohexyl ring. In a particular embodiment of the present invention, Rs independently represents H, -RIl or -COR11 • -C02RI1 • -S02Rt 1.

10

In another particular embodiment, R7 independently represents hydrogen, C1-C20 alkyl or CY4.

I S

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 that may be optionally substituted by one or two R1 5.

In one form it represents R'2.

from realization particular, every Rg independently

twenty

In another particular embodiment, each R, or independently represents C, -C40 alkyl optionally substituted by one or more R, Jo

25

In a preferred embodiment, each Rquot; represents H or C, -C 10 alkyl, where C \ -ClO alkyl substituted by one or more -OH or -OC, -C4 alkyl. independently it is optionally

In another preferred embodiment, each Rquot; independently represents CYJ optionally substituted by one or more C, -C6 alkyl.

30

In a form representing C, -C6 plus -OH, -OC, -C, particular embodiment, each R'2 independently alkyl optionally substituted by one or alkyl, and where C, -C4 alkyl is optionally substituted by one or more - OH

35

In another particular embodiment, each R, J independently represents -OR'2 or CYJ, where CY3 is optionally substituted by one or more c, -e6 alkyl.

'3

In another particular embodiment, each R14 independently represents -OR12 or CY3. where CY3 is optionally substituted by one or more et · is alkyl.

In another particular embodiment, each R15 independently represents R12_

In a preferred embodiment, each CY1 independently represents tenyl.

In a particular embodiment, each CY2 independently represents a monocyclic saturated ring of 3 to 7 carbocyclic or heterocyclic members, where CY2 can be attached to the rest of the molecule through any available atom of N, 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 CYJ independently represents a 5- or 6-membered aromatic heterocycle containing 1 or 2 heteroatoms selected from N, OYS, and where CYJ can be attached to the rest of the molecule through any atom of C 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 a through any available eo N atom.

In another aspect, the present invention relates to a process for preparing the compounds of structural formula 1, as previously defined, their regioisomers and mixtures thereof,

which comprises reacting a compound of structural form 11, its regioisomers and mixtures thereof, with a compound of structural formula 111, its regioisomers and mixtures thereof.

111 5 where: each R R2 • RJ, R4, Rs and Rs independently have the same meaningquot;

than for compound 1; each R'6 independently represents hydrogen, halogen or OS02RlI1 with the proviso that the two cannot be hydrogen at the same

R'6 10 time; R17 represents -B (OR9) (OR, g), -SnR'9R, gR, Q;

'

R'8 represents C, -ClO alkyl, -CF3. -C4Fg, -CH 2CF3 or CYs, where CYs is optionally substituted by one or more halogen, C, -C4 alkyl or N02: each R 9 independently represents hydrogen, e, -e, or alkyl or phenyl,

'

I S where C1-C10 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, and which may be optionally substituted by one or more Rll;

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 a preferred embodiment, in the compound of formula 11, each R2 is a 1-hexyl hexyl chain.

In another preferred embodiment. In the compound of formula 11, each R2 is a 2,5-d i-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, -R '1. -COR ll • -C02R 11 • -S02Rl1_

In a preferred embodiment, in the compound of formula 11, R1 is H.

In a particular embodiment of the present invention, each Rl1 independently represents H or Cl ~ C10 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 (OR19) (OR19).

In a preferred embodiment, R19 independently represents hydrogen, the -C10 alkyl or phenyl, wherein the -C1D alkyl is optionally substituted by one or more R1

or two R19 groups can be joined to form a saturated 5- to 7-membered heterocycly with the atom of B and the atoms of O, and which may be optionally substituted by one or more R11;

In a particular embodiment of the present invention, the compound of formula I is selected from

POI1

POI 2

v

quot; or

POI 3

~ ~ Q

~ I'l, ~ /.I'l

l ..- ~ l ..- ~

6

prn, POI 7

POI S

Q

jo

, ~

~ \ r

6

POl8

POI9

POI 10

ES 2 619109 Al

Q Q

: ~ 1quot; 'OR

;; r

POI 14

POI 13

V V

POI 15

POI 16

POI 17 PDIHI

Q Q

, ~ ~ ~ ~

¡Üy :,

, '. ';'one..

Nquot; 'J..quot; 1

'-. ~

~

6th

Chicken

POI 19

An additional 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 acetone triperoxide (TATP).

t5

Embodiment of the invention

The present invention is further illustrated by the following examples, which cannot be considered as limiting its scope.

Elem 010 1, N, N'-dI (l'-he xII heplyl) -l-rP- (Nquot; '- tert-buloxycarboniIpiperazinNquot; -yl) phenyl] -3.4: 9,10-perylenelelracarboxyidiimide (POli)

v

Cop

A mixture of N, N'-di (1'-hexylheptyl) -1-bromo-3,4: 9.1 O- is added, under argon atmosphere, Pd (PPh,) (27 mg, 0.024 mmol) over 10. perylenetetracarboxy diimide (200 mg, 0.24 mmol), p- (N '· tert-butoxycarbonylpiperazin pinacholate

N-yl) phenylboro (110 mg, 0.28 mmol), sodium carbonal (73 mg, 0.7 mmol), THF (20 mL) and water (2.5 mL). Heats up to 70'C last all night. He

Crude is dissolved in CH 2CI 2 and washed with water. The organic phase dries

15 with Na2S04. Filter and remove the solvent under reduced pressure. Purify by column chromatography with silica gel and CH2Ch / methanol (97: 3) as eluent to obtain the POli compound as a red solid (190

mg, 78%).

• 'H-NMR (CDCI3) ~ 0.75 (1, 12H), 1.15 (br, 32H), 1.44 (s, 9H), 1.76 (m,

20 4H), 2.15 (m, 4H), 3.22 (1, 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 (CDCI3) ~ 14.02, 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: 1M '] calculated for Cquot; Hquot; N, O, 1014.62, found 1014.20

•

IR (KBr): 2920, 2856, 1695, 1660, 1590, 1403, 1333, 1228, 1170,808

cm- '

• UV Vis (CH, CI,), Am., Inm (Iog e): 490 (4.4)

5 Example 2, N, N'-Di (1'-hexylheptyl) -1- (p-piperazln-Nquot; -ylfenll) -3.4: 9.1 0perllenotetracarboxldlimide (POI 2)

v

POI2

Trifluoacetic acid (0.33 mL, 4.6 mmol) is added to a solution of POI 1 (80 mg, 0.078 mmol) in dichloromethane (0.5 ml). 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 511 ice gel and CH2Cl2 / methanol (6: 0.5) as eluent to obtain the POI 2 compound as a red solid (65 mg, 90%).

15 • 'H-NMR (COCI,) ~ 0.82 (1, 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, 1H) , 8.17 (br, 1H), 8.60 (m, 5H)

• 13C-NMR (COC ;,) ~ 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

•

MALOI-TOF MS miz: 1M '] calculated for C60Hquot; N, O, 914.57, experimental 914.55

•

IR (KBr): 3416, 2926,2844, 1695, 1648, 1590,1461, 1327,1246,1100,

1018,814 cm '25 • UV Vis (CH, CI,), Am., Inm (Iog e): 489 (4.3)

Example 3. N, N'-OI (1 '-hexllheptll) -1, 7 -di (p- (Nquot;' - tertbutoxycarbonylplperazin-Nquot; -II) fenll] -3.4: 9,10-perilenotetracarboxldlimide

(POI 3)

POI3

5 Pd (PPhJ) 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-perilenotetracarboxidiimide (200 mg of the

mixture of isomers in which isomer 1.7 predominates. 0.22 mmol),

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 70GC overnight. The crude is dissolved in CH2CI 2 and washed with water. The organic phase is dried with Na2S04. Filter and remove the solvent under reduced pressure. It is purified by column chromatography with silica gel and CH2Cb / melanol

(100: 1) as eluent obtaining compound POI 3 (pure 1.7 isomer) in the form of a black solid (163 mg, 60%).

•

'H-NMR (CDCI3) S 0.82 (t. 12H). 1.25 (br. 32H), 1.51 (s, 18H), 1.82 (m, 4H), 2.22 (m, 4H), 3.28 (1. 4H). 3.65 (1. 4H), 5.15 (m, 2H). 7.01 (m, 4H). 7.31 (d, 1H), 7.46 (d, 3H), 7.91 (m, 2H), 8.12 (m, 2H), 8.59 (m, 2H)

•

13C_RMN (CDCI,) S 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

• EM MALDI-TOF miz: lM- + j theoretical for C8oH102N608 1274.77,

Experimental 1274.60 25 • IR (KBr): 2932. 2850, 1699. 1654. 1596. 1409. 1327, 1228. 1158. 815

cm-1

• UV Vis (CH, CI,). Am.Jnm (Iog E): 457 (4.3). 582 (4.2)

Example 4. N, N'-Di (1 '-hexllheptll) -1, 7 -di (p-p iperazin-Nquot; -ilfenll) -3.4: 9.1 0perilenotetracarboxidllmide (PDI 4)

POI4

On a solution of PDI 3 (30 mg, 0.02 mmol) in dichloromethane (0.5 mL)

5 Trifluoroacetic 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 CH2Ch / methanol (5: 0.5) as eluent

10 obtaining the compound PDI 4 as a black solid (23 mg, 90%).

•

'H-NMR (CDCI,) 6 0.81 (1, 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-NMR (CDCI,) 6 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 MALDI-TOF miz: [M'I le6rico for C70H..N, O, 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 cmquot;

• UV Vis (CH, CI,), quot;, quot;,. Inm (Iog E): 450 (4.3), 581 (4.3)

Example s, N, N'-bis (2 ', 5'-di-tert-bulylphenyl) -1- (p- (Nquot;' - tertbutoxycarbon ilpiperazi n-Nquot; -il) fenIIJ-3,4: 9, 1 O-perilenotetracarboxldiimid a

(POI 5)

PDI5 5 Pd (PPh,), (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) pinacolate butoxycarbonylpiperazin-N-il) phenylboro

(31 mg, 0.08 mmol), sodium carbonate (35 mg, 0.34 mmol), THF (5 mL) and

water (0.5 mL) under argon atmosphere. It is heated at 70 ° C 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 CH2CI2ftanol (5: 0.2) as eluent to obtain the POI 5 compound as a purple solid (58 mg, 96%).

15 • 'H-NMR (CDCI3) ~ 1.24-1.28 (m, 36H), 1.45 (s, 9H), 3.24 (m, 4H), 3.59 (m, 4H), 6.92 (d, 1 H), 6.97 (d, 2H), 7.42 (m, 4H), 7.56 (m, 2H), 8.10 (d, 1H) 8.22 (d , 1 H), 8.63 (m, 3H), 8.70 (d, 2H)

• 13C-NMR (CDCI,) ~ 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 MALDI-TOF mIz: 1M ') theoretical for Cquot; H70N, O, 1.026.53,

experimental 1026.56 25 • IR (KBr): 2949, 1706, 1660, 1601, 1403, 1339, 1246, 1181,825 cmquot;

• UV Vis (CH, CI,), l.quot ;, ../nm (lag e): 493 (4.4), 549 (4.3)

Example 6. N-N'-bis (2 ', 5' -di-tere-bu! Llfen 1I) -l- (p-piperazin-Nquot; -ilfeni 1)

3,4: 9,10-perilenotetracarboxidlimide (PDI6)

POI6

On a solution of POI 5 (30 mg, 0.029 mmol) in dichloromethane (0.5

5 mL) is added; Irifluoacetic acid (0.15 mL, 1.9 mm 01). After shaking 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 CH2CI2 / methanol (2: 0.2) as eluent

JO obtaining the POI 6 compound as a purple solid (23 mg, 88%).

•

'H-NMR (CDCI3) ¡; 1.29-1.33 (m, 36H). 3.29 (m, 4H), 3.47 (m. 4H). 6.97 (d, lH). 7.02 (d. 2H). 7.47 (m, 4H), 7.58 (m. 2H). 8.13 (d, lH) 8.27 (d, 1 H), 8.68 (m. 3H), 8.74 (d, 2H)

•

quot; C-NMR (CDCI,) B 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

•. EM 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 cmquot;

•

UV Vis (CH, CI,), Aquot; ,,, / nm (lag E): 493 (4.4), 540 (4.2)

Example 7. N, N'-dlcyclohexyl-1- (p- (Nquot; '. Tert-butoxycarbonylpiperazin-Nquot;

iI) fenll] -3.4: 9, 1 O-perllenotetracarboxldllmlda (POI 7)

Q

POl7 THF: H20 (20: 2 ml) is added over a mixture of N, N-dicyclohexyl-1-bromo 5 3,4: 9,10-perylenetetracarboxyidiimide (100 mg, 0.16 mmol) and Pd (PPh, ). (two

spatula tips). The mixture is stirred 5 minutes and p (N'-tert-butoxycarbonylpiperazin-N-yl) phenylboro pinacolate (68 mg, 0.17 mmol) and carbonate are added

cesium (156 mg, 0.48 mmol). After 24 hours under reflux, the mixture is extracted

with dichloromethane and dried with Na2S04. The product is purified by column chromatography (silica gel, CH2Ch: CH3CN), obtaining PDI 7 as a dark violet solid (84 mg, 65%).

• 'H-NMR (COCI3) 61.37 (dd, J = 28.5.15, .0 Hz, 5H), 1.52 (s, 9H), 1.58 (s, lH), 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. 1H). 8.09 (d. J = 8.3 Hz, 1 H). 8.47-8.41 (m. 1 H). 8.49 (s. LH). 8.56 (d. J = 8.0 Hz, 1 H), 8.60 (d, J = 8.0 Hz. 1H)

• quot; C-NMR (COCI) 6 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, D1, 132.11, 133.36, 134.62, 135.10.136.26.141.81.163.94. 164.07, 164.12

•. EM MALOI-TOF miz: IMquot; I theoretical for Cquot; H50N, O, 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 cmquot;

• UV Vis (CH, CI,),, quot;,., / Nm (Iog E): 485 (4.3), 530 (sh, 4.2)

Example 8. N, N'-dlclclohexyl-1, 7 -bislP- (Nquot; '- tert-butoxycarbon IIpiperazinNquot; -11) len 11] -3.4: 9.1 O-perilenotetracarboxldiimlda (PO I 8)

Q

PDI8 THF: H, O (40: 4 mL) is added on a mixture of N, N 'dicyclohexyl-1.7 (6)

5 dibromo-3.4: 9.10-perilenotetracarboxyidiimide (220 mg, 0.31 mmol) and Pd (PPhJ) 4 (two spatula tips). The mixture is stirred 5 minutes and p- (N: quot; 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 Na2S0 4_ The crude is

10 purified by column chromatography (silica gel, CH2CI2: CH3CN), obtaining a mixture of isomers 1.6 and 1.7 (200 mg, 60%). Pure 1.7 isomer (PDI 8) can be obtained by repeated chromatography as a dark violet solid (33 mg, 10%).

• 'H-NMR (CDCI3) ¡; 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 (1, 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, 1H), 8.12 (d, J = 8.2 Hz, 1H), 8.55 (d, J = 10.6 Hz, 1 H)

• quot; C-NMR (CDCI,) ¡; 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 MALDI-TOF miz: (theoretical M + J for CSSH 7oNsOe 1074.5250,

25 experimenlal 1074.6237

•

IR (KBr): 3453, 2976,2931,2851,1700,1658,1582,1513,1409,1326, 1233,1167,1122, 1046, 994,915, 863,808,759 cm- '

•

UV Vis (CH, CI,), l.quot; ,,, lnm (Iog E): 457 (4.3), 583 (4.2)

Example 9. N, N'-di (1'~ hexylheptyl) e1- [2 '- (4quot; -terc-butoxycarbon ilpiperazin1quot; -yl) pyridine-S'-iI1-3.4: 9, 1 O-perylenetetracarboxyidiimide (POI 9)

v

POl9 Pd (PPh,) is added. (27 mg, 0.024 mmol) on a suspension of N, N '

S di (1'-hexylheptyl) -1-bromo-3,4: 9, 10-perylenetetracarboxyidiimide (200 mg. 0.24 mmol), 2- (4'-ether-butoxycarbonylpiperazin-1 '-yl) pyridine pinacolate -S-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 atmosphere. It is heated at 70 ° C overnight. The crude is dissolved in CH2CI2 and washed with water. The organic phase is dried with Na2S0,., Filtered and the solvent is removed under reduced pressure. It is purified by column chromatography with silica gel and CH2Cl2 / methanol (100: 1) as eluent to obtain the compound

POI 9 in the form of red solid (220 mg, 90%),

• 'H-NMR (COCI,) ¡; 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-NMR (CDCI,) ¡; 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

•

MALDI-TOF MS miz: [M ') calculated Cquot; Hquot; N, O, 1015.6181, experimental 1015.6987

•

IR (KBr): 2920, 2850, 1689, 1654, 1564, 1409, 1316, 1246, 1158, 814

cmquot; 1

25 • UV Vis (CH, CI,), Ámquot; / nm (Iog E): 485 (4.5), 545 (4.4)

quot;, Equot;, jequot;, mquot; pquot; loquot; ----, 1 ,,, O. N, N'-di (1 '-hexllheplil) -1- [2' - (plpe, azin-1quot; -i I) pi'idin-S '-il]

3,4: 9,10-perilenotetracarboxldiimlda (POliO)

POI10

On a solution of POI 9 (80 mg, 0.078 mmol) in dichloromethane (0.5

5 mL) trifluoroacetic 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 CH 2CI: dmetanol (6: 0.5) as eluent

10 obtaining the PDI10 compound as a red solid (66 mg, 93%).

•

'H-NMR (CDCI,) 8 0.75 (1, 12H), 1.15 (b,. 32H), 1.77 (b'. 4H). 2.16 (b '. 4H). 3.58 (s, 4H). 3.83 (s. 4H). 5.12 (m. 2H). 6.67 (d, 1 H). 7.54 (d.1H). 8.05 (d, 1H), 8.16 (br, 1H). 8.30 (s, 1H), 8.52 (m. 5H)

•

"C-NMR (CDCI,) 8 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

• MALDI-TOF MS miz: [M '2Hj' calculated Cquot; H73N, O. 917.5735. 20 experimental 917.5800

•

IR (KBr): 3416.2920.2856,1695,1654,1578,1491,1403,1333,1251, 1117,808 cm- '

•

UV Vis (CH, CI,), l.m, Jnm (Iog E): 485 (4.5), 535 (4.4)

Element 11. N, N'-d1 (1 '-hexllheplil) -1, 7 -di [2' - (4 "; -Ierc-buloxicarbonllplperazln-1"; -II) plrldln-5'-II] -3.4 : 9.1 O-perlenoletracarboxidlimide (PDI 11)

POI11

Pd (PPh3) 4 (25 mg, 0.022 mmol) is added on a suspension of N, N '

5 di (1 · -hexylheplil) -I, 7 (6) -bromo-3,4: 9.1 O-perilenotetracarboxyidiimide (200 mg of

the mixture of isomers in which isomer 1.7, 0.22 mmol), 2- (4'-tert-butoxycarbonylpiperazin-1'-yl) pyridin-S · ilboro pinacolate (175 mg,

0.45 mmol) and sodium carbonate (146 mg, 1.4 mmol) in a mixture of THF (20 mL) and water (2.5 mL) under argon. Heats to 70'C for

10 overnight, the crude is dissolved in CH2CI2 and washed with water. The organic phase is dried with Na2S04. Filter and remove the solvent under reduced pressure. It is purified by column chromatography with silica gel and CH2Cl2Jmethanol (100: 0.5) as eluent to obtain compound POI 11 (pure 1.7 isomer) as a black solid (87 mg. 30%).

15 • 'H-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 (COCI,) ¡; 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: [M] 'calculated Cquot; H, ooN, D, 1276.7658, experimental 1276.7770

• IR (KBr): 2926.2850.1695, 1648, 1584.1491.1409, 1234.814 cm- '25 • UV Vis (CH, CI,), Am ,, / nm (lag E): 453 (4.4), 595 ( 4.3)

Example 12. N, N'-di (1'-hexylheplll) -1, 7-dl [2 '- (piperazin-1quot; -II) pyrldin-S'-yl] 3,4: 9,10-perllenotetracarboxidiimide ( POI 12)

/ \

POI12

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%).

•

'H-NMR (CDCI,) ~ 0.82 (1, 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 (CDCI,) ~ 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: ¡M'H¡ 'calculated Cquot; H84N.O, 1077.6688, experimental 1077.6453

20 • IR (KBr): 3434.2914.2844, 1689,1660, 1584,1485,1403,1316,1240, 1123, 948, 808 cmquot;

• UV Vis (CH, CI,), A..quot; / nm (Iog E): 451 (4.3), 595 (4.2)

Example 13. N, N'-dicyclohexll-1- [2 '- (4 "-terc-butoxycarbonylplperazln-1"; · 1) pyrldin-5'-yl] -3.4: 9.1 O-perilenotetracarboxyidiimide (PDI 13 )

Q

PDI13 THF: H, O (20: 2 mL) is added over a mixture of N, N'-dicyclohexyl-1-bromo5 3,4: 9,10-perylenetetracarboxyidiimide (100 mg, 0.16 mmol) and Pd (PPh ,). (two

spatula tips). The mixture is stirred 5 minutes and 2 (4'-tert-butoxycarbonylpiperazin-1'-yl) pyridin-5-ylboro pinacholate (67 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: CHJCN), obtaining PDI 13 as a dark violet solid (78 mg, 60%).

• 'H-NMR (CDCI,) O1.50 -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, 1H), 7.52 (dd, J = 8.8, 2.5 Hz, 1H), 8.06 (d, J = 8.2

15 Hz, 1H), 8.20 (d, J = 8.2 Hz, 1H), 8.31 (d, J = 2.5 Hz, 1H), 8.66 -8.50 (m, 5H), 8.49 (s, 1 H)

• 13C-NMR (CDCI,) S 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.Q1, 138.07, 138.63, 147.77, 154.92, 158.62, 163.74, 163.77, 163.82, 163.92,163.96

• MALDI-TOF MS miz: [Mr calculated CSOH49Ns0 6 815.3683, experimental 815.3683

25 • IR (KBr): 3464, 2953, 2851, 1623, 1559, 1523, 1326, 1401, 1356, 1232, 1177, 1191, 995, 901, 823 cmquot;

• UV Vis (CH, CI,), Am., Inm (lag E): 484 (4.4), 521 (4.4)

Eiem Dio 14. N, N'-diclclohexil-1. 7 -di [2 '- (4 "-terc-butoxycarbonylpiperaz.in1"; -yl) pyridin-S'-yl] -3.4: 9,10-perylenetetracarboxyidiimide (POI 14)

POI14

THF: H, O (12: 1, 2 mL) is added on a mixture of N, N'-dicyclohexyl-1, 75 dibromo-3.4: 9.1 O-perylenedotelracarboxyidiimide (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%).

• 'H-NMR (CDCt,) ¡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 (CDCt,) ¡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 mIz MS: [MOl leor for Cquot; H., N.O, 1076.5155, experimental 1076.5156

• IR (KBr): 3446, 2924, 2851, 1 696,1658,1589,1492,1409, 1319,1236, 1167,1122,998, 929,859,811 cmquot;

• UV Vis (CH, CI,), quot; quot; ,,. In m (Iog E): 445 (4.1), 590 (4 .0) 25

Example 15. N, N '.. d1 (1 1-hexyl heptyl) -1- [2' - (41 '· tert-butoxycarbonylpiperazin

1``-II) plrlmldln-5'-IIJ-3,4: 9, 1 O-perilenotetracarboxldllmlda (PDI15)

v

PDI15 Pd (PPh,) is added. (13 mg, 0.012 mmol) on a suspension of N, N '

5 di (1'-hexylheptyl) -1-bromo-3,4: 9, 1 O-perilenotetracarboxidiimide (100 mg, 0.12 mmol), 2- (4'-tert-butoxycarbonylpiperazin-1 '-yl) pyrimidine- S-ilboro (55 mg, 0.14 mmol) and sodium carbonate (35 mg, 0.35 mmol) in a mixture

THF (10 mL) and water (1.25 mL) under argon. It warms up to 70'C

All night long . The crude is dissolved in CH2CI2 and washed with water. the

10 organic phase is dried with Na2S04. Filter and remove the solvent under reduced pressure. It is purified by column chromatography with silica gel and CH2Cl2 / methanol (97: 3) as eluent to obtain the POI compound

15 in the form of red solid (110 mg, 90%).

• 'H-NMR (CDCI,) ¡; 0.85 (1, 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, lH), 8.47 -8.91 (m, 5H), 9.47 (s, lH), 9.79 (s , lH), 9.88 (s, lH)

• 13C-NMR (CDCI,) ¡; 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

• MALDI-TOF MS miz: [M] 'calculated Cquot; HaoN, O, 1016.6133,

Experimental 1016.6272 25 • IR (K8r): 2920,1695, 1654, 1590.1520, 1421, 1321,1246,1164,808

cm

• UV Vis (CH, CI,), quot; quot; ,, 1nm (lag E): 438 (4.3), 466 (4.5), 543 (4.3)

Example 16. N, N'-di (l'-hexylheptyl) -1- [2 '- (plperazln-lquot; -1I) pyrimidin-5'-11] 3,4: 9,10-perilenotetracarboxldllmlda (POI 16)

5 POl16

On a solution of POI 15 (80 mg, 0.078 mmol) in dichloromethane (0.5

mL) Irifluoroacetic 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%).

• 'H-NMR (COCt,) B0.81 (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, 1H), 8.48 (m, 7H)

•

13C_RMN (COCI,) 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

•

MS MALOI-TOF miz: 1M] 'calculated Cquot; Hquot; N.O., 910,5609,

experimental 916,5546 20 • IR (KBr): 3434, 2932, 2844,1695,1654,1596, 1321, 1100, 814 cmquot;

• UV Vis (CH, CI,), quot; quot; quot; In m (lag E): 464 (4.3), 503 (4.3), 535 (4.4) Example 17. N, N ' -di (1'-hexylheplil) -1, 7 · di [2 '- (4 "; -terc-buloxlcarbonyl

piperazin-1 '· .j I) pirim ¡din-S' -i 1] -3.4: 9, 1 O-perilenotetracarboxyidiim (POI)

17)

PDI17 5 Pd (PPh3), (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-ylboro pinacolate (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. Heats up to 70'C

All night long. The crude is dissolved in CH2Cb and washed with water. The organic phase is dried with Na 2S04. it is filtered and the solvent is removed under reduced pressure. It is purified by column chromatography with silica gel and CH2Cl2 / methanol (100: 1) as eluent to obtain the compound

PDI17 (pure 1.7 isomer) in the form of a red solid (40 mg, 30%).

•

'H-NMR (CDC !,) ~ 0.82 (1, 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, 1H), 8.53 (s, 5H)

•

13C-NMR (CDC !,) 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

• MALDI-TOF MS miz: [M + H] 'calculated Cquot; Hquot; N100, 1278,7563,

Experimental 1278,7936 25 • IR (K8r): 2926, 2856, 1706, 1660, 1596, 150B, 1321, 1240, 1164, 1000

cm

• UV Vis (CH2CI2), Am.Jnm (Iog E): 438 (4.4), 570 (4.3)

Example 18. N, N'-di (l'-hexiIheplll) -l, 7 -dI [2 '- (pl perazin-lquot; -i I) pirim idin-5' -11] 3,4: 9,10 -perilenotetracarboxidiimide (PDI18)

! \

5 PDI18

On a solution of PDI 17 (30 mg, 0.02 mmol) in dichloromethane (0.5

mL) trifluoroacetic 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 Na2S0., Filtered and

10 removes the solvent under reduced pressure. It is purified by column chromatography with silica gel and CH2Cl2 / methanol (5: 0.5) as eluent to obtain compound PDI18 as a red solid (22 mg, 80%).

• 'H-NMR (CDCI,) 00.82 (1, 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), M8 (s, 15 2H), 8.76 (s, 2H), 8.93 (s, 4H)

• 13C-NMR (CDCI,) 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 • MALDI-TOF MS miz: [M'Hf calculated Cquot; Hquot; Nw04 1078.6515, experimental 1078.6745

• IR (KBr): 3429, 2932, 2858, 1746, 1656, 1594.1525, 1485, 1320.1 240, 1164, 1000, 808 cmquot;

• UV Vis (CH2CI 2l, Amquot; / nm (Iog E): 451 (4.4), 470 (4.4), 530 (4.4) 25

Example 19. N, N'-dlclclohexll-l- [2 '- (4 "; -terc-butoxycarbonylpiperazin-1";

iI) pyrimidin-5'-II] -3.4: Q, 1 Q-perilenotetracarboxyidiimide (POI 19)

POI19

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 (PPhJ). (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, CH2 CI 2: CH3CN). obtaining POI 19 as a dark violet solid (81 mg, 60%).

• 'H-NMR (CDCI3) 6 1.52 (s, 9H), 1.93-1.73 (m, l1H), 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, 1 H), 8.24 (d, J"; 8.2 Hz, 1 H), 8.67 -8.32 (m, 7H)

15 • quot; C-NMR (CDCI3) 625.58.26.69.28.62, 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

• MALDI-TOF MS miz: [MI 'calculated Cquot; H..N, O, 816.3640, experimental 20 816.376

•

IR (KBr): 3496, 2925, 2867,1644,1567,1494,1312,1445,1325,1283, 1168, 1200, 983, 895, 816 cmquot;

•

UV Vis (CH, CI,), quot; quot; ,, / nm (Iog E): 459 (4 .6), 537 (4.7)

Eiemolo 20. N, N'-dicyclohexyl-1, 7-di [2 '- (4 "; .tarc-butoxycarbonylpiperazin

1 quot; -II) plrlmldln-S'-II] -3.4: 9,10-perllenotetracarboxldiimide (POI 20)

PDI20

THF: H20 (50: 5 ml) is added on a mixture of N, N '· dicyclohexyl-1.7

5 dibromo-3,4: 9,10-perilenotetracarbmcidiirnide (250 mg, 0.35 rnmol) and Pd (PPh3) 4 (two spatula tips). The mixture is stirred for 5 minutes and 2- (4'-tert-butoxycarbonylpiperazin-1'-yl) pyrimidin-5-ylboro 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 NazS04. The crude

10 is purified by column chromatography (silica gel. CH2CI2: CHJCN), obtaining PDI 20 as a dark green solid (226 mg, 60%).

• 'H-NMR (COCI,) 01 .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, lH)

• `` C-NMR (COCI), O24.94, 25.55, 26.67, 28.61, 29.26, 43.62, 43.87, 54.23,80.31,122.75,123.46,124.46,126.10,129.33, 129.90, 132.28, 134.79,134.87,134.91, 154.95,158.09,160.84, 163.72, 163.80,

•. MS MAlDI-TOF miz: 1M ·) theoretical for Cquot; Hquot; N, oO, 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- '

•

UV Vis (CH, CI,), Aquot; ,,, / nm (Iog E): 430 (4.2), 575 (4.3)

Description of the figures Figure 1 - Fluorescence titration curves of compound PDI 1

(concentration 5 x la · 'M, CHCI,: MeOH 9: 1 vlv) with TATP (from O wing'

TATP equivalents)

Figure 2 - Representation of the fluorescent emission intensity of the

compound PDI1 (concentration 5 x 10 '', 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 viv, 0.5 ml) before (left) and after the addition of 1.5

TATP mg (right)

Claims (38)

1.-A compound of structural formula I 5 where: R, X-H ~ -, • J! .J4 Rs Rs R, R'quot; '- J (: R, N- quot; fR, R, ~ N, R-, l'R R. R, ' each R, and R3 independently represent hydrogen, halogen, C, -C20 alkyl, -CN. -COR ,. -CO, R ,. -CONR, R ,. -OR ,. -OCOR ,. -MR,. -NR, R ,. -NR, COR ,. -SOR ,. -SO, R ,. -SO, NR, R, or Cy,. where C, -Cquot; alkyl is independently optionally substituted by one or more Ra and CYl is 10 optionally substituted by one or more Rg: each R2 independently represents C, · C4D alkyl or CY2: where C, -C40 alkyl is optionally substituted by one or more Re Y where CY2 is optionally substituted by one or more R10; Each R4 independently represents nitrogen or C-R3: Each Rs independently represents hydrogen, C, -C20 alkyl. -CN. -COR ,. -CO, R ,. -CONR, R ,. -OR ,. -OCOR ,. -MR,. -NR, R ,. -NR, COR7. -SOR7. -S02R7. -S02NR7R7 or CY1. where C, -C20 alkyl is independently optionally substituted by one or more Re and CYl is optionally substituted by one or more Rg: 20 each Re independently represents -R11. -CORn, -C0 2Rl1. -S02Rll; each R1 independently represents hydrogen, e, - alkyl or CY4. where C, · C20 alkyl is optionally substituted by one or more and R'4 where CY4 is optionally substituted by one or more R, s; or two R7 groups can be joined to form a heterocycle with the atom of N 5 to 5 saturated members which additionally may contain a heteroatom selected from N, O, and S, Y that may be optionally substituted by one or two R, s; each R6 independently represents CY3, -OR'2. -SR'2 or -NR, 2R, 2 • where CY3 is optionally substituted by one or more Rg; Each R1O independently represents C, -C40 alkyl, CY4. -OR'2. -SR12 or NR12R, 2. 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 Rl1 independently represents H, el-C 10 alkyl or CY3, where C l-ClO alkyl is optionally substituted by one or more -OH, -OC 1-C4 alkyl 15 and where CY3 is optionally substituted by one or more -e6 alkyl; each R12 independently represents hydrogen, Cl -C6 alkyl or CY3, where the -C6 alkyl is optionally substituted by one or more -OH, -OC1-C4 alkyl, where Cl -C4 alkyl is optionally substituted by one or more -OH and where CY3 is optionally substituted by one or more 20 Cl -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 C 1 -C 6 alkyl; each CYl 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 aromaticQ, 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, and where one or more C to S atoms of CY2 may optionally be Oxidized forming ca, SO or S02 groups: and each CY4 independently represents a saturated carboxylic or heterocyclic ring, partially unsaturated or aromatic of 3 to 7 members, optionally containing 1 to 4 heleroatoms selected from N, OYS, where CY4 is attached to the rest of the molecule through any atom of eo N available, and where one or more atoms of eo S of CY4 can be optionally oxidized forming groups CO, SO or S02: 5 as well as its regioisomers, and mixtures of two or more compounds of formula l. 2.-Compound according to claim 1, wherein X is hydrogen. 3. 3. Compound according to claim 1, wherein X is R, X1 ' R.R. R, R4 ......... NX.fR. R. ~ _N ~ R-. 1'R R. R. • 4.-Compound according to claim 1 to 3, wherein R4 is C-R3. 5.-Compound according to claim 1 to 3, wherein R4 is nitrogen. 6. A compound according to claim 1 to 3, wherein one R. of the aromatic ring is C-R3 and the other R4 is nitrogen. 7, - Compound according to any one of claims 1 to 6. wherein each R3 20 independently represents hydrogen, halogen, C, -C20 alkyl, -OR7, -SR7 • -NR7R7. -SOR7, -S02R7 or Cyl, where C, -C20 alkyl is independently optionally substituted by one or more Rs and CYl is optionally substituted by one or more Rg, and where R ,. R2, Rs. Rs. R7, RB, Rg and Cy, 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.-Compound according to any of claims 1 to 8, wherein each Rs 30 independently represents hydrogen, C, -C20 alkyl, -CN, -CORquot; -CO, R ,. -CONR, Rquot; -ORquot; -MR,. -NR, R ,. -SORquot; -SO, R, or Cy ,. where C, -C20 alkyl is independently optionally substituted by one or more Re Y Cy, is optionally substituted by one or more Rg • and where Rlo R2, R60 R7. Re. Rg • R, or. R, l, R, 2 • R13. R'4. R, S. Cyquot; CY2, CY3 and CY4 have the same meaning as in claim 1. 10.-Compound according to any of claims 1 to 8, wherein Rs is hydrogen. 11. Compound according to any of claims 1 to 10, wherein R, is hydrogen, halogen, C, -C20 alkyl, -OR1, -SRT, -NR7Rr, -SOR7, -S02R7 or CY1, wherein C, -C20 alkyl it is optionally substituted by one or more Ra and CYl is optionally substituted by one or more Rg, and where R2 • R6. R7 Re. Rg and Cy, have the same meaning as in claim 1. 12. A compound according to any one of claims 1 to 11, wherein each R2 independently represents C1-C40 alkyl or CY2; where Cl-C40 alkyl is optionally substituted by one or more Re Y where CY2 is optionally substituted by one or more RlO. 13.-Compound according to any of claims 1 to 11, wherein each R2 is a 1-hexylheptyl chain. 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. 16.-Compound according to any of claims 1 to 15, wherein R6 independently represents H, -R ,,, -CORl1, -C02Rll, -S02Ru. 17.-Compound according to any of claims 1 to 16, wherein each R7 independently represents hydrogen. C1-C20 alkyl or CY4. 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 and S. and which may be optionally substituted by one or two R15. 19.-Compound according to any of claims 1 to 18, wherein each R9 independently represents R12. 20.-Compound according to any of claims 1 to 19, wherein each R10 independently represents C1-C40 alkyl optionally substituted by one or more Re]. 21. Compound according to any one of claims 1 to 20, wherein each R1 independently represents H or e1-alkyl, wherein the alkyl is optionally substituted by one or more -OH or -OC, -C4 alkyl. 22.-Compound according to any of claims 1 to 20, wherein each RlI independently represents CY3 optionally substituted by one or more C1-C6 alkyl. 23.-Compound according to any one of claims 1 to 22, wherein each R12 independently represents C1-C6 alkyl optionally substituted by one or more -OH, -OC1-C4 alkyl, and where C1-C4 alkyl is optionally substituted by one or more -OH. 24.-Compound according to any of claims 1 to 23, wherein each R13 independently represents -DR12 or CY3, wherein CY3 is optionally substituted by one or more C1-C6 alkyl. 25. Compound according to any one of claims 1 to 24, wherein each R14 independently represents -DRI2 or CYJ, wherein CYJ is optionally substituted by one or more C1-C6 alkyl. 26.-Compound according to any of claims 1 to 25, wherein each R15 independently represents R12 • 27. A compound according to any one of claims 1 to 26, wherein each CYl independently represents phenyl. 28. A compound according to any one of claims 1 to 27, wherein each CY2 independently represents a saturated carbocyclic or heterocyclic monocyclic 3 to 7 membered ring, where CY2 can be attached to the rest of the molecule through any available eo N atom , and where CY2 5 contains 1 to 3 heteroatoms selected from N, O and S. 29. A compound according to any one 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 from 1 02 heteroatoms selected from N, OY S. and where CYJ can be attached to the rest of the molecule through any available eo N atom. 31. A compound according to any one of claims 1 to 30, 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. 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, R, I N R'6 JlI where:

5 JO 15

every Rquot; R2, RJ, R4, Rs and Re independently have the same meaning as in claim 1: each R16 independently represents hydrogen, halogen or OS02R18 with the proviso that the two R'6 cannot be hydrogen at the same time R17 represents -B (OR19) (OR19), -SnR19R19R ,,; R'8 represents e, -C'D alkyl, -CF3, -C4F9. -CH 2CF3 or CYs. where CYs is optionally substituted by one or more halogens, C, -C4 alkyl or N02; each R'9 independently represents hydrogen, e, -c, or alkyl or phenyl, where e, · c, or alkyl is optionally substituted by one or more R 'or the two R'9 groups can be joined to form with the alomo of B and the atoms of O a saturated 5- to 7-membered heterocycle that may additionally contain a heteroatom selected from N, OYS, Y that may be optionally substituted by one or more R11; Each CYs represents phenyl. 33. · Method according to claim 32, wherein R4 is C-RJ.

34. Method according to claim 32, wherein R4 is nitrogen.

twenty

35. The method according to claim 32, wherein aromatic is C-RJ and the other R4 is nitrogen. a R4 from every ring

25

36. Method of any of claims 32 to 35, wherein RJ is hydrogen. 37. Method according to any of claims 32 to 36, wherein Rs is hydrogen.

30

38. Method according to any of claims 32 to 37, wherein each R2 is a 1-hexylheptyl chain.

39. Method according to any of claims 32 to 37, wherein each R2 is a 2,5-di-t-butylphenyl ring.

35

40. Method according to any of claims 32 to 37, wherein R2 is a cyclohexyl ring.

48

41. Method according to any of claims 32 to 40, wherein Re independently represents H, -Rl1 • -COR11 • -C02R11 • -S02Rll. 42.- Method according to any of claims 32 to 41, wherein 5 R, is H. 43.-Method according to any of claims 32 to 42, wherein each R'1 independently represents H or Cr and 10 alkyl, where e, -ClD alkyl is optionally substituted by one or more -OH or -OC, -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. Method according to any one of claims 32 to 43, wherein one R 16 is a bromine atom, and the other R 16 is an atom selected from hydrogen or bromine. 46.- Method according to any of claims 32 to 45, wherein R17 is -B (OR19) (OR19). 47. Process according to any of claims 32 to 46, wherein R19 independently represents hydrogen, e, -cl or alkyl or phenyl, wherein C1-C \ O alkyl is optionally substituted by one or more Rll 25 or two R19 groups can be joined to form a saturated 5- to 7-membered heterocycle with the atom of B and the ties of O, which may be optionally substituted by one or more R'l. 48.-A compound selected from POI 1 POI 2 K K ~ PDI6 PDI7 POI5 Q POI 8 or ~ %% ', o o gt; ~. ~ ~ ~ ,, or ~ ,,, quot; • « or 'quot; 'quot; 'quot; % N 'D o ~ ogt; X- ~ 'quot; ,, ', cY ~ n. ,, ~ RRk '~ •OR ~ , quot; r ~ r ~ ~ ~ " Y' OR ~ POI 15 v or Dick Q Q POI 20 PDl19 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. Use according to claim 49, wherein the oxidizing agent is an oxidizing explosive. 51. Use according to any of claims 49 to 50, wherein the oxidizing explosive agent is Acetone Iriperoxide (TATP).