ES2558260B1 - Procedure for obtaining PDI derivatives - Google Patents

Abstract

Method of obtaining PDI derivatives. # The present invention relates to a process for preparing perilenediimide derivatives of formula I where the meaning for R {sub, 1}, R {sub, 2} and R {sub, 3} It is the one indicated in the description. These compounds are useful for the preparation of dyes, pigments, paints, fluorescent agents, optical devices, electronic devices, electro-optical devices, light emitting diodes and organic or hybrid photovoltaic cells.

Description

image 1

Procedure for obtaining PDI derivatives

DESCRIPTION

The present invention relates to a process for repairing perilenediimide derivatives of formula I, characterized by being substituted in positions 1, 6, 7 and / or 12 (bay positions).

STATE OF THE TECHNIQUE

10 Perimin-3, 4,9,10-tetracarboxylic acid diimides, also known as perylenediimides (PDI) or as perylene bisimides (PBI), are very stable compounds both chemically and thermally, and also against electromagnetic radiation. The POIs absorb intmente in the ultraviolet-visible region of the electromagnetic spectrum, so they exhibit very vivid colorations that, depending on the

15 substituents that present, can vary from orange to blue, through red and green. The POIs are highly fluorescent, with quantum fluorescence effects that can reach the unit. Other properties of IDPs include their high electronic affinity and their great capacity to transport electrons under the influence of an electric field. For all these characteristics, they are used

20 widely in the industry with dyes, pigments in paints and fluorescent agents. They are also used in research for the development of optical, electronic and electro-optical devices such as field effect transistors, light emitting diodes and photovoltaic devices (solar cells).

25 The optical, electronic and electro-optical properties of IDPs can be modified depending on the substituents. Important changes in the properties are obtained by introducing, modifying or varying the substituents on the bay positions (1, 6, 7 and / or 12) of the POI. The introduction on the bay positions (1, 6, 7 and / or 12) of Oalkyl and O-aryl groups, linked to the PDI by the oxygen atom, and azacycloalkanes, attached to

30 the PDI for the nitrogen atom, has been widely used.

The O- or N-substituted POIs in the bay positions are obtained in two stages. The first is to halogen (chlorate or brominate) the PDI not substitute. The POI can be tetrahalogenated (usually with chlorine) at positions 1, 6, 7 and 12. On the other

On the other hand, the PDI (usually with bromine) can be dihalogenated by obtaining a mixture of two regioisomers, 1,6-dibromoPDI (minor isomer) and 1,7-dibromoPDI

image2

(majority isomer), which cannot be separated by the usual techniques.

In a second stage the halogen atoms (chlorine or bromine) are substituted, for example

5 reaction in basic medium, with alcoholates, phenolates or amines. In the case of disubstituted IDPs, the mixture of isomers 1.6 (minor) and 1.7 (majority) is still maintained, although in some cases they can be separated by chromatographic techniques.

10 These and other properties and characteristics of IDPs are found in many scientific photographs and articles, such as (a) F. Würthner. Chem. Commun. 2004, 1564-1579. (b) H. Langhals. Helv. Chim. Minutes 2005, 88, 1309-1343.

(c) A. Herrmann, K. Müllen. Chem. Lett. 2006, 35, 978-985. (d) F. Würthner. Pure Appl. Chem. 2006, 78, 2341-2349. (e) C. Huang, S. Barlow, S. R. Marder. J. Org.

15 Chem. 2011, 76, 2386-2407. (f) X. Zhan, A. Facchetti, S. B arlow, T. J. Marks, M. A. Ratner, M. R. Wasielewski, S. R. Marder. Adv. Mater. 2011, 23, 268-284. (g) C. Li, H. Wonneberger. Adv. Mater. 2012, 24, 613-636.

Therefore, these procedures must be carried out in at least two stages, of

20 which one corresponds to a halogenation (chlorination or bromination) of the POIs to function the positions that are susceptible to being replaced. On the other hand, by means of the procedures described, only monosubstituted, disubstituted POIs can be obtained (as a mixture of regioisomers, where isomer 1.7 over 1.6 predominates) and tetrasubstituted.

25 Thus, it would be desirable to have an alternative, more selective and more efficient method that would facilitate the obtaining in one stage of the substituted PDI compounds. It would also be desirable for the method to allow, in addition to monosubstituted POIs, disubstituted POIs in which the 1,6 isomer was higher

30 proportion Finally, a method is needed that makes it possible to obtain the isomer of 1.12 and trisubstituted IDPs.

DESCRIPTION OF THE INVENTION

The present invention relates to a process for preparing the compounds of formula I: where: each R 1 and R 3 independently represents n hydrogen, halogen, C 1-C20 alkyl, C2-C20 alkenyl, C 2-C20 alkylo, -CN, -COR 4, -CO 2R4, -CONR 4R4, -OR 4, -OCOR 4,

image3

image4

5 -OCONR4R4, -OCO2R4, -SR4, -SeR4, -NR4R4, -NR4COR4, -NR4CONR4R4, -NR4CO2R4, -PR4R4, -SOR 4, -SO 2R4, -SO 2NR4R4 or Cy 1, where C 1 -C alkyl , C2-C20 alkenyl and C2-C20 alkynyl are independently optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R2 independently represents C 1 -C40 alkyl or Cy 2; gift of C 1-C40 alkyl

10 is optionally substituted by one or more R 5 and where Cy 2 is optionally substituted by one or more R7; each R4 independently represents hydrogen, C1-C20 alkyl or Cy4, where C1-C20 alkyl is optionally substituted by one or more R 10 and where Cy 4 is optionally substituted by one or more R11;

15 or two R4 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, and which may be optionally substituted by one or two R11; each R 5 independently represents Cy 3, -OR 8, -SR 8 or -NR8R8, where Cy3 is optionally substituted by one or more R6;

Each R 7 independently represents C 1 -C40 alkyl, Cy 4, -OR 8, -SR8 or -NR 8R8, where C1-C40 alkyl is optionally substituted by one or more R9 and where Cy4 is optionally substituted by one or more R6; each R8 independently represents hydrogen, C1-C6 alkyl or Cy3, where C 1-C6 alkyl is optionally substituted by one or more -OH, -OC 1-C4 alkyl, where

C1-C4 alkyl is optionally substituted by one or more -OH and where Cy 3 is optionally substituted by one or more C1-C6 alkyl;

image5

5 5 or 6 members containing 1 to 3 heteroatoms selected from N, O, S and Se, and where each Cy 1 and Cy 3 can be independently linked to the rest of the molecule through any available C or N atom; each Cy2 independently represents a saturated, partially unsaturated ring

or aromatic, monocyclic 3 to 7 members or bicyclic 6 to 11 members that can

10 being carbocyclic or heterocyclic, where Cy2 can be attached to the rest of the molecule through any available C or N atom, where Cy 2 contains 1 to 4 heteroatoms selected from N, O, S and Se, and where one or more atoms of C, S or Se of Cy2 may optionally be oxidized forming groups CO, SO, SO 2, SeO or SeO2; Y

Each Cy 4 independently represents a saturated carbocyclic or heterocyclic ring, partially unsaturated or aromatic with 3 to 7 members, optionally containing 1 to 4 heteroatoms selected from N, O, S and Se, where Cy4 is attached to the rest of the molecule through any available C or N atom, and where one or more atoms of C, S or Se of Cy 4 may optionally be oxidized

20 forming groups CO, SO, SO2, SeO or SeO2, with the proviso that at least one R3 independently represents -OR 4, -SR4, -SeR4, -NR4R4 or -PR4R4, which comprises reacting a formula compound to II with a compound of formula III in the presence of a fluorine source:

R1

R12 R12

R1

R13-H R2

II III

image6

where:

image7

5 -NR4CONR4R4, -NR4CO2R4, -PR4R4, -SOR4, -SO2R4 or -SO2NR4R4; R13 represents –OR4, -SR4, -SeR4, -NR4R4 or -PR4R4; and each R 4 independently has the meaning described for a compound of formula I, with the proviso that at least one R 12 independently represents hydrogen or

10 halogen.

Another aspect of the present invention relates to a compound selected from:

image8

25

,,,

image9

, Y

Another aspect of the present invention relates to the use of a compound selected from:

image10

image11

image12

image13

OR NOT

image14

image15

image16

image17

N

image18

image19

N

image20 N

N

image21 N

image22

OR NOT

image23

image24

24 25

5 , , ,

image25

, or, for the preparation of colorant, pigments, paint, fluorescent agents, optical devices, electronic devices, electro-optical devices, light emitting diodes and organic or hybrid photovoltaic cells.

Throughout the present invention "C1-C40 alkyl", "C 1-C20 alkyl", "C1-C6 alkyl" and "C1-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 6 and from 1 to 4 C atoms respectively. "C 1-C4 alkyl" includes methyl groups,

Ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl; "C1-C6 alkyl" includes the groups of "C1-C4 alkyl" and, among others, pentyl iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, hexyl, iso-hexyl and sec-hexyl; "C1-C20 alkyl" includes the groups of "C1-C6 alkyl" and, among others, heptyl, iso-heptyl, octyl, isooctyl, 2-ethylhexyl, decyl, nonyl and dodecyl, 2-pr opylheptyl, 2- butylnonyl and 3-butylnonyl; "C 1-C40 alkyl" includes

15 "C1-C20 alkyl" groups and, among others, tridecyl and tetradecyl.

A group "C 2-C20 alkenyl" means a linear or modified alkyl body containing from 2 to 20 C atoms, and which also contains or does not contain more or more two bonds. Examples include, among others, the groups ethenyl, 1-propenyl, 2-prope nyl,

Isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-but adienyl, 3-pentenyl, 5pentenyl, 2-hexenyl, 2,4-hexadienyl and 2-propyl-2-hexenyl.

A "C 2-C20 alkynyl" group means a linear or branched alkyl chain containing from 2 to 20 C atoms, and which also contains one or more triple bonds.

image26

Examples include the ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl and 1,3-butadiinyl groups.

Cy1 and C3 independently refer to a phenyl or a 5 or 6 oaryl heter

5 members containing 1 to 3 heteroatoms selected from N, O, S and Se. Cy1 and C3 bind to the rest of the molecule through any C or N atom of the available ring. In addition, Cy1 and C3 may be optionally substituted as indicated in the definition of formula I, the substituents may be the same or different and may be located in any available position of the system of

10 rings Examples include, among others, phenyl, thienyl, furyl, pyrrolyl, thiazoyl, 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, 1,4,4-thiadiazolyl, p-iridyl, pyrazinyl, pyrimidinyl and pyridazinyl.

15 Cy2 refers to a monocyclic ring of 3 to 7 members or bicyclic of 6 to 11 members which can be carbocyclic or heterocyclic. When it is heterocyclic, it can contain 1 to 4 heteroatoms selected from N, O, S and Se. 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 ring with

20 bridge, or they can be formed by two rings or nests through a single C atom forming a spirane-like ring. The group or Cy 2 can be saturated, partially unsaturated or aromatic. Cy 2 can be attached to the rest of the molecule through any available C or N atom. In Cy 2 one or more atoms of C, S or Se of Cy2 may optionally be oxidized forming groups CO, SO, SO 2, SeO

25 or SeO2. 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 at any available position of the ring system. Examples include, among others, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, azetidinyl, aziridinyl, oxyranyl, oxetanyl, imidazolidinyl,

30 isothiazolidinyl, isoxazole idinyl, oxa zolidinyl, p irazolidinyl, pyrrolidini lo, thiazolid inyl, dioxanyl, morpholinyl, thio morpholinyl, 1,1-dioxothiomorpholinyl, pip erazinyl, homopiperazinyl, p iperidinyl, pyranyl oxypropyl oxyinyl, pyranyl oxypropyl oxyninyl, pyranyl oxypropyl oxyninyl, pyranyl oxypropyl oxyninyl oxazolinyl, pyrrolinyl, thiazolinyl, pyr azolinyl, imidazolinyl, isoxazolinyl, linyl isothiazo, 2-oxo-pyrrolidinyl, 2-oxo-piperidinyl, 4-oxo-piperidinyl, 2-oxo-piperazinyl, 2-oxo-1,2

Dihydropyridyl, 2-oxo-1, 2-dihydropyrazinyl, 2-oxo-1,2-dihydropyrimidinyl, 3-oxo-2,3-dihydropyridazyl, phenyl, naphthyl, thienyl, furyl, pyr rolyl, tia zolyl, isothia zolyl, oxazolyl,

image27

isoxazolyl, imidazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, trazolyl, 1, 3,4oxyadiazolyl, 1,3,4-thiadia zolyl, 1,2,4-oxadiazolyl, 1, 2,4-thiadiazolyl, p-iridyl, pyrazinyl, pyrimidinyl, pyridazinyl, ben zimidazolyl, benzooxazolyl, benzof uranyl, isobenzofuranyl, indo lilo, isoindolyl, ben zothiophenyl, b enzyothiazolyl, quinolinyl,

5 isoquinolinyl, phthalazinyl, linilo quinazo, quinoxalinyl, cinnoline yl, naphthyridinyl, inda zolilo, imidazopyridinyl, lopiridinilo pirro, nopiridinilo tie, imidazopyrimidinyl, imidazopirazin yl, imidazopyridazinyl, pirazolopirazinilo, pirazolopirid ynyl, zolopirimidinilo pyre, benzo [1,3] dioxolyl, ft alimidyl, 1-oxo-1,3-dihydroisobenzofuranyl, 1,3-dioxo-1,3-dihydroisobenzofuranyl, 2-oxo-2,3-dihydro-1 H-indolyl, 1-oxo -2,3-dihydro-1H-isoindolyl ,

10 perhydroquinolinyl, 1-oxo-perhydroisoquinolinyl, 1-oxo-1,2-d ihydroisoquinolinyl, 4-oxo3,4-dihydroquinazolinyl, 2-aza-bicyclo [2.2.1] heptanyl, 5-aza-unicyclo [2.1.1] hexanyl, 2Hspiro [benzofuran-3,4'-piperidinyl], 3 H-spiro [isobenzofuran-1,4'-piperidinyl], 1-oxo2,8-diazaspiro [4.5] decanyl and 1-oxo-2,7-diazaspiro [4.5] decanyl.

15 In the previous definition r of Cy 2, when the specified examples s 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

20 aromatic, which may be carbocyclic or rocyclic hete. If it is heterocyclic, it contains 1 to 4 heteroatoms selected from N, O, S and Se, which can be optionally oxidized, forming groups CO, SO, SO 2, SeO or SeO 2. Cy4 joins 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

The 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, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, azetidinyl, aziridinyl, oxyranyl, oxetanyl, imid azolidinyl, isothiazolidinyl, isoxazolidinyl, oxazolidinyl, pyrazolidyl, pyrrolidinyl, thiazolyl, thiazolyl

30 morpholinyl, thiomorpholinyl, 1,1-dioxothiomorpholinyl, p iperazinyl, ho mopiperazinyl, piperidinyl, pyranyl, tetrahydro pyranyl, h omopiperidinyl, oxazinyl, oxazolinyl, pyrrolinyl, thiazolinyl, isozolinyl, zolinylyl, zolinylyl, iazolinyl oxo pyrrolidinyl, phenyl, thienyl, furyl, p irrolyl, tia zolyl, isotiazolyl, oxazolyl, isoxazolyl, imidazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, te trazolyl, 1,3, 4-oxadiazolyl,

1,3,4-thiadiazolyl, 1,2,4-oxadiazolyl, 1,2,4-thiadia zolyl, p-iridyl, pyrazinyl, pyrimidinyl and pyridazinyl.

image28

The term "fluorine source" refers to a chemical compound capable of releasing fluoride ions (F -). Examples include, but are not limited to, tetrabutyl monium fluoride (TBAF), tetraphenylphosphonium fluoride (TPPF), CsF, RbF, KF, NaF, LiF, BaF 2, SrF 2, CaF 2, and

5 MgF2.

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, tie nyl or indolyl, all positions of

10 possible union. Thus, for example, in the definitions of Cy 1 to Cy 4, which do not include any limitation with respect to 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 of a

15 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 available positions likely to be substituted. If present, said substituents may be the same or different and may be located over any available position.

20 When two or more groups with the same numbering appear in a definition of a substituent (for example -NR 4R4, -NR 8R8, etc.), this does not mean that they had to be identical. Each of them is independently selected from the list of possible meanings given for that group, and therefore they can be the same or

25 different

In another embodiment the invention relates to the process described above, where the fluorine source is selected from tetrabutylammonium fluoride (TBAF), tetraphenylphosphonium fluoride (TP PF), CsF, RbF, KF, NaF, LiF, BaF 2, SrF 2, CaF 2, and MgF 2, and

30 preferably where the source of fluorine is selected from tetrabutylammonium fluoride (TBAF) and KF.

In another embodiment, the invention relates to the process described below, where each R 1 independently represents hydrogen, halogen, C 1 -C 20 alkyl,

-OR4, -SR4, -SeR4, -NR4R4, -PR4R4 or Cy 1, where C 1-C20 alkyl is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6.

image29

In another embodiment, the invention relates to the process described below, wherein C 1 to C 2 independently represents C 1 -C 40 alkyl optionally substituted by one or more R 5.

In another embodiment, the invention relates to the process described below, where each R 2 independently represents Cy 2 optionally substituted by one or more R7.

In another embodiment, the invention relates to the process described below, where each R 3 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4, -SR4, -SeR4, -NR4R4, -PR4R4 or Cy 1, where C 1-C20 alkyl is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6.

In another embodiment, the invention relates to the process described below, where each R4 independently represents hydrogen, C1-C20 alkyl or Cy4, where C1-C20 alkyl is optionally substituted by one or more R 10 and where Cy 4 is optionally replaced by one or more R11.

In another embodiment, the invention relates to the process described below, wherein C 1 to C 4 independently represents C 1 -C 20 alkyl optionally substituted by one or more R 10.

In another embodiment, the invention relates to the process described below,

Where two R4 groups can be joined to form a saturated 5-7-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 R11.

In another embodiment, the invention relates to the process described below, where each R6 independently represents R8.

In another embodiment, the invention relates to the process described below, where C to R 7 independently represents C 1 -C 40 alkyl optionally

35 replaced by one or more R9.

image30

In another embodiment, the invention relates to the process described above where each R8 independently represents C1-C6 alkyl optionally substituted by one or more -OH, -OC 1-C4 alkyl and where C 1-C4 to the alkyl is optionally substituted by one or more –OH.

In another embodiment the invention relates to the process described above where CAD to R 9 independently represents -OR 8 or Cy 3, where Cy 3 is optionally substituted by one or more C1-C6 alkyl.

In another embodiment the invention relates to the process described above where each R 10 independently represents -OR 8 or Cy 3, where Cy 3 is optionally substituted by one or more C1-C6 alkyl.

In another embodiment, the invention relates to the process described below, where each R11 independently represents R8.

In another embodiment the invention relates to the process described above, where each Cy1 independently represents phenyl.

In another embodiment the invention relates to the process described above, where each Cy 1 independently represents a 5 or 6 membered aromatic heterocycle containing 1 or 2 heteroatoms selected s of N, O and S, and where Cy1 may be attached to the rest of the molecule through any available type of C or N.

In another embodiment the invention relates to the procedure described above, where each Cy1 independently represents:

image31

image32

image33

image34

image35

;

image36 ;

image37 or

image38 .

image39

image40

In another embodiment the invention relates to the process described above, where each Cy2 independently represents phenyl.

image41

In another embodiment, the invention relates to the process described above, where each Cy 2 independently represents a saturated, non-cyclic 3 to 7 carbocyclic ring.

In another embodiment the invention relates to the process described above, where each Cy 2 independently represents a saturated, non-cyclic 3 to 7 heterocyclic ring, where Cy 2 can be attached to the rest of the molecule through any att mo of C or N available, where Cy 2 contains 1 to 3 heteroatoms selected from N, O and S, and where one or more C or S atoms of Cy 2

10 may optionally be oxidized forming groups CO, SO or SO2.

In another embodiment, the invention relates to the method described above, where each Cy 2 independently represents a saturated, non-cyclic 3 to 7 heterocyclic ring, where Cy 2 can be attached to the rest of the molecule a

15 through any available C or N atom, and where Cy 2 contains 1 to 3 heteroatoms selected from N, O and S.

In another embodiment the invention relates to the process described above, where each Cy3 independently represents phenyl.

In another embodiment, the invention relates to the process described above, where each Cy 3 independently represents a 5 or 6-membered aromatic heterocycle containing 1 or 2 heteroatoms selected s of N, O and S, and where Cy3 can be attached to the rest of the molecule through any other way of C or N

25 available.

In another embodiment the invention relates to the process described above, where each Cy4 independently represents a saturated heterocyclic ring, from 3 to 7 members, optionally containing from 1 to 3 heteroatoms selected from

30 N, O and S, where Cy4 is attached to the rest of the molecule through any available C or N atom, and where one or more C or S atoms of Cy 4 can be optionally oxidized forming CO, SO or SO2.

In another embodiment the invention relates to the process described above,

Where each Cy4 independently represents a saturated heterocyclic ring, 3 to 7 members, optionally containing 1 to 3 heteroatoms selected from N, O and S, and where Cy4 is attached to the rest of the molecule through any C atom or N available.

image42

In another embodiment the invention relates to the process described above, where each Cy4 independently represents phenyl.

In another embodiment the invention relates to the process described above, where each R 12 independently represents hydrogen, halogen, -OR 4, -SR4, -SeR4, -NR4R4 or -PR4R4.

In another embodiment, the invention relates to the process described below, wherein the compound of formula I is selected from a compound of formula Ia:

image43

fifteen

where R1 and R3 have the meaning described for a compound of formula I.

twenty

In another embodiment, the invention relates to the process described below, wherein the compound of formula I is selected from a compound of formula Ib:

image44

image45 Ib where R1 and R3 have the meaning described for a compound of formula I.

In another embodiment, the invention relates to the process described below, wherein the compound of formula I is selected from a compound of formula Ic:

image46

Ic where R1 and R3 have the meaning described for a compound of formula I.

In another embodiment, the invention relates to the process described above, where: each R 1 independently represents hydrogen, halogen, C 1 -C 20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the quilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; and each R2 independently represents C 1 -C40 alkyl optionally substituted by one or more R5.

image47

In another embodiment the invention relates to the process described above,

5 where: each R 1 ind independently represents hydrogen, halogen, C 1-C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the quilo is optionally e substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; and each R2 independently represents Cy2 optionally substituted by one or more s

10 R7.

In another embodiment, the invention relates to the process described above, wherein: each R 1 independently represents hydrogen, halogen, C 1 -C 20 alkyl, -OR 4,

-SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the quilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; and each R 3 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6.

In another embodiment, the invention relates to the process described above, where: each R 1 independently represents hydrogen hydrogen, halo, C 1 -C 20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 per kilo is optionally

25 substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; and each R4 independently represents hydrogen, C1-C20 alkyl or Cy4, where C1-C20 alkyl is optionally substituted by one or more R 10 and where Cy 4 is optionally substituted by one or more R11.

In another embodiment, the invention relates to the process described above, where: each R 1 independently represents hydrogen hydrogen, halo, C 1 -C 20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the quilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; Y

Each R 4 independently represents C 1-C20 alkyl optionally substituted by one or more R10.

image48

In another embodiment, the invention relates to the process described above, wherein: each R 1 independently represents hydrogen, halogen, C 1 -C 20 alkyl, -OR 4,

5 -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the quilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; and two R4 groups can be joined together with the N atom forming a saturated 5- to 7-membered heterocycle that may additionally contain a heteroatom selected from N, O and S, and which may be optionally substituted by one or two R11.

In another embodiment, the invention relates to the process described above, where: each R 1 independently represents hydrogen hydrogen, halo, C 1 -C 20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 per kilo is optionally

15 substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; and each R6 independently represents R8.

In another embodiment the invention relates to the process described above, where:

Each R 1 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; and each Cy1 independently represents phenyl.

In another embodiment, the invention relates to the process described above, where: each R 1 independently represents hydrogen hydrogen, halo, C 1 -C 20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the quilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; Y

Each Cy1 independently represents a 5 or 6-membered aromatic heterocycle containing 1 or 2 heteroatoms selected from N, O and S, and where Cy1 can be attached to the rest of the molecule through any available C or N atom.

In another embodiment, the invention relates to the process described above, wherein: each R 1 independently represents hydrogen hydrogen, halo, C 1 -C 20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the quilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; and each Cy1 independently represents:

image49

image50

image51

image52

image53

image54

;

image55 ;

image56 or

image57 .

image58

image59

In another embodiment, the invention relates to the process described above, where: each R 1 independently represents hydrogen, halogen, C 1 -C 20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the quilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R 2 independently represents C 1-C40 alkyl optionally substituted by one or more R 5, preferably each R 2 independently represents Cy 2 optionally substituted by one or more R 7; and each R 3 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6.

In another embodiment, the invention relates to the process described above, where: each R 1 independently represents hydrogen, halogen, C 1 -C 20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the quilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R 2 independently represents C 1-C40 alkyl optionally substituted by one or more R 5, preferably each R 2 independently represents Cy 2 optionally substituted by one or more R 7; each R 3 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; and each R4 independently represents hydrogen, C1-C20 alkyl or Cy4, where C1-C20 alkyl is optionally substituted by one or more R 10 and where Cy 4 is optionally substituted by one or more R11.

image60

In another embodiment, the invention relates to the process described above, where: each R 1 independently represents hydrogen, halogen, C 1 -C 20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally

5 substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R 2 independently represents C 1-C40 alkyl optionally substituted by one or more R 5, preferably each R 2 independently represents Cy 2 optionally substituted by one or more R 7; each R 3 independently represents hydrogen, halogen, C 1 -C 20 alkyl, -OR 4,

10 -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; and each R 4 independently represents C 1-C20 alkyl optionally substituted by one or more R10.

In another embodiment, the invention relates to the process described above, where: each R 1 independently represents hydrogen hydrogen, halo, C 1 -C 20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the quilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6;

Each R 2 independently represents C 1-C40 alkyl optionally substituted by one or more R 5, preferably each R 2 independently represents Cy 2 optionally substituted by one or more R 7; each R 3 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally e

25 substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R 4 independently represents C 1-C20 alkyl optionally substituted by one or more R10; and two R4 groups can be joined by forming with the N atom a saturated 5- to 7-membered heterocycle that may additionally contain a heteroatom selected

30 of N, O and S, and which may be optionally substituted by one or two R11.

In another embodiment, the invention relates to the process described above, wherein: each R 1 independently represents hydrogen, halogen, C 1 -C 20 alkyl, -OR 4,

35 -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6;

image61

each R 2 independently represents C 1-C40 alkyl optionally substituted by one or more R 5, preferably each R 2 independently represents Cy 2 optionally substituted by one or more R 7; each R 3 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R4 independently represents hydrogen, C1-C20 alkyl or Cy4, where C1-C20 alkyl is optionally substituted by one or more R 10 and where Cy 4 is optionally substituted by one or more R11; and each R6 independently represents R8.

In another embodiment, the invention relates to the process described above, where: each R 1 independently represents hydrogen, halogen, C 1 -C 20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the quilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R 2 independently represents C 1-C40 alkyl optionally substituted by one or more R 5, preferably each R 2 independently represents Cy 2 optionally substituted by one or more R 7; each R 3 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R 4 independently represents C 1-C20 alkyl optionally substituted by one or more R10; and each R6 independently represents R8.

In another embodiment, the invention relates to the process described above, where: each R 1 independently represents hydrogen, halogen, C 1 -C 20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the quilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R 2 independently represents C 1-C40 alkyl optionally substituted by one or more R 5, preferably each R 2 independently represents Cy 2 optionally substituted by one or more R 7; each R 3 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R 4 independently represents C 1-C20 alkyl optionally substituted by

image62

5 one or more R10; two R4 groups can be joined together with the N atom forming a saturated 5- to 7-membered heterocycle that may additionally contain a heteroatom selected from N, O and S, and which may be optionally substituted by one or two R11; and each R6 independently represents R8.

In another embodiment, the invention relates to the process described above, where: each R 1 independently represents hydrogen hydrogen, halo, C 1 -C 20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 per kilo is optionally

15 substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R 2 independently represents C 1-C40 alkyl optionally substituted by one or more R 5, preferably each R 2 independently represents Cy 2 optionally substituted by one or more R 7; each R 3 independently represents hydrogen, halogen, C 1 -C 20 alkyl, -OR 4,

20 -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R4 independently represents hydrogen, C1-C20 alkyl or Cy4, where C1-C20 alkyl is optionally substituted by one or more R 10 and where Cy 4 is optionally substituted by one or more R11;

25 each R6 independently represents R8; and each Cy1 independently represents phenyl.

In another embodiment the invention relates to the process described above, where:

30 each R 1 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R 2 independently represents C 1-C40 alkyl optionally substituted by one or more R 5, preferably each R 2 independently represents Cy 2

35 optionally substituted by one or more R7;

image63

each R 3 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R 4 independently represents C 1-C20 alkyl optionally substituted by

5 one or more R10; each R6 independently represents R8; and each Cy1 independently represents phenyl.

In another embodiment the invention relates to the process described above,

10 where: each R 1 ind independently represents hydrogen, halogen, C 1-C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the quilo is optionally e substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R2 independently represents C 1-C40 alkyl optionally substituted by

15 one or more R 5, preferably each R 2 independently represents Cy 2 optionally substituted by one or more R7; each R 3 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6;

20 each R 4 independently represents C 1-C20 alkyl optionally substituted by one or more R10; two R4 groups can be joined together with the N atom forming a saturated 5- to 7-membered heterocycle that may additionally contain a heteroatom selected from N, O and S, and which may be optionally substituted by one or two R11;

25 each R6 independently represents R8; and each Cy1 independently represents phenyl.

In another embodiment the invention relates to the process described above, where:

30 each R 1 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R 2 independently represents C 1-C40 alkyl optionally substituted by one or more R 5, preferably each R 2 independently represents Cy 2

35 optionally substituted by one or more R7;

image64

each R 3 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R4 independently represents hydrogen, C1-C20 alkyl or Cy4, where C1-C20 alkyl is optionally substituted by one or more R 10 and where Cy 4 is optionally substituted by one or more R11; each R6 independently represents R8; and each Cy1 independently represents a 5 or 6 membered aromatic heterocycle containing 1 or 2 heteroatoms selected from N, O and S, and where Cy1 can be attached to the rest of the molecule through any available C or N atom.

In another embodiment, the invention relates to the process described above, where: each R 1 independently represents hydrogen, halogen, C 1 -C 20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the quilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R 2 independently represents C 1-C40 alkyl optionally substituted by one or more R 5, preferably each R 2 independently represents Cy 2 optionally substituted by one or more R 7; each R 3 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R 4 independently represents C 1-C20 alkyl optionally substituted by one or more R10; each R6 independently represents R8; and each Cy1 independently represents a 5 or 6 membered aromatic heterocycle containing 1 or 2 heteroatoms selected from N, O and S, and where Cy1 can be attached to the rest of the molecule through any available C or N atom.

In another embodiment, the invention relates to the process described above, where: each R 1 independently represents hydrogen, halogen, C 1 -C 20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the quilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R 2 independently represents C 1-C40 alkyl optionally substituted by one or more R 5, preferably each R 2 independently represents Cy 2 optionally substituted by one or more R 7; each R 3 independently represents hydrogen, halogen, C 1 -C 20 alkyl, -OR 4,

image65

5 -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the quilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R 4 independently represents C 1-C20 alkyl optionally substituted by one or more R10; two R4 groups can be joined to form a heterocycle of 5 to 7 with the N atom

10 saturated members which may additionally contain a heteroatom selected from N, O and S, and which may be optionally substituted by one or two R11; each R6 independently represents R8; and each Cy1 independently represents a 5 or 6 member aromatic heterocycle containing 1 or 2 heteroatoms selected from N, O and S, and where Cy1 may be

15 bound to the rest of the molecule through any available C or N atom.

In another embodiment, the invention relates to the process described below, wherein the compound of formula I is selected from a compound of formula Ia: where: each R 1 independently represents hydrogen hydrogen, halo, C 1 -C 20 alkyl, - OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; Y

image66

image67

5 each R 3 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6.

In another embodiment, the invention relates to the process described below, wherein the compound of formula I is selected from a compound of formula Ib:

image68 Ib

where:

15 each R 1 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; and each R 3 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally e

20 substituted by one or more R5 and Cy1 is optionally substituted by one or more R6.

In another embodiment, the invention relates to the process described below, wherein the compound of formula I is selected from a compound of formula Ic:

image69

image70

Ic

where: each R 1 ind independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4,

5 -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the quilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; and each R 3 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR4, -SR4, -Se R4, -NR 4R4, - PR4R4 or Cy1, where C 1-C20 to the kilo is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6.

In another embodiment, the invention relates to the process described above, wherein the compound of formula I is selected from the list of compounds described in examples 1 to 56.

The compounds of the present invention contain one or more basic nitrogen and could therefore form salts with acids, both organic and inorganic acids. Examples of such salts include: salts with inorganic acids s such as hydrochloric acid, hydrobromic acid, acid or iodine, nitric acid, pyloric acid, sulfuric acid or phosphoric acid; and salts with or acidic acids, such as methanesulfonic acid,

20 trifluoromethanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, ptoluenesulfonic acid, acidic or fumaric acid, oxalic acid, acetic acid, maleic acid, ascorbic acid, citric acid, lactic acid, tartaric acid, malonic acid, glycolic acid, succinic acid and propionic acid , among others. Some compounds of the present invention may contain one or more acidic prototypes and therefore may form

25 you also go out with b aces. Examples of such sales are included: salts with cations

image71

inorganic such as sodium, potassium, calcium, magnesium, lithium, aluminum, zinc, etc .; and salts formed with pharmaceutically acceptable amines such as ammonia, alkylamine s, hydroxyalkylamines, lysine, arginine, N-methylglucamine, procaine and the like.

5 There is no limitation on the type of salt that can be used, with the condition that when used for therapeutic purposes they are pharmaceutically acceptable. It is understood that these salts are pharmaceutically acceptable salts which, in medical judgment, are suitable for use in contact or with the tissues of being human or other mammals without causing an undue toxicity, irritation, allergic response or

10 similar. Pharmaceutically acceptable salts are widely known to any person skilled in the art.

The salts of a compound of formula I can be obtained during the final isolation and purification of the compounds of the invention or they can be prepared by

The treatment of a compound of formula I with a sufficient amount of the acid or base desires two to give the salt in a conventional manner. The salts of the compounds of formula I can in turn be transformed into other salts of compounds of formula I by ion exchange by means of an ion exchange resin.

The compounds of formula I and their salts may differ in certain physical properties, but are equivalent for the purposes of the invention. All salts of the compounds of formula I are included within the scope of the invention.

The compounds of the present invention can form complexes with dissolvent in which they are reacted or from which they are precipitated or crystallized. These complexes are known as solvate s. As used herein, the term "solvate" refers to a complex of variable stoichiometry formed by a solute (a compound of formula I or a salt thereof) and a solvent. Examples of solvents included in

30 pharmaceutically acceptable solvents such as water, ethanol and the like. A complex with water is known as hydrate. Solvates of the compounds of the invention (or salts thereof), including hydrates, are included within the scope of the invention.

The compounds of formula I can exist in different physical forms, that is, in amorphous form and crystalline forms. Also, the compounds of the present invention

image72

They may have the ability to crystallize in more than one way, a characteristic known as polymorphism. The polymorphs can be distinguished by several physical properties well known to those skilled in the art such as their diffracted X-ray grams, melting points or solubility. All the ways

The physics of the formula I compounds, including all their polymorphic forms ("polymorphs"), are included within the scope of the present invention.

Some compounds of the present invention could exist in the form of several diastereoisomers and / or several optical isomers. The diastereoisó mere can

10 separated by conventional techniques such as chromatography or fractional crystallization. Optical isomers can be resolved by using conventional optical resolution techniques to give optically pure isomers. This resolution can be made on synthesis intermediates that are chiral or on products of formula I. Optically pure isomers can also be

15 obtained individually using specific enantioe synthesis. The present invention covers both the individual isomers and their mixtures (for example racemic mixtures or mixtures of diastereoisomers), whether they are obtained by synthesis or by physically mixing them.

As mentioned above, the method of the present invention allows substituents (R3) to be introduced into the bay positions of a POI at a stage in which a source of fluoride and an alcohol, thiol, selenol, amine or phosphine

As will be apparent to a person skilled in the art, the precise or useful method for

The preparation of a given compound may vary depending on its chemical structure. Also, in some of the procedures detailed below, it may be necessary or convenient to protect reactive or labile groups by conventional protecting groups. Both the nature of these protecting groups and the procedures for their introduction and elimination are well known and form

30 part of the state of the art (see for example Gree ne T.W. and Wuts P.G. M, "Protective Groups in Organic Synthesis", Jo hn Wiley & Sons, 4th edition, 06-20). Whenever a protective group is present, a subsequent stage of deprotection will be necessary, which is carried out in the usual conditions in organic synthesis, such as those described in the reference mentioned above.

35

image73

Also, some compounds of the present invention can be obtained from other compounds of formula I by suitable functional group transformation reactions, in one or more stages, using widely known reactions in organic chemistry under the usual experimental conditions. These

5 interconversions can be carried out independently on R1, R 2 and R 3 and include:

the replacement of a primary mine or would be covered by a tie with an alkylating agent on condition is standard, or by reductive amination, that is, for treatment with an aldehyde or ketone in the presence of a reducing agent such as sodium cyanoborohydride or sodium triacetoxyborohydride;

the transformation of an amine into a sulfon amide by reaction with a sulfonyl halide, such as sulfonyl chloride, optionally in the presence of amounts

Catalysts of a base such as 4-dimethylaminopyridine, in a suitable solvent such as dioxane, chloroform, dichloromethane or pyridine, optionally in the presence of a base such as triethylamine or pyridine;

the transformation of an amine into an amide under standard conditions;

20 the alkylation of an amide by treatment with an alkylating agent under basic conditions;

the conversion of an alcohol into an ether or ester under standard conditions; 25 the alkylation of a thiol to obtain a thioether, under standard conditions;

partial or total oxidation of an alcohol to obtain ketones, aldehydes or carboxylic acids under standard oxidation conditions;

30 the reduction of an aldehyde or ketone to alcohol, by treatment with a reducing agent such as sodium borohydride;

the reduction of a carboxylic acid or a derivative of carboxylic acid to alcohol by treatment with a reducing agent such as diisobutylaluminum hydride or LiAlH4; the reduction of an amide to amine by treatment with a reducing agent such as LiAlH4;

image74

the oxidation of a thioether to sulfoxide or sulfone under standard conditions;

5 the transformation of an alcohol into a halogen by treatment with SOCl 2, PBr 3, tetrabutylammonium bromide in the presence of P2O5, or PI3;

the transformation of a halogen atom into an amine by reaction with a

10 amine, optionally in the presence of a suitable solvent, and preferably heating; Y

the transformation of a primary amide into a group -CN or vice versa, of a group -CN into an amide using standard conditions.

Similarly, any of the aromatic rings of the compounds of the present invention can undergo aromatic electrophilic substitution or aromatic nucleophilic substitution reactions, widely described in the literature.

The compounds of formula II and III may be commercial or prepared by methods widely described in the literature from commercial products or by the interconversion reactions of functional groups described above for a compound of formula I, and may be conveniently protected. .

Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention. The following are examples provided by way of illustration, and are not

30 is intended to be limiting of the present invention.

EXAMPLES

The invention is illustrated below by tests carried out by the inventors, which demonstrates the effectiveness of the product of the invention.

image75

ALCOXI-PDI

Method 1: Synthesis of 1-alkoxyperylene-3,4: 9,10-tetracarboxyidiimide

In a flask with a heart shape 0.1 mmol of p-erylene-3,4: 9,10 are dissolved

5 tetracarboxyidiimide in 0.3 mL of dry THF. Then 0.4 mmol of the corresponding alcohol and 0.24 mmol of TBAF (1M solution in THF) are added. Heat at 70 ° C under argon for 24 hours. The crude is dissolved in CH 2 Cl 2 and washed with water. The organic phase is dried with Na 2SO4, filtered and the solvent is removed under reduced pressure. It is purified by column chromatography with gel

10 of silica and toluene as eluent, unless otherwise specified.

Method 2: Synthesis of 1,6 (7) -dialkoxyperylene-3,4: 9,10-tetracarboxyidiimide

0.1 mmol of perylene-3,4: 9,10 are dissolved in a round bottom mat

Tetracarboxyidimide in 2 mL of dry T HF. Next, 1.2 mmol of the

15 corresponding alcohol and 0.48 mmol of TBAF (1M solution in THF). Heat at reflux of THF under argon for 24 hours. The crude is dissolved in CH2Cl2 and washed with water. The organic phase is dried with Na2SO4, filtered and the solvent is removed under reduced pressure. It is purified by cro column chromatography with silica gel and toluene as eluent, unless otherwise specified.

twenty

Method 3: Synthesis of 1-alkoxyperylene-3,4: 9,10-tetracarboxyidiimide

In a cora zon-shaped flask, 0.1 mmol of 1-bromoperylene3.4: 9,10-tetracarboxyidiimide is dissolved in 0.3 mL of dry T HF. Then 0.4 mmol of the corresponding cohol and 0.24 mmol of TBAF (1M solution in THF) are added. Be

25 heats at 70oC under the atmosphere of argon for 24 hours. The crude is dissolved in CH2Cl2 and washed with water. The organic phase is dried with Na2SO4, filtered and the solvent is removed under reduced pressure. It is purified by cro column chromatography with silica gel and toluene as eluent.

Method 4: Synthesis of 1,6 (7) -dialkoxyperylene-3,4: 9,10-tetracarboxydiimide. 0.1 mmol of 1-butoxyperylene-3,4: 9,10 tetracarboxyidiimide are dissolved in 2 mL of dry T HF in a round bottom flask. Next, 1.2 mmol of the corresponding alcohol and 0.48 mmol of TBAF (1M solution in THF) are added. Heat at reflux of THF under argon for 24 hours. The crude dissolves in

35 CH2Cl2 and wash with water. The organic phase is dried with Na2SO4, filtered and the solvent is removed under reduced pressure. It is purified by cro column chromatography with

image76

silica gel and toluene as eluent.

Method 5: Synthesis of N, N’-di- (1’-hexylheptyl) -2,5,8,11-tetrabutoxyperylene

5 3,4: 9,10-tetracarboxyidiimide, N, N'-di- (1'-hexylheptyl) -2-bromo-5,8,11-tributyloxyperylene-3,4: 9,10-tetracarboxyidiimide and N, N'- di- (1'-hexylheptyl) -2,5-dibromo-8,11-dibutoxyperylene-3,4: 9,10-tetracarboxyidiimide

0.05 mmol of 2.5, 8.11 dissolve in a heart-shaped flask

Tetrabromoperylene-3,4: 9,10-tetracarboxyidiimide in 0.5 mL of THF is co. Then 0.5 mmol of the corresponding alcohol, 0.15 mmol of CsF and 0.03 mmol of 18-crown-6 are added. It is heated at 70 oC under an argon atmosphere for 24 hours. The crude is dissolved in CH 2 Cl 2 and washed with water. The organic phase is dried with Na 2SO4, filtered and removed to the solvent under reduced pressure. It is purified

15 by column chromatography with silica gel and CH 2 Cl 2: Hexane 1: 1 as eluent.

Example 1: N, N’-di- (1’-hexylheptyl) -1-methoxyperylene-3,4: 9,10-tetracarboxy diimide

(one)

image77

Compound 1 is prepared for following method 1. Yield: 33%. It is purified by column chromatography with silica gel and chloroform: hexane 4: 1 as

eluent 1H-NMR (CDCl3) G 0.83 (t, 12H), 1.24 (broad s, 32H), 1.87 (m, 4H), 2.25 (m, 4H), 4.34 (s, 3H), 5.20 (m, 2H), 8.57 (m, 6H), 9.49 (d, 1H); 13C-NMR (CDCl3) G 14.02,

image78

22.57, 26.9 4, 29.21, 2 9.22, 31.76, 32.38, 54, 61, 56.84, 120.74, 1 21.46, 121, 87, 123.01 , 123, 41, 124.46, 126.96, 1 28.39, 128, 53, 129.20, 133.92, 1 34.30, 134, 48, 158.29, 163, 54, 164.54 ; MALDI-TOF MS m / z. > M + H + @ theoretical C 51H64N2O5 785.48, found 785.46; IR (KBr): 2855, 1695, 1658, 1597, 1462, 1409, 1327, 1262, 1094, 804, 747 cm -1; UV Vis (CH2Cl2), Omax / nm (log H): 514 (5.7), 552 (5.9).

Example 2: N, N’-di- (1’-hexylheptyl) -1.6 (7) -dimethoxyperylene-3.4: 9,10 tetracarboxidiimide (2)

image79

Compound 2 is obtained following method 2. Yield: 6% (50% isomer 1.6; 50% isomer 1.7 approx.). It is purified by column chromatography with silica gel and chloroform: hexane 4: 1 as eluent. 1H-NMR (CDCl3) G 0.83 (t, 12H), 1.23 (broad s, 32H), 1.87 (m, 4H), 2.28 (m, 4H), 4.31 (d, 6H), 5.21 (m, 2H), 8.64 (m, 4H),

9.46 (is, omero 1.6) (d, 1H) 9.54 (isomer 1.7) (d, 1H); 13 C-NMR (CDCl 3) G 14.03, 22.58, 26.9 4, 29.21, 2 9.22, 29.24, 31.75, 31, 76, 31.77, 32.42, 54.4 6, 54.96, 5 6.85, 119.38, 120, 86, 121.56, 121.97, 1 23.51, 124, 54, 127.07, 127.36, 1 27, 92, 128, 50, 128.61, 128, 68, 129.27, 130.79, 1 32.58, 133, 75, 134.14, 134.41, 1 57.33, 158, 45, 163, 88, 164.77; EM BAD DI-TOF m / z. > M + H + @ Oric C 51H64N2O5 815, 49,

20 experimental 815.52; IR (KBr): 2920, 2850, 1695, 1654, 1590, 1456, 1397, 1327, 808, 150 cm -1; UV Vis (CH2Cl2), Omax / nm (log H): 523 (4.6), 556 (4.7).

Example 3: N, N’-di- (1’-hexylheptyl) -1-ethoxyperylene-3,4: 9,10-tetracarboxyidiimide (3)

image80

Compound 3 is obtained following method 1. Yield: 36%. 1H-NMR (CDCl3) G 0.83 (t, 12H), 1.24 (broad s, 32H), 1.73 (t, 3H), 1.89 (m, 4H), 2.27 (m, 4H),

5.54 (m, 2H), 5.20 (m, 2H), 8.48 (m, 6H), 9.50 (d, 1H); 13 C-NMR (CDCl 3) G 14.01, 15.01, 22.5 6, 26.94, 2 6.95, 29.19, 29.22, 29, 65, 31.74, 31.75, 32.3 5, 54.56, 5 4.80, 66.11, 70.55, 120.31, 121.63, 123.18, 124.20, 126.79, 128.20, 129.06, 133.64, 134.29, 157.56, 163, 54, 164.52; MALDI-TOF MS m / z. > M + H + @ teó rico C 52H66N2O6 799.50, experimental 799.53; IR (KBr): 2855, 1770, 166 2, 1585, 14 58, 1323, 1 258, 804, 7 47;

10 UV Vis (CH2Cl2), Omax / nm (log H): 518 (4.7), 553 (4.8).

Example 4: N, N’-di- (1’-hexylheptyl) -1.6 (7) -diethoxyperylene-3.4: 9.10

tetracarboxyidiimide (4)

image81

4

Compound 4 is obtained following method 2. Yield: 5% (60% isomer 1.6; 40% isomer 1.7 approx.). 1H-NMR (CDCl3) G 0.83 (t, 12H), 1.23 (broad s, 32H), 1.74 (t, 6H), 1.86 (m, 4H), 2.27 (m, 4 H), 4.57 (c, 4H), 5.20 (m, 2H), 8.39-8.67 (m, 4 H), 9.57

5 (1.6 isomer) (d, 1H), 9.64 isomer 1.7 (d, 1H); 13C-NMR (CD Cl3) G 14.02, 15.07, 22.57, 26.91, 29.22, 29.24, 31.75, 31.76, 32.40, 54.48, 66, 13, 119.21, 123.86, 127.21, 128.56, 128.64, 129.31, 130.78, 133.91, 133.98, 134 30, 135.87, 136.00, 144 , 10, 144.68, 150.12, 156.68, 157.68, 163.61, 164.68; MALDI-TOF MS m / z. > M + H + @ theoretical C54H70N2O6 843.53, experimental 843.54; IR (KBr): 2920, 2838, 173 6, 1706, 16 60,

10 1590, 1333, 796, 750 cm -1; UV Vis (CH2Cl2), Omax / nm (log H): 531 (4.5), 568 (4.6).

Example 5: N, N’-di- (1’-hexylheptyl) -1-butoxyperylene-3,4: 9,10-tetracarboxyidiimide

(5)

image82

Compound 5 is obtained following method 3. Yield: 88%. 1H-NMR (CDCl3) G 0.82 (t, 12H), 1.10 (t, 3H), 1.25 (broad s, 32H), 1.68 (m, 2H), 1.87 (m, 4 H), 2.07 (m, 2H), 2.26 (m, 4 H), 4.53 (t, 2H), 5.20 (m, 2H), 8.6 0 (m, 6H) , 9, 60 (d, 1 H); 13C5 NMR (CDCl3) G 13.86, 14.02, 19.56, 22.57, 26.94, 29.20, 29.23, 29.67, 31.37, 31.75, 31.76, 32.36, 54.57, 70, 36, 120.47, 121.73, 12 3.31, 124.25, 126.90, 1 28.25, 128.30, 129.16, 133.76, 134.42, 157.82, 163.67, 164.53; EM BAD DI-TOF m / z. > M + @ theoretical C54H70N2O5 826.52, experimental 826.51; IR (KBr): 2955, 2926, 2838, 1701, 16 54, 1590, 1456, 1333, 1251, 814, 755 cm -1; UV Vi s (CH2Cl2), Omax / nm (log H): 518 (4, 8),

10 554 (4.9).

Alternatively, compound 5 is obtained following method 1. Yield: 75%.

Example 6: N, N’-di- (1’-hexylheptyl) -1.6 (7) -dutoxyperylene-3.4: 9,1015 tetracarboxyidiimide (6)

image83

Compound 6 is obtained following method 3. Yield: 4%. 1 H-NMR (CDCl 3) G 0.82 (t, 12 H), 1.08 (t, 6 H), 1.25 (broad s, 32 H), 1.68 (m, 4 H), 1.87 ( m, 4H), 2.07 (m, 4H), 2.27 (m, 4H), 4.50 (t, 4H), 5.15 (m, 2H), 8.50 (m, 4H), 9.56 (1.6 isomer) (d, 1H),

5 9.63 (isomer 1.7) (d, 1 H); 13C-NMR (CDCl3) G 13.85, 14.02, 19.57, 22.57, 22.58, 26.90, 26.92, 29.20, 29.22, 29.25, 29.68 , 31.42, 31, 74, 3 1.75, 31.77, 32.41, 54.43, 54.88, 70.31, 119.06, 120.70, 123.84, 127.17, 127.95, 128.54, 128.70, 129.27, 129.81, 130.76, 134, 31, 156.86, 158.02, 16 3.81, 164.7 4; MAL DI-TOF MS m / z:> M + @ theoretical C58H78N2O6 898.58, experimental 898.57; IR (KBr): 2955, 2920, 2844, 1695, 1649,

10 1596, 1467, 1327, 814, 744 cm -1; UV Vis (CH2Cl2), Omax / nm (log H): 530 (4.2), 569 (4.3).

Alternatively, compound 6 can be obtained following method 2.

Yield: 50% (72% isomer 1.6; 28% isomer 1.7 approx.).

Example 7: N, N’-di- (1’-hexylheptyl) -1-s-butoxyperylene-3,4: 9,10-tetracarboxyidiimide

(7)

image84

Compound 7 is obtained following method 1. Yield: 35%; 1H-NMR (CDCl3) G 0.83 (t, 12H), 1.12 (t, 3H), 1.25 (broad s, 35H), 1.87 (m, 4H), 2.10 (m, 2 H), 2.26 (m, 4H), 4.98 (m, 1H), 5.20 (m, 2H), 8.49-8.66 (m, 6H), 9.72 (d, 1 HOUR) ; 13C-NMR

5 (CDCl3) G 9.83, 14.02, 19.83, 22.57, 26.57, 26.92, 29.20, 29.23, 29.63, 29.68, 31.74, 31 , 75, 54.57, 78.78, 121.86, 123.44, 124.37, 127.12, 128.36, 128.68, 129.27, 133.91, 134.65, 157.75 , 163.12, 164.85; MALDI-TOF MS m / z. > M + @ theoretical C54H70N2O5 826.52, experimental 826.53; IR (KBr): 292 0, 2850, 1695, 1660, 1584, 1403, 1327, 1251 cm 1; UV Vis (CH2Cl2), Omax / nm (log H ): 520 (4.8), 554 (4.9).

10

Example 8: N, N’-di- (1’-hexylheptyl) -1.6 (7) -di-s-butoxyperylene-3.4: 9.10

tetracarboxyidiimide (8)

image85

image86

Compound 8 is obtained following method 2. Yield: 6% (58% isomer 1.6; 42% isomer 1.7 approx.). 1H-NMR (CDCl3) G 0.83 (t, 12H), 1.09 (t, 6H), 1.25 (broad s, 38H), 1.88 (m, 4H), 2.21 (m, 4H), 2.27 (m, 4H), 4.94 (m, 2H), 5.22 (m, 2H), 8.39-8.76 (m, 4H), 9.6 0 (isomer 1 , 6) (d, 1H), 9.67 (1.7 isomer) (d, 1H); 13C-NMR (C DCl3) G 5 9.83, 14.02, 14.11, 19, 69, 22.53, 22.68, 26.9 0, 28.21, 2 9.20, 29.36 , 29.69, 30, 91, 31.23, 31.4 3, 31.76, 3 1.92, 32.43, 33.14, 33, 21, 3.80, 3 3.82, 37, 09, 38.14, 39, 22, 54.84, 59.57, 114.05, 1 27.25, 128.08, 128.74, 129.0, 129.25, 129.31, 129.54 , 129.83, 130.15, 130.19, 139.26, 157.43, 163.24, 164.76; EM BAD DI-TOF m / z. > M + @ theoretical C58H78N2O6 898.58, experimental 898.55; IR (KBr): 2932, 2844, 169 5, 1666, 16 01,

10 1467, 1321, 814 cm -1; UV Vis (CH2Cl2), Omax / nm (log H): 525 (4.0), 564 (4.0).

Example 9: N, N’-di- (1’-hexylheptyl) -1-i-butoxyperylene-3,4: 9,10-tetracarboxyidiimide

(9)

image87

The compound 9 is obtained following method 1. Yield: 46%. 1H-NMR (CDCl3) G 0.82 (t, 12H), 1.25 (broad s, 38H), 1.89 (m, 4H), 2.27 (m, 4H), 2.44 (m, 2H), 4.30 (d, 2H), 5.20 (m, 2H), 8.59 (m, 6H), 9.6 3 (d, 1H); 13 C-NMR (CDCl 3) G 14, 01, 19.54, 22.57, 22.58, 26.93, 28.56, 29.20, 29.23, 29.66, 31.75, 32, 36, 54.58, 120.56,

20 121.75, 123, 34, 124.26, 126.90, 1 28.29, 128, 32, 129.17, 133.78, 1 34.43, 157, 90, 163.80, 164.85 ; MALDI-TOF MS m / z. > M + @ theory C 54H70N2O5 826.52, experimental 826.51; IR (KBr): 2949, 2926, 2850, 1695, 1654, 1584, 1456, 1333, 1263, 808, 744 cm -1; UV Vis (CH2Cl2), Omax / nm (log H): 517 (4.4), 554 (4.6).

image88

image89

Compound 10 is obtained following method 2. Yield: 18% (75% isomer

5 1.6; 25% isomer 1.7 approx.). 1H-NMR (CDCl3) G 0.84 (t, 12H), 1.25 (broad s, 44H), 1.8 (m, 4H), 2.29 (m, 4H), 2.41 (m, 2H), 4.27 (d, 4H), 5.20 (m, 2H), 8.50 (m, 4H), 9.57 (1.6 isomer) (d, 1H), 9.64 (isomer ro 1.7) (d, 1 H); 13C-NMR (CD Cl3) G 14.03, 19.56, 22.57, 22.5 8, 26.88, 2 6.93, 28.61, 29.20, 29, 23, 29.26, 29.68, 31.7 5, 31.76, 3 2.42, 54.46, 54.89, 119.06, 120.80, 123.85, 127.29, 127.98, 128.74, 129.29, 130.79, 134.29,

10 156.98, 158.14, 163.82, 164.91; EM MALDI-T OF m / z. > M + @ theoretical C58H78N2O6 898.58, experimental 898.54; IR (KBr): 2955, 2920, 2858, 1696, 1648, 1596, 1458, 1327, 802, 755 cm -1; UV Vis (CH2Cl2), Omax / nm (log H): 539 (4.5), 570 (4.6).

Example 11: N, N’-di- (1’-hexylheptyl) -1-decanoxyperylene-3,4: 9,1015 tetracarboxyidiimide (11)

image90

eleven

Compound 11 is obtained by method 1. Yield: 60%. 1H-NMR (CDCl3) G 0.82 (t, 15H), 1.25 (broad s, 44H), 1.6 (m, 2H), 1.87 (m, 4H), 2.12 (m, 2 H),

5.26 (m, 4H), 4.53 (t, 2H), 5.20 (m, 2H), 8.60 (m, 6H), 9.64 (d, 1H); 13C-NMR (CDCl3) G 14.02, 14, 08, 22.57, 22.65, 26.30, 2693, 29.20 29.23, 29.28, 29.33, 29.55, 29, 56, 31.75, 31.75, 31.87, 32.37, 54.58, 70.69, 120.55, 121.80, 123.38, 124.31, 126.98, 128.33, 128.38, 129.21, 133.84, 134.51, 157.89, 163.54, 164.62; EM MALDI-T OF m / z. > M + @ theoretical C 60H82N2O5 910.62, experimental 910.63; IR (KBr): 2926, 2844, 1701,

10 1660, 1584, 1461, 1316, 1257, 855, 802, 744 cm -1; UV Vis (CH 2Cl2), Omax / nm (log H): 518 (4.5), 554 (4.6).

Example 12: N, N’-di- (1’-hexylheptyl) -1.6 (7) -didecanoxyperylene-3.4: 9,10 tetracarboxyidiimide (12)

image91

Compound 12 is obtained according to method 2. Yield: 20% (74% isomer 1.6; 26% isomer 1.7 approx.). The reaction time was 72 h. 1 H-NMR (CDCl 3) G 0.82

5 (m, 18H), 1.25 (broad s, 56H), 1.6 (m, 4H), 1.87 (m, 4H), 2.08 (m, 4H), 2.27 (m, 4H), 4.49 (t, 4H), 5.20 (m, 2H), 8.39-8.67 (m, 4H), 9.57 (1.6 isomer) (d, 1H), 9 , 64 (isomer 1.7) (d, 1 H); 13 C-NMR (CDCl 3) G 1 4.03, 14.09, 22.58, 22, 66, 26.30, 26.93, 29.28, 29.55, 29.69, 31.75, 31 , 76, 31.77, 31.87, 32.43, 37.10, 54.44, 54.90, 70.65, 119.10, 120.77, 123, 88, 127.22, 128.01 , 1 28.74, 130, 82, 134.34, 156.91, 1 58.07, 163, 69,

10 164.88; EM BAD DI-TOF m / z. > M + H + @ theoretical C 70H102N2O6 1067.78, experimental 1067.81; IR (KBr): 2908, 2844, 1701, 1642, 1590, 1461, 1321 cm -1; UV Vis (CH 2Cl2), Omax / nm (log H): 535 (4.6), 571 (4.7).

Example 13: N, N’-di- (1’-hexylheptyl) -1-phenylmethoxyperylene-3,4: 9,1015 tetracarboxy diimide (13)

image92

Compound 13 is obtained following method 1. Yield: 18%. 1H-NMR (CDCl3) G 0.83 (t, 12H), 1.25 (broad s, 32H), 1.88 (m, 4H), 2.27 (m, 4H), 5.18 (m, 2H), 5.59 (s, 2H) 8.62 (m, 6H), 9.58 (d, 1H); 13C-NMR (CDCl3) G 14.01, 22.56, 26.91, 29.19,

5 29.21, 31.74, 32.37, 54.58, 70.56, 72.49, 121.12, 121.98, 123.52, 124.62, 127.04, 128.10, 128 , 52, 128.76, 128.98, 1 29.07, 129, 22, 134.05, 134.30, 1 35.06, 157, 41, 163.79, 164.66; MALDI-TOF MS m / z. > M + H + @ theoretical C57H68N2O5 861.52, experimental 861.53; IR (KBr): 2920, 2938, 1695, 1636, 1601, 1327, 125 7, 802, 744 cm -1; UV Vis (CH2Cl2), Omax / nm (log H): 514 (4.5), 550 (4.7).

10 Example 14: N, N’-di- (1’-hexylheptyl) -1-phenethoxyperylene-3,4: 9,10 tetracarboxyidiimide (14)

image93

Compound 14 is obtained following method 1. Yield: 44%. The reaction time for this compound was 72 hours. 1 H-NMR (CDCl 3) G 0.83 (t, 12H), 1.25 (broad s, 32H), 1.90 (m, 4H), 2.26 (m, 4H), 3.42 (t, 2H), 4.75 (m, 2H), 5.20 (m, 2H),

5.33-7.46 (m, 5H), 8.47 (m, 6H), 9.20 (d, 1H); 13C-NMR (CDCl3) G 14.02, 22.57, 26.93, 26.96, 29.2 0, 29.23, 2 9.67, 31.75, 31.76, 32, 36, 32 , 39, 35.82, 54.6 1, 54.88, 7 1.02, 120.70, 121, 76, 122.87, 123.34, 1 24.36, 126, 82, 127.13, 128.32, 1 28.67, 128, 89, 129.10, 133, 84, 134.11, 134.35, 13 7.42, 157.4 5, 163.80, 164.57; E M BAD DI-TOF m / z. > E + M t @ C 58H70N2O5 874.53, experimental 874.24; IR (KBr): 2955, 2932,

10 2850, 1695, 1648, 1590, 1421, 132 7, 1263, 80 8, 744 cm -1; UV Vis (CH 2Cl2), Omax / nm (log H): 517 (4.6), 552 (4.78).

Example 15: N, N’-di- (1’-hexylheptyl) -1.6 (7) - diphenethoxyperylene-3.4: 9,10 tetracarboxyidiimide (15)

image94

Compound 15 is obtained following method 2. Yield: 54% (72% isomer 1.6; 28% isomer 1.7 approx.); 1 H-NMR (THF-d8) G 0.84 (t, 12H), 1.30 (broad s, 32 H), 1.85 (m, 4H), 2.35 (m, 4H), 3.37 (t, 4H), 4.73 (t, 4H), 5.22 (m, 2H), 7.25 (t, 2H), 7.39 (t,

5 4H), 7.51 (d, 4H), 8.35 (m, 4H), 9.12 (1.6 isomer) (d, 1H), 9.20 (1.7 isomer) (d, 1H ); 13C-NMR (CDCl3) G 1 4.02, 22.57, 22.59, 26.87, 26.92, 26.96, 29.19, 29.22, 29.26, 29.35, 29, 6 9, 31.74, 3 1.76, 31.78, 32.39, 32, 42, 32.44, 35.85, 54.4 7, 54.89, 7 1.00, 71.06, 119, 26, 123.86, 127.04, 1 27.06, 127.58, 127.82, 128.53, 1 28.85, 128, 89, 130.76, 137.56, 156.47, 157.60; EM MALDI-TOF m / z:> M + @ theoretical C66H78N2O6: 994.58,

10 experimental: 994.58; IR (KBr): 2955, 2914, 2850, 1695, 1642, 1590, 1467, 1231 cm -1; UV Vis (CH2Cl2), Omax / nm (log H): 534 (4.6), 570 (4.7).

Example 16: N, N’-di- (1’-hexylheptyl) -1-butoxy-6 (7) -decanoxyperylene3,4: 9,10-tetracarboxyidiimide (16)

image95

Compound 16 is obtained following method 4. Yield: 23% (72% isomer 1.6; 28% isomer 1.7). 1H-NMR (CDCl3) G 0.83 (m, 18H), 1.29 (broad s, 42H), 1.45 (m, 4H), 1.63 (m, 4H), 1.8 6 (m , 4H), 2.08 (m, 2H), 2.28 (m, 4H), 4.49 (t, 4H), 5.20 (m, 2H), 5 8.55 (m, 4H), 9.56 (1.6 isomer) (d, 1H), 9.65 (1.7 isomer) (d, 1H); 13C-NMR (CDCl3) G 14.02, 14.08, 22.57, 2 2.65, 26.30, 26.90, 26.9 3, 29.20, 29, 22, 29.25, 29 , 28, 29.31, 29.36, 29.54, 31.75, 31.77, 31.87, 32.42, 54.43, 54.88, 70.63, 119.06, 120.72 , 123.85, 127.19, 127, 97, 128.56, 128.72, 1 29.29, 130, 45, 130.78, 131.17, 1 34.32, 156, 88, 158.04 , 163.70, 164.10, 164.64, 165.14; MALDI-TOF MS m / z. > M + @ theoretical C64H90N2O6

10 982.68, experimental 981.54; IR (KBr): 2955, 2926, 2844, 1686, 168 5, 1596, 14 67, 1321, 855, 802, 744 cm -1; UV Vis (CH2Cl2), Omax / nm (log H): 536 (5.1), 570 (5.2).

Example 17: N, N'-di- (1'-hexylheptyl) -1- {2 '[2' '- (2' '- hydroxyethoxy) ethoxy] ethoxy} perylene3,4: 9,10-tetracarboxyidiimide (17 )

image96

Compound 17 is obtained following method 1. Yield: 7% The reaction time for this compound was 72 hours. It is purified by column chromatography with silica gel and toluene: methanol 9: 1 as eluent. 1 H-NMR (CDCl 3) G 5 0.83 (t, 12 H), 1.25 (broad s, 32 H), 1.86 (m, 4 H), 2.26 (m, 4 H), 3.69 ( m, 2H), 3.77 (m, 2H), 3.84 (m, 2H), 3.90 (m, 2H), 4.13 (m, 2H), 4.68 (m, 2H), 5.20 (m, 2H), 8.48 (m, 6H), 9.79 (d, 1H); 13C-NMR (CDCl3) G 14.03, 22.57, 26.91, 29.20, 29.21, 29.68, 31.74, 31.75, 32.3 8, 54.65, 3 1 , 74, 68.45, 69.26, 69, 54, 70.60, 70.65, 71.0 0, 71.08, 7 1.19, 72.44, 72.72, 121.24, 122 , 01, 123.56, 124.67, 127.11, 128.53, 129.14, 129.25, 134.12,

10 134.49, 157.59, 163.73, 164.82; MALDI-TOF MS m / z. > M + @ theoretical C56H74N2O8 902.54, experimental 902.55; I R (KBr): 29 55, 2926, 2 844, 1736, 1683, 1596, 1666, 146 1, 1333, 1129, 808, 744 cm1; UV Vis (CH2Cl2), Omax / nm (log H): 516 (4.6), 551 (4.75).

Example 18: N, N’-di- (1’-hexylheptyl) -1- (2’-hydroxyethoxy) perylene-3,4: 9,1015 tetracarboxyidiimide (18)

image97

18

Compound 18 is obtained following method 1. Yield: 43%. The reaction time for this compound was 72 hours. It is purified by column chromatography with silica gel and toluene: methanol 9: 1 as eluent. 1 H-NMR (THF-d8) G

5 0.86 (t, 12H), 1.35 (broad s, 32H), 1.88 (m, 4 H), 2.32 (m, 4H), 4.17 (t, 2H), 4, 57 (t, 2H), 5.18 (m, 2H), 8.40 (m, 6H), 9.60 (d, 1H); 13C-NMR (CDCl3) G 14.02, 22.58, 26.97, 29.23, 31.76, 32.35, 47.17, 54.67, 61.25, 63.03, 69.32 , 70.53, 71.62, 121.78, 122.0 3, 123.29, 124.45, 126.76, 128.22, 128.47, 129.03, 129.80, 134.14, 134.22, 157.39; MALDI-TOF MS m / z:> M + @ theoretical C52H66N2O6: 81 4.49, experimental: 814.48; IR (KBr):

10 3451, 2955, 2926, 2850, 1695, 164 8, 1578, 1339 cm -1; UV Vis (CH 2Cl2), Omax / nm (log H): 512 (4.6), 547 (4.7).

Example 19: N, N’-di- (1’-hexylheptyl) -1- (8’-hydroxyoctyloxy) perylene-3,4: 9,10 tetracarboxidiimide (19)

image98

Compound 19 can be prepared following method 1. Yield: 26%. 1H-NMR (THF-d8) G 0.86 (t, 12H), 1.42 (broad s, 42H), 1.88 (m, 4H), 2.1 6 (m, 2H), 2.33 (m, 4H), 3.51 (t, 2H), 4.50 (t, 2H), 5.19 (m, 2H), 8.41 (m, 6H), 9.44 (d, 1H) ; 13C-NMR

5 (CDCl3) G 22.57, 25.70, 26.24, 26.92, 29.20, 29.22, 29.25, 29.34, 31.75, 32.38, 32.71, 54 , 64, 62.90, 70.71, 12 0.63, 121.91, 123.52, 1 24.38, 127.06, 128.38, 128.46, 128.64, 129.26, 13 3.95, 134.6 3, 157.96; MAL DI-TOF MS m / z:> M + @ theoretical C 58H78N2O6: 898.58, experimental: 998.61; IR (KBr): 3440, 2958, 2921, 2847, 1699, 1650, 1580, 1323 cm -1; UV Vis (CH2Cl2), Omax / nm (log H): 518 (4.8), 554 (4.9).

10 Example 20: N, N’-di- (1’-hexylheptyl) -1.6 (7) -di- (8’-hydroxyoctyloxy) perylene-3.4: 9,10 tetracarboxyidiimide (20)

image99

image100

Compound 20 is obtained following method 2. Yield: 48% (75% isomer 1.6; 25% isomer 1.7 to prox.); 1H-NMR (THF-d8) G 0.85 (t, 1 2H), 1.40 (broad s, 52H), 1.86 (m, 4H), 2.12 (m, 4H), 2.35 (m, 4H), 3.50 (t, 4H), 4.49 (t, 4H), 5.20 (m, 2H), 8.278.55 (m, 4H), 9.48 (1.6 isomer ) (d, 1H), 9.56 (1.7 isomer) (d, 1H); 13C-NMR (CDCl3)

5 G 14.03, 22.58, 25.68, 26.24, 26.91, 26.92, 29.20, 29.22, 29.24, 29.36, 29.68, 31.75, 31, 76, 32.4 0, 32.73, 5 4.54, 54.92, 62.91, 70, 63, 72.23, 123.41, 1 23.82, 127, 17, 127.93, 128 , 71, 130.73, 131.96, 13 4.39, 158.08; MALDI-TOF MS m / z:> M + @ theoretical C66H94N2O8: 1042.70, experimental: 1042.72; IR (KBr): 3444, 2917, 2855, 1699, 1650, 1585 cm -1; UV Vis (CH2Cl2), Omax / nm (log H): 539 (4.7), 569 (4.7).

Example 21: N, N’-di- (1’-hexylheptyl) -2,5,8,11-tetrabutoxyperylene-3,4: 9,10 tetracarboxyidiimide (21)

image101

Compound 21 is obtained according to method 5. Yield: 8%. 1H-NMR (CDCl3) G 0.83 (t, 12H), 1.05 (t, 12H), 1.25 (br, 32H), 1.65 (m, 8H), 1.86 (m, 4H ), 2.04 (m, 8H), 2.23 (m, 4 H), 4.44 (m, 8H), 5.19 (m, 2 H), 7, 99 (s, 4H). 13C-NMR (CDCl3) G 13, 76, 13.96, 19.0 8, 22.48, 2 6.90, 29.20, 29.56, 31, 24, 31.70, 32.22, 53 , 2 7, 53.86, 7 0.37, 98.82, 109.73, 116.65, 133.87, 162.74. EM MALDI-T OF m / z:> M + H + @ theoretical

20 C66H94N2O8 1043.70, experimental 1043.71. IR (KBr): 2973, 2920, 28 44, 1689, 1 648, 1590, 1351, 1257, 855 cm-1. UV Vis (CH2Cl2), Omax / nm (log H): 412 (4.2), 497 (4.5), 535 (4.6).

image102

Example 21a: N, N’-di- (1’-hexylheptyl) -2-bromo-5,8,11-tributoxyperylene-3,4: 9,10 tetracarboxyidiimide (21a)

image103

Compound 21a is obtained according to method 5. Yield: 28%. 1 H-NMR (CDCl3)

5 G 0.83 (t, 12H), 1.06 (m, 9H), 1.24 (br, 32H), 1.65 (m, 6H), 1.86 (m, 4H), 2.04 (m, 6H), 2.22 (m, 4H), 4.45 (m, 6H), 5.19 (m, 2H), 7.95 (s, 1H), 8.00 (s, 1H) , 8.09 (s, 1 H), 8.52 (s, 1 H). 13 C-NMR (CDCl 3) G 13.86, 13.89, 14.05, 19.19, 19.21, 22.58, 22.61, 27.00, 27.03, 29.2 5, 29 , 33, 3 1.31, 31.35, 31.38, 31, 78, 31.82, 32.27, 32.3 3, 54.04, 7 0.40, 70.57, 110, 00, 116.46, 120.63, 1 28.49, 132, 08, 133.26, 133.36, 1 33.95, 134, 06,

10 162.65, 162.83, 162.87. MALDI-TOF MS m / z:> M + @ theoretical C 62H85N2O7Br 1048, 55, experimental 1048.72. I R (KBr): 2949, 2926, 2 862, 2360, 1695, 1642, 1549, 133 9, 1251, 1100, 796 cm -1. UV Vis (CH2Cl2), Omax / nm (log H): 403 (4.3), 496 (4.7), 535 (4.8).

image104

Example 21b: N, N’-di- (1’-hexylheptyl) -2,5-dibromo-8,11-dibutoxyperylene-3,4: 9,10 tetracarboxyidiimide (mixture of isomers) (21b)

image105

21b Compound 21b is obtained according to method 5. Yield: 29%. 1 H-NMR

5 (CDCl3) G 0.83 (t, 12H), 1.06 (m, 6H), 1.24 (br, 32H), 1.67 (m, 4H), 1.89 (m, 4H), 2.05 (m, 4H), 2.22 (m, 4H), 4.48 (q, 4H), 5.17 (m, 2H), 8.12 (d, 2H), 8.54 (d , 2H). 13C-NMR (CDCl3) G 12.86, 13.05, 18.17, 18.19, 21.58, 25.99, 28.24, 28.68, 30.32, 30.77, 31.25 , 69.57, 69.70, 110.93, 119.34, 119.45, 127.54, 128.13, 131.03, 131.59, 132.28, 133.28, 133.81, 161 , 63. EM MALDI-T OF m / z:> M + H + @ theoretical C 58H76N2O6Br2 1055.40,

10 experimental 1055.34. IR (KBr): 2973, 2920, 2844, 1689, 1648, 1590, 1351, 1257, 855 cm-1. UV Vis (CH2Cl2), Omax / nm (log H): 405 (4.1), 494 (4.5), 530 (4.6).

Example 22: N, N’-di- (1’-hexylheptyl) -1-hydroxyperylene-3,4: 9,10-tetracarboxy diimide

(22)

fifteen

image106

Compound 22 is obtained following method 1. Yield: 40%. Water is used as reagent instead of alcohol l. It is purified by column chromatography with silica gel and hexane: dioxane 4: 1 as eluent. 1H-NMR (T HF-d8) G 0.85 (t, 5 12H), 1.27-1.29 (m, 32H), 1.88 (m, 4H), 2.32 (m, 4H) , 5.21 (m, 2H), 8.08-8.49 (m, 6H), 9.48 (d, 1H), 11.03 (s, 1H); 13C-NMR (CDCl3) G 13.94, 14.03, 22.5, 22.60, 26. 96, 27.025, 29.18, 29.25, 31.67, 31.80, 32.41, 70.46, 118.70, 121.59, 122.89, 122.92, 122.95, 124 .15, 124.24, 126.49 , 1 28.35, 128. 98, 129.03, 132.71, 1 34.27, 134. 32, 140.52, 156.05, 219.99; MALDI-TOF MS m / z:> M-H @ theoretical C 50H61N2O5: 769.4 5,

10 experimental: 769.44; IR (KBr): 35 52, 2949, 2929, 2847, 1736, 1695, 1658, 1580, 1331 cm -1; UV Vis (CH2Cl2), Omax / nm (log H): 504 (4.6), 541 (4.8).

RENT-POI

Method 1: Synthesis of 1-alkyl (aryl) aminoperylene-3,4: 9,10-tetracarboxyidiimide N, N'-disubstituted

0.2 mmol of N, N'-disubstituted tetracarboxyidiimide, 0.48 mL of t-tetrabutylammonium fluoride (1M solution in THF, 0, are added in a 5 mL cor azon flask. 48 mmol), 0.48 mmol of the corresponding amine and 4 drops

20 of dry THF to mogenize the mixture. It was heated at reflux of THF under an argon atmosphere for 24 hours. The crude is dissolved in CH 2 Cl 2 and washed with water. The organic phase is dried with Na 2SO4, filtered and the solvent is removed under a red pressure. It is purified by column chromatography with silica gel

image107

using a mixture of dichloromet anus: hexane (1: 1) as eluent unless otherwise indicated.

Method 2: Synthesis of 1.6 (7) -di [alkyl (aryl) amino] perylene-3,4: 9,10

5, N'-disubstituted tetracarboxyidiimide In a 10 mL round bottom flask 0.2 mmol of perylene-3,4: 9,10 N, N'-disubstituted tetracarboxyidimide was dissolved in 4 mL of dry THF. It is then added in 0.48 mmol of the corresponding amine and 0.48 mL of TBAF (1M solution in THF, 0.48 mmol). It is heated under reflux of THF under an argon atmosphere for 24 hours. He

10 crude is dissolved in CH 2 Cl 2 and washed with water. The organic phase is dried with Na2SO4, filtered and the solvent is removed under a red acid pressure. It is purified by column chromatography with silica gel and using a mixture of dichloromethane: hexane (1: 1) as eluent, unless otherwise indicated.

Method 3: 1,6,7-tri [alkyl (aryl) amino] perylene-3,4: 9,10-tetracarboxyidiimide N, N-substituted N and [1,12-dialkyl (aryl) amino] perylene-3, 4: 9,10-tetracarboxyidiimide N, N-substituted To a 5 mL heart flask is added 0.2 μmol of per ileum-3,4: 9,10 tetracarboxyidiimide N, N'-disubstituted, 1.2 mL tetrabutylammonium fluoride (solution

1M in THF, 1.2 mmol), 3.2 mmol of the corresponding amine (16 eq) and 4 drops of dry THF to homogenize the mixture. It is heated to ref luxury of THF under an argon atmosphere for 24 hours. The crude is dissolved in CH 2 Cl 2 and washed with water. The organic phase is dried with Na 2SO4, filtered and the solvent is removed under reduced pressure. It is purified by cro column chromatography with silica gel and used

25 a mixture of dichloromethane: hexane (1: 1) as eluted te, unless otherwise indicated.

Example 23: N, N’-bis (1’-hexylheptyl) -1- (piperidin-N-yl) perylene-3,4: 9,10 tetracarboxidiimide (23)

30

image108

Compound 23 is obtained following method 1. Amine: piperidine. Yield: 53%. 1H-NMR (CDCl3) į 0.82 (t, 1 2H, CH3), 1.27 (broad s, 34H, C H2 and CH2 piperidine),

5.85 (m, 8H, C H2 and CH2 piperidine), 2.26 (m, 4H, C H2), 2.96 (m, 2H, C H2 piperidine), 3.49 (m, 2H, CH2 piperidine), 5.20 (m, 2H, N-CH), 8.57 (m, 6H, ArH), 9.87 (d, 1H, ArH); MALDI-TOF MS m / z:> M + @ theoretical C 55H71N3O4: 837.54, experimental: 837.52; IR (KBr) (cm -1): 2,952, 2,925, 2,854, 1,695, 1,654, 1,589, 1,409, 1,330, 1,249; UV-vis (CHCl 3) Ȝmax / nm (log İ): 447 (4.25), 601 (4.35).

10 Example 24: N, N’-bis (1’-hexylheptyl) -1,6,7-tri (piperidin-N-yl) perylene-3,4: 9,10 tetracarboxyidiimide (24)

image109

image110

OR NOT

N N

image111 N

image112

image113

OR NOT

image114

image115

image116

image117

image118

24

Compound 24 is obtained according to method 3. Amine: piperidine. Yield: 55%.

1H-NMR (CDCl3) į 0.83 (t, 12H, CH3), 1.26 (broad s, 40H, CH2 and CH2 piperidine), 1.70 (m,

4H, CH2 piperidine), 1.89 (m, 14H, C H2 and CH2 piperidine), 2.27 (m, 4H, C H2), 2.41 (t, 1H, CH 2

5 piperidine) 3.22 (m, 2H, C H2 piperidine), 3.46 (m, 2H, C H2 piperidine), 3.66 (m, 1H, C H2 piperidine), 4.22 (m, 2H, C H2 piperidine), 5.21 (m, 2H, N-CH), 8.36 (m, 1H, Ar H), 8.44 (m, 2H, ArH), 8.57 (m, 1 H, ArH), 9.84 (d, 1H, ArH); MALDI-TOF MS m / z:> M + @ theoretical C65H89N5O4: 1,003.69, experimental: 1,003.68; I R (KBr) (cm -1): 2,925, 2 .854, 1,687, 1,650, 1,558, 1,452, 1,438, 1,413, 1,380, 1,334, 1,305, 1,265, 1,257; UV-vis (CHCl 3) Ȝmax / nm (log İ):

10 571 (4.16), 708 (4.52)

Example 25: N, N’-bis (1’-hexylheptyl) -1,12-di (piperidin-N-yl) perylene-3,4: 9,10 tetracarboxyidiimide (25)

image119

Compound 25 is obtained according to method 3. Amine. Piperidine Yield: 13%. 1H-NMR (CDCl3) į 0.83 (t, 12H, C H3), 1.26 (broad s, 36H, CH2 and CH2 piperidine), 1.47 (m,

5 4H, CH2 piperidine), 1.74 (m, 2H, C H2 piperidine), 1.89 (m, 6H, C H2 and CH2 piperidine), 2.00 (m, 2H, C H2 pipe ridicule), 2 , 13 (t, 2H, C H2 piperidine), 2.29 (m, 4 H, C H2), 3.48 (t, 2H, Į-CH2 piperidine), 4.32 (m, 2H, CH2 piperidine) , 5.24 (m, 2H, N-CH), 8.58 (m, 4H, ArH), 8.64 (m, 2H, ArH). MALDI-TOF MS m / z:> M + @ theoretical C60H80N4O4: 920.62, experimental: 920.39. IR (KBr) (cm -1): 2,954, 2,925, 2,854, 1,689, 1,665 2, 1,585, 1,461, 1,438, 1,411, 1,376,

10 1,307, 1,259, 806. UV-vis (CHCl3) Ȝmax / nm (log İ): 436 (3.97), 556 (4.01), 676 (4.43).

Example 26: N, N’-bis (1’-hexylheptyl) -1.6 (7) -di (piperidin-N-yl) perylene-3.4: 9,10 tetracarboxyidiimide (26)

image120

26

Compound 26 is obtained according to method 2. Amine: piperidine. Performance: 30% (67% isomer 1.6; 33% isomer 1.7 approx.). 1H-NMR (CDCl 3) į 0.83 (t, 12H, C H3), 1.26 (broad s, 36H, C H2 and CH2 piperidine), 1.80 (m, 12H, CH2 and CH2 piperidine), 2 , 25 (m, 4H,

5 CH2), 2.93 (m, 4H, C H2 piperidine), 3.39 (m, 2H, C H2 piperidine), 3.54 (m, 2H, C H2 piperidine), 5.19 (m, 2H , N-CH), 8.58 (m, 4H, Ar H), 9.68 (1.6 isomer) (d, 1H, Ar H), 9.74 (1.7 isomer) (d, 1H, ArH). MALDI-TOF MS m / z:> M + @ theoretical C60H80N4O4: 920.62, experimental: 920.39. IR (KBr) (cm-1): 2,924, 2,853, 1,692, 1,653, 1,584, 1,451, 1,411, 1,338, 1,321, 1,249, 1,219, 809. UV-vis (CHCl3) Ȝmax / nm (log İ): 400 ( 4.04), 435 (3.91), 659 (4.36).

10 Example 27: N, N’-bis (1’-hexylheptyl) -1.6 (7) -di (morpholin-N-yl) perylene-3.4: 9,10 tetracarboxyidiimide (27)

image121

Compound 27 is obtained following method 3. Amine: Morpholine. Eluent used in column chromatography: dichloromethane to obtain 27 followed by dichloromethane: ethyl acetate (9: 1) to obtain 28. Yield: 22% (50% isomer

5 1.6; 50% isomer 1.7 approx.). 1H-NMR (CDCl3) į 0.84 (t, 12H, C H3), 1.26 (sa ncha, 32H, CH2), 1.86 (m, 4H, CH2), 2.26 (m, 4H, CH2), 3.14 (m, 4H, CH2 morpholine), 3.30 (d, 2H, CH2 morpholine), 3.46 (d, 2H, C H2 morpholin), 3.96 (m, 8H, C H2 mor folina), 5.19 (m, 2H, NC H), 8.47 (m, 4H, ArH), 9.84 (1.6 isomer) (d, 1H, ArH), 9.90 (isomer 1.7) (d, 1H, ArH). EM

-

MALDI-TOF m / z:> M + @ theoretical C58H76N4O6: 924.58, experimental: 924.12. IR (KBr) (cm

10 1): 2,958, 2,923, 2,854, 1,693, 1,652, 1,594, 1,585, 1,413, 1,334, 1,322, 1,259, 1,118, 1,093, 1,024. UV-vis (CHCl3) Ȝmax / nm (log İ): 400 (3.92), 426 (3.95), 640 (4.31).

Example 28: N, N’-bis (1’-hexylheptyl) -1,6,7-tri (morpholin-N-yl) perylene-3,4: 9,10 tetracarboxidiimide (28)

fifteen

image122

Compound 28 is obtained by method 3. Amine: morpholine. Eluent used in column chromatography: dichloromethane to obtain 27 followed by dichloromethane: ethyl acetate (9: 1) to obtain 28. Yield: 40%. 1 H-NMR

5 (CDCl3) į 0.84 (t, 12H, C H3), 1.26 (broad s, 32H, C H2), 1.88 (m, 6H, C H2 and C H2 morpholine), 2.26 ( m, 6H, CH2 and C H2 mor folina), 2.45 (m, 1H, C H2 morpholine), 2.65 (m, 1H, CH2 morpholine), 3.17 (m, 2H, CH2 morpholin), 3.37 (m, 2H, CH2 morpholine), 3.51 (m, 2 H, CH2 morpholine), 3.80 (m, 4H, C H2 morpholine), 4.09 (m, 8H, C H2 morph oline ), 5.21 (m, 2H, NC H), 8.48 (m, 4H, ArH), 9.82 (d, 1H, Ar H). MALDI-TOF MS m / z:> M + @ theoretical C 62H83N5O7: 1,009.63,

10 experimental: 1,009.09. IR (KBr) (cm -1): 2,954, 2,923, 2,853, 1,689, 1,651, 1,585, 1,457, 1,415, 1,364, 1,332, 1,305, 1,254, 1,114. UV-vis (CHCl3) Ȝmax / nm (log İ): 556 (4.23), 681 (4.53).

Example 29: N, N’-bis (1’-hexylheptyl) -1- (4-methylpiperazin-1-yl) perylene-3,4: 9,1015 tetracarboxyidiimide (29)

image123

29

Compound 29 is obtained following method 3. Amine: 1-Methylpiperazine. Eluent used in column chromatography: dichloromethane: ethyl acetate (1: 2). Yield: 43%. 1H-NMR (CDCl3) į 0.83 (t, 12H, C H3), 1.28 (broad s, 32H, C H2),

5.85 (m, 4 H, C H2), 2.23 (m, 4H, C H2), 2.53 (s, 3H, C H3 piperazine), 2.69 (m, 2 H, C H2 piperazine), 3.00 (m, 2H, CH2 piperazine), 3.27 (m, 2H, CH2 piperazine), 3.52 (m, 2H, CH2 piperazine), 5.18 (m, 2 H, N- CH), 8.60 (m, 6H, ArH), 9.93 (d, 1H, Ar H). MAL DI-TOF MS m / z:> M + @ theoretical C55H72N4O4: 852.56, experimental: 852.08. IR (KBr) (cm-1): 2,952, 2,925, 2,854, 1,695, 1,654, 1,589, 1,459, 1,409, 1,332, 1,249, 809. UV-vis (CHCl3) Ȝmax / nm (log İ):

10 446 (3.16), 591 (3.34).

Example 30: N, N’-bis (1’-hexylheptyl) -1,6-di (4-methylpiperazin-1-yl) perylene-3,4: 9,10 tetracarboxyidiimide (30)

image124

OR NOT

image125

N

image126 N

N

N

image127

image128

image129

OR image130 N image131 OR

image132

image133

Compound 30 is obtained following method 3 Amine: 1-Methylpiperazine. Yield: 19%. 1H-NMR (CDCl3) į 0.84 (t, 12H, C H3), 1.26 (broad s, 32H, C H2), 1.87 (m, 4 H, C H2), 2.25 (m , 4H, C H2), 2.51 (s, 6H, C H3 piperazine), 2.63 (m, 4 H, C H2

5 piperazine), 2.96 (m, 4H, CH2 piperazine), 3.18 (m, 4H, CH2 piperazine), 3.42 (m, 4H, CH2 piperazine), 5.21 (m, 2 H, NC H), 8.40 (s, 2H, Ar H), 8.62 (m, 2 H, Ar H), 9.77 (d, 2H, Ar H). EM

-

MALDI-TOF m / z:> M + @ theoretical C60H82N6O4: 950.64, experimental: 950.40. IR (KBr) (cm1): 2,924, 2,852, 1,693, 1,653, 1,585, 1,460, 1,426, 1,339, 1,319, 1,261, 1,246, 1,142. UV-vis (CHCl3) Ȝmax / nm (log İ): 634 (4.30).

10

Example 31: N, N’-bis (1’-hexylheptyl) -1,7-di (4-methylpiperazin-1-yl) perylene-3,4: 9,10 tetracarboxidiimide

image134

Compound 31 is obtained following method 3. Amine: 1-methylpiperazine. Yield: 5%. 1H-NMR (C DCl3) į 0.83 (t, 12H, C H3), 1.25 (broad s, 32H, C H2),

5.83 (m, 4 H, C H2), 2.23 (m, 4H, C H2), 2.56 (s, 6H, C H3 piperazine), 2.70 (m, 4 H, C H2 piperazine), 3.02 (m, 4H, CH2 piperazine), 3.31 (m, 4H, CH2 piperazine), 3.59 (m, 4H, CH2 piperazine), 5.18 (m, 2 H, N- CH), 8.46 (m, 4H, ArH), 9.69 (d, 2H, Ar H). MAL DI-TOF MS m / z:> M + @ theoretical C60H82N6O4: 950.64, experimental: 950.89. IR (KBr) (cm-1): 2,954, 2,925, 2,854, 1,693, 1,652, 1,594, 1,583, 1,413, 1,340, 1,324, 1,255. UV-vis (CHCl 3) Ȝmax / nm (log İ):

10 429 (3.82), 661 (3.96).

Example 32: N, N’-di- (1’-hexylheptyl) -1- (phenylamino) -3.4: 9,10-tetracarboxyidiimide

(32)

image135

Compound 32 is obtained by method 1. Amine: Aniline. Yield: 72%. 1H-NMR (CDCl3) į 0.82 (t, 12H, C H3), 1.25 (broad s, 32H, C H2), 1.85 (m, 4 H, CH2), 2.20 (m, 4H, CH2), 5.50 (m, 2H, N-CH), 6.94 (broad s, 1H, NH) 7.17 (m, 3H, ArH), 7.41

5 (m, 1H, ArH), 8.50 (m, 4H, ArH), 8.65 (m, 2H, ArH), 9.17 (d, 1H, ArH). MALDI-TOF MS m / z:> M + @ oric te C 56H67N3O4: 845.5 1, experimental: 845.31. IR (KBr) (cm -1): 3,319, 2,954, 2,924, 2,854, 1,694, 1,654, 1,589, 1,418, 1,332, 1,270, 1,248. UV-vis (CHCl 3) Ȝmax / nm (log İ): 449 (3.81), 606 (3.93).

10 Example 33: N, N’-bis (1’-cyclohexyl) -1,6-di (piperidin-N-yl) perylene-3,4: 9,10 tetracarboxidiimide (33)

image136

33

Compound 33 is obtained following method 1. Amin: Piperidine. Eluent used in column chromatography: dichloromethane: hexane (9: 1). Yield: 19%. 1H-NMR (CDCl3) į 1.45 (m, 10H, CH2 and CH2 piperidine), 1.77-1.89 (m, 18H, CH2 and CH2 piperidine),

5 2.58 (m, 4H, CH2), 2.86 (m, 4H, CH2 piperidine), 3.37 (m, 4H, CH2 piperidine), 5.05 (m, 2H, N-CH), 8 , 37 (s, 2H, ArH), 8.58 (d, 2H, ArH), 9.73 (d, 2H, ArH). MALDI-TOF MS m / z:> M + @ theoretical C 46H48N4O4: 7 20.37, experimental: 719.83. L. Fan, Y. X u and H. Tian; Tetrahedron Lett. 2005, 46, 4443-4447.

10 Example 34: N, N’-bis (1’-cyclohexyl) -1,7-di (piperidin-N-yl) perylene-3,4: 9,10 tetracarboxidiimide (34)

image137

Compound 34 is obtained following method 1. Amin: Piperidine. Eluent used in column chromatography: dichloromethane: hexane (9: 1). Yield: 9%. 1 HOUR

image138

NMR (CDCl3) į 1.46 (m, 10H, CH2 and CH2 piperidine), 1.76-1.94 (m, 18H, CH2 and CH2 piperidine), 2.58 (m, 4H, CH2), 2.91 (m, 4H, CH2 piperidine), 3.48 (m, 4H, CH2 piperidine), 5.05 (m, 2H, N-CH), 8.38 (d, 2H, ArH), 8.44 (d , 2H, ArH), 9.61 (d, 2H, ArH). MALDI-TOF MS m / z:> M + @ theoretical C 46H48N4O4: 7 20.37, experimental: 720.21. L. Fan, Y. Xu and H. Ti an; Tetrahedron Lett. 2005, 46, 4443-4447.

Example 35: N, N’-bis (1’-cyclohexyl) -1,6,7-tri (piperidin-N-yl) perylene-3,4: 9,10 tetracarboxidiimide (35)

image139

Compound 35 is obtained following method 1. Amine: Piperidine. Eluent used in column chromatography: dichloromethane: hexane (9: 1). Yield: 4%. 1H-NMR (CDCl3) į 1.41 (m, 12H, CH2 and CH2 piperidine), 1.61-2.19 (m, 26H, CH2 and CH2 piperidine), 2.40 (m, 1H, C H2 piperidine) , 2.62 (m, 4H, C H2), 3.20 (m, 2H, C H2 piperidine), 3.46 (m, 2H, CH2 piperidine), 3.64 (m, 1H, CH2 piperidine), 4.19 (m, 2H, C H2 piperidine), 5.10 (m, 2H, N-CH),

8.34 (s, 1H, Ar H), 8.44 (d, 2H, ArH), 8.54 (s, 1H, ArH), 9.83 (d, 1H, Ar H). MALDI-TOF MS m / z:> M + @ theoretical C 51H57N5O4: 803.44, experimental: 802.89. IR (KBr) (cm -1): 2.927, 2.85 2, 1.687, 1. 650, 1.581, 1.450, 1.4 40, 1.413, 1.334, 1.30 5, 1.259, 1.022,

804. UV-vis (CHCl3) Ȝmax / nm (log İ): 577 (4.04), 706 (4.37).

Example 36: N, N’-bis (1’-cyclohexyl) -1- (piperidin-N-yl) perylene-3,4: 9,10 tetracarboxyidiimide (36)

image140

36

Compound 36 is obtained following method 1. Amin: Piperidine. Eluent used

in column chromatography: dichloromethane: hexane (9: 1). Yield: 5%. 1 HOUR-

NMR (CDCl3) į 1.46 (m, 8H, C H2 and CH2 piperidine), 1.76 (m, 8H, C H2 and CH2 piperidine), 1.85

5 (m, 6H, C H2 and CH2 piperidine), 2.58 (m, 4H, C H2), 2.92 (m, 2H, C H2 piperidine), 3.44 (m, 2H, CH2 piperidine), 5.06 (m, 2 H, NC H), 8.48 (m, 3H, ArH), 8.54 (s, 1H, Ar H), 8.59 (d, 1H, ArH), 8.62 (d, 1H, Ar H), 9.82 (d, 1H, Ar H). MALDI-TOF MS m / z:> M + @ theoretical C41H39N3O4: 637.29, experimental: 636.96. K-Y. Chen, T-C. Fang and M-J. Chan g; Dyes Pigments. 2011, 92, 517-523.

10 Example 37: N, N’-bis (1’-cyclohexyl) -1,12-di (piperidin-N-yl) perylene-3,4: 9,10 tetracarboxidiimide (37)

image141

image142

Compound 37 is obtained following method 1. Amin: Piperidine. Eluent used in column chromatography: dichloromethane: hexane (9: 1). Yield: 8%. 1H-NMR (CDCl3) į 1.45 (m, 12H, CH2 and CH2 piperidine), 1.65-2.02 (m, 18H, CH2 and CH2 piperidine), 2.11 (m, 2H, C H2 piperidine) , 2.62 (m, 4H, C H2), 3.49 (m, 2H, C H2 piperidine), 4.30 (m, 2H,

5 CH2 piperidine), 5.11 (m, 2H, N-CH), 8.54 (m, 4H, ArH), 8.64 (s, 2H, ArH). MALDI-TOF MS m / z:> M + @ oric C 46H48N4O4: 720.3 7, experimental: 719.86. IR (KBr) (cm -1): 2.923, 2.852, 1.68 9, 1.650, 1. 585, 1.438, 1.409, 1.3 75, 1.307, 1.259, 1.02 2, 804. UV-vis (CHCl3) Ȝmax / nm (log Й): 417 (3.79), 437 (3.82), 558 (3.87), 674 (4.20).

10 RENT-POI

Method 1: Synthesis of 1-aquylthioperylene-3,4: 9,10-tetracarboxyidiimide

In a heart-shaped flask 0.1 mmol of p-erylene-3,4: 9,10 tetracarboxyidiimide are dissolved in 0.3 mL of dry THF. Then 0.4 mmo l of the

15 corresponding thiol, 0.24 mmol of potassium fluoride and 0.48 mmol of 18-crown-6. It is heated at 70 ° C under the atmosphere of argon for 24 hours. The crude is dissolved in CH2Cl2 and washed with water. The organic phase is dried with Na2SO4, filtered and the solvent is removed under reduced pressure. It is purified by cro column chromatography with silica gel and toluene as eluent.

twenty

Method 2: Synthesis of 1,6 (7) -dialkylthioperylene-3,4: 9,10-tetracarboxyidiimide

0.1 mmol of perylene-3,4: 9,10 tetracarboxyidiimide are dissolved in 2 mL of dry THF in a round bottom mat. Then, 1.4 mmol of the corresponding thiol, 0.36 mmol of potassium fluide and 0.72 mmol of 1-8-crown-6 are added. Be

25 heats under reflux of THF under the atmosphere of argon for 24 hours. The crude is dissolved in CH2Cl2 and washed with water. The organic phase is dried with Na2SO4, filtered and the solvent is removed under reduced pressure. It is purified by column chromatography with silica gel and toluene as eluent.

Method 3: Synthesis of 2,5,8-trialkylthio-11-bromoperylene-3,4: 9,10-tetracarboxyidiimide and 2,5-dialkitio-8,11-dibromoperylene-3,4: 9,10-tetracarboxyidiimide In a bottom flask round, 0.05 mmol of 2,5,8,1-1-tetrabromoperylene-3,4: 9,10-tetracarboxyidiimide are dissolved in 2 mL of dry THF. Then

0.25 mmol of the corresponding thiol 0.25 mmol of potassium fluoride and 0.5 mmol of 18-crown-6 are added. It is heated under reflux of THF under an argon atmosphere for 24 hours. The crude is dissolved in CH2Cl2 and washed with water. The organic phase dries

image143

with Na 2SO4, filter and remove the solvent under reduced pressure. Purify by column a chromatography with silica gel and dichloromethane: hexane 1: 1 as eluent.

5 Method 4: Synthesis of 2,5,8,11-tetraalkylthioperylene-3,4: 9,10-tetracarboxyidiimide 0.03 mmol of 2,5,8,1 1 tetrabromoperylene-3,4 are dissolved in a round bottom flask : 9,10-tetracarboxyidiimide in 2 mL of dry THF. Then 0.21 mmol of the corresponding thiol, 0.20 mmol of potassium fluoride and 0.40 mmol of 18-crown-6 are added. It is heated at reflux of THF under argon atmosphere for

10 24 hours. The crude is dissolved in CH2Cl2 and washed with water. The organic phase is dried with Na 2SO4, filtered and the solvent removed under reduced pressure. It is purified by column chromatography with silica gel and chloroform: hexane 1: 1 as eluent.

Method 5: Synthesis of 1-alkoxy-6 (7) -alkylthioperylene-3,4: 9,10-tetracarboxyidiimide 0.1 mmol of 1-alkylthioperylene-3,4: 9,10 tetracarboxidiimide are dissolved in a round bottom flask in 2 mL of dry T HF. Then, 1.4 mmol of the corresponding alcohol and 0.36 mmol of TBAF (1M solution in THF) are added. Heat at reflux of THF under argon for 24 hours. The crude dissolves in

20 CH2Cl2 and wash with water. The organic phase is dried with Na2SO4, filtered and the solvent is removed under reduced pressure. It is purified by cro column chromatography with silica gel and toluene as eluent.

Method 6: synthesis of 2-alco xi-5,8,11-trialkylthioperylene-3,4: 9,10

Tetracarboxyidiimide In a round bottom mat 0.025 mmol of 2-bromine-5,8,11 trialkylthioperylene-3,4: 9,10-tetracarboxyidiimide is dissolved in 0.5 mL of dry THF. Then 0.175 mmol of the corresponding alcohol, 0.12 mmol of T BAF (1M solution in THF) are added. It was heated at reflux of THF under an argon atmosphere for 24 hours.

The crude is dissolved in CH 2 Cl 2 and washed with water. The organic phase is dried with Na2SO4, filtered and the solvent removed under a reddish pressure. It is purified by column chromatography with silica gel and chloroform: hexane 1: 1 as eluent.

Method 7: Synthesis of 1-alkylthioperylene-3,4: 9,10-tetracarboxyidiimide and 1,6 (7) 35 dialkylthioperylene-3,4: 9,10-tetracarboxyidiimide

image144

0.1 mmol of perylene-3,4: 9,10 tetracarboxyidiimide are dissolved in 2 mL of dry THF in a round bottom mat. Then 1.2 mmol of the corresponding thiol, 0.36 mmol of ce sium fluoride and 1.44 mmol of 1-8-crown-6 are added. It is heated to THF reflux under an argon atmosphere for 24 hours. The oil is

5 dissolve in CH2Cl2 and wash with water. The organic phase is dried with Na2SO4, filtered and the solvent is removed under reduced pressure. It is purified by column chromatography with silica gel and toluene as eluent.

Example 38: N, N’-di- (1’-hexylheptyl) -1.6 (7) -dihexylthioperylene-3.4: 9,1010 tetracarboxyidiimide (38)

image145

38

Compound 38 is obtained by method 7. Yield: 35%. 1H NMR (300 MHz, CDCl3) į 0.82 (m, 18H), 1.25 (broad s, 40H), 1.44 (m, 4H), 1.68 (m, 4H), 1.87 ( m, 4H), 2.28 (m, 4H), 3.22 (t, 4H), 5.20 (m, 2H), 8.68 (s, 2H), 8.76 (s, 2H), 8.85 (m,

15 2H). 13C NMR (CDCl3) į 13.79, 13.90, 22.26, 22.45, 26.79, 28.27, 28.39, 29.09, 31.09, 31.63, 32.30, 35.83, 54, 67, 121.89, 122.60, 12 5.54, 128.37, 128.81, 1 30.59, 131.30, 132.32, 132.58, 138.42, 163.57, 164.53. MALDI-TOF MS m / z. > M + @ theoretical C62H86N2O4S2 986.60, experimental 986.78. IR (KBr): 2949, 2926, 2856, 1695, 1660, 1584, 1461, 1409, 1321, 1240, 802, 750 cm -1. UV Vis (CH 2Cl2), Omax / nm (log H):

20 430 (4.2), 565 (4.6).

Alternatively, cost 38 is obtained following method 2. Yield: 82%.

image146

Example 39: N, N’-di- (1’-hexylheptyl) -1-hexylthioperylene-3,4: 9,10-tetracarboxyidiimide

(39)

image147

5 Compound 39 is obtained by method 7. Yield: 32%. 1H NMR (300 MHz, CDCl3) 0.82 (m, 15H), 1.26 (broad s, 36H), 1.46 (m, 2H), 1.72 (m, 2H), 1.86 (m , 4H), 2.25 (m, 4H), 3.25 (t, 2H), 5.20 (m, 2H), 8.62 (m, 6H), 8.94 (d, 1H). 13C NMR (CDCl3) į 13.90, 14.01, 22.38, 22.56, 26.91, 26.92, 28.36, 28.53, 29.19, 29.21, 31.22, 31.74, 32.3 7, 36.18, 5 4.66, 54.81, 122, 34, 12 2.71, 123.0 6, 123.46, 126.50, 127, 06,

10 127.77, 128, 91, 129.17, 130.45, 1 31.22, 132, 69, 133.34, 133.96, 1 39.82, 163, 51, 164.52. EM MALDI-T OF m / z. > + @ theoretical C56H74N2O4S 870.54, experimental 870.59. IR (KBr): 2955, 2920, 2856, 1689, 1660, 1578, 1450, 1391, 1327, 8142, 738 cm-1. UV Vis (CH2Cl2), Omax / nm (log H): 445 (4.2), 543 (4.6).

Alternatively, the cost 39 is obtained following method 1. Yield: 15 41%.

Example 40: N, N’-di- (1’-hexylheptyl) -1-s-butylthioperylene-3,4: 9,10 tetracarboxyidiimide (40)

image148

Compound 40 is obtained following method 1. Yield: 33% (50% with method 2 after 3 days). 1H NMR (300 MHz, CDCl3) į 0.82 (m, 12H), 1.04 (t, 3H), 1.27 (broad s, 32H), 1.61 (m, 3H), 1.75 ( m, 1H), 1.86 (m, 4 H), 2.25 (m, 4H), 3.66 (m, 2H),

5.20 (m, 2H), 8.65-8.82 (m, 6H), 8.99 (d, 1H). 13C NMR (C DCl3) į 11.4, 14.02, 20.47, 22.56, 22.5 7, 26.91, 2 9.18, 29.22, 29.41, 29, 54, 29 , 60, 31.74, 31.7 5, 32.38, 4 7.04, 54.68, 63.10, 122.45, 123.48, 126.80, 127.11, 127.96, 128 , 89, 129.79, 130.39, 131.19, 133.52, 134.00, 138.67, 163.63, 164.56. MS MALDI-T OF m / z,> M + H + @ theoretical C54H70N2O4S 842.51, experimental 842.51. IR (KBr): 2921, 2851, 1695, 1662, 1 589,

10 1462, 1397, 1343, 1241, 1070, 808, 747 cm -1. UV Vis (CH 2Cl2), Omax / nm (log H): 450 (4.0), 535 (4.4).

Example 41: N, N’-di- (1’-hexylheptyl) -1.6 (7) -di-s-butylthioperylene-3.4: 9.10

tetracarboxyidiimide (41)

image149

Compound 41 is obtained by method 2. Yield: 20% (the proportion of each isomer cannot be determined). 1H NM R (300 MHz, CDCl 3) į 0.82 (m, 12H), 1.04 (t, 6H), 1.29 (broad s, 32H), 1.59 (m, 6H), 1, 75 (m, 2H), 1.86 (m, 4H), 2.24

5 (m, 4H), 3.64 (m, 4H), 5.20 (m, 2H), 8.67-8.89 (m, 6H). 13C NMR (C DCl3) į 11.43, 11.53, 14.0 3, 20.49, 2 2.57, 26.92, 29.21, 29, 39, 29.69, 31.75, 32 , 4 3, 46.53, 4 6.58, 54.74, 122, 06, 125.79, 125.81, 1 28.61, 129.40, 129.96, 132.26, 1 32.70 , 133, 37, 137.52, 138, 73, 163.62, 164.75. E M BAD DI-TOF m / z,> M + H + @ theoretical C 58H78N2O4S2 930.54, experimental 930.58. IR (KBr): 2925, 2855, 169 5, 1654, 15 85, 1458, 1 397,

10 1319, 1249, 1172, 808 cm-1. UV Vis (CH2Cl2), Omax / nm (log H): 445 (4.0), 557 (4.4).

Example 42: N, N’-di- (1’-hexylheptyl) -1.6 (7) -di-t-butylthioperylene-3,4: 9,10

tetracarboxyidiimide (42)

image150

Compound 42 is obtained following method 1. Yield: 21% (81% isomer 1.6; 9% isomer 1.7 approx.). 1H NMR (300 MHz, CDCl 3) į 0.82 (m, 12H), 1.27 (broad s, 50H), 1.88 (m, 4H), 2.24 (m, 4H), 5.18 (m, 2H), 8.64 (s, 2H), 8.96 (s, 2H), 9.33

5 (d, 1H), 9.43 (d, 1H). 13C NMR (CDCl3) į 14.02, 22.57, 26.95, 29.2 0, 31.04, 3 1.74, 32.39, 50.88, 54.79, 12 2.38, 123 , 16, 127.15, 1 28.44, 129.41, 130.01, 131.61, 133.61, 13367, 138.05, 139.75, 140.61, 163.46, 164.60. EM BAD DI-TOF m / z,> M + H + @ theoretical C58H78N2O4S2 930.54, experience l 930.62. IR (KBr): 292 6, 2850, 1706, 1660, 1584, 1450, 1403, 1316, 1246, 1176, 802 cm-1. UV Vis (CH2Cl2), Omax / nm (log H): 545 (4.6).

10

Example 43: N, N’-di- (1’-hexylheptyl) -1-t-butylthioperylene-3,4: 9,10

tetracarboxyidiimide (43)

image151

43

Compound 43 is obtained following method 1. Yield: 12%. 1H NMR (300 MHz, CDCl3) į 0.82 (m, 12H), 1.27 (broad s, 41H), 1.87 (m, 4H), 2.24 (m, 4H), 5.18 ( m, 2H), 8.65 (m, 5H), 8.96 (s, 1H), 9.80 (d, 1H). 13C NMR (CDCl 3) į 14.02, 22.5 5,

5 22.57, 26.93, 29.17, 29.21, 29.68, 31.14, 31, 74, 32.40, 51.52, 54.74, 122.82, 123.37, 127 , 16, 128, 05, 128.47, 128.78, 1 30.89, 131, 20, 131.88, 133.85, 1 34.30, 163, 66, 164.32. MALDI-TOF MS m / z,> M + @ theoretical C54H70N2O4S 842.51, experimental 842.53 IR (KBr): 2926, 2862, 1 701, 1660, 1578, 1461, 1397, 1333, 1251, 808, 750. UV Vis (CH2Cl2), Omax / nm (log H): 496 (4.4), 530 (4.6).

10 Example 44: N, N’-di- (1’-hexylheptyl) -1.6 (7) -dioctylthioperylene-3.4: 9,10 tetracarboxyidiimide (44)

image152

44 Compound 44 is obtained following method 2. Yield: 71% (75% isomer 1.6; 25% isomer 1.7 approx.). 1H NMR (300 MHz, CDCl 3) į 0.83 (m, 18H), 1.24 (broad s, 48H), 1.43 (m, 4H), 1.69 (m, 4H), 1.87 (m, 4H), 2.24 (m, 4H), 3.22 (t, 4H), 5.20

5 (m, 2H), 8.67 (m, 2H), 8.76 (m, 2H), 8.85 (m, 2H). 13C NMR (CDCl3) į 14.03, 2 2.57, 26.92, 28.4 2, 28.84, 2 8.87, 29.01, 29.02, 29, 19, 29.22, 29 , 25, 31.6 9, 31.76, 3 2.43, 35.98, 54.78, 121.43, 122.00, 123.17, 125.65, 127.82, 128.05, 128 , 49, 128.93, 130.59, 131.48, 132.43, 132.68, 138.57, 163.59, 164.68. EM BAD DI-TOF m / z,> M + H + @ theoretical C66H94N2O4S2 1042.67, experimental 1042.71. IR (KBr): 2920, 2838, 1701, 16 54,

10 1592, 1461, 1397, 1321, 1240, 808 cm-1. UV Vi s (CH2Cl2), Omax / nm (log H): 430 (4.2), 564 (4.6).

Example 45: N, N’-di- (1’-hexylheptyl) -1-octylthioperylene-3,4: 9,10-tetracarboxyidiimide

(Four. Five)

image153

Compound 45 is obtained following method 1. Yield: 43%. 1H NMR (300 MHz, CDCl3) į 0.82 (m, 15H), 1.25 (broad s, 40H), 1.46 (m, 2H), 1.72 (m, 2H), 1.87 ( m, 4H), 2.24 (m, 4H), 3.25 (t, 2H), 5.18 (m, 2H), 8.64 (m, 6H), 8.96 (d, 1H) . 13C NMR

5 (CDCl3) į 14.02, 22.57, 26.91, 28.40, 28.85, 29.02, 29.03, 29.19, 29.22, 31.70, 31.74, 31 , 75, 32.39, 36.24, 54, 68, 122.39, 123.52, 12 6.54, 127.11, 127.82, 1 28.94, 129.23, 130.55, 131 , 28, 132.79, 133.41, 134.03, 134.23, 139.87, 163.59, 164.58. MALDI-TOF MS m / z,> M + H + @ theory C 58H78N2O4S 898.57, experiment at 898.54. I R (KBr): 2926, 2862, 1706, 1654, 159 0, 1456, 14 15, 1345, 1 246, 802, 7 50 cm -1. UV Vis (CH 2Cl2),

10 Omax / nm (log H): 445 (4.1), 543 (4.5).

Example 46: N, N’-di- (1’-hexylheptyl) -1-decylthioperylene-3,4: 9,10-tetracarboxy diimide

(46)

image154

Compound 46 is obtained following method 1. Yield: 40%. 1H NMR (300 MHz, CDCl3) į 0.82 (m, 15H), 1.23 (broad s, 44H), 1.43 (m, 2H), 1.73 (m, 2H), 1.87 ( m, 4H), 2.25 (m, 4H), 3.25 (t, 2H), 5.20 (m, 2H), 8.61 (m, 6H), 8.95 (d, 1H) . 13C NMR

5 (CDCl3) į 14.01, 14.05, 22.56, 22.61, 26.91, 26.92, 28.39, 28.85, 29.07, 29.19, 29.21, 29 , 22, 29.3 6, 29.44, 3 1.74, 31.81, 32.37, 36, 20, 54.66, 122.32, 1 23.44, 126, 48, 127.04, 127, 75, 128.89, 129.16, 1 30.42, 131, 28, 133.31, 133.94, 1 34.17, 139, 86, 163.51, 164.61. MALDI-TOF MS m / z,> M + @ theoretical C 60H82N2O4S 926.59, experiment at 926.76. IR (KBr): 2961, 2961, 2926, 2850, 1689, 1660, 1601, 1456, 1391, 1339, 1240,

10 802, 738 cm -1. UV Vis (CH2Cl2), Omax / nm (log H): 446 (4.3), 542 (4.7).

Example 47: N, N’-di- (1’-hexylheptyl) -1.6 (7) -didecylthioperylene-3.4: 9,10 tetracarboxidiimide (47)

image155

Compound 47 is obtained following method 2. Yield: 62%. (The proportion of each isomer cannot be determined). 1H NM R (300 MHz, CDCl 3) į 0.82 (m, 18H), 1.22 (broad s, 56H), 1.4, (m, 4H), 1.69 (m, 4H), 1 , 87 (m, 4H), 2.25 (m, 4H), 3.22

5 (t, 4H), 5.20 (m, 2H), 8.66 (m, 2H), 8.75 (m, 2H), 8.84 (m, 2H). 13C NMR (C DCl3) į 14.02, 14.0 6, 22.57, 2 2.62, 26.92, 28.43, 28, 85, 29.07, 29.22, 29.3 6, 29.45, 3 1.76, 31.82, 32.42, 35.96, 54, 72, 121.41, 121.84, 12 2.17, 122.66, 123.15, 1 25.63 , 127.87, 128.04, 128, 48, 128.89, 128.95, 1 29.35, 130, 58, 131.42, 132.36, 1 32.67, 138, 58, 139.89 , 163.66, 164.69. EM MALDI-TOF m / z,> M + @ theoretical C 70H102N2O4S2 1098.73,

10 experimental 1098.54. I R (KBr): 2949, 2943, 2 838, 1689, 1654, 1584, 1473, 139 7, 1321, 1240, 1321, 802, 744 cm -1. UV Vis (CH 2Cl2), Omax / nm (log H): 4 29 (4.3), 566 (4.65).

Example 48: N, N’-di- (1’-hexylheptyl) -1.6 (7) -dibenzylthioperylene-3.4: 9,1015 tetracarboxidiimide (48)

image156

Compound 48 is obtained by method 2. Yield: 20% (The proportion of each isomer cannot be determined). 1H NMR (300 MHz, CD2Cl2) į 0.83 (t, 12H), 1.26 (broad s, 32H), 1.85 (m, 4H), 2.27 (m, 4H), 4.40 ( s, 4H), 5.17 (m, 2H), 7, 16

5 (m, 6H), 7.2 6 (m, 4H), 8.58 (broad s, 2H), 8.85 (d, 4H). 13C NMR (CDCl 3) į 14.23, 1.29, 23.02, 23.11, 27, 29, 29.65, 2965, 30.07, 30.11, 32, 22, 32.35, 32 , 78, 41.2 7, 125.28, 126, 42, 127.98, 128.78, 1 28.92, 129, 59, 133.05, 135.83, 1 37.51, 163, 56, 164.93. EM BAD DI-TOF m / z,> M + 1 + @ theoretical C 64H74N2O4S2 999.51, experiment at 999.58. IR (KBr): 2938, 2850, 1689, 1654, 1590, 1397, 1321, 1246, 709 cm -1. UV Vis

10 (CH2Cl2), Omax / nm (log H): 455 (4.1), 531 (4.4), 555 (4.4).

Example 49: N, N’-di- (1’-hexylheptyl) -1-benzylthioperylene-3,4: 9,10 tetracarboxidiimide (49)

image157

Compound 49 is obtained by method 1. Yield: 30%. 1H NMR (30 0 MHz, CDCl3) į 0.83 (t, 12H), 1.24 (broad s, 32H), 1.87 (m, 4H), 2.24 (m, 4H), 4.47 (s, 2H), 5.19 (m, 2H), 7.2 3 (m, 3H), 7, 34 (d, 2H), 8.64 (m, 6 H), 8.88 (m, 2H). 13C NMR

5 (CD2Cl3) į 14.23, 14.2 4, 23.02, 2 7.33, 29.66, 32.22, 32, 78, 41.37, 122.89, 123, 91, 127.16 , 127, 36, 128.15, 129.04, 1 29.26, 129, 70, 129.76, 133.56, 1 33.76, 134, 23, 34.37, 135, 57, 138.81 , 163.80, 1 64.82. MS MALDI-T OF m / z,> M + H + @ theoretical C57H68N2O4S 877.49, experimental 877.50. IR (KBr): 2920, 2850, 1712, 1642, 1 596, 1450, 1327, 1240, 808, 744 cm-1. UV Vis (CH2Cl2), Omax / nm (log H): 444 (4.3) 542 (4.7).

10 Example 50: N, N’-bis- (di-2 ’, 5’-t-butylphenyl) -1.6 (7) -dihexylthioperylene-3,4: 9,10 tetracarboxyidiimide (50)

image158

image159

Compound 50 is obtained by method 2. Yield: 23% (The proportion of cad to isomer cannot be determined). The reaction time for this compound was 72 hours. 1H NMR (300 MHz, CDCl3) į 0.85 (m, 6H), 1.30 (d, 44H), 1.44 (m, 4H), 1.70 (m, 4H), 3.24 (m , 4H), 7.02 (s, 2H), 7.50 (d, 2H), 7.60 (d, 2H), 8.75

5 (d, 2H), 8.85 (s, 2H), 8.95 (d, 2H). 13C NMR (CDCl3) į 2 2.38, 22.62, 22.68, 25, 43, 28.44, 28.5 3, 29.35, 2 9.56, 25.69, 31.22, 31 , 70, 31.79, 31.92, 34.2 5, 35.58, 3 5.95, 47.18, 63.03, 69.34, 70, 54, 121.99, 122.06, 12 2.42, 125.87, 126.37, 1 27.63, 128.84, 129.10, 129, 38, 129.82, 130.27, 1 30.89, 131, 23, 132.63, 132.82, 1 33.15, 138, 92, 143.86, 150, 17, 164.46, 164.50. E M BAD DI-TOF m / z,> M + @ theoretical C 64H74N2O4S2

10 998.51, experimental 988.55. IR (KBr): 2920, 2868, 170 6, 1671, 15 96, 1450, 1 246, 802 cm-1. UV Vis (CH2Cl2), Omax / nm (log H): 434 (3.9), 567 (4.3).

Example 51: N, N’-bis- (di-2 ’, 5’-t-butylphenyl) -1-hexylthioperylene-3,4: 9,10 tetracarboxidiimide (51)

image160

Compound 51 is obtained following method 1. Yield: 25%. 1H NMR (300 MHz, CDCl3) į 0.85 (m, 3H), 1.26 (s, 4H), 1.32-1.34 (d, 36H), 1.47 (m, 2H), 1 , 74 (m, 2H), 3.26 (m, 2H), 7.04 (s, 2H), 7.50 (d, 2H), 7.60 (d, 2H), 8.74 (s, 3H), 8.85 (m, 3H), 9.02 (d, 1H). 13C NMR (CDCl 3) į 13.92, 22.3 8, 28.43, 2 8.54, 29.68, 31.21, 31, 74,

20 34.24, 35.54, 36.18, 36, 24, 122.25, 122.65, 12 2.84, 123.24, 123.84, 1 36.34, 126.40, 126.77 , 127, 47, 127.62, 127.72, 1 28.19, 128, 80, 129.24, 129.40, 1 30.16, 131, 26, 131.95, 132, 46, 132.66 , 133.26, 1 33.89, 134, 53, 134.55, 134.75, 1 40.22, 143, 78, 143.81, 150.16, 164.27, 164.40, 164.50 , 164.70. EM MALDI-TOF m / z,> M + @ theory

image161

C58H62N2O4S 882.44, experimental 882.49. IR (KBr): 2967, 2926, 1706, 1677, 1 584, 1403, 1339, 1257, 802, 750 cm-1. UV Vis (CH2Cl2), Omax / nm (log H): 447 (3.9), 546 (4.4).

Example 52: N, N’-di- (1’-hexylheptyl) -2,5,8,11-tetrahexylthioperylene-3,4: 9,10 tetracarboxidiimide (52)

image162

Compound 52 is obtained following method 4. Yield: 90%. 1H NMR (300 MHz, CDCl3) į 0.83 (t, 12H), 0.93 (t, 12H), 1.30 (broad s, 52H), 1.65 (m, 4H), 1.94 ( m, 12H), 2.25 (m, 4H), 3.20 (t, 8H), 5.23 (m, 2H), 8, 37 (s, 4H). 13C NMR (CDCl3) į 13.83,

10 13.89, 13.9 0, 13.93, 2 2.34, 22.41, 22.46, 26, 99, 27.79, 29.12, 31.4 2, 31.46, 3 1 , 59, 31.64, 32.11, 32.63, 54, 81, 116.77, 117.93, 12 0.13, 124.01, 131.93, 1 50.47, 163.30, 164 , 04. MALDI-TOF MS m / z,> M + H + @ theoretical C 74H110N2O4S4 1219.73, experimental 1219.77. IR (KBr): 2932, 2844, 1677, 1636, 1555, 1345, 1234, 849, 738 cm -1. UV Vis (CH2Cl2), Omax / nm (log H): 489 (5.1), 543 (5.1).

Example 53: N, N’-di- (1’-hexylheptyl) -2-bromo-5,8,11-trihexylthioperylene-3,4: 9,10 tetracarboxyidiimide (53)

image163

Compound 53 is obtained following method 3. Yield: 66%. 1H NMR (300 MHz, CDCl3) į 0.83 (t, 12H), 0.93 (t, 9H), 1.32 (broad s, 46H), 1.65 (m, 4H), 1.93 ( m

5 10H), 2.22 (m, 4H), 3.1 7 (t, 6H), 5.20 (m, 2H), 8.13 (s, 1H), 8.22 (s, 1H), 8.30 (s, 1 H), 8.41 (s, 1 H). 13C NMR (CDCl 3) į 14.02, 22.5 1, 22.59, 2 7.13, 27.20, 27.82, 28, 07, 29.14, 29.2 3, 29.25, 2 9.66, 31.57, 31.59, 31, 60, 31.61, 31.64, 32.2 3, 32.54, 3 2.67, 32.77, 32.85, 55.00 , 55, 39, 117.96, 118.53, 11 9.36, 119.67, 120.08, 1 22.13, 122.43, 128.84, 128.95, 130.30, 131.30 , 131.69, 132, 09, 132.19, 132.30, 132.80, 133.29,

10 150.62, 151.15, 161.21, 163.29. EM MALDI-T OF m / z,> M + H + @ theoretical C68H97N2O4S3Br 1181.58 experimental 1181.61. IR (KBr): 2926, 2862, 1683, 1636, 1555, 1456, 1345, 1240, 814, 744 cm-1. UV Vis (CH2Cl2), Omax / nm (log H): 501 (4.7), 540 (4.8).

Example 54: N, N’-di- (1’-hexylheptyl) -2,5-dibromo-8,11-dihexylthioperylene-3,4: 9,1015 tetracarboxyidiimide (54)

image164

Compound 54 is obtained following method 3. Yield: 25%. 1H NMR (300 MHz, CDCl3) į 0.84 (t, 12H), 0.93 (t, 6H), 1.31 (broad s, 44H), 1.64 (m, 4H), 1.93 ( m, 4H), 2.21 (m, 4H), 3.1 9 (t, 4H), 5, 19 (m, 2 H), 8.43 (s, 2H), 8.54 (s, 2H ). 13C NM R

5 (CDCl3) į 13.83, 13.90, 13.91, 13.93, 22.34, 22.37, 22.39, 22.46, 23.46, 26.79, 26.93, 27 , 73, 27.9 6, 28.16, 2 7.73, 27.96, 28.16, 28, 74, 28.95, 29.08, 31.2 6, 31.43, 3 1.54 , 31.58, 31.62, 31.62, 32.08, 32.76, 55.32, 119.71, 122.19, 126.10, 129.57, 129.86, 131.31, 131 , 62, 131.77, 131.95, 132.21, 133.00, 134.45, 151.28, 161.37, 163.29. MALDI-TOF MS m / z,> M + H + @ theoretical C 62H84N2O4S2Br2 1143.42, experiment at 1143.52. GO

10 (KBr): 2958, 2917, 2855, 1695, 1646, 1229, 1025 cm -1. UV Vis (CH 2Cl2), Omax / nm (log H): 487 (4.6), 540 (4.5).

Example 55: N, N’-di- (1’-hexylheptyl) -1-butoxy-6 (7) -hexylthioperylene-3,4: 9,10 tetracarboxyidiimide (55)

image165

55

Compound 55 is obtained following method 5. Yield: 25%. 1H NMR (300

MHz, CDCl3) į 0.83 (t, 15H), 1.07 (t, 3H), 1.24 (broad s, 38H), 1.66 (m, 4H), 1.87 (m,

4H), 2.07 (m, 2H), 2.2 8 (m, 4H), 3.22, (m, 2H), 4.52 (m, 2H), 5.21 (m, 2H) , 8.5 1 (s

5 wide, 1H), 8.64 (wide s, 2H), 8.79 (m, 2H), 9.52 (1.6 isomer) 9.65 (1.7 isomer) (d, 1H). 13C NMR (CDCl3) į 13.83, 13.91, 14.02, 19.53, 19.57, 22.38, 22.57, 26.92, 28.39, 28.51, 29.22, 31.22, 31.39, 31.76, 32.42, 35.96, 36.47, 54.67, 70.24, 120.67, 121.9 6, 123.47, 123, 87, 125 , 65, 125.99, 1 28.21, 128, 49, 128.57, 128.94, 1 29.22, 129, 31, 129.50, 133.06, 133.30, 137.81, 138 , 53, 156.88, 157.24, 157.86, 163.79, 164.87. EM

10 MALDI-TOF m / z,> M + @ theoretical C60H82N2O5S 9 42.59, experimental 942.64. IR (KBr): 2955, 2932, 2862, 169 5, 1654, 1 607, 1397, 1333, 122 8, 808, 75 0 cm -1. UV Vis (CH2Cl2), Omax / nm (log H): 566 (4.8).

Example 56: N, N’-di- (1’-hexylheptyl) -2-butoxy-5,8,11-trihexylthioperylene-3,4: 9,1015 tetracarboxyidiimide (56)

image166

Compound 56 is obtained following method 6. Yield: 28%. 1H NMR (300 MHz, CDCl3) į 0.83 (t, 12H), 0.93 (t, 9H), 1.06 (t, 3H), 1.2 5 (broad s, 32H), 1.39 (broad s, 14H), 1.64 (m, 4 H), 1.94 (broad s, 12H), 2.04 (m, 2 H), 2.24 (m, 4H), 3.20 ( s 5 wide, 6H), 4.45 (t, 2H), 5.24 (m, 2 H), 8.07 (s, 1H), 8.34 (s, 1H), 8.36 (s, 1H), 8.40 (s, 1H). 13C NMR (CDCl3) į 13.86, 14.02, 14.05, 19.25, 22.53, 22.56, 22.58, 22.60, 27.07, 27.92, 27.9 6 , 29.23, 2 9.29, 29.69, 31.30, 31, 56, 31.57, 31.76, 31.7 9, 31.92, 3 2.23, 32.27, 32, 58, 32.75, 54, 91, 117.64, 118.11, 11 8.59, 120.21, 123.03, 1 23.22, 123.93, 125.25, 129.72, 131, 99, 132.08, 133.15, 161.55, 162.72, 163.54, 164.28. EM MALDI

10 TOF m / z. > M + H + @ theoretical C 72H106N2O5S3 1175, 73, experimental 1175.75. IR (KBr): 2914, 2844, 1671, 1636, 1590, 156 1, 1479, 13 39, 1257, 8 02 cm -1. UV Vis (CH 2Cl2), Omax / nm (log H): 473 (4.4), 501 (4.5), 540 (4.5).

Claims (20)

image 1 CLAIMS 1.- preparation procedure for the compounds of formula I: image2 5 where: each R 1 and R3 independently represents n hydrogen, halogen, C 1-C20 alkyl, C2-C20 alkenyl, C 2-C20 alkynyl, -CN, -COR 4, -CO 2R4, -CONR 4R4, -OR 4, -OCOR 4, -OCONR4R4, -OCO2R4, -SR4, -SeR4, -NR4R4, -NR4COR4, -NR4CONR4R4, -NR4CO2R4, –PR4R4, -SOR 4, -SO 2R4, -SO 2NR4R4 or Cy 1, R4R4 or Cy 1 where C 1-C20 alkyl, C 2-C20 alkenyl and C2-C20 alkynyl are independently optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6; each R2 independently represents C 1 -C40 alkyl or Cy 2; where C 1-C40 alkyl is optionally substituted by one or more R 5 and where Cy 2 is optionally substituted by one or more R7; Each R4 independently represents hydrogen, C1-C20 alkyl or Cy4, where C1-C20 alkyl is optionally substituted by one or more R 10 and where Cy 4 is optionally substituted by one or more R11; or two R4 groups can be joined by forming a saturated 5-7 membered heterocycle with the N atom which may additionally contain a heteroatom selected 20 of N, O and S, and which may be optionally substituted by one or two R11; each R 5 independently represents Cy 3, -OR 8, -SR 8 or -NR8R8, where Cy3 is optionally substituted by one or more R6; each R 7 independently represents C 1-C40 alkyl, Cy 4, -OR 8, -SR8 or -NR 8R8, where C1-C40 alkyl is optionally substituted by one or more R9 and where Cy4 is 25 optionally substituted by one or more R6; image3 5 each R6 and R11 independently represent R8, -OR8, -SR8 or -NR8R8; each R9 and R10 independently represent -OR8, -SR8, -NR8R8 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, O, S and Se, and 10 where each Cy 1 and Cy 3 can be independently linked to the rest of the molecule through any available C or N atom; each Cy2 independently represents a saturated, partially unsaturated ring 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 a 15 through any available C or N atom, where Cy 2 contains 1 to 4 heteroatoms selected from N, O, S and Se, and where one or more atoms of C, S or Se of Cy2 may optionally be oxidized forming CO, SO, SO 2, SeO or SeO2 groups; and each Cy 4 independently represents a carbocyclic or heterocyclic ring 20 saturated, partially unsaturated or aromatic of 3 to 7 members, optionally containing 1 to 4 heteroatoms selected from N, O, S and Se, where Cy4 is attached to the rest of the molecule through any atom of C or N available, and where one or more atoms of C, S or Se of Cy 4 may optionally be oxidized forming groups CO, SO, SO2, SeO or SeO2, With the proviso that at least one R3 independently represents -OR 4, -SR4, -SeR4, -NR4R4 or -PR4R4, which comprises reacting a formula compound to II with a compound of formula III in the presence of a source of fluorine: image4 image5 R2 R1 R12 R12 R1 R13-H  II III where: each R1 and R2 independently have the meaning described for a compound of formula I; 5 each R12 independently represents hydrogen, halogen, -CN, -COR 4, -CO2R4, -CONR4R4, -OR 4, -OCOR 4, -OCONR 4R4, -OCO 2R4, -SR4, -SeR 4, -NR 4R4, - NR 4COR4, -NR4CONR4R4, -NR4CO2R4, -PR4R4, -SOR4, -SO2R4 or -SO2NR4R4; R13 represents –OR4, -SR4, -SeR4, -NR4R4 or -PR4R4; and each R 4 independently has the meaning described for a compound of Formula I, with the proviso that at least one R 12 independently represents hydrogen or halogen. 2. The method according to claim 1, wherein the fluorine source is selected from tetrabutylammonium fluoride (TBAF), tetraphenylphosphonium fluoride (TPPF), CsF, RbF, KF, NaF, LiF, BaF2, SrF2, CaF2, and MgF2 3. The process according to claim 2, wherein the fluorine source is selected from tetrabutylammonium fluoride (TBAF) and KF. The method according to any one of claims 1 to 3, wherein each R 1 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR 4, -SR 4, -SeR4, -NR4R4, -PR4R4 or Cy1, where C1-C20 alkyl is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6. The method according to any one of claims 1 to 4, wherein each R 2 independently represents C1-C40 alkyl optionally substituted by one or more R5. image6 The method according to any of claims 1 to 4, wherein each R 2 independently represents Cy2 optionally substituted by one or more R7. 7. The method according to any of claims 1 to 6, wherein each R 3 independently represents hydrogen, halogen, C 1 -C20 alkyl, -OR 4, -SR 4, 10 -SeR4, -NR4R4, -PR4R4 or Cy1, where C1-C20 alkyl is optionally substituted by one or more R5 and Cy1 is optionally substituted by one or more R6. 8. The method according to any of claims 1 to 7, wherein each R 4 independently represents hydrogen, C1-C20 alkyl or Cy4, where C 1-C20 alkyl 15 is optionally substituted by one or more R10 and where Cy 4 is optionally substituted by one or more R11. 9. The process according to any of claims 1 to 7, wherein each R 4 independently represents C1-C20 alkyl optionally substituted by one or more R10. 10. The method according to any one of claims 1 to 7, wherein two R 4 groups can be joined to form a saturated 5- to 7-membered heterocycle atom with the N atom which additionally can contain a heteroatom selected 25 of N, O and S, and which may be optionally substituted by one or two R11. 11. The method according to any of claims 1 to 10, wherein each R6 independently represents R8. 12. The method according to any of claims 1 to 11, wherein each R7 independently represents C1-C40 alkyl optionally substituted by one or more R9. 13. The method according to any of claims 1 to 12, wherein each R8 independently represents C1-C6 alkyl optionally substituted by one or more -OH, -OC 1-C4 alkyl and wherein C 1-C4 alkyl is optionally substituted for one more year - OH. image7 14. The method according to any of claims 1 to 13, wherein each R9 independently represents -OR 8 or Cy3, where Cy3 is optionally substituted by one or more C1-C6 alkyl. 15. The method according to any of claims 1 to 14, wherein each R10 independently represents -OR 8 or Cy3, wherein Cy3 is optionally substituted by one or more C1-C6 alkyl. 16. The method according to any of claims 1 to 15, wherein each R11 independently represents R8. 17. The process according to any of claims 1 to 16, wherein each Cy1 independently represents phenyl. 18. The method according to any of claims 1 to 16, wherein each Cy1 independently represents: image8 20. The method according to any of claims 1 to 18, wherein each Cy2 independently represents a saturated, monocyclic 3 to 7 heterocyclic ring, where Cy 2 can be attached to the rest of the molecule through any atom of C or N available, and where Cy 2 contains 1 to 3 heteroatoms selected from N, O and S. 21. The process according to any of claims 1 to 20, wherein each Cy3 independently represents phenyl. image9 22. The method according to any one of claims 1 to 20, wherein each Cy3 independently represents a 5 or 6-membered aromatic heterocycle containing 1 or 2 heteroatoms selected from N, O and S, and where Cy 3 can be attached to the rest of the molecule through any available C or N atom. 23. The method according to any of claims 1 to 22, wherein each Cy4 independently represents a saturated heterocyclic ring, of 3 to 7 member s, which optionally contains 1 to 3 heteroatoms selected from N, O and S , and where Cy4 is attached to the rest of the molecule through any atom of C or N 10 available. 24. The process according to any of claims 1 to 22, wherein each Cy4 independently represents phenyl. The method according to any one of claims 1 to 24, wherein each R12 independently represents hydrogen, halo, -OR 4, -SR 4, -SeR 4, -NR 4R4 or -PR4R4. 26.- A compound selected from: image10 24 25 twenty , , . image11 , Y 27.- Use of a compound according to claim 26, for the repair of dyes, pigments, paints, fluorescent agents, optical devices, electronic devices, electro-optical devices, light emitting diodes and organic photovoltaic cells or hybrids