FR3024730A1 - MOLECULAR SPACERS BASED ON NON-SYMMETRIC CHROMOGENIC SPIROXAZINES - Google Patents

Abstract

A non-symmetric chromogenic compound having the following general formula (I): wherein; R 1 and R 2 are identical or different and represent a linear or branched alkyl group of 1 to 12 carbon atoms, or represent an alkenyl, alkynyl, aryl, alkylaryl or cycloalkyl group, and R 2 may optionally form a single group to form a carbocyclic or heterocyclic group of 5 to 10 atoms; Y 1 is a halogen selected from -Cl, -Br or -I; Y 2 is a halogen selected from -Cl, -Br or -I; with the proviso that Y1 ≠ Y2; and X is an electron donor substituent chosen from the following groups of formulas: -CH3 or -HC = CH-R3 in which R3 represents an aromatic residue, optionally substituted and / or polysubstituted, and optionally comprising one or more selected heteroatoms; from N, S and / or O; Z is a heteroatom selected from N, S, O.

Description

FIELD OF THE INVENTION The present invention relates to novel spiroxazine-type compounds having photoacid, acid, solvate or thermochromic properties for the preparation of donor-acceptor systems. energy or electron. STATE OF THE ART Photochromism is a reversible transformation of a chemical species induced in at least one direction by the absorption of electromagnetic radiation between two forms having two different absorption spectra. The return reaction can take place photochemically (photochromism type P), photochemical and thermal (photochromism type T), or thermal only or in the presence of a chemical reagent such as an acid. Chromogenic compounds are molecules capable of changing color under the effect of a light source (monochromatic or polychromatic), under the influence of temperature and / or a light source, or even under the influence of a change in pH and / or a light source or a chemical reagent. These color changes are explained by the modification of the structure of the molecule, for example by a ring opening or a cis-trans isomerization, which generally leads to the modification of the absorption spectrum, which can most often be translated by the transition from a colorless state to a colored state.

A number of organic chromogenic compounds have already been proposed in the state of the art, including diarylethene compounds, fulgides, azobenzenes, spiropyrans, and finally spiroxazines. Among these chromogens, spiropyran and spiroxazine are molecules derived from the combination of an indoline with a pyran or an oxazine, covalently bound by a hybrid carbon called Cspiro. The chromogenic properties of these two types of molecules come from the cleavage of the [Cspi, -0] bond following their irradiation by an ultraviolet light source or the presence of a chemical reagent or a solvent of a given polarity. This photoactivation leads, via a structural rearrangement, to the formation of a molecule with an open structure, of the merocyanine type, strongly colored by the extension of the conjugation and the presence of ammonium (positively charged) and phenolate (charged negatively). The chromogenic properties of these molecules are also influenced by the nature of their substituents, their concentration in solution, as well as the polarity of the solvents in which they are dissolved. For example, in an apolar solvent, such as diethyl ether, the closed form is dominant, while the open form is stabilized in a polar solvent, for example in acetonitrile or ethanol.

In 2005, Tomasulo et al. have published a new family of spiroxazine photochromics in which indoline and oxazine are fused [Fast and Stable Photochromic Oxazines, J. Org. Chem. 70, 8180-8189 (2005)]. These molecules have an indoline and benzooxazine fragment sharing a common bond, and more specifically the bond connecting the positions 1 and 2 of the indoline fragment and the bond 10 linking the 2 and 3 positions of the benzooxazine moiety. A remarkable feature of these photochromes lies in the possibility of assembling them with fluorophores or phosphorescent derivatives, ie compounds capable of emitting light (fluorescence or phosphorescence) after excitation, and thus of creating molecules called "dyads" or "Triads" whose luminescence can be modulated. The phosphor substituent can emit light depending on the case where the photochromic is "open" or "closed". In other cases, electron or energy transfer occurs between the phosphor and the photochromic which may have the effect of suppressing luminescence. Many dye-type "fluorophore-photochromic" systems have been reported. In particular, the following documents can be cited according to the family of photochromics used: for spiroxazines, the publication of E. Deniz, M. Tomasulo, J. Cusido, S. Sortino, and FM Raymo, entitled "Fast and Stable Photochromic Oxazines for Fluorescence Switching "[Langmuir 27, 11773-11783 (2011)], and for diarylethenes and spiropyrans the publication of I. Yildiz, E. Deniz, and FM

Raymo entitled "Fluorescence Modulation with Photochromic Switches in Nanostructured Constructs", published in Chem. Soc. Rev. 38, 1859-1867 (2009). Another category of photochromic system is based on the combination of three molecules, called triads. Triad-like molecules consist of the combination of a chromogenic compound, covalently bonded with an energy (or electron) donor compound and an energy (or electron) acceptor compound. The advantage of triads designed with chromogens as a spacer is the ability to vary the absorption wavelengths of the energy (or electron) donor substituent and the energy accepting substituent (or electron) and the absorption wavelengths of the chromogen in the closed and open form and that in one and the same molecule. There are a number of publications in the literature relating to this category of photochromic system of the triad type, and particularly based on the molecules of the "energy donor-dithienylcyclopentene-energy acceptor" type. The publication of J.H. Hurenkamp, J.J.D. de Jong, W. R. Browne, J. H. van Esch, and B. L. Feringa, "Tuning Energy Transfer in Switchable Donor-Acceptor Systems," Org. Biomol. Chem. 6, 1268-1277 (2008). An example of this type of molecule is shown in Figure 1. However, the photochromic compounds disclosed in this publication have the disadvantage of having two identical reactive functions which leads to statistical coupling to connect an energy donor compound (or donor). electron) and an energy accepting compound (or electron acceptor), which prevents any selective grafting of these compounds. The presence of two identical functions on the photochromic limits the synthesis yields and causes great difficulty in the purification of the products. Another system of the "Diarylethene-Receptor Donor" type has been described in the publication by JM Endtner, F. Effenberger, A. Hartschuh, and H. Port, entitled "Optical ON / OFF Switching of Intramolecular Photoinduced Charge Separation". Donor-Bridge-Acceptor System Containing Dithienylethene, J. Am. Chem. Soc. 122, 3037-3046 (2000) is shown in Figure 2. This triad type system allows the transfer of charge from the donor to the acceptor in a first state, and to block the charge transfer in the second state. On the other hand, it does not aim in any case the modulation of the fluorescence of photochromic compounds.

Finally, another example of a "donor-Diarylethene-acceptor" type system which has been made to allow the photodetection of ions, in particular cyanide ions CN-, is exemplary; this system has been described in the publication of J. Jin, J. Zhang, L. Zou, and H. Tian, "Near-lnfrared Photochromic Behavior in a Donor-acceptor Type Diarylethene Modulated by the Cyanide Anion", Analyst 138, 1641 -1644 (2013).

Other triad-type systems are described in the article "Mit Molekülen Schalten" by U. Pischel and A. Schiller, published in the journal Nachrichten aus der Chemie 62 (Januar 2014), p. 31-36. OBJECTS OF THE INVENTION The object of the present invention is to provide new chromogenic compounds, as a molecular spacer, ie as a molecule segment providing a link between two parts of said molecule, for the synthesis of triad-like compounds. , ie of the "donor-chromogenic-acceptor" type by successive and controlled grafting of the donor (or acceptor) group and then of the acceptor (or donor) group on said chromogenic compound having orthogonal reactivity functions.

The present invention relates to a non-symmetric chromogenic compound corresponding to the following general formula (I): in which: R 1 and R 2 are identical or different and represent a linear or branched alkyl group of 1 to 12 atoms; carbon, or represent an alkenyl, alkynyl, aryl, alkylaryl, cycloalkyl, R1 and R2 group which may optionally form a single carbocyclic or heterocyclic group of 5 to 10 atoms, saturated or unsaturated, optionally substituted and / or polysubstituted; Y1 is a halogen selected from Cl, Br, or I; Y 2 is a halogen selected from Cl, Br or I; it being understood that Y1 # Y2; and X is an unsaturated substituent selected from the following groups: -CH3 or -HC = CH-R3 wherein R3 represents an optionally substituted and / or polysubstituted aromatic residue, and optionally comprising one or more heteroatoms selected from N , S and / or O. - Z is an atom selected from N, S, O. The radical R3 is an aromatic residue which may be selected from the group consisting of aromatic, possibly fused residues (especially phenyl, naphthyl, phenanthryl , anthracyl, chrysene derivatives, pyrene, tetracene, fluoranthene, coronene, benzo [a] anthracene), substituted or unsubstituted; aromatic heterocyclic radicals, optionally fused, substituted or unsubstituted, such as substituted or unsubstituted furan residues (possibly fused with one or more benzene rings, in particular benzofuran and isobenzofuran), and pyrrole residues, substituted or unsubstituted; no (possibly fused with one or more benzene rings, especially indole and isoindole) and substituted or unsubstituted thiophene residues (possibly fused with one or more benzene rings, especially benzothiophene and benzo [ c] thiophene) and the remains of indazole, pyrazole, oxazole, isoxazole, thiazole, substituted or unsubstituted. In an advantageous embodiment, R3 is selected from the group consisting of p-dimethylaminophenyl 5 / 5a, triphenylamine 6 / 6a, 2,2'-bipyridine 7 / 7a, ferroocene 8 / 8a, 9-methylanthracene 9 / 9a, 2-hexyl-bis-thiophene 10/10a, 2-hexyl-tris-thiophene 11/11a, thiophene 12/12a, dihexyl-bis-thiophene fused 13 / 13a, pyrene 14 / 14a, boranils 15 / 15a.

In a particularly advantageous embodiment, R3 is an optionally substituted julolidine aromatic heterocyclic radical. In another embodiment R3 is an organometallic compound selected from metallocene compounds, optionally substituted, and is preferably an organometallic compound selected from the optionally substituted ferrocene compounds. In the compound (I) Y1 and Y2 are advantageously selected exclusively from halogens, and even more preferably chosen from Cl, Br, I.

The radicals R 1 and R 2 may be identical or different and may represent a linear alkyl group of 1 to 12 carbon atoms, and more preferably a methyl group.

Another object of the invention is a process for the preparation of a chromogenic compound of the triad type, in which process: a) a non-symmetric chromogenic compound is provided according to the invention, b) selective substitution of the group is carried out Y1 by an energy donor or electron donor substituent, or an energy acceptor or electron acceptor substituent respectively; and c) a step of selective substitution of the Y 2 group by an energy acceptor substitute or electron acceptor substituent (respectively an energy donor or electron donor substituent), and d) a step of transforming the -CH 3 into - HC = CH-R3 with R3 being a derivative of julolidine or any R3 group selected from the group consisting of p-dimethylaminophenyl 5 / 5a, triphenylamine 6 / 6a, 2,2'-bipyridine 7 / 7a, ferroocene 8 / 8a 9, 9-methylanthracene 9 / 9a, 2-hexyl-bis-thiophene 10 / 10a, 2-hexyl-tris-thiophene 11 / 11a, thiophene 12 / 12a, dihexyl-bis-thiophene fused 13 / 13a, pyrene 14 / 14a, boranils 15 / 15a. Advantageously, said energy donor (or electron) substituent is biocompatible and is selected from xanthenes, acenes, cyanines, alexas, coumarins, squaraines, boron-dipyrromethenes, rhodamines, dansyls, perylenes, pyrenes, diketopyrrolopyrroles, boranils and phosphorescent transition metals such as Ru, Os, Ir, Pt and Re; and the energy accepting substituent is selected from xanthenes, cyanines, aza-boron-dipyrromethenes, rhodamines, porphyrins, phthalocyanines and subphthalocyanines, diketopyrrolopyrroles, extended boranils and metal complexes of phosphorescent transitions such as Ru, Os, Ir, Pt and Re. Yet another subject of the invention is a triad type chromogenic compound obtainable by the process according to the invention.

Yet another object of the invention is the use of the triad type chromogenic compound according to the invention for high density optical storage, or as a molecular logic function. This use can be made to control an electronic energy transfer depending on the opening or closing of the chromogen according to FIG. 13 below. Yet another subject of the invention is an optical storage medium, characterized in that it comprises at least one photochromic compound according to the invention.

A final object of the invention is the use of a biocompatible chromogenic compound according to the invention for cell imaging, cellular signaling and biomedical analysis. DETAILED DESCRIPTION OF THE FIGURES FIGS. 3 to 13 illustrate the invention, FIGS. 1 and 2 illustrate the state of the art.

Figure 1 schematically shows a triary-type diarylethene compound functionalized with a donor substituent and an energy accepting substituent. Figure 2 schematically shows a triad, donordiarylethene-acceptor compound used to control charge transfer between the donor and the electron acceptor.

Figure 3 shows the synthesis scheme of precursors 1 and 2.

FIG. 4 represents the synthesis scheme of the chromogenic compound 4 which is representative of the non-symmetrical family according to the invention, i.e. of the "chromogenic donor-acceptor" type. FIG. 5 represents a synthetic scheme of the chromogens 5a to 15a from the aldehydes with a high electron density -X according to the invention. FIG. 6 represents the scheme for the preparation of compounds 15-1 and 15. FIG. 7a represents the absorption spectrum of a non-symmetric chromogenic compound according to the invention (compound of structure 4) in solution in ethanol, then after 2 minutes and 10 minutes of irradiation with white light.

FIG. 7b shows the absorption spectrum of a non-symmetric chromogenic compound according to the invention (compound of structure 4) in solution in acetonitrile, then after 2 minutes and 4 minutes of irradiation with a white light. FIG. 8 represents the acid chromic properties of the non-symmetric chromogenic compound 4 according to the invention.

Figure 9 shows a synthetic scheme of triad 17 from compound 2 using the acetylenic compounds of the donor (TB2-acetylene) or the donor (Boranilacetylene). Figure 10 shows the proton NMR spectrum of triad 17 in chloroform deuterated at 400 MHz.

Figure 11 shows the mass spectrometry spectrum of electrospray triad 17. FIG. 12 represents the absorption spectrum of the triad 17 in solution in tetrahydrofuran, then after treatment with HCI hydrochloric acid vapors and treatment with a solution of tetramethylammonium hydroxide Me4NOH.

Figure 13 schematically illustrates the use of a triad-type chromogenic compound obtained via a non-symmetric chromogenic compound according to the invention as logic function molecules. The donor D and the acceptor A are independently related to either the iodo or bromo side.

DETAILED DESCRIPTION OF THE INVENTION 1. Definition The term "chromogenic" compound for the purpose of the present invention means a compound comprising at least one of the following properties: photochromic and / or acidochromic and / or solvatochromic and / or thermochromic.

For the purposes of the present invention, the term "molecular spacer" means a molecule segment providing a bond between two ends (i.e. between Y1 and Y2) of said molecule. For the purpose of the present invention, the term "non-symmetric compound" means a compound whose two ends (ie Y1 and Y2) are different chemical groups, ie Y1 # Y2. Description Non-symmetric chromogenic compounds according to US Pat. are [1,3] oxazine compounds comprising an indoline moiety fused to a benzooxazine moiety, ie the indoline and benzooxazine moieties share a common bond, and more specifically, share the link connecting positions 1 and 2 of the indoline moiety and the link connecting positions 2 and 3 of the benzooxazine moiety. The chromogenic compounds represented by the general formula (I) produce a phenolate derivative when exposed under a light source, the phenolate derivative being formed by breaking [C-O] bond in the ring [1 , 3] oxazine. The rupture of the [C-0] bond in the [1,3] oxazine ring and the opening of the ring is carried out according to the invention by the presence of a high electron density substituent -X, the latter playing a role. for the determination of the reactivity of the chromogenic compound to be reacted in the presence of light (for example, the wavelength and the intensity which induces cleavage of the cycle after excitation) and for the determination of the wavelength of absorption of the compound derived from phenolate. Indeed, the chromogenic compounds corresponding to the general formula (I) and whose substituent (-X) rich in electron density is chosen from the following groups of formulas: -CH3, or -HC = CH-R3 in which R3 represents an aromatic residue, optionally substituted and / or polysubstituted, and optionally comprising one or more heteroatoms chosen from N, S and / or O; allow cleavage of the [C-0] bond in the [1,3] oxazine ring. Indeed, the publication of M. Tomasulo, S. Sortino, and F. M. Raymo and entitled "Bichromophoric Photochromic Based on the Opening and Closing of a Single Oxazine Ring", J. Org. Chem. 73, 118-126 (2008) discloses a molecule of [1,3] oxazine type with inter alia the methyl group, phenyl or diphenyl X position of the general formula (I). For these compounds the opening of the [1,3] oxazine ring is favored essentially by the presence of a nitro function on the phenol moiety, however the open form merocyanine absorbs in the ultraviolet at 355 nm.

The colored state of the chromogenic compounds according to the invention can be activated by irradiation with a light source of determined wavelength and intensity; the initial state 3024730 9 can be restored by removing the light source to allow for example a thermal recycling. Advantageously, the chromogenic compounds according to the invention can be indifferently activated by irradiation with light sources known to those skilled in the art, and for example by the use of dye lasers, in particular gas or laser lasers. solid, poly-chromatic or monochromatic lamps, or by the use of light-emitting diodes. The light source may have a wavelength of between 200 nm and 1300 nm, 400 nm or more, at least 600 nm or more, at least 800 nm or more, 800 nm or less, 1000 nm or less, 1,300 nm or less, or any range between them. The light source may for example be a laser diode, for example with a wavelength of 200 nm to 800 nm, or a light emitting diode (LED), for example with a wavelength of 800 nm to 1300 nm. The light rays can be indifferently made by means of a constant or pulsed light.

In another particular embodiment according to the invention, the cleavage [C-O] in the [1,3] oxazine ring of the non-symmetric chromogenic compounds according to the invention can be carried out by modifying the pH of the solution in which the chromogenic compound is supplied, and this without resorting to irradiation of the compound by means of a light source. The return to the closed form can be achieved by treating the solution with a base. The chromogenic compounds according to the invention allow the subsequent synthesis of a triad, i.e., of the "donor-chromogenic-acceptor compound" type. The method comprises a step of supplying a non-symmetric chromogenic compound according to the invention, a step of selective substitution of the Y1 or Y2 group by a donor energy donor or electron donor substituent (or an acceptor substituent, respectively). energy or electron acceptor); and a step of selective substitution of the Y2 group (respectively Y1) by an energy acceptor substitute or electron acceptor (respectively an energy donor or electron donor substituent). The energy (or electron) donor compounds can be biocompatible and selected from xanthenes, acenes, cyanines, alexas, coumarins, squaraines, borondipyrromethenes, rhodamines, dansyls, perylenes, pyrenes, diketopyrrolopyrroles, boranils and metal complexes. phosphorescent transitions such as Ru, Os, Ir, Pt and Re. The energy accepting (or electron) compounds can be biocompatible and selected from xanthenes, cyanines, aza-boron-dipyrromethenes, rhodamines, porphyrins, phthalocyanines and subphthalocyanines, diketopyrrolopyrroles, extended boranils and metal complexes of phosphorescent transitions such as Ru, Os, Ir, Pt and Re. The triad-type chromogenic compounds according to the invention make it possible to envisage applications such as photodetection by modulation of fluorescence, high density optical storage and more particularly the molecular logic functions. Logic functions are the basic tool of digital electronics. Indeed, digital electronic devices such as computers, telephones and the like use logical binary functions or logic gates for the processing, transmission and storage of information. The information is encoded as 0 or 1. The logic gates function as a switch whose output 0 or 1 depends on the input conditions. The variation of the number of entries can lead to more or less complex logical functions. A single entry can lead for example to the logical gate "YES". The fact of having two entries can make it possible, for example, to create the "AND" or "OR" gate (see Table 1 below). B out Input A Output B AETB 0 0 0 0 1 0 1 1 B Out Input Output ABA OR B 0 0, a 1 Table 1: Logic gates among the most common The recognized advantages are a much faster switching, the possibility of greater miniaturization and greater flexibility. In principle, simple logic functions such as "YES" or "NO" can be performed by the chromogenic fluorophore dyads. More complex functions can be obtained thanks to the donor-chromogen-acceptor triads. Such a triad type chromogenic compound can be synthesized from the non-symmetrical chromogenic compounds according to the invention. A triad type chromogenic system is shown in Figure 9. In principle, when the form is open, energy transfer is possible from the donor to the acceptor via the chromogen and light is emitted by the acceptor. Thus this system with two inputs, the wavelength to open the chromogen and that to excite the donor, and an output. This molecule corresponds to the "AND" function. Currently all electronic digital devices are based on the use of silicon which is currently reaching its physical limits of miniaturization. To overcome the limitations imposed by silicon technology, triad-type chromogenic compounds according to the invention can be employed as organic molecular logic functions. EXAMPLES Example 1 Synthesis of Non-Symmetric Precursor [1,3] Spiroxazine 2. In the context of the present example, the inventors have synthesized a non-symmetrical precursor compound 2 according to the invention corresponding to the general formula (I) and whose synthetic scheme is given in FIG. 3. For this compound - R1 and R2 are identical and represent a methyl group; Y1 is I; Y2 is Br; X is CH3; Z is 0; The chromogenic compound corresponds to molecule 2 illustrated below: Compound 2 is prepared by a two-step synthesis from (4-iodophenyl) hydrazine (CAS No. 13116-27-3). The first step consists of the reaction between (4-iodophenyl) hydrazine and 3-methylbutan-2-one (CAS no: 563-80-4) forming the indole represented by the compound corresponding to structure 1. This compound was prepared according to [M. Tomasulo, S. Sortino, F. M. Raymo, J. Org. Chem. 2008, 73, 118-126]. In a second step, compound 1 reacts with 5-bromo-2-hydroxybenzyl alcohol (CAS No. 2316-64-5) to give compound 2. Preparation of compound 2: PBr3 (0.15 mL, 1.603 mmol ) is added dropwise to a solution of 5-bromo-2-hydroxybenzyl alcohol (217 mg, 1.069 mmol) in CH3CN 3024730 under argon flow. The solution is kept at 0 ° C during the addition and then at room temperature for about 30 minutes. Subsequently a solution of 3H-indole (305 mg, 1.069) in CH3CN is introduced and finally the reaction medium is stirred for 3 days at room temperature. Then a solution of sodium phosphate (pH = 7) is added to the solution which is subsequently extracted with CH2Cl2. The organic phase is washed once more with the sodium phosphate solution, then with a saturated solution of NaCl and finally with H 2 O. After drying on hydrophilic cotton and concentration on the rotary evaporator crude and purified by chromatographic column (SiO2, CH2Cl2 / petroleum ether: 5/5, v / v) in order to obtain the final product in the form of a colorless oil 10 (100 mg, 21%). 1H NMR (C6D6, 300 MHz) δ 0.82 (s, 3H), 1.06 (s, 3H), 1.24 (s, 3H), 3.76, 3.85 (ABq, JAB = 17.7Hz, 2H), 5.82 (d, 3H); = 8.1 Hz, 1H), 6.31 (d, 3J = 8.3 Hz, 1H), 6.876.92 (m, 2H), 7.25 (dd, 3J = 8.1 Hz, 4J = 1.5 Hz, 1H), 7.35-7.36 (m , 1H); 13 C NMR (C6 D6, 100 MHz) δ 15.6, 18.6, 25.5, 39.8, 47.9, 82.0, 100.6, 110.8, 112.4, 119.7, 120.6, 127.7, 128.0, 128.3, 129.7, 131.2, 131.4, 136.6, 141.5, 147.4, 152.3; MS-E1: m / z (intensity,%) calc. for [M] 468.9 Found 469.0 (100); Anal. calc. for C 18 H 17 BrINO: C, 45.98; H, 3.64; N, 2.98 found: C, 45.72; H, 3.41; N, 2.77. EXAMPLE 2 Synthesis of the Non-Symmetric [1,3] Spiroxazine Chromogen 4. The inventors have synthesized a non-symmetric chromogenic compound 4 according to the invention corresponding to the general formula (I) and whose synthetic scheme is given in FIG. 4.

For this compound - R1 and R2 are identical and represent a methyl group; Y1 is I; Y2 is Br; X is a derivative of julolidine functionalized by a solubilizing chain; - Z is O.

The reaction scheme of the synthesis of compound 4 is shown in FIG. 4. Compound 2 reacts with the compound derived from julolidine 3 synthesized according to reference [J. Y. Jung, S.J. Han, Chun J., Lee C., Yoon J., Dyes & Pigments, 2012, 94, 423-426] to form by condensation the chromogenic compound of formula 4.

Preparation of compound 4: In the solution of compound 2 (25 mg, 0.056 mmol) and 9-formyl-10-hexoxy-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro- / H, 5H-pyrido [3,2,1-ii] quinoline (24 mg, 0.068 mmol) in anhydrous ethanol (5 mL) is added TFA (40 μL, 0.392 mmol). The reaction medium is left stirring at room temperature overnight. After evaporation of the solvent, the crude reaction product is purified by a short chromatographic column (Al 2 O 3 activated with 6% H 2 O) starting with CH 2 Cl 2 and then CH 2 Cl 2 / MeOH 1%. The product is obtained as a dark blue fine powder (43 mg, 95%). 1 H NMR (C6 D6 400 MHz) δ 0.93 (t, 3 J = 7.1 Hz, 3H), 1.14 (s, 3H), 1.18 (s, 3H), 1.20 (s, 3H), 1.22-1.36 (m, 8H); ), 1.38 (s, 3H), 1.43 (s, 3H), 1.49-1.53 (m, 2H), 1.56 (s, 3H), 1.58-1.75 (m, 4H), 2.75-2.88 (m, 4H), 3.62 (t, 3 J = 7.1 Hz, 2H), 3.84, 4.20 (ABq JAB = 17.3 Hz, 2H), 5.93 (d, 3 J = 8.7 Hz, 1H), 6.23 (d, 3 J = 16.3 Hz, 1H), 6.50. (d, 3J = 8.7Hz, 1H), 6.84 (d, 2J = 2.2Hz, 1H), 6.91 (dd, 3J = 8.8Hz, 2J = 2.4Hz, 1H), 7.28 (d, 3J = 16.3Hz, 1H), 7.29 (dd, 3J = 8.2 Hz, 2J = 1.7 Hz, 1H), 7.40 (d, 2 J = 1.7 Hz, 1H), 7.47 (s, 1H); 13 C NMR (C6 D6, 100 MHz) δ: 14.0, 18.1, 22.8, 25.8, 26.0, 30.1, 30.0, 30.1, 30.3, 31.1, 31.4, 32.0, 32.0, 32.7, 36.9, 40.3, 40.6, 46.7, 47.1, 49.8, 75.0, 81.8, 102.5, 110.9, 112.0, 117.7, 118.0, 118.9, 121.5, 122.5, 123.0, 126.6, 126.9, 126.9, 128.3, 128.5, 129.4, 130.8, 131.1, 133.0, 136.3, 141.6, 143.4, 147.1, 152.6, 156.6; DEPT 135 (C6D6, 100 MHz) b CH2, 20: 14.0, 18.1, 26.1, 30.2, 30.4, 31.1, 31.4; CH3, CH pos .: 22.8, 25.8, 30.1, 32.0, 40.3, 40.6, 46.7, 47.2, 75.0, 110.9, 118.0, 118.9, 122.9, 129.4, 130.8, 131.1, 133.0, 136.3; MS-E1: m / z (intensity,%) calc. for [M]: 808.2 found 808.1; 681.1 (30) [M-1]; Anal. calc. for C41 H50BrI N2O2: C, 60.82; H, 6.22; N, 3.46 found: C, 60.66; H, 5.84; N, 3.22. Examples 3 to 13 - Synthesis of the non-symmetric chromogenic [1,3] spiroxazine 5a to 15a.

The reaction scheme of the synthesis of compounds 5a to 15a is shown in FIG. 5, and the compounds of general formula (I) according to the invention. The general synthesis procedure is as follows: In the solution of compound 2 and the aldehydes 5-15 (1 equivalent) in anhydrous ethanol (5 mL) is added TFA (4-5 equivalent). The reaction medium is stirred at room temperature or at reflux overnight. After evaporation of the solvent, the crude is solubilized in CH 2 Cl 2 and is washed several times with H 2 O and then dried over hydrophilic cotton and concentrated. Purification of the product by chromatographic column on silica or alumina (activated with 6% H 2 O). The chromogenic compounds prepared correspond to formulas 5a to 15a. N 7a C 6 H 13 C 6 H 13 O 13a 13a 14a Compound 5a: (30 mg, 69%). 1H NMR (C6D6, 300MHz) δ: 1.05 (s, 3H), 1.38 (s, 3H), 2.43 (s, 6H), 3.95 (ABq, JAB = 17.1Hz, 2H), 5.92 (d, 3J = 8.2); Hz, 1H), 6.09 (d, 3 J = 15.9 Hz, 1H), 6.45-6.50 (m, 3H), 6.81 (d, 4 J = 2.3 Hz, 1H), 6.90 (d, 3 J = 15.9 Hz, 1H), 6.93 (dd, 3J = 8.6 Hz, 4J = 2.2 Hz, 1H), 7.28 (d, 3J = 8.8 Hz, 2H), 7.30 (dd, 3J = 8.2 Hz, 4J = 1.5 Hz, 1H), 7.41 (d , 4J = 1.4 Hz, 1H); 13 C NMR (C6 D6, 100 MHz) δ 18.1, 26.0, 39.5, 40.2, 49.6, 81.7, 102.4, 110.9, 112.1, 118.6, 118.7, 121.5, 124.2, 129.5, 130.8, 131.1, 136.1, 136.3, 141.6, 147.1, 150.6, 152.6; DEPT 135 δ: CH 3, CH pos .: 18.1, 26.0, 39.5, 110.9, 112.0, 112.1, 118.6, 118.7, 128.0, 129.5, 130.8, 131.1, 136.1, 136.3; Negative CH2: 40.2; MS-E1: m / z (intensity,%) calc. for [M]: 602.0 found 602.0; 521.0 (30) [M-Br]; Anal. calc. for C271-126BrIN2O: C, 53.93; H, 4.36; N, 4.66 found: C, 53.72; H, 4.18; N, 4.31.

Compound 6a: (35mg, 33%). 1 H NMR (CDCl 3, 400 MHz) δ: 1.17 (s, 3H), 1.47 (s, 3H), 4.43 (ABq, JAB = 17.3 Hz, 2H), 6.14 (d, 3 J = 16.0 Hz, 1H), 6.38 ( d, 3 J = 8.0 Hz, 1H), 6.70 (d, 3 J = 24.0 Hz, 1H), 6.69 (s, 1H), 6.70-6.09 (m, 8H), 7.12-7.17 (m, 2H), 7.23-7.25 (m, 4H), 7.38 (m, 2H); 13C NMR (CDCl3, 100 MHz) δ 18.4, 26.4, 29.7, 40.7, 49.9, 81.6, 7.35-101.9, 110.9, 112.2, 119.1, 121.4, 121.7, 123.2, 124.6, 127.7, 129.3, 129.6, 130.8, 131.2 135.5, 136.2, 141.4, 147.0, 147.4, 148.1, 152.4; DEPT 135 δ: CH 3, CH pos. 18.1, 26.0, 110.9, 118.8, 121.9, 123.1, 123.7, 124.5, 127.8, 128.0, 129.3, 129.5, 130.8, 131.1, 135.4, 136.4; Negative CH2: 40.2; MS-E1: m / z (intensity,%) calc. for [M]: 724.1 found 724.0; Anal. calc. for C371-130BrIN20: C, 61.26; H, 4.17; N, 3.86 found: C, 60.92; H, 3.82; N, 3.62.

Compound 7a: (23 mg, 32%). 1 H NMR (CDCl3, 300 MHz) δ: 1.21 (s, 3H), 1.50 (s, 3H), 4.46 (ABq, JAB = 17.1 Hz, 2H), 6.40 (d, 3 J = 8.0 Hz, 1H), 6.43 ( d, 3 J = 16.2 Hz, 1H), 6.73 (d, 3 J = 149.2, CH2 neg: 40.7, Compound 8a: (36 mg, 48%) .1H NMR (CDCl3, 400MHz) δ: 1.17 (s, 3H), 1.48 (s, 3H), 3.96 (s, 5H), 4.23 (s, 2H), 4.34 (s, 2H), 4.44 (ABq, JAB = 17.2 Hz, 2H), 5.84 (d, 3 J = 15.9; Hz, 1H), 6.37 (d, 3 J = 8.1 Hz, 1H), 6.54 (d, 3 J = 15.9 Hz, 1H), 6.71 (d, 3 J = 8.5 Hz, 1H), 7.16-7.20 (m, 2H). 7.36-7.39 (m, 2H) 13C-NMR (CDCl3, 100 MHz) δ 18.4, 26.3, 40.7, 49.3, 67.0, 67.4, 69.1, 69.4, 81.2, 81.5, 101.8, 110.8, 112.3, 119.2, 119.9, 121.6, 129.2, 130.8, 131.2, 134.7, 136.1, 141.3, 146.9, 152.5, DEPT 135 δ: CH3, CH pos .: 18.4, 26.3, 67.0, 67.4, 69.1, 69.4, 77.2, 110.8, 119.2, 119.8, 129.2, 130.8, 131.2, 134.7, 136.1, CH2 neg 40.7, MS-E1: m / z (intensity,%) calc for [M]: 664.9 found 665.0, 586.0 (20) [M-Br]; for C 29 H 25 BrFeINO: C, 52.29; H, 3.78; N, 2.10 found: C, 51.93; H, 3.52; N, 1.83. Compound 9a: (10 mg, 26%). 1H NMR (C6D6, 400MHz) δ 0.92 (s, 3H), 1.43 (s, 3H), 1.77 (s, 3H), 3.81 (ABq, JAB = 17.6Hz, 2H), 5.82 (d, 3J = 8.2); Hz, 1H), 6.28 (d, 3 J = 7.7 Hz, 1H), 6.41 (s, 1H), 6.40 (d, 3 J = 24.8 Hz, 1H), 6.88 (d, 4 J = 2.4 Hz, 1H), 6.92 ( dd, 3J = 7.4 Hz, 4J = 1.1 Hz, 1H), 6.94-7.02 (m, 7H), 7.30 (dd, 3J = 8.1 Hz, 4J = 1.7 Hz, 1H), 7.31-7.34 (m, 1H) 7.37 (d, 4 J = 1.7 Hz, 1H); 13C NMR (C6D6.100 MHz) δ: 13.2, 18.0, 25.4, 40.1, 49.2, 79.7, 80.5, 101.4, 110.6, 112.7, 119.2, 120.6, 120.8, 121.5, 122.4, 127.2, 129.1, 129.7, 130.3, 130.8, 131.1, 136.4, 140.6, 140.7, 140.8, 140.9, 141.1, 146.8, 152.6; DEPT 135 δ: CH 3, CH pos .: 13.2, 18.0, 25.4, 110.6, 119.2, 120.6, 120.8, 121.5, 127.2, 127.4, 128.0, 129.1, 129.7, 130.3, 130.8, 131.1, 136.4; Negative CH2: 40.1; MS-E1: m / z (intensity,%) calc. 8.5 Hz, 1H), 6.85 (d, 3 J = 16.2 Hz, 1H), 7.16-7.21 (m, 2), 7.30-7.33 (m, 1H), 7.36-7.41 (m, 2H); 13 C NMR (CDCl3, 100 MHz) δ 18.5, 26.4, 40.7, 50.1, 81.9, 101.6, 111.0, 112.5, 119.0, 120.8, 120.9, 121.2, 123.8, 126.6, 129.4, 131.0, 131.2, 132.5, 134.0, 136.3, 136.9, 141.1, 146.8, 148.2, 142.2, 149.3, 152.2; DEPT 135 δ: CH3, CH pos .: 18.5, 26.4, 111.0, 119.0, 120.9, 121.2, 123.9, 126.6, 129.4, 131.0, 131.2, 132.5, 134.0, 136.3, 136.9, 148.2, 3024730 for [M]: 671.0 found 671.0; Anal. calc. for C34H27BrINO: C, 60.73; H, 4.05; N, 2.08 found: C, 60.44; H, 3.77; N, 1.77. Compound 10a: The reaction is carried out in THF (38 mg, 38%). 1 H NMR (CDCl 3, 400 MHz) δ: 0.97 (t, 3 J = 6.8 Hz, 3H), 0.99 (s, 3H), 1.14-1.23 (m, 6H), 1.31 (s, 3H), 1.48-1.55 ( m, 2H), 2.53 (t, 3 J = 7.6 Hz, 2H), 3.86 (ABq, JAB = 17.4 Hz, 2H), 5.88 (d, 3 J = 8.2 Hz, 1H), 6.07 (d, 3 J = 15.7 Hz, 1H), 6.41 (s, 1H), 6.43-6.44 (m, 1H), 6.47 (d, J = 3.4 Hz, 1H), 6.78 (d, J = 3.6 Hz, 1H), 6.81 (d, 4J = 2.4 Hz, 1H), 6.87 (d, 3J = 15.7 Hz, 1H), 6.92 (d, 4J = 2.4 Hz, 1H), 6.95 (d, J = 3.6 Hz, 1H), 7.29 (dd, 3J = 8.3 Hz, 4J = 1.7Hz, 1H), 7.38 (d, J = 1.7Hz, 1H), 13C NMR (C6D6, 100MHz) δ: 13.9, 18.0, 22.5, 25.9, 28.6, 29.9, 30.0, 31.5, 40.1, 49.9 , 82.0, 101.5, 110.9, 112.4, 118.6, 121.3, 123.0, 123.3, 123.9, 125.0, 129.6, 130.9, 131.1, 134.6, 136.4, 138.0, 138.9, 141.2, 145.9, 146.8, 152.2; DEPT 135 δ: CH 3, CH pos .: 13.9, 18.0, 25.9, 110.9, 118.6, 123.0, 123.3, 123.9, 125.0, 128.0, 128.5, 129.0, 129.6, 130.9, 131.1, 136.4; CH2 neg: 22.5, 28.6, 30.0, 31.5, 40.1; MS-E1: m / z (intensity,%) calc. for [M] 731.0 found 731.0; 650 (25) [M-Br]; Anal. calc. for C33H33BrINOS2: C, 54.25; 15H, 4.55; N, 1.92 found: C, 54.04; H, 4.31; N, 1.72. Compound 11a: 1H NMR (CDCl3, 300 MHz) δ: 0.88-0.91 (m, 3H), 1.18 (s, 3H), 1.46 (s, 3H), 1.29 (s, 3H), 1.60-1.72 (m, 6H). ), 2.79 (t, 3J = 7.6 Hz, 2H), Hz, 3.62 (q, 3J = 7.3 Hz, 2H), 4.43 (ABq, JAB = 17.2 Hz, 2H), 5.64 (s, 1H), 6.06 (d. , 3J = 15.9 Hz, 1H), 6.37 (d, 3J = 8.1 Hz, 1H), 6.67-6.69 (m, 2H), 6.82 (d, 3J = 13.0 Hz, 1H), 6.85 (s, 1H), 6.70. -6.99 (m, 2H), 7.03 (d, 4 J = 3.7 Hz, 1H), 7.14-7.16 (m, 1H), 7.18-7.19 (m, 1H), 7.34-7.36 (m, 1H), 7.38-. 7.39 (m, 1H); 13C NMR (CDCl3, 100 MHz) δ: 8.2, 14.1, 18.4, 22.6, 26.4, 28.8, 29.7, 30.2, 31.6, 32.0, 40.7, 50.1, 63.5, 81.8, 101.5, 110.9, 112.3, 119.0, 121.3, 123.2, 123.6, 124.6, 124.9, 128.4, 129.0, 129.4, 130.9, 131.2, 134.2, 135.0, 136.2, 137.1, 137.4, 139.4, 141.2, 145.9, 146.8, 152.2; (38 mg, 39-42%). MS-E1: m / z (intensity,%) calc. for [M]: 811.0 found 811.0; 732.0 (30) [M-Br]. Compound 12a: (37 mg, 48%). 1H NMR (C6D6, 300MHz) δ: 0.87 (s, 3H), 1.29 (s, 3H), 3.84 (ABq, JAB = 17.2Hz, 2H), 5.87 (d, 3J = 8.3Hz, 1H), 6.12 ( d, 3J = 15.8 Hz, 1H), 6.39 (d, 3J = 8.7 Hz, 1H), 6.53-6.59 (m, 2H), 6.66-6.68 (m, 1H), 6.78 (d, 4J = 2.4 Hz, 1H). ), 6.91 (dd, 3J = 8.6 Hz, 4J = 2.3 Hz, 1H), 6.92 (d, 3J = 15.8 Hz, 1H), 7.28 (dd, 3J = 8.3 Hz, 4J = 1.8 Hz, 1H), 7.36 (d, 4J = 2.4 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 18.4, 26.3, 40.6, 50.0, 81.7, 101.5, 110.9, 112.3, 119.0, 121.3, 123.2, 125.3, 127.2, 127.6, 129.1, 129.4, 131.0, 131.2, 136.2, 140.8, 141.3, 146.8, 152.2; DEPT 0: CH3, CH pos .: 18.4, 26.3, 110.9, 119.0, 123.2, 125.3, 127.2, 127.6, 129.1, 129.4, 130.9, 131.2, 136.2; Negative CH2: 40.6; MS-E1: m / z (intensity,%) calc. for [M]: 564.9 found 565.0; 484.0 (20) [M-Br]; Anal. calc. for C23H19BrINOS: C, 48.96; H, 3.39; N, 2.48 found: C, 48.68; H, 3.12; N, 2.24.

Compound 13a: (43mg, 41%). 1H NMR (CDCl3, 400 MHz) δ: 0.77-0.84 (m, 6H), 0.90-0.99 (m, 4H), 1.11-1.15 (m, 12H), 1.20 (s, 3H), 1.47 (s, 3H). , 1.73-1.79 (m, 4H), 4.44 (ABq, JAB = 16.8 Hz, 2H), 6.03 (d, 3 J = 15.7 Hz, 1H), 6.38 (d, 3 J = 8.2 Hz, 1H), 6.68 (d, 3J = 8.4 Hz, 1H), 6.79 (s, 1H), 6.86 (d, 3 J = 15.7 Hz, 1H), 6.91 (d, J = 4.9 Hz, 1H), 7.16-7.19 (m, 3H), 135 Δ: CH 3, CH pos: 14.1, 18.4, 26.4, 110.9, 119.0, 120.5, 121.7, 122.2, 125.6, 129.4, 130.2, 130.9, 131.2, 136.2; CH2 neg. : 22.6, 24.5, 29.7, 31.6, 37.5, 37.6, 40.6; MS-E1: m / z (intensity,%) calc. for [M] 827.1 found 827.1; 746.1 (20) [M-Br]; Anal. calc. for C40H45BrINOS2: C, 58.11; H, 5.49; N, 1.69 found: C, 58.54; H, 6.04; N, 2.22. Compound 14a: 1H NMR (CDCl3, 300 MHz) δ: 1.32 (s, 3H), 1.61 (s, 3H), 4.55 (ABq, JAB = 17.7Hz, 2H), 6.44 (d, 3J = 8.2Hz, 1H) , 6.51 (s, 1H), 6.87 (d, 3 J = 8.8 Hz, 1H), 7.20 (s, 1H), 7.28-7.29 (m, 1H), 7.41-7.44 (m, 2H), 7.88 (d, 3H). = 15.8 Hz, 1H), 7.98-8.10 (m, 5H), 8.14 (s, 2H), 8.17-8.20 (m, 2H), 13C-NMR (CDCl3, 100 MHz) δ: 18.6, 26.5, 40.9, 49.9 , 81.7, 102.0, 110.9, 112.5, 119.1, 121.6, 122.6, 124.0, 124.8, 124.9, 125.3, 125.5, 126.1, 127.1, 127.3, 127.7, 128.0, 128.4, 129.4, 130.4, 130.8, 131.0, 131.3, 131.4, 133.9 136.3, 141.3, 147.0, 152.6; DEPT 135 δ: CH 3, CH pos .: 18.6, 26.5, 110.9, 119.1, 122.6, 142.0, 124.9, 125.3, 125.5, 126.1, 127.1, 127.3, 127.7, 128.0, 129.4, 131.0, 131.3, 133.9, 136.3; 20 CH2, negative: 40.9; MS-E1: m / z (intensity,%) calc. for [M] 683.0 found 683.0; 602.0 (30) [M-Br]; Anal. calc. for C35H27BrINO: C, 61.42; H, 3.98; N, 2.05 found: C, 61.95; H, 3.79; N, 1.69. Preparation of compound 15-I according to Figure 6: 9-formyl-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro- / H, 5H-pyrido [3,2,1-i] quinoline (300 mg, 1.10 mmol) and 4-iodoaniline (360 mg, 1.64 mmol) were placed in a Schlenk tube and solubilized in anhydrous ethanol (15 mL). Then a p-TsOH crystal is added to the solution. The reaction medium is stirred at 95 ° C. overnight. After evaporation of the solvent, the crude reaction product is solubilized in CH 2 Cl 2 and washed several times with H 2 O. The organic phase is dried over hydrophilic cotton, concentrated on an evaporator and purified on a chromatographic column (SiO 2, CH 2 Cl 2 / petroleum ether: 7/3, v / v). The product is obtained as a viscous oil which solidifies at room temperature to give a yellow solid (300 mg, 75%). 1H NMR (CDCl3, 300MHz) δ: 1.27 (s, 6H), 1.49 (s, 6H), 1.71-1.79 (m, 4H), 3.18 (t, 3J = 5.6Hz, 2H), 3.27 (t, 3H); = 5.9 Hz, 2H), 6.96 (s, 1H), 6.98 (d, 3 J = 8.7 Hz, 2H), 7.65 (d, 3 J = 8.6 Hz, 2H), 8.34 (s, 1H), 13.87 (s, 1H). ); 13C-NMR (CDCl3, 100 MHz) δ: 28.4, 30.9, 31.8, 32.2, 36.3, 39.9, 47.1, 47.5, 89.0, 109.1, 114.6, 122.7, 123.0, 128.4, 138.2, 146.7, 149.0, 160.6, 161.6; IR-ATR (cm-1): 488, 818, 944, 1029, 7.34-7.38 (m, 2H); 13C NMR (CDCl3, 100 MHz) δ: 14.0, 18.4, 22.6, 24.5, 26.4, 29.7, 31.6, 37.5, 37.6, 40.7, 50.1, 81.7, 101.8, 110.9, 112.2, 119.0, 120.5, 121.4, 121.7, 122.2, 125.6, 129.4, 130.2, 130.9, 131.1, 136.2, 136.7, 140.7, 141.4, 146.8, 152.3, 158.1, 158.8; DEPT 3024730 181216, 1309, 1514, 1576, 1619, 2854, 2926; MS-E1: m / z (intensity,%) calc. for [M]: 474.1 found: 474.0 (100); Anal. calc. for C23H27IN2O: C, 58.23; H, 5.74; N, 5.91 found: C, 57.98; H, 5.39; N, 5.59; Preparation of Compound 15: Compound 15-I (200 mg, 0.42 mmol), Pd (PPh 3) 2 Cl 2 (29 mg, 0.04 mmol) and sodium formate (32 mg, 0.46 mmol) are solubilized in anhydrous DMF (9 mL) in a two-necked flask equipped with a condenser. The reaction mixture is then placed at 75 ° C. under a continuous stream of CO for 3 hours. Subsequently, the reaction medium is allowed to return to ambient temperature. The organic phase is extracted into CH2Cl2 and washed several times with H2O. The product is purified by chromatography column on silica with CH 2 Cl 2 and is recovered as a viscous oil which solidifies at room temperature to give a yellow solid (111 mg, 70%). 1H NMR (CDCl3, 300 MHz) δ: 1.27 (s, 6H), 1.50 (s, 6H), 1.72-1.79 (m, 4H), 3.14 (t, 3 J = 5.8Hz, 2H), 3.23 (t, 3H); = 6.1 Hz, 2H), 7.0 (s, 1H), 7.27 (d, 3J = 8.4 Hz, 2H), 7.81 (d, 3J = 8.4 Hz, 2H), 8.4 (s, 1H), 10.0 (s, 1H) ), 13.9 (s, 1H, OH); 13C NMR (CDCl3, 100 MHz) δ: 28.3, 30.7, 31.8, 32.2, 36.1, 39.7, 47.1, 47.5, 109.2, 114.4, 121.3, 123.1, 128.7, 131.2, 133.1, 147.3, 154.7, 161.2, 162.3, 191.2 ; MS-E1: m / z (intensity,%) calc. for [M]: 376.2 found 376.2, Anal. calc. for C24H28BrN2O2: C, 76.56; H, 7.50; N, 7.44 Found: C, 76.38; H, 7.32; N, 7.09. Compound 15a: 1H NMR (CDCl3, 300MHz) δ: 1.27 (s, 12H), 1.50 (s, 6H), 1.71-1.79 (m, 4H), 3.18 (t, 2J = 6Hz, 2H), 3.27 ( t, 2J = 6Hz, 2H), 4.44 (ABq, JAB = 17.4Hz, 2H), 6.23 (d, 3J = 16.0Hz, 1H), 6.39 (d, 3J = 8.1 Hz, 1H), 6.70 (d, 3J = 8.6 Hz, 1H), 6.77 (d, 3J = 16.0 Hz, 1H), 6.97 (s, 1H), 7.13-7.15 (m, 2H), 7.19 (d, 3J = 8.3 Hz, 2H), 7.35- 7.39 (m, 4H), 8.38 (s, 1H), 14.07 (s, 1H); 13C NMR (CDCl3, 100 MHz) δ: 14.1, 18.4, 19.8, 22.7, 26.4, 27.2, 30.3, 30.9, 31.8, 31.9, 32.2, 36.3, 39.9, 40.7, 47.0, 47.4, 50.0, 81.7, 101.8, 109.2, 110.9, 112.2, 114.6, 119.0, 121.0, 121.4, 122.7, 127.8, 128.4, 129.3, 129.7, 130.9, 131.2, 132.6, 135.6, 136.2, 141.4, 146.7, 147.0, 149.2, 151.3, 152.4, 160.8, 161.0; DEPT 135 δ: CH 3, CH pos .: 14.1, 18.4, 26.4, 28.4, 30.9, 110.9, 119.0, 121.0, 122.7, 127.8, 128.4, 129.3, 130.9, 131.2, 135.6, 136.2, 161.0, CH2 negative: 36.3, 39.9 , 40.7, 47.0, 47.4. a) Photophysical Characteristics of Compound 4 The chromogenic compound 4 in solution in ethanol gives a slightly bluish color to the solution, indicating that the solution comprises a mixture of compounds whose unopened ring with a small amount of open molecule . This state of affairs could be confirmed by proton NMR. The absorption spectrum shown in FIG. 7a shows a weak band around 600 nm which corresponds to the open form of the photochromic compound. Irradiation of the solution for 2 to 10 minutes with a lamp (500 Watts) moves the equilibrium to the open form, as indicated by the intensity of the band at 600 nm and the reduction of that to about 300 nm. The chromogenic compound 4 in solution in acetonitrile is colorless. There is no absorption band around 600 nm (see Figure 7b). However, UV irradiation causes an immediate coloring of the solution in dark blue. The appearance of the absorption band at 600 nm after 2 minutes of irradiation attests to the opening of the ring. There is no change in spectrum after 4 minutes of irradiation compared to the spectrum after 2 minutes of irradiation. The ring opening kinetics of compound 4 in acetonitrile is therefore rapid and the equilibrium is rapidly shifted to the open form of the photochromic compound which is stabilized in a polar solvent. Discoloration of the blue solution is slow by heat and takes several days. On the other hand, the dissolution of the chromogenic compound 4 in an apolar solvent such as diethyl ether is colorless and its UV irradiation does not cause coloration, which probably indicates that the open form of the photochromic compound is not stable in an apolar solvent. and aprotic. b) Acidochromic Characteristic of Compound 4 Cleavage of the [C-O] bond in the [1,3] oxazine ring of chromogenic compound 4 can also be achieved when the compound in solution in acetonitrile and treated with hydrochloric acid (in the form of gas). The return to the closed form is achieved by treating the phenol derivative compound with a solution of tetramethylammonium hydroxide Me4NOH (see FIG. 8). Example 14 - Grafting of an energy donor moiety on bromo and an energy acceptor moiety on iodo to obtain a non-symmetric [1,3] spiroxazine compound. The synthetic scheme is given in FIG. 9. Compound 16: Two successive cross-couplings of Sonogashira, catalyzed with Palladium (II) / Cul have made it possible to obtain the compound 16. 1 H NMR (CDCl 3, 300 MHz) in ppm: 0.88 0.93 (m, 6H), 1.20 (s, 3H), 1.26 (s, 6H), 1.30-1.36 (m, 8H), 1.39-1.43 (m, 4H), 1.48 (s, 6H), 1.54 (s). , 6H), 1.57 (s, 6H), 1.65-1.79 (m, 8H), 2.81 (t, 3J = 7.6 Hz, 4H), 3.29-3.32 (m, 2H), 3.38-3.42 (m, 2H), 4.57 (s, 2H), 6.51-6.59 (m, 3H), 6.67 (dd, 3J = 8.6 Hz, 4J = 2.6 Hz, 1H), 6.72 (d, J = 3.6 Hz, 2H), 6.99-6.70 (m.p. , 1H), 7.05 (d, J = 3.6 Hz, 2H), 7.107.13 (m, 4H), 7.27-7.33 (m, 8H), 7.43-7.55 (m, 6H), 7.60-7.64 (m, 2H). ), 7.94 (s, 1H).

EXAMPLE 15 Grafting of an electron density rich group on the methyl group of compound 16 to obtain a triad-like non-symmetric chromogenic [1,3] spiroxazine compound. The synthesis scheme is given in FIG. 9.

Preparation of Compound 17: Compound 16 (15 mg, 0.009 mmol) and Julolidine-aldehyde 3 (27 mg, 0.075 mmol) are solubilized in a mixture of ethanol / acetonitrile / toluene distillate solvents (6 mL). TFA (7 μL, 0.095 mmol) is then added under argon flow and the reaction medium is refluxed for 1 h 30 min. After evaporation of the solvents, the crude reaction product is solubilized in dichloromethane and washed several times with water. The organic phase is then dried over anhydrous Na 2 SO 4 and then evaporated in vacuo. The triad is finally purified on a chromatographic column on silica (dichloromethane / methanol 1 to 4%) and by precipitation in a tetrahydrofuran / pentane mixture (9 mg, 49%). 1 H NMR (CDCl 3, 400 MHz) in ppm: 0.88-0.92 (m, 9H), 1.28-1.34 (m, 24H), 1.40-1.43 (m, 8H), 1.48 (s, 3H), 1.49 (s, 3H). ), 1.53-1.57 (m, 16H), 1.66-1.81 (m, 14H), 2.81 (t, 3J = 7.6 Hz, 4H), 3.05-3.09 (m, 2H), 3.15 (t, 3J = 6.0 Hz); , 2H), 3.31 (t, 3J = 6.0 Hz, 2H), 3.40 (t, 3J = 6.0 Hz, 2H), 3.54-3.64 (m, 2H), 4.47-4.51 (m, 2H), 6.05 (d, 3J = 16.5 Hz, 1H), 6.57-6.59 (m, 2H), 6.72 (d, J = 3.3 Hz, 2H), 6.78-6.81 (m, 1H), 6.97-7.01 (m, 2H), 7.05 (d , J = 3.6 Hz, 2H), 7.10 (d, J = 3.6 Hz, 2H), 7.12 (d, J = 3.6 Hz, 2H), 7.28-7.34 (m, 6H), 7.42-7.55 (m, 8H) 7.59-7.63 (m, 2H), 7.65-7.73 (m, 2H), 7.94 (s, 1H). ES-MS (m / z): calculated 1889.89, found 1890.89 [M + H] +. This compound 17 was characterized by proton NMR (FIG. 10) and not mass spectrometry (FIG. 11). Spectroscopic Characteristics of Compound 17: This compound has three absorption bands in THF; around 740 nm for the energy acceptor (BODIPY, boron-dipyromethene), around 380-450 nm for the energy acceptor (vinyl part of BODIPY) and Boranil and, around 340 nm for spiroxazine closed, a characteristic spectrum is given in FIG. 12. This absorption spectrum is characteristic of a closed chromogen. In the presence of acid trace a new electronic transition is observed around 600 nm. This transition is characteristic of the open form of the chromogen as previously observed in FIGS. 7a and 7b. A basic treatment of this solution confirms the reversibility of the system and the perfect superimposition of the absorption spectra before the acid treatment / basic treatment cycle.

Claims (11)

REVENDICATIONS1. Non-symmetric chromogenic compound corresponding to the following general formula (I): in which: R1 and R2 are identical or different and represent a linear or branched alkyl group of 1 to 12 carbon atoms, or represent an alkenyl group, alkynyl, aryl, alkylaryl, cycloalkyl, R1 and R2 may optionally form a single group to form a carbocyclic or heterocyclic group of 5 to 10 atoms; Y 1 is a halogen selected from Cl, Br or I; Y 2 is a halogen selected from Cl, Br or I; it being understood that Y1 # Y2; and X is an electron donor substituent chosen from the following groups of formulas: -CH3 or -HC = CH-R3 in which R3 represents an aromatic residue, optionally substituted and / or polysubstituted, and optionally comprising one or more selected heteroatoms; from N, S and / or O. - Z is an atom selected from N, S, O. 2. Compound according to claim 1, characterized in that R3 is an aromatic residue selected from the group formed by the aromatic residues, possibly fused (in particular phenyl, naphthyl, phenanthryl, anthracyl, chrysene derivatives, pyrene, tetracene, fluoranthene, coronene, benzo [a] anthracene), substituted or unsubstituted; aromatic, optionally fused, substituted or unsubstituted heterocyclic radicals, such as substituted or unsubstituted furan residues (possibly fused with one or more benzene rings, in particular benzofuran and isobenzofuran), and substituted or unsubstituted pyrrole radicals (possibly condensed with one or more benzene rings, in particular indole and isoindole) and thiophene residues, substituted or unsubstituted (possibly fused with one or more benzene rings, in particular benzothiophene and benzo [c thiophene) and the remains of indazole, pyrazole, oxazole, isoxazole, thiazole, substituted or unsubstituted. 5 3. Compound according to claim 2, characterized in that R3 is p-dimethylaminophenyl 5 / 5a, triphenylamine 6 / 6a, 2,2'-bipyridine 7 / 7a, ferroocene 8 / 8a, 9-methylanthracene 9 / 9a, 2-hexyl-bis-thiophene 10 / 10a, 2-hexyl-tristhiophene 11 / 11a, thiophene 12 / 12a, dihexyl-bis-thiophene fused 13 / 13a, pyrene 14 / 14a, boranils 15 / 15a. 10 4. Compound according to any one of claims 1 to 3, characterized in that R3 is a julolidine aromatic heterocyclic residue, optionally substituted. 15 5. Compound according to any one of claims 1 to 4, characterized in that R3 an organometallic compound selected from compounds of metallocene type, optionally substituted, and is preferably an organometallic compound selected from compounds of ferrocene type, optionally substituted. 20 6. Compound according to any one of claims 1 to 5, characterized in that R1 and R2 are identical or different and represent a linear alkyl group, from 1 to 12 carbon atoms, and more preferably represent a methyl group. 25 A process for the preparation of a triad type chromogenic compound, wherein process a) a non-symmetrical chromogenic compound is provided according to any one of claims 1 to 6; b) selective substitution of the Y1 group by an energy donor or electron donor substituent or an energy acceptor or electron acceptor substituent; and c) a step of selective substitution of the Y 2 group by an energy acceptor substitute or electron acceptor substituent (respectively an energy donor or electron donor substituent), and d) a step of transforming the -CH 3 into - HC = CH-R3 with R3 being a derivative of julolidine or any R3 group selected from the group consisting of pdimethylaminophenyl 5 / 5a, triphenylamine 6 / 6a, 2,2'-bipyridine 7 / 7a, ferroocene 3024730 238 / 8a, 9-methylanthracene 9/9a, 2-hexyl-bis-thiophene 10/10a, 2-hexyl-tristhiophene 11/11a, thiophene 12/12a, dihexyl-bis-thiophene fused 13 / 13a, pyrene 14 / 14a, boranils 15 / 15a. 5 The process according to claim 7, wherein the energy donor (or electron) substituent can be biocompatible and selected from xanthenes, acenes, cyanines, alexas, coumarins, squaraines, boron-dipyrromethenes, rhodamines, dansyls, perylenes. pyrene, diketopyrrolopyrroles, boranils and metal complexes of phosphorescent transitions such as Ru, Os, Ir, Pt and Re; and the energy accepting substituent is selected from xanthenes, cyanines, aza-boron-dipyrromethenes, rhodamines, porphyrins, phthalocyanines and subphthalocyanines, diketopyrrolopyrroles, extended boranils and metal complexes of phosphorescent transitions such as Ru, Os, Ir, Pt and Re. 15 9. A triad type chromogenic compound obtainable by the process according to claim 7 or 8. Use of the triad chromogenic compound of claim 9 for high density optical storage, for cellular imaging, for cell signaling and biomedical analysis, or as a molecular logical function. 11. Optical storage medium, characterized in that it comprises at least one photochromic compound according to any one of claims 1 to 6 or 9.