LT6012B - NOVEL 1,5-DISUBSTITUTED 11-OXA-3-AZA-3H-3-ALKYL- (OR ARYL-)DIBENZO[a,m]INDENO[2.1.7.6-ghij]PLEIADENE DERIVATIVES, SYNTHESIS THEREOF AND USES THEREOF IN OPTOELECTRONICS - Google Patents

Abstract

The present invention is a new heterocyclic system comprising ortho-fused system (NOP) of carbazole and two anthracene molecules. The process for preparing heterocyclic derivative NOP claimed is not restricted by any technological process and may be exercised both in laboratory and industrial scale. The heterocyclic system claimed, its monomeric, oligomeric and polymeric derivatives can be useful in the field of organic electronics.

Description

Technical field

The work was done in the field of organic chemistry. This document discloses and describes novel heterocyclic derivatives comprising an ortho-condensed system (NOP) of carbazole and two anthracene molecules and a process for their synthesis. The synthesized materials, their monomeric, oligomeric or polymeric derivatives are potentially applicable in the field of organic electronics, and the method of synthesis discovered can be used, without much limitation, for the synthesis of analogous heterocyclic derivatives.

State of the art

Anthracene derivatives have long been known in the literature, Alizarin, a red dye, was the first natural pigment to be synthetically duplicated as early as 1869. Of course, more anthracene-based paints were synthesized later, but the anthracene's toxic properties delayed the development of anthracene derivatives for some time.

In recent years, the demand for new, variously modified, anthracene, tetracene, pentacene and longer homologues (acenes) and their hetero-functionalized derivatives (heterocenes) has grown dramatically to accommodate them in the field of organic electronics [1. Functionalized Acenes and Heteroacenes for Organic Electronics, John E. Anthony, Chem. Rev. 2006, 106, 5028-5048.]. This was due to the excellent conductivity, fluorescence and thermal stability properties of anthracene derivatives. The most commonly used anthracene derivatives used in organic electronics are modified by the introduction of aromatic, continuously conjugated, or aliphatic, trialkylsilyl substituents at the 2,6 or 9,10 position, thereby altering the physical and optoelectric properties of the materials. Most commonly used are phenyl, biphenyl, naphthalene, diphenyl, triphenylamino, 9H-carbazole, hexyl, trimethylsilyl substituents. 9.9 '[2. H. S. Jang, K. H. Lee, S. J. Lee, Y. K. Kim, S. S. Yoon, Mol. Cryst. Liq. Cryst., 2012, 563, 173-184.] And 2,2 '[3. K. Ito, T. Suzuki, Y. Sakamoto, D. Kubota, Y. Inoue, F. Shato, S. Tokito, Angew. Chem. Int. Ed., 2003, 42, 10, 1159-1162.] Anthracene dimers (bianthracenes) and corresponding oligomeric derivatives. Heterocenes are known to a much lesser extent, but have recently been synthesized more and more to be applied in organic electronics [1. Functionalized Acenes and Heteroacenes for Organic Electronics, John E. Anthony, Chem. Rev. 2006, 106, 5028-5048.].

Summary of the Invention

The aim of the work was to synthesize an ortho condensed system of carbazole and two anthracene molecules. This type of molecule would be flat, would have strong π-π interactions, and large spatial substitutions would alter material solubility, glass transition temperature, and intermolecular interactions.

Very little is known in the literature about this type of compound. The classical scheme for the synthesis of anthracene derivatives was chosen for the work, but over time due to numerous literary inaccuracies and failures, the scheme has been modified in various ways, and the final result is surprising. In the final stage of the synthesis, an additional cyclization reaction occurred which resulted in the synthesis of the structure NOP (Formula I). The novel compounds of the invention are not disclosed in the scientific or patent literature. A completely new heterocyclic derivative was created containing nitrogen and oxygen heteroatoms and two ortho / peri fused anthracene moieties.

For the first time, the synthesis of this derivative was carried out using N-hexyl-9H-carbazole as the starting material. Due to the formation of three possible products in the final reaction, the yield of the product was only 6%. After considering the various synthesis pathways and considering that the regioselectivity can be easily regulated by substitution of the carbazole derivative of the starting material, position 2.7, the synthesis was repeated and optimized.

The double acid intramolecular cyclization of acids found has no synthetic limitations for the production of large amounts of material, does not require sophisticated technological equipment, does not produce any highly toxic byproducts, is simple and easily modified to synthesize analogous derivatives.

Brief description of the drawing figures

FIG. Use of compounds of the invention which are -1,5-disubstituted 11-oxa-3-aza-3H-3-alkyl- (or aryl) -dibenzo [a, m] indene [2,1,7,6-g / 7 H]. ] Synthesis Scheme of Pleiadene Derivatives.

FIG. C2O6NOP second compound of the invention (where R, R is C2H5, and R is C ₆ Hi _third) absorption and emission spectra.

Detailed Description of the Invention

The present invention relates to novel compounds represented by the general formula I:

where:

R, R ', R' are the same or different and are:

aliphatic saturated or unsaturated (regardless of the degree of chain saturation) branched, cyclic or linear hydrocarbons having from C1 to C30 carbon atoms;

aliphatic saturated or unsaturated (regardless of the degree of chain saturation) branched, cyclic or linear hydrocarbons having in their chain side hydroxy (-OH) or inner etheric (-O-) groups having from C1 to C30 carbon atoms;

aliphatic saturated or unsaturated (regardless of the degree of chain saturation) branched, cyclic or linear hydrocarbons having terminal or internal amino groups;

cyclic aliphatic hydrocarbons having from C3 to C15 carbon atoms, having one or more heteroatoms in their cyclic or ring outer structure;

aryl substituents having one, two, three, four or five rings interconnected via: C-C bonds, aliphatic chains, alkene moiety, acetylene moiety, one or two heteroatoms, regardless of the order of ring fusion and the number of linkages and linking moieties; as well as ortho- or trans-condensed derivatives, irrespective of merger order or position; (Aryl substituents include: aromatic and non-aromatic cyclic derivatives containing from one to six heteroatoms; regardless of the number or position of heteroatoms in the heterocyclic derivative; chains with or without oxygen or nitrogen atoms, any functional group or other substituent.

R, R '- may be the same or different halogen atoms.

Method of obtaining the object of the invention, illustrated in Scheme 1:

Scheme 1

Reagents and conditions for the reactions depicted in Scheme 1: a) AcOH, HNO ₃ , H2SO4, 20-50 ° C; b) o-Dichlorobenzene, PPh ₃ (2.5 eq), Vir. t .; c) BnEt ₃ NCI, Alkyl-Hal, NaOH (aq.), Ph-CH ₃ , 80 ° C; d) Phthalic r. anhydride (2.5 equiv), AlCl ₃ (5 equiv), CH 2 Cl 2, kt; e) Zn / Hg, 1,4-dioxane, HCl (machine), 50 ° C; f) POCl ₃ , 1,4-dioxane, 40 ° C.

The process for preparing the compounds of the invention comprises the following steps:

a) Nitration of 4,4'-Diphenated biphenyl derivative (1). The synthesis of these derivatives with different or identical substituents has been extensively studied in the current literature. Both Suzuki cross-linking and Friedel-Krafts acylation reactions are used for this purpose. One of the most convenient methods for the synthesis of symmetric 4,4'-dialkylbiphenyls is the dimerization of 4-alkyl-1-bromobenzene Grignard reagent using iron trichloride as a catalyst [4. T. Nagano, T. Hayashi, Org. Lett. 2005, 7, 3, 491-493]. The nitration reactions of the corresponding biphenyl derivatives have not been extensively studied, but the nitration can be readily carried out under standard synthesis conditions using mixtures of acetic, sulfuric and nitric acids. Depending on the substituents, the temperatures of the nitration reactions range from 20 ° C to the boiling point. The syntheses of the 2-nitrobiphenyl (2) derivatives thus synthesized are close to 100%.

b) The synthesis of the carbazole derivative (3) from 2-nitrobiphenyls is also known as Cadogan synthesis. This reaction is carried out in o-dichlorobenzene solutions under argon atmosphere using 2.5 eq. of triphenylphosphine [5. A. W. Freeman, M. Urvoy, M. E. Crisvvell, J. Org. Chem. 2005, 70, 5014-5019].

c) N-alkylation of carbazole. Carbazole N alkylation reactions are also known to a considerable extent. In most cases, all of these reactions have no particular differences, only the base and solvent used vary. In this work, we used an interfacial alkylation reaction using BnEtsNCI as a catalyst [6. H. Nishi, H. Kohno, T. Kano, Bull. Chem. Soc. Jpn., 1981, 54, 1897-1898], The synthesis yields of N-alkylcarbazoles (4) are also very high by this method.

d) Acylation of the N-alkyl-9H-carbazole derivative with phthalic anhydride is carried out under standard reaction conditions. Two equivalents of aluminum chloride to one equivalent of phthalic anhydride are commonly used for this purpose. Under these conditions, 2,2 '- (9H-carbazolyl-3,6-dicarbonyl) dibenzoic acid is easily synthesized. Only a few N-H derivatives of this type are known in the literature [7. M. Zander, W. Franke, Chem. Ber., 699-705, 1963], N-methyl [8. M. Copisarov, C. Weizmann, J. Chem. Soc., 1915, 878-886], N-ethyl [9. Polaroid Corp. inventor, P. S. Huyffer, US Patent: US3933849 (1976)]. In most of the cases described, the yields of such acids are very low, but various variations in the reaction conditions during the work have led to their optimization and the average yields.

e) Reduction of ketone groups. No reductions of the ketone groups of acids (5) are known, and Clemmensen reduction conditions have been applied during the work [10. N. O. Mahmoodi, M. Salehpour, J. Het. Chem. 40: 875-878 (2003). However, toluene was used in the literature as a solvent, in this case toluene was completely inappropriate. The starting material was extremely insoluble, the reaction was very slow and no complete conversion was achieved. After testing several solvents, the best results were obtained with 1,4-dioxane, where the reaction lasts for up to two days, and the resulting acids (6) are generally completely pure and can be used without further purification.

f) Cyclizacia. Similarly, the acid (6) literature is also not known, by analogy, cyclization of the latter using phosphoryl chloride [11. S. El-Sayrafi, S. Rayyan, Macromolecules, 2001, 6, 279-286], in 1,4-dioxane solutions. At the beginning of the work, the reaction was expected to occur with the formation of a dianthron derivative. During the analysis of the resulting product, it was found that a third step of intramolecular cyclization also occurred, resulting in the formation of a product (7). Literary analysis has shown that such heterocyclic systems are not captured.

It can be stated that the reaction proceeds in several steps, the hypothetical reaction mechanism is shown in Scheme 2:

Scheme 2

POCI,

-H, O

POCI,

Insufficient data are available to prove the exact mechanism of the reaction.

NOP-type heterocyclic derivatives can be applied in the field of organic electronics (organic semiconductors, transistors, solar cells, etc.) as light-emitting, absorptive, charge transfer or other functions. Their potential users are companies in the organic electronics industry.

The NOP derivative has a relatively high extinction coefficient (maximum value 17300 L'1-mol · ¹ cm ' ¹ at 440 nm) and emission of dilute solutions in the green-red spectrum and in the near-ultraviolet region of the thin film. The relatively low fluorescence efficiency of the solution (2.5%) indicates the existence of possible charge transfer states. The NOP derivative is characterized by an average hole motile in the polycarbonate matrix (about 1.5-10 ' ⁵ cmA / s) and low ionization potential (4.67 eV). Molecular semiconductors with low ionization potential could serve as hole injection enhancers.

The experimental part

The purity of the materials was determined using Agilent Technologies 6890N Network GC System and Agilent Technologies 7890C GC systems gas chromatographs. Mass spectral analysis was performed on an Agilent Technologies 5975C gas chromatograph with a triple-axis mass detector (GC / MS). HRMS mass spectrometric analysis was performed using: Brucker Daltonik GmbH, a quadrupole timeof-flight (Q-TOF) mass spectrometer (micrOTOF-Q II). ¹ H and ¹³ C NMR spectra were characterized "BRUKER ASCEND 400 (400 MHz) and using a Varian Unity INOVA (300 MHz) spectroscopy.

The following example illustrates the invention without limiting its scope.

EXAMPLE. Synthesis of 1,5-Diethyl-3-hexyl-3 H - [11] -oxa-3-azadibenzo [a, [77] indeno [2,1,7,6-grA7]] pleiadene

2-Nitro-4,4'-diethylbiphenyl (2), CH

H, C.

O

Ή

I.

A mechanical stirring flask was charged with 28.0 g (0.133 mol) of 4,4'-diethylbiphenyl and added with 200 ml of acetic acid. The suspension was cooled to 0 ° C and treated with 180 ml of nitric acid (65%) followed by 3 ml of sulfuric acid. The suspension was stirred under refrigeration for an additional 5 min. and allowed to warm to 20 ° C. The reaction mixture was stirred for 2 hours at 20 ° C, poured into 3 L of water and extracted three times with dichloromethane. The organic layer was dried over sodium sulfate, concentrated, and dried in vacuo at 1 mmHg.

Yield: 33.6 g (99%), tan oil (GC = 98.5%).

GC-MS = 255.1 m / z.

¹ H-NMR (CDCl ₃ , 300MHz): 1.28-1.37 (m, 6H); 2.69-2.83 (m, 4H); 7.22-7.31 (m, 4H); 7.36 (d, J = 7.8 Hz, 1H); 7.45 (dd, J = 8.1 Hz, J = 1.8 Hz, 1H); 7.69 (d, J = 1.5 Hz, 1H) ppm.

¹³ C-NMR (CDCl 3): 15.3; 15.5; 28.4; 28.8; 123.4; 128.1; 128.4; 132.0; 132.0; 133.8; 134.9; 144.3; 144.8; 149.5 ppm.

2,7-Diethyl-9 / - / - carbazole (3)

A magnetic stirrer flask was charged with 33.6 g (0.131 mol) of 2-nitro-4,4'-diethylbiphenyl, 85.8 g (0.327 mol) triphenylphosphine and 150 ml of odichlorobenzene under argon. The reaction mixture was stirred for 14 hours. at reflux, under argon, and concentrated on a rotary evaporator. The resulting mixture was crystallized from 300 mL of a 1: 1 mixture of toluene: 2-propanol.

Obtained: 14.0 g (48%), white crystals (GC = 99.3%). Ti _y d = 251255 ° C.

IR ν max = 3400 cm ^-1 (NH); GC-MS = 223.2 m / z.

¹ H-NMR (d ⁶ -DMSO, 300MHz): 1.27 (t, J = 7.8Hz, 6H); 2.72 (dd, J = 7.5 Hz, 4H); 6.97 (d, J = 8.1 Hz, 2H); 7.26 (s, 2H); 7.92 (d, J = 7.8 Hz, 2H); 10.9 (s, 1H) ppm.

¹³ C-NMR (d ⁵ -DMSO): 16.8; 29.4; 110.2; 119.4; 120.2; 121.1; 140.9; 141.6 ppm.

2,7-Diethyl-9-hexyl-9 H - carbazole (4)

A magnetic stirrer flask was charged with 14.0 g (0.0627 mol) of 2,7-diethyl-9/7-carbazole, 11.3 g (0.068 mol) of 1-bromohexane, 1.42 g (0.00627 mol) of benzyltriethylammonium chloride. , 100 ml of toluene and 3.75 g (0.093 mol) of sodium hydroxide dissolved in 3.7 ml of water. The reaction mixture was stirred at 80 ° C for 12 h, poured into water and acidified to pH ~ 2 with hydrochloric acid. The organic layer was separated and further extracted with dichloromethane. The extracts were combined and concentrated on a rotary evaporator. The product was dissolved in 400 mL of hexane and passed through 30 g of silica gel, the solution concentrated.

Obtained: 19.1 g (99%), a clear colorless oil (GC = 99.2%).

GC-MS = 307.3 m / z.

¹ H-NMR (CDCl 3, 400 MHz): 0.95 (t, J = 7.2, 3H); 1.32-1.52 (m, 12H); 1.92 (p, J = 7.3 Hz, 2H); 2.91 (k, J = 7.6 Hz, 4H); 4.31 (t, J = 7.6 Hz, 2H); 7.11 (d, J = 8.0 Hz, 2H) 7.24 (s, 2H); 8.00 (d, J = 8.0 Hz, 2H) ppm.

¹³ C-NMR (CDCl 3): 14.0; 16.3; 22.6; 27.0; 28.9; 29.7; 31.6; 42.8; 107.5; 119.0; 119.8; 120.9; 141.0; 141.7 ppm.

2,2 '- (2,7-Diethyl-9-hexyl-9 H -carbazole-3,6-dicarbonyl) dibenzoic acid (5)

A magnetic stirrer flask was charged with 32.50 g (0.243 mol) of AlCl 2 and 100 ml of dichloromethane, cooled to -5 ° C and slowly added with 22.2 g (0.364 mol) of nitromethane, preventing the temperature from rising above 0 ° C. A solution of 2,7-diethyl-9-hexyl-9/7-carbazole (18.5 g, 0.06 mol) in 50 ml of dichloromethane was then added dropwise. A mixture of phthalic anhydride (18.01 g, 0.121 mol) and AlCl 3 (16.25 g, 0.121 mol) in 100 ml of dichloromethane was added dropwise to the reaction mixture at 0-5 ° C. The reaction mixture was allowed to warm to room temperature and stirred for 98 h. The resulting dark reaction mixture was poured onto ice-ice with HCl, the product filtered, dried and crystallized from 600 mL of acetone.

Obtained: 22.62 g (62%), white crystals. _Yd Ti = 246-248 ° C. IR ν _max = 3435 cm ^-1 (-CO ₂ H); 1659 cm ^-1 (C = O).

HRMS: C38H37NO6 calcd: 626.2514, found: 626.2513 (EI) m / z (M + Na).

¹ H-NMR (d ⁶ -DMSO, 400 MHz): 0.82 (t, J = 7.3 Hz, 3H); 1.22-1.36 (m, 12H); 1.76-1.82 (m, 2H); 3.08 (dd, J = 7.3 Hz, 4H); 4.44 (t, J = 7.1 Hz, 2H); 7.37-7.41 (m, 2H); 7.57-7.62 (m, 8H (clearly seen mixed singlet 7.61 ppm)); 7.67 (s, 2H); 7.82-7.86 (m, 2H); 13.01 (s, 2H) ppm.

¹³ C-NMR (d ⁶ -DMSO): 14.2; 16.5; 22.5; 26.5; 27.7; 28.9; 31.3; 42.8; 111.4; 119.4; 124.3; 128.7; 129.4; 129.9; 130.3; 131.5; 131.9; 143.1; 143.2; 144.6; 168.2; 198.0 ppm.

2,2 '- [(2,7-Diethyl-9-hexyl-9 H -carbazole-3,6-diyl) bis (methylene)] dibenzoic acid (6)

A flask with magnetic stirrers was charged with 22.21 g (0.0368 mol) of acid (5), 60 g (0.93 mol) of zinc dust, 0.5 g (0.0018 mol) of HgCl2, 0.5 L, 4-dioxane, 3 mL HCl (machine). The reaction mixture was stirred for 24 h at 40-50 ° C, every 3 h. with 3 ml of HCl (approximately). The reaction mixture was filtered, the amalgam was washed with 50 mL of 1,4-dioxane on the filter and the filtrate was poured into 3.5 L of water. 2 hours later the product was filtered off and dried. The resulting white crystalline material was suspended in 100 mL of toluene and filtered.

Obtained: 18.5 g (87%), white crystals. Ti _yc = 232-235 ° C. IR ν _max = 3435 cm ^-1 (-CO ₂ H).

HRMS: C38H41NO4 calcd: 598.2932, found: 598.2928 (EI) m / z (M + Na).

¹ H-NMR (d ⁶ -DMSO, 400 MHz): 0.81 (t, J = 7.1 Hz, 3H); 1.16-1.33 (m, 12H); 1.76-1.79 (m, 2H); 2.62 (dd, J = 7.3 Hz, 4H); 4.30 (t, J = 6.8 Hz, 2H); 4.47 (s, 4H); 6.91 (d, J = 7.8 Hz, 2H), 7.26 (t, J = 7.5 Hz, 2H); 7.32-7.38 (m, 4H, (clearly seen mixed singlet 7.35 ppm)), 7.55 (s, 2H); 7.83 (d, J = 7.5 Hz, 2H); 12.87 (s, 2H) ppm.

¹³ C-NMR (d ⁶ -DMSO): 14.2; 15.7; 22.5; 26.4; 26.6; 28.9; 31.3; 36.2; 42.5; 108.9; 120.5; 121.4; 126.3; 128.9; 130.4; 130.5; 131.1; 131.9; 139.9; 140.2; 142.8; 169.4 ppm.

1,5-Diethyl-3-hexyl-3H-11-oxa-3-aza-dibenzo [a, m] indeno [2,1,7,6 g (7)) lpleadiene (NOP)

POClj

1,4-dioxane

A magnetic flask was charged with 10.0 g (0.0173 mol) of acid (6), 100 ml of 1,4-dioxane and 5 ml of POCl 3. The reaction mixture was stirred at 40 ° C for 6 h, cooled to room temperature and poured into ice. The mixture was extracted three times with methylene chloride, the organic layer was dried over CaCl ₂ and concentrated. The resulting dark mixture was dissolved in cold toluene and passed through 20 g of silica gel, the silica gel being further washed with 50 ml of toluene. The toluene solution was concentrated and the product was recrystallized from 60 ml of toluene.

Obtained: 6.03 g (66%), yellow-orange crystals. Ti _yc = 173-175 ° C.

HRMS: C38H35NO calcd: 544.2607, found: (EI) m / z 544.2611 (M + Na).

¹ H-NMR (CDCl 3, 400 MHz): 0.87 (t, J = 6.8 Hz, 3H); 1.30-1.39 (m, 6H); 1.46 (t, J = 7.5 Hz, 6H); 1.81-1.85 (m, 2H); 3.20 (dd, J = 7.3 Hz, 4H); 4.11 (t, J = 7.3 Hz, 2H); 7.20 (s, 2H); 7.49 (t, J = 7.5 Hz, 2H); 7.65 (t, J = 7.5 Hz, 2H); 7.99 (d, J = 8.3 Hz, 2H); 8.24 (s, 2H); 9.06 (d, J = 8.7 Hz, 2H) ppm.

13th

C-NMR (CDCl 3): 14.0; 14.9; 22.5; 26.7; 27.0; 30.3; 31.4; 42.8; 110.4; 114.1; 117.3; 118.9; 122.0; 124.0; 124.2; 125.2; 127.6; 128.9; 131.3; 133.7; 136.6; 148.5 ppm.

References Functionalized Acenes and Heteroacenes for Organic Electronics, by John E.

Anthony, Chem. Rev., 2006, 106, 5028–5048.

2. H. S. Jang, K. H. Lee, S. J. Lee, Y. K. Kim, S. S. Yoon, Mol. Cryst. Liq. Cryst., 2012, 563, 173-184.

K. Ito, T. Suzuki, Y. Sakamoto, D. Kubota, Y. Inoue, F. Shato, S. Tokito, Angew. Chem. Int. Ed., 42, 10, 1159-1162, 2003.

T. Nagano, T. Hayashi, Org. Lett. 2005, 7, 3, 491-493.

A. W. Freeman, M. Urvoy, M. E. Criswell, J. Org. Chem. 2005, 70, 50145019.

H. Nishi, H. Kohno, T. Kano, Bull. Chem. Soc. Jpn., 1981, 54, 1897-1898.

M. Zander, W. Franke, Chem. Ber., 1963, 699-705.

M. Copisarow, C. Weizmann, J. Chem. Soc., 1915, 878-886.

Polaroid Corp. inventor P. S. Huyffer, US Patent: US3933849 (1976).

N. O. Mahmoodi, M. Salehpour, J. Het. Chem., 2003, 40, 875-878.

S. El-Sayrafi, S. Rayyan, Macromolecules, 2001,6, 279-286.

Claims (6)

Definition of the Invention 1. A compound of general formula I: where: R, R ', R' are the same or different and are: aliphatic saturated or unsaturated (regardless of the degree of chain saturation) branched, cyclic or linear hydrocarbons having from C1 to C30 carbon atoms; aliphatic saturated or unsaturated (independently of the degree of chain saturation) branched, cyclic or linear hydrocarbons having in their chain side hydroxy (-OH) or inner ether (-O-) groups having from C1 to C30 carbon atoms; aliphatic saturated or unsaturated (regardless of the degree of chain saturation) branched, cyclic or linear hydrocarbons having terminal or internal amino groups; cyclic aliphatic hydrocarbons having from C3 to C15 carbon atoms, having one or more heteroatoms in their cyclic or ring outer structure; aryl substituents having one, two, three, four or five rings interconnected via: C-C bonds, aliphatic chains, alkene moiety, acetylene moiety, one or two heteroatoms, regardless of the order of ring fusion and the number of linkages and linking moieties; as well as ortho- or trans-condensed derivatives, irrespective of merger order or position; (Aryl substituents include: aromatic and non-aromatic cyclic derivatives of one to six heteroatoms per molecule; regardless of the number of atoms in the heterocyclic derivative or the position of the heteroatoms in the ring and the order of attachment; having side-chain saturated or unsaturated (independently of the degree of chain saturation) branched, cyclic or linear chains with or without oxygen or nitrogen atoms, any functional group or other substituent); R, R * - may be the same or different halogen atoms. 2. A compound according to claim 1, which is 1,5-diethyl-3-hexyl-3 H - 11-oxa-3-azadibenzo [a, m] indene [2,1,7,6-gh / /] pleiadene having the following structural formula: 3. A process for the preparation of a compound according to claim 1, further comprising the steps of; a) nitration of 4,4'-disubstituted biphenyl derivatives (1) with nitric acid, acetic acid and sulfuric acid solution at 20-50 ° C to form 2-nitrobiphenyl derivatives (2); b) Synthesis of carbazole derivatives (3) from 2-nitrobiphenyls (2) in o-dichlorobenzene solution under argon atmosphere using 2.5 eq. triphenylphosphine; c) N-alkylation of the carbazole (3) to give N-alkylated carbazoles (4); R 'R ^R (3) R' (4) d) Acylation of N-alkyl-9/7-carbazole derivatives (4) with phthalic anhydride in the presence of 2 eq. aluminum chloride per equivalent of phthalic anhydride to form 2,2 '- (9,7-carbazolyl-3,6-dicarbonyl) dibenzoic acid (5); e) reduction of the ketone groups of 2,2 '- (9 H -carbazolyl-3,6-dicarbonyl) dibenzoic acid (5) in a 1,4-dioxane solution in the presence of Zn / Hg and HCl to form the carboxylic acid (6); f) cyclization of the acid (6) in 1,4-dioxane with POCb to form the pleiadene derivative (7); Use of compounds of formula (I) according to claim 1 in the field of organic electronics. Compounds 2,2 '- [(2,7-disubstituted-9-alkyl (or aryl) -9 / 7-carbazole-3,6-diyl) bis (methylene)] dibenzoic acid of the general formula (6) wherein R is substituted. , R 'and R have the meanings defined in claim 1. 6. A process for the preparation of compounds according to claim 5 wherein the 2,2 '- (2,7-diethyl-9-hexyl-9H-carbazole-3,6-dicarbonyl) dibenzoic acid is reduced with a mixture of Zn / Hg and concentrated HCl in a solvent. using 1,4-dioxane.