An electron injecting layer and electron transport layer comprising quinolin-8-olate derivatives and optoelectronic device comprising the same field

Abstract

The subject of the invention is an electron injecting layer or an electron transport layer comprising quinolin-8-olate derivative, an electroluminescent device comprising the compound and the use of the compound as an intermediate for electron transport or injection in the electroluminescent device. The electroluminescent device comprises an anode, a cathode, and the compound disposed between the anode and cathode. The present invention belongs to the field of light-emitting diodes / devices.

Description

AN ELECTRON INJECTING LAYER AND ELECTRON TRANSPORT LAYER COMPRISING QUINOLIN-8-OLATE DERIVATIVES AND OPTOELECTRONIC DEVICE COMPRISING THE SAME FIELD

[0001] The present disclosure generally relates to an electron injecting material and an electron transport layer, and an optoelectronic device comprising the same. The invention belongs to the field of optoelectronic devices.

[0002] The electron injecting layer (EIL) and electron transport layer (ETL) are crucial to the functionality of electroluminescent devices such as OLED, organic phototransistors, organic photovoltaic cells, and organic photodetectors, and other optoelectronic devices. The stability and characteristics of the materials comprising these layers have a fundamental impact on the device's current efficiency, operational lifespan, and overall performance. The electron injecting layer is crucial for enabling the injection of electrons from the cathode into the electron transport layer. The electron transport layer plays an essential role in transporting electrons from the EIL to the emissive layer, where they recombine with holes to emit light. Typical materials for the ETL include organic molecules like tris(8-hydroxyquinolinato)aluminiumaluminium (Alq3) and inorganic materials such as zinc oxide (ZnO). Common materials used in the EIL include low-work function metals like calcium (Ca) or lithium fluoride (LiF), organometallic compounds such as 8-quinolinolato lithium (Liq), and other organic materials such as polyethyleneimine (PEI).

[0003] Patent application US2013015431A1 disclosed lithium, sodium, or potassium 8-hydroxyquinoline optionally having at least one substituent selected from the group consisting of alkyl, alkoxy, aryl, alkoxy, amino, amido. The compound can be used as an electron injecting layer and electron transport layer in electronic devices.

[0004] Yet another patent application US2006286405A1 provides alkali or alkaline earth metal 8-hydroxyquinoline optionally having at least one substituent selected from the group consisting of a methyl group, a phenyl group, a fluoro substituent, and a fused benzene ring group formed by combining two substituents. That alkali or alkaline earth organic salt is present in one of the OLED device’s layers as an electron-injecting layer.

[0005] An electron injecting layer (EIL) or electron transport layer (ETL) comprises a compound according to Formula 1,

[0006] wherein:

[0007] M+is Li+, Na+, K+, Rb+, or Cs+;

[0008] R1- R2, together or independently, are hydrogen, deuterium, halogen, cyano, nitro, hydrazine, hydrazone, C1-C60alkyl, C2-C60alkenyl, C1-C60haloalkanyl, C2-C60haloalkenyl, C2-C60haloalkynyl, C2-C60alkynyl, C1-C60alkoxy group, C3-C60cycloalkyl, C3-C60cycloalkenyl, C1-C60heterocycloalkyl, C1-C60heterocycloalkenyl group, C3-C60cycloalkynyl group, C1-C60heterocycloalkynyl group, C6-C60aryl, C1-C60heteroaryl group, C5-C60aryloxy, C1-C60heteroaryloxy group, C2-C60ether group, C6-C60thioaryl, C1-C60heterothioaryl, C1-C60amino, C1-C60alkylamino, C1-C60dialkylamino, C6-C60arylamino, C6-C60diarylamino, C6-C60heteroarylamino group, C6-C60heterodiarylamino group, C4-C60non-aromatic fused polycyclic group, C1-C60non-aromatic fused heteropolycyclic group or deuterated analogues thereof;

[0009] HAis, together with the carbon atom explicitly drawn in, a group of Formula 2 or Formula 3:

[0010] wherein:

[0011] Q1- Q4, together or independently, are C(R8) or -N;

[0012] X1- X3, together or independently, C(R8) or -N;

[0013] Y1is N;

[0014] Y2is N(R8), O, S, or Se;

[0015] where the dashed bonds in Formula 2 and Formula 3 denote the linking of this group in Formula 1;

[0016] R8is hydrogen, deuterium, halogen, cyano, nitro, hydrazine, hydrazone, C1-C60alkyl, C2-C60alkenyl, C2-C60alkynyl, C1-C60haloalkanyl, C2-C60haloalkenyl, C2-C60haloalkynyl, C1-C60alkoxy group, C3-C60cycloalkyl, C3-C60cycloalkenyl, C1-C60heterocycloalkyl, C1-C60heterocycloalkenyl group, C3-C60cycloalkynyl group, C1-C60heterocycloalkynyl group, C6-C60aryl, C1-C60heteroaryl group, C5-C60aryloxy, C1-C60heteroaryloxy group, C2-C60ether group, C6-C60thioaryl, C1-C60heterothioaryl, C1-C60amino, C1-C60alkylamino, C1-C60dialkylamino, C6-C60arylamino, C6-C60diarylamino, C6-C60heteroarylamino group, C6-C60heterodiarylamino group, C4-C60non-aromatic fused polycyclic group, C1-C60non-aromatic fused heteropolycyclic group or deuterated analogues thereof;

[0017] A is, together with the two carbon atoms explicitly drawn in, a group of Formula 4, Formula 5, Formula 6, or Formula 7:

[0018] wherein:

[0019] R3- R7, together or independently, are hydrogen, deuterium, halogen, cyano, nitro, hydrazine, hydrazone, C1-C60alkyl, C2-C60alkenyl, C2-C60alkynyl, C1-C60haloalkanyl, C2-C60haloalkenyl, C2-C60haloalkynyl, C1-C60alkoxy group, C3-C60cycloalkyl, C3-C60cycloalkenyl, C1-C60heterocycloalkyl, C1-C60heterocycloalkenyl group, C3-C60cycloalkynyl group, C1-C60heterocycloalkynyl group, C6-C60aryl, C1-C60heteroaryl group, C5-C60aryloxy, C1-C60heteroaryloxy group, C2-C60ether group, C6-C60thioaryl, C1-C60heterothioaryl, C1-C60amino, C1-C60alkylamino, C1-C60dialkylamino, C6-C60arylamino, C6-C60diarylamino, C6-C60heteroarylamino group, C6-C60heterodiarylamino group, C4-C60non-aromatic fused polycyclic group, C1-C60non-aromatic fused heteropolycyclic group or deuterated analogues thereof;

[0020] where the dashed bonds in Formula 4, Formula 5, Formula 6, and Formula 7 denote the linking of this group in Formula 1;

[0021] HBis, together with the carbon atom explicitly drawn in, a group of Formula 8 or Formula 9:

[0022] wherein:

[0023] Z1- Z5, together or independently, are C(R9) or N, O, S, Se;

[0024] Z6-Z8, together or independently, are C(R9) or N;

[0025] Z9is C(R9)(R10) or N(R9), O, S, Se;

[0026] R9-R10, together or independently, are hydrogen, deuterium, halogen, cyano, nitro, hydrazine, hydrazone, C1-C60alkyl, C2-C60alkenyl, C2-C60alkynyl, C1-C60alkoxy group, C3-C60cycloalkyl, C3-C60cycloalkenyl, C1-C60heterocycloalkyl, C1-C60heterocycloalkenyl group, C3-C60cycloalkynyl group, C1-C60heterocycloalkynyl group, C6-C60aryl, C1-C60heteroaryl group, C5-C60aryloxy, C1-C60heteroaryloxy group, C2-C60ether group, C6-C60thioaryl, C1-C60heterothioaryl, C1-C60amino, C1-C60alkylamino, C1-C60dialkylamino, C6-C60arylamino, C6-C60diarylamino, C6-C60heteroarylamino group, C6-C60heterodiarylamino group, C4-C60non-aromatic fused polycyclic group, C1-C60non-aromatic fused heteropolycyclic group or deuterated analogues thereof;

[0027] where the dashed bonds in Formula 8 and Formula 9 denote the linking of this group in Formula 7.

[0028] In a preferred embodiment of the invention, wherein the compound according to Formula 1 is selected from Formula 10 - Formula 19:

[0029] wherein:

[0030] Y1, Y2, X1- X3, Q1- Q4, Z1- Z9, R1- R10, M+are the same as described in claim 1.

[0031] In a preferred embodiment of the invention, wherein the compound according to Formula 1 is selected fromCompound 1-Compound 999.

[0032] An electroluminescent device comprising an anode, a cathode, and a compound according to Formula 1 disposed between the anode and cathode.

[0033] In a preferred embodiment of the invention, wherein the electron injecting layer is according to the invention or / and the electron transport layer is according to the invention.

[0034] In a preferred embodiment of the invention, wherein comprises at least one layer selected from: a hole injection layer, hole transport layer, electron blocking layer, hole blocking layer, and emissive layer.

[0035] The use of a compound according to Formula 1 as the compound intermediating a transport or injection of electrons in an electroluminescent device.

[0036] Low-work function materials are commonly utilized in the electron injecting layer to enhance electron injection. However, these materials can be chemically reactive and susceptible to degradation, which can impact their stability. Organic materials, while offering flexibility and reduced costs, may have lower stability compared to inorganic materials such as metal oxides. A hybrid approach, combining organic and inorganic materials, can sometimes provide enhanced stability and performance by leveraging the advantages of both types of materials.

[0037] The materials used in the electron injecting layer and electron transport layer must exhibit high electron mobility and appropriate energy alignment to facilitate efficient electron injection and transport. Poor stability in these materials can result in increased resistance and lower electron mobility, thereby diminishing current efficiency. The stability of EIL and ETL materials is also crucial for the longevity of optoelectronic devices such as OLEDs and photovoltaic cells. Materials that degrade under operational conditions, such as exposure to moisture, oxygen, or thermal stress, can lead to device failure. Contrarily, stable materials ensure consistent performance over time, thereby extending the device's lifetime. Efficient charge injection and transport minimize energy losses and enhance overall device efficiency. Additionally, materials with high thermal and chemical stability prevent the formation of defects that could act as non-radiative recombination centres, which would otherwise reduce efficiency. Therefore, the aim of the compounds according to the invention used as electron transport and / or electron injecting material is to improve the lifetime of the electroluminescent device and its general efficiency.

[0038] One object of the disclosure is to provide a new electron injecting layer (EIL) or electron transport layer (ETL) comprising the compound according to Formula 1I as a compound intermediating a transport or injection of electrons in an electroluminescent device, that can better withstand operational stresses and environmental factors, thus enhancing device performance and durability. The second objective of the invention is to provide an electroluminescent device having an increased efficiency and operational lifetime, which comprises the compound. The subsequent objective of the disclosure is to provide a use of the compound as the compound intermediating a transport or injection of electrons in an electroluminescent device.

[0039] The bond dissociation energy (in an endothermic process) is the energy required to break a bond and form two atomic or molecular fragments, each with one electron of the original shared pair. Therefore, a very stable bond has a large bond dissociation energy (BDE), since more energy must be added to cleave the bond. A high bond dissociation energy means that the bond (and consequently the molecule) is of low energy and stable.

[0040] In a working optoelectronic device, which is a class of device that use either electric charge to generate light, like light emitting diodes (LED), electroluminescent devices, and laser, or use light to generate electric current, like photodetectors and solar cells), the materials of the electron injection layer and electron transfer layer are in a charged state, since one electron was added to the EIL and ETL materials. These materials with an additional electron form an anionic state. For this reason, the well-based approach to measure the bond dissociation energy of EIL’s and ETL’s materials is in an anionic state.

[0041] EIL’s and ETL’s materials contain a quinolate ring substituted with e.g. a pyridine ring, pyrrole, furan, thiophene, or selenophene (a pendant fragment) in an ortho position (see the compound according to Formula 1) have a stronger bond C-C between the quinolate ring and the pendant fragment than the bond C-C between the quinolate ring and the phenyl ring in 2-(2’,2”-bipyridine-6’-yl)phenolate. The BDE of all compounds was calculated by means of quantum chemical calculations in Gaussian 09 package with B3LYP / 6-31G(d) level of theory. Firstly, the ground state of the molecule was optimised and then Single-Point calculations of both bond fragments of interest were performed. The BDE value was calculated by subtracting the energy of the molecule from the sum of the energies of the fragments.

[0042] The introduction of nitrogen in a C6heteroaryl in the pendant fragment leads to a significant increase in the BDE of C-C bond between the pendant fragment and the core structure of the molecules (e.g. a quinolate or biphenyl ring), as it is shown in.

[0043] Regardless of the kind a core structure of EIL’s and ETL’s materials, the presence of a nitrogen atom in a C6 heteroaryl as the pendant fragment is essential, because it improves BDE and makes C-C bond between the pendant fragment and the core structure stronger. It contributes to an increase in the stability of the structure of EIL’s and ETL’s materials. The stronger the bond is, the more stable the structure is when applied in an optoelectronic device.

[0044] The pendant fragment is substituted for the core in the ortho position; therefore, the compounds according to the invention show higher thermal stability during a sublimation process than their derivatives in which the pendant fragment is substituted in the meta or para position (). The sublimation was performed by a pilot Lever Sublimation Equipment for OLED Material BOF-8-210 at the pressure of 10-5Pa.

[0045] Compound 1, in comparison with Compounds EIL-D and EIL-E, has a BDE value due to the location of the pendant ring in the ortho position. The technical effect of this feature is the ability to sublimate the compound at 380°C with a yield of 85%. However, Compounds EIL-D and EIL-E decompose at 340°C and 350°C,

[0046] Unexpectedly, the structures of these compounds exhibit high crystallinity with strong π-π interactions which may lead to well-ordered films and thus enhance electron transport and electron injection efficiency in the device. The high crystallinity of the compounds was confirmed by single-crystal XRD and powder XRD methods. The crystallographic parameters ofCompound 1are presented inTable 3.

[0047] The core of the crystal structure ofCompound 1is a Na4O4cube consisting of alternately arranged sodium and oxygen atoms. The sodium ion is pentacoordinated, bonded coordinatively to three oxygen atoms and two nitrogen atoms. The compounds exhibit excellent diffraction, as indicated by the R(int) factor equal to 0.0244. R1 parameter is close to 0, with a value of 0.0678, indicating that the crystallographic model confirms this structure. The Δρ max parameter is 0.489 (i.e., less than half electron), confirming the completeness of the model and it seems as if it lacks significant defects in this lattice.shows the crystal lattice ofCompound 1along the [1-10] direction. The parallel arrangement of the rings indicates the presence of π-π interactions. π-π stacking interactions and edge-to-face interactions are observed, which facilitate electron transport and transfer in the device.

[0048] Additionally, it appeared that the structure has no significant structural defects or aggregates ensuring the uniform electron distribution. Such aggregates and defects may trap electrons and thus lower the conductivity. Additionally, the use ofCompound 1andCompound 2does not result in the formation of aggregates or electron traps, thus no energy losses are present. The examinedCompound 1is pure, as confirmed by comparing the single-crystal and powder diffractograms (). There are only minor discrepancies in peak matching, related to different temperatures of the measurements and thus lattice stresses. Furthermore, the structure of the compounds does not have significant lattice defects, as confirmed by the diffractogram (narrow, high intensity peaks, high peak-to-noise ratio).

[0049] The BDE of the compounds from the prior art and the compounds according to the invention.

[0050] The BDE of the compounds according to the invention.

[0051] Crystal structure of Compound 1 (view 1-1-0).

[0052] Single-crystal and powder diffractograms of Compound 1.

[0053] General definition of terms and substituents

[0054] As used herein, the terms “or” and “and / or” include any and all combinations of one or more of the associated listed items. The term “or” is not an exclusive term, e.g., A or B means: A, B, or A and B. The expression “at least one” comprises at least one, two, three, four, five or more mentioned elements (etc.).

[0055] It should be understood that the terms “comprises,” “comprising,” “includes,” “including,” “has”, “have,” “having,” “contains,” “containing,” and the like are intended to specify the presence of stated features, integers, steps, operations, elements, components, or combinations thereof in the disclosure, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

[0056] Certain chemical compounds can have one or more hydrogen atoms of the compound replaced by one or more deuterium atoms including perdeuterated analogues. Further, it should be noted that the term "deuterated analogue" as used herein refers to compounds where at least one hydrogen atom has been replaced by a deuterium atom. The term "deuterated" as used herein alone or as part of a group, means substituted deuterium atoms. When a particular position is designated as holding deuterium (stated as "D" or "deuterium"), it is understood that the abundance of deuterium at that position is substantially greater than the natural abundance of deuterium, which is 0.015% (i.e., at least 50.1% incorporation of deuterium). The deuterated analogue of the present disclosure may be a fully or partially deuterium substituted derivative. For example, the deuterium substituted compound of the present disclosure can hold a fully or partially deuterium substituted alkyl, aryl or heteroaryl group. In one embodiment, the deuterium substituted compound of the present disclosure holds a fully or partially deuterium substituted alkyl group, e.g., -CD3, CD2, CD3, -CD2, and the like. In another embodiment, the deuterium substituted compound of the present disclosure holds a fully or partially deuterium substituted aryl, such as phenyl, e.g., C6D5or a fully or partially deuterium substituted heteroaryl, e.g., pyridyl-d3, and the like.

[0057] The term “Ph” used herein refers to a phenyl group, the term “Me” used herein refers to a methyl group, the term “Et” used herein refers to an ethyl group, the term “Bu” as used herein refers to a butyl group and the term “tert-Bu” or “t-Bu” as used herein refers to atert-butyl group, the term “Pr” used herein refers to a propyl group, the term “iPr” used herein refers to an isopropyl group, the term “TMS” used herein refers to a trimethylsilyl group, and the term “OMe” used herein refers to a methoxy group, the term “DMF” used herein refers to dimethylformamide, the term “AcOEt” used herein refers to ethyl acetate, the term “MeOH” used herein refers to methanol, the term “t-BuONa” used herein refers to sodiumtert-butoxide.

[0058] Organic groups include both substituted and unsubstituted forms of such groups unless otherwise denoted. The term “substituted” refers to at least one hydrogen replaced by deuterium, halogen, C1-C60alkyl, C2-C60alkenyl, C2-C60alkynyl, C1-C60alkoxy group, C3-C60cycloalkyl, C3-C60cycloalkenyl, C1-C60heterocycloalkyl, C1-C60heterocycloalkenyl, C3-C60cycloalkynyl group, C1-C60heterocycloalkynyl group, C2-C60ether group, C5-C60aryloxy, C6-C60thioaryl, C1-C60heterothioaryl, C1-C60amino, C1-C60alkylamino, C1-C60dialkylamino, C6-C60arylamino, cyano, nitro, hydrazine, hydrazone, C6-C60diarylamino, C6-C60heteroarylamino group, C6-C60heterodiarylamino group, C6-C60aryl, C1-C60heteroaryl group, C1-C60heteroaryloxy group, C4-C60non-aromatic fused polycyclic group, C1-C60non-aromatic fused heteropolycyclic group, or deuterated analogues thereof.

[0059] The term “C1-C60alkyl group” as used herein refers to a linear or branched aliphatic saturated hydrocarbon group having 1 to 60 carbon atoms, and examples thereof include methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, atert-butyl group, a pentyl group, an isoamyl group, a neopentyl group, a hexyl group, 2-methylpentyl group, a 3-methylpentyl group, a heptyl group, a 4-methylhexyl group, a 2,2-dimethylpentyl group, an octyl group, a 3-methylheptyl group, a nonyl group, a 4-methyloctyl group, a 3-ethylheptyl group, a decyl group, a 2-methylnonyl group, a 3,3-dimethyloctyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a heneicosyl group, a docosyl group, a tricosyl group, a tetracosyl group, a pentacosyl group, a hexacosyl group, a heptacosyl group, an octacosyl group, a nonacosyl group, a triacontyl group, a hentriacontyl group, a dotriacontyl group, a tritriacontyl group,a tetratriacontyl group, a pentatriacontyl group, a hexatriacontyl group, a heptatriacontyl group, an octatriacontyl group, a nonatriacontyl group, a tetracontyl group, a hentetracontyl group,a dotetracontyl group, a tritetracontyl group, a tetratetracontyl group, a pentatetracontyl group, a hexatetracontyl group, a heptatetracontyl group, an octatetracontyl group, a nonatetracontyl group, a pentacontyl group, a hentapentacontyl group, a dotriacontyl group, a tritriacontyl group, a tetratetracontyl group, a pentapentacontyl group, a hexapentacontyl group,a heptapentacontyl group, a octapentacontyl group, a nonapentacontyl group, a hexacontyl group and others.

[0060] The term “C2-C60alkenyl group” as used herein refers to a linear or branched aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond in the middle or at the terminus of the C2-C60alkyl group, and examples thereof include an ethenyl group, a propenyl group, a isopropenyl group, a butenyl group, a 2-methyl-1-propenyl group, a 2-methyl-2-butenyl group, a 3-methyl-2-butenyl group, a pentenyl group, a 4-methyl-2-butenyl group, a hexenyl group, a 2,3-dimethyl-2-butenyl group, a 4,4-dimethyl-1-butenyl group, a heptenyl group, a 3,4-dimethyl-3-butenyl group, an octenyl group, a 2,3-dimethyl-2-hexenyl group, a nonenyl group, a 2-methyl-3-heptenyl group, a decenyl group, a 4-ethyl-4-octenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a nonadecenyl group, an eicosenyl group, a heneicosenyl group, a docosenyl group, a tricosenyl group, a tetracosenyl group, a pentacosenyl group, a hexacosenyl group, a heptacosenyl group, an octacosenyl group, a nonacosenyl group, a triacontenyl group, a hentriacontenyl group, a dotriacontenyl group, a tritriacontenyl group, a tetratriacontenyl group, a pentatriacontenyl group, a hexatriacontenyl group, a heptatriacontenyl group, an octatriacontenyl group, a nonatriacontenyl group, a tetracontenyl group, a hentetracontenyl group, a dotetracontenyl group, a tritetracontenyl group, a tetratetracontenyl group, a pentatetracontenyl group, a hexatetracontenyl group, a heptatetracontenyl group, an octatetracontenyl group, a nonatetracontenyl group, a pentacontenyl group, a hentapentacontenyl group, a dotriacontenyl group, a tritriacontenyl group, a tetratetracontenyl group, a pentapentacontenyl group, a hexapentacontenyl group, a heptapentacontenyl group, an octapentacontenyl group, a nonapentacontenyl group, a hexacontenyl group and others.

[0061] The term “C2-C60alkynyl group” as used herein refers to a linear or branched aliphatic unsaturated hydrocarbon group having at least one carbon-carbon triple bond in the middle or at the terminus of the C2-C60alkyl group, and examples thereof include an ethynyl group, and a propynyl group, a butynyl group, a 2-methyl-2-propynyl group, a pentynyl group, a 3-ethyl-2-butynyl group, a hexynyl group, a 3,3-dimethyl-1-butynyl group, a heptynyl group, a 3-propyl-3-pentynyl group, an octynyl group, a 2,3-dimethyl-2-hexynyl group, a nonynyl group, a 3,4-dimethyl-3-heptynyl group, a decynyl group, a 2-ethyl-2-octynyl group, an undecynyl group, a dodecynyl group, a tridecynyl group, a tetradecynyl group, a pentadecynyl group, a hexadecynyl group, a heptadecynyl group, an octadecynyl group, a nonadecynyl group, an eicosynyl group, a heneicosynyl group, a docosynyl group, a tricosynyl group, a tetracosynyl group, a pentacosynyl group, a hexacosynyl group, a heptacosynyl group, an octacosynyl group, a nonacosynyl group, a triacontynyl group, a hentriacontynyl group, a dotriacontynyl group, a tritriacontynyl group, a tetratriacontynyl group, a pentatriacontynyl group, a hexatriacontynyl group, a heptatriacontynyl group, an octatriacontynyl group, a nonatriacontynyl group, a tetracontynyl group, a hentetracontynyl group, a dotetracontynyl group, a tritetracontynyl group, a tetratetracontynyl group, a pentatetracontynyl group, a hexatetracontynyl group, a heptatetracontynyl group, an octatetracontynyl group, a nonatetracontynyl group, a pentacontynyl group, a hentapentacontynyl group, a dotriacontynyl group, a tritriacontynyl group, a tetratetracontynyl group, a pentapentacontynyl group, a hexapentacontynyl group, a heptapentacontynyl group, an octapentacontynyl group, a nonapentacontynyl group, a hexacontynyl group, and others.

[0062] The term “C3-C60cycloalkyl group” as used herein refers to a monocyclic or polycyclic and non-aromatic saturated group that has 3 to 60 carbon atoms. When the C3-C60cycloalkyl group includes two or more rings, the rings may be fused to each other. The examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, a cyclododecyl group, a cyclotridecyl group, a cyclotetradecyl group, a cyclopentadecyl group, a cyclohexadecyl group, a cycloheptadecyl group, a cyclooctadecyl group, a cyclononadecyl group, a cycloeicosyl group, a cycloheneicosyl group, a cyclodoecosyl group, a cyclotricosyl group, a cyclotetracosyl group, a cyclopentacosyl group, a cyclohexacosyl group, a cycloheptacosyl group, a cyclooctacosyl group, a cyclononacosyl group, a cyclotriacontyl group, a cyclohentriacontyl group, a cyclodotriacontyl group, a cyclotritriacontyl group, a cyclotetratriacontyl group, a cyclopentatriacontyl group, a cyclohexatriacontyl group, a cycloheptatriacontyl group, a cyclooctatriacontyl group, a cyclononatriacontyl group, a cyclotetracontyl group, a cyclohentetracontyl group, a cyclodotetracontyl group, a cyclotritetracontyl group, a cyclotetratetracontyl group, a cyclopentatetracontyl group, a cyclohexatetracontyl group, a cycloheptatetracontyl group, a cyclooctatetracontyl group, a cyclononatetracontyl group, a cyclopentacontyl group, a cyclohentapentacontyl group, a cyclodotriacontyl group, a cyclotritriacontyl group, a cyclotetratetracontyl group, a cyclopentapentacontyl group, a cyclohexapentacontyl group, a cycloheptapentacontyl group, a cyclooctapentacontyl group, a cyclononapentacontyl group, a cyclohexacontyl group, and others.

[0063] The term “C1-C60haloalkanyl” as used herein refers to an alkyl group having at least one halogen substituent and 1 to 60 carbon atoms.

[0064] The term “C2-C60haloalkenyl” as used herein refers to an alkyl group having at least one halogen substituent and 2 to 60 carbon atoms.

[0065] The term “C2-C60haloalkynyl” as used herein refers to an alkyl group having at least one halogen substituent and 1 to 60 carbon atoms.

[0066] The term “C1-C60heterocycloalkyl group” as used herein refers to a cycloalkyl group having at least one heteroatom selected from N, O, Si, P, and S as a ring-forming atom and 1 to 60 carbon atoms. When C1-C60heterocycloalkyl group includes two or more rings, the rings may be fused to each other. The examples thereof include 1,2,3,4-oxatriazolidinyl group, a tetrahydrofuranyl group, and a tetrahydrothiophenyl group, a pyrrolidinyl group, an oxetanyl group, a thiiranyl group, a piperidinyl group, an azetidinyl group, a silacyclopropyl group, a furan group, a pyridinyl group, a dithianyl group, a phospholanyl group, a thiazolyl group, a siloxanyl group, a morpholinyl group, an oxazolyl group, a thiophenyl group, and an aziridinyl group, tetrahydropyranyl group, a silacyclohexyl group, a phosphabicycloheptyl group, and others.

[0067] The term “C3-C60cycloalkenyl group” used herein refers to a monocyclic or polycyclic and non-aromatic unsaturated group that has 3 to 60 carbon atoms and at least one carbon-carbon double bond in the ring thereof. When the C3-C60cycloalkenyl group includes two or more rings, the rings may be fused to each other. The examples thereof include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a cyclononenyl group, a cyclodecenyl group, a cycloundecenyl group, a cyclododecenyl group, a cyclotridecenyl group, a cyclohexadecenyl group, a cyclooctadecenyl group, a cyclotetradecenyl group, a cyclotriacosenyl group, a cyclotetracontenyl group, a cyclopentacontenyl group, a cyclohexacontenyl group and others.

[0068] The term “C1-C60heterocycloalkenyl group” as used herein refers to a cycloalkenyl group that has at least one heteroatom selected from N, O, Si, P, and S as a ring-forming atom, having 1 to 60 carbon atoms, and at least one double bond in its ring. When the C1-C60heterocycloalkenyl group includes two or more rings, the rings may be fused to each other. The examples of thereof include a 4,5-dihydro-1,2,3,4-oxatriazolyl group, a 2,3-dihydrofuranyl group, a 2,3-dihydrothiophenyl group, a pyrrolenyl group, a furanyl group, a thiophenyl group, a pyrrolopyridenyl group, an oxetanyl group, an azetidinyl group, a dioxasilolanyl group, a phospholanyl group, a pyrrolizidinyl group, an oxepinyl group, a thiepinyl group, a silacyclohexenyl group, a piperidinylidene group, an oxocyclooctenyl group, an azononacyclohexenyl group and others.

[0069] The term “C3-C60cycloalkynyl group” used herein refers to a monocyclic or polycyclic and non-aromatic unsaturated group that has 3 to 60 carbon atoms and at least one carbon-carbon triple bond in the ring thereof. When the C3-C60cycloalkynyl group includes two or more rings, the rings may be fused to each other. The examples thereof include a cyclopropynyl group, a cyclobutynyl group, a cyclopentynyl group, a cyclohexynyl group, a cycloheptynyl group, a cyclooctynyl group, a cyclononylyl group, a cyclodecynyl group, a cycloundecynyl group, a cyclododecynyl group, a cyclotridecynyl group, a cyclotetradecynyl group, a cyclopentadecynyl group, a cyclohexadecynyl group, a cycloheptadecynyl group, a cyclooctadecynyl group, a cyclononadecynyl group, a cyclotriacontynyl group, a cyclotriacosynyl group, a cyclotetracontynyl group, a cyclopentacontynyl group, a cyclohexacontynyl group.

[0070] The term “C1-C60heterocycloalkynyl group” as used herein refers to a cycloalkynyl group that has at least one heteroatom selected from N, O, Si, P, and S as a ring-forming atom, having 1 to 60 carbon atoms, and at least one triple bond in its ring. When the C1-C60heterocycloalkynyl group includes two or more rings, the rings may be fused to each other. The examples thereof include a pyridinylcyclopropynyl group, an oxazolylcyclobutynyl group, a thiophenylcyclopentynyl group, a silylcyclohexynyl group, a phosphacycloheptynyl group, a pyrazinylcyclooctynyl group, an oxacyclononynyl group, a thiasilacyclodecynyl group, an isoxazolylcycloheptenyl group, a pyrimidinylcyclopentadienyl group, a triazinylcyclohexadienyl group, a phosphoranylpyridinylcycloheptenyl group, an oxathiacyclononadienyl group, a silylpyrazinylcyclooctadienyl group, a pyridazinylcyclooctatrienyl group, an isothiazolylsilylcyclononatrienyl group, a thiophenylphosphacyclodecatrienyl group, a pyrimidinylsilylcycloheptadienyl group, an oxazinylphosphoranylcyclodecadienyl group, a silylthiasilacyclohexatrienyl group

[0071] The term “C6-C60aryl group” as used herein refers to a carbocyclic aromatic group having 6 to 60 carbon atoms. When the C6-C60aryl group includes two or more rings, the rings may be fused to each other. The examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a chrysenyl group, a biphenyl group, a triphenylenyl group, a fluorenyl group, a perylenyl group, a coronene-ovalenyl group, a dibenzo[a,e]pentalenyl group, a tetrabenzo[a,c,f,h]pentaphenyl group, a hexabenzo[a,c,f,h,k,n]pentadecaphenyl group, an octabenzo[a,c,f,h,k,n,q,u]icosaphenyl group, a toluyl group, a xylyl group, a diphenylmethyl group, a terphenyl group and others.

[0072] The term “C1-C60heteroaryl group” as used herein refers to an aryl group having a at least one heteroatom selected from N, O, Si, P, and S as a ring-forming atom, and having 1 to 60 carbon atoms. When the C1-C60heteroaryl group includes two or more rings, the rings may be fused with each other. The examples thereof include a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a furan-2-yl group, a thiophen-3-yl group, an imidazol-4-yl group, a thiazol-2-yl group, an oxazol-5-yl group, a pyrrole-2-yl group, an indol-3-yl group, a benzofuran-4-yl group, a benzothiophen-2-yl group, a benzimidazol-1-yl group, a benzothiazol-4-yl group, an isoxazol-3-yl group, a pyridin-4-ylmethyl group, a quinoxalin-2-yl group, a naphtho[1,2-d]imidazol-4-yl group, a tetrazol-1-yl group, a 1,2,3-triazol-4-yl group, a pyridin-2-ylmethoxy group, a thieno[2,3-c]pyridin-4-yl group, a 3,4-dihydro-2H-pyran-2-yl group, a 1,3-dioxol-2-yl group, a pyrazolo[1,5-a]pyridin-3-yl group, a benzofuran-2-ylmethyl group, a carbazole group, an indolocarbazole group, a phenoxazine group, a phenothiazine group, a benzimidazoquinazoline group, a pyridocarbazole group, a pyrrolopyrazine group, a quinoxaline-2,3-dione group, an isoxazole-3,5-dione group, an indole-3-carboxylic acid group, a dibenzofuranone group, a pyrroloquinoxaline group, an imidazo[1,2-a]pyrimidine group, a thiazolo[4,5-d]pyrimidine group, a benzothiazole-5-sulfonamide group, a 1H-pyrazolo[3,4-b]quinolin-3-amine group, a furo[3,2-c]pyridin-4(5H)-one group, a 1,3-dihydro-2H-indol-2-one group, a 2H-indazole-3-carboxylic acid group, a pyrazolo[1,5-a]pyrimidin-3-amine group, a 3H-indole-4-carbonitrile group, a benzoxazin-3-one group, a benzothiophene-2-carboxylic acid group, an isothiazole-3-carboxylic acid group, a pyrido[2,3-b]pyrazin-7-one group, a 3H-quinazolin-4-one group, a benzofurazan-5-amine group, a 1,2,4-triazolo[4,3-a]pyridine group, a 1,3,4-oxadiazole-2(3H)-thione group, a 2H-thiopyran-4,6-dione group, a pyrrolo[1,2-a]quinoxaline-4,7-dione group, a silylpyridine group, a phosphorylpyrazole group, an oxiranylpyrimidine group, a thioxanthyl group, a siloxazinyl group, a phosphonaphthyl group, a dioxaphenanthrenyl group, a thiophenylsiloxane group, an oxatriazinyl group, a silylpyrrole-2-carboxylic acid group, a phosphinophenoxazine group, a silathiazolyl group, an oxadithienyl group, a phosphabenzimidazole group, a silaquinolinyl group, an oxepino[2,3-b]pyridinyl group, a dioxaphenanthrenylpyrazinyl group, a phosphorothiazolidinyl group, a silaisoxazolyl group, an oxazolidinylpyridyl group and others.

[0073] The term “C1-C60alkoxy group” as used herein refers to an alkyl group which is singularly bonded to oxygen forming thus R−O-. The examples thereof include a methoxy group, an ethoxy group, and an isopropyloxy group, a propoxy group, a butoxy group, atert-butoxy group, a sec-butoxy group, an iso-butoxy group, a pentoxy group, an iso-amyloxy group, a neo-pentoxy group, a hexoxy group, a heptoxy group, an octoxy group, a nonoxy group, a decoxy group, an undecoxy group, a dodecoxy group, a pentadecoxy group, an eicosoxy group, a pentacosoxy group, a triacontoxy group, a pentatriacontoxy group, a tetracontoxy group, a pentatetracontoxy group, a pentacontoxy group, a pentapentacontoxy group, and a hexacontoxy group and others.

[0074] The term “C5-C60aryloxy group” as used herein refers to an aryl which is singularly bonded to oxygen forming thus Ar−O-. The examples thereof include a methoxyphenyl group, an ethoxyphenyl group, a propoxyphenyl group, an isopropoxyphenyl group, a butoxyphenyl group, a pentoxyphenyl group, a hexoxyphenyl group, a heptoxyphenyl group, an octoxyphenyl group, a nonoxyphenyl group, a decoxyphenyl group, a dodecoxyphenyl group, a hexadecoxyphenyl group, a triacontaoxyphenyl group, a hexacontaoxyphenyl group, a phenylmethoxy group, a naphthoxy group, a biphenyloxy group, an anisoyloxy group, a toluoyloxy group, a xylyloxy group, a benzoyloxy group, a napththoyloxy group, an anthryloxy group, a perylenyloxy group, a fluorenyloxy group, a triphenyloxy group, a phenoxyphenyl group, a naphthoxyphenyl group, a pyrenyloxy group and others.

[0075] The term “C1-C60heteroaryloxy group” as used herein refers to an aryloxy group having a at least one heteroatom selected from N, O, Si, P, and S as a ring-forming atom, and having 1 to 60 carbon atoms. The examples thereof include a pyridinyloxy group, a furanoyloxy group, a thiophenoyloxy group, a siloxanoyloxy group, a phosphinoyloxy group, a pyrimidinyloxy group, a pyrazinyloxy group, a thiazolinyloxy group, an isoxazolinyloxy group, a benzoxazinoyloxy group, a benzothiazolinyloxy group, an imidazolinyloxy group, a pyridazinyloxy group, a silathiazolinyloxy group, an isothiazolinyloxy group, an oxazolinyloxy group, a silabenzoxazinoyloxy group, a phosphabenzothiazolinyloxy group, a dibenzofuranyloxy group, a silaisoxazolinyloxy group. and others.

[0076] The term “C2-C60ether group” as used herein refers to a group containing an ether group - an oxygen atom connected to two selected from: alkyl, alkenyl, alkynyl, and aryl group, where the ether group having 2 to 60 carbon atoms. The examples thereof include: a methyl ether group, an ethyl ether group, an isopropyl ether group, atert-butyl ether group, a phenyl ether group, an anisyl ether group, a benzyl ether group, an allyl ether group, a methoxyethyl ether group, an ethoxyethyl ether group, a methylphenyl ether group, an ethylphenyl ether group, an isobutyl ether group, a cyclohexyl ether group, a methoxymethyl ether group, an ethoxymethyl ether group, a propyl ether group, a butyl ether group, a pentyl ether group, a hexyl ether group, a methoxypropyl ether group, an ethoxypropyl ether group, a dimethyl ether group, a diethyl ether group, a dipropyl ether group, a dibutyl ether group, a dipentyl ether group, a methoxyisopropyl ether group, an ethoxyisopropyl ether group, a methoxytert-butyl ether group, a methoxyphenyl ether group, an ethoxyphenyl ether group, a p-tolyl ether group, an o-anisyl ether group, a naphthyl ether group, a biphenyl ether group, a 2-methylphenyl ether group, a 4-ethylphenyl ether group, a 3-methoxyphenyl ether group, a 2,4-dimethylphenyl ether group, a 3,5-diethylphenyl ether group, a 2,4,6-trimethylphenyl ether group, a 2,3-dimethoxyphenyl ether group, a 2,4-diethylphenyl ether group, a 4-methoxynaphthyl ether group, a 3,4-diphenylnaphthyl ether group and others.

[0077] The term “C6-C60thioaryl group” as used herein refers to a group derived from a thioether with R as an aryl group. The group has 6 to 60 carbon atoms. When the C6-C60thioaryl group includes two or more rings, the rings may be fused to each other. The examples thereof include a thiophenyl group, a thionaphthyl group, a thioanthryl group, a thiophenanthryl group, a thiopyryl group, a thiobenzofuranyl group, a thioindolyl group, a thioquinolyl group, a thiopyridazinyl group, a thionaphthoquinolyl group, a thiopyrimidinyl group, a thiochromenyl group, a thioacridinyl group, a thiodibenzothiophenyl group, a thiotriphenylmethyl group and others.

[0078] The term “C1-C60heterothioaryl” as used herein refers to a thioaryl group having 1 to 60 carbon atoms, where two or more rings fused to each other, at least one heteroatom selected from N, O, Si, P, and S, other than carbon atoms, as a ring-forming atom. Examples of the thereof include a pyrimidothioaryl group, a thieno[2,3-b][1,4]dioxinyl group, a pyrazinothioaryl group, a benzothiazolyl group, a dibenzothiophenyl group, a thiopheno[3,4-b]pyrrolyl group, an isothiazolylthioaryl group, a naphthothiophenyl group, a thianthrenyl group, an indolizinothioaryl group, a dithiolo[3,4-b]pyrrolyl group, a selenopheno[2,3-b]pyridinyl group, a pyrrolo[2,3-b]thiophenyl group, an oxazolo[2,3-b]pyridinylthioaryl group, a pyrrolizinothioaryl group and others.

[0079] The term “C1-C60amino group” as used herein refers to an organic compound comprises -N(R)2, where R is, together or independently, selected from: hydrogen, deuterium, alkyl, alkenyl, alkynyl, aryl group, and heteroarylo group. The amino group has 1 to 60 carbon atoms. The term “C1-C60alkylamino” as used herein refers amino group wherein R is an alkyl group. The term “C1-C60dialkylamino” as used herein refers amino group wherein both R are alkyl groups. The term “C6-C60arylamino group” as used herein refers amino group wherein R is an aryl group. The term “C6-C60diarylamino group” as used herein refers amino group wherein both R are aryl groups. The term “C6-C60heteroarylamino group” as used herein refers amino group wherein R is a heteroaryl group. The term “C6-C60heterodiarylamino group” as used herein refers amino group wherein both R are heteroaryl groups. The examples of the amino group includes a methylamino group, a phenylamino group, a diphenylamino group, a naphthylamino group, a 9-methyl-anthracenylamino group, an ammonium group, a dimethylamino group, a diethylamino group, a methylanilino group, an ethylanilino group, an ethylphenylamino group, a diethylphenylamino group, a methoxymethylamino group, a methylbenzylamino group, an anilino group, a phenanthrylamino group, an ethoxyethylamino group, a pyridinylamino group, a quinolinylamino group, an isoquinolinylamino group, an imidazolylamino group, a benzimidazolylamino group, a triazolylamino group, a pyrazinylamino group, a pyrimidinylamino group, a thiazolylamino group, an oxazolylamino group, an isoxazolylamino group, an indolylamino group, a quinoxalinylamino group, a benzothiazolylamino group, a benzoxazolylamino group, a carbamoyl group, a thiocarbamoyl group, a sulfonylamino group, a sulfamoyl group, an amidoaryl group, a hydrazinyl group, a hydrazinoaryl group, a guanidinyl group, a guanidinoaryl group, an amidinyl group, an amidinoaryl group, a thiosemicarbazidyl group, a triazolethioamide group and others.

[0080] The term “a cyano group” as used herein refers to a -C≡N functional group.

[0081] The term “a nitro group” as used herein refers to a −NO2 functional group.

[0082] The term “a halogen” as used herein refers to fluorine, chlorine, bromine, or iodine.

[0083] The term “C4-C60non-aromatic fused polycyclic group” as used herein refers to a group, having 4 to 60 carbon atoms, where two or more rings fused with each other, only carbon atoms as ring-forming atoms, and no aromaticity in its entire molecular structure. The examples thereof include a fluorenyl group, a cyclobutylcyclopentyl group, a cyclopentylcyclohexyl group, a decalinyl group, a bicyclo[3.2.1]octanyl group, a dicyclo[4.4.0]decanyl group, a spiro[4.4]nonanyl group, a tetracyclo[5.3.0.0²,⁶.0³,⁵]decanyl group, a pentacyclo[6.4.0.0²,⁶.0³,¹⁰.0⁵,⁹]dodecanyl group, a tricyclo[3.2.1.0²,⁴]octanyl group, a bicyclo[4.3.1]decanyl group, a tetradecahydrophenanthrenyl group, a tricyclo[5.3.1.0²,⁶]dodecanyl group, a dicyclo[6.4.0]tetradecanyl group, a pentacyclo[7.3.1.0²,⁷.0³,⁶]tetradecanyl group, a tetracyclo[8.3.1.0²,⁸.0³,¹⁰.0⁶,⁹]hexadecanyl group, a hexacyclo[9.3.1.0²,⁹.0³,¹¹.0⁶,¹⁰]octadecanyl group and others.

[0084] The term “C1-C60non-aromatic fused heteropolycyclic group” as used herein refers to a group, having 1 to 60 carbon atoms, where two or more rings fused to each other, at least one heteroatom selected from N, O, Si, P, and S, other than carbon atoms, as a ring-forming atom, and no aromaticity in its entire molecular structure. The examples thereof include an oxazolidinyl group, a silathiophenyl group, a pyrrolidinyl group, a phosphaseleninyl group, a dithiiranyl group, an oxathianyl group, a silaoxazinyl group, a thiaselenopyryl group, a phosphaoxazepinyl group, a pyrimidothiopyranyl group, a siladihydrothiazepinyl group, a pyrazinothiadiazinyl group, a phosphoazepinothiazinyl group, a triazolothiadiazinyl group, a sulfinylpyrazolopyridinyl group, an isoxazinothiopyranyl group, a thiadiazinylthiophenyl group, a dioxasilolanyl group, an oxatriazolothiopyridinyl group and others.

[0085] The present invention is illustrated by the following examples in detail.Examples

[0086] Example 1:An electron injecting layer and electron transport layer according to the invention

[0087] An electron injecting layer and electron transport layer comprise a compound according toFormula 1. Examples of inventive compounds in the EIL and / or ETL are included in the compounds described according to Formula 1 and they do not limit the scope of protection of this application. The compound according toFormula 1may be selected from:

[0088] The compound according to Formula 1 can be used as a compound intermediating transport or injection of electrons in an electroluminescent device.

[0089] Example 2:Process for obtaining compounds with the structure according toFormula 1

[0090] The process of obtaining compounds with the structure represented byFormula 1is presented in the following examples, which do not limit its scope of protection. The process of synthesising the compounds of the embodiment will be exemplified through descriptions of processes for synthesisingCompounds1, 2,5a-5f, 14a, 14b,19, 25, 29, 32,44, 45, 51a-d,55, 63,75a, 75b.

[0091] Process for the preparation of sodium 2-(pyridin-2-yl)quinolin-8-olate (Compound 1) by a three-step synthesis

[0092] a. Synthesis of 8-methoxy-2-(pyridin-2-yl)quinoline (intermediate1.1)

[0093] 2-amino-3-methoxybenzaldehyde (30 g, 0.2 mol) in 100 ml of absolute ethanol, 2-acetylpyridine (24.5 g, 0.21 mol), and potassium hydroxide are added into a pressure bottle and kept stirring at 120° C overnight. Then, the crude mixture was allowed to cool down to room temperature and concentrated using a rotary evaporator. The concentrated crude was dissolved in dichloromethane at ambient temperature. Then, transferred to a separation funnel and treated with 1M hydrochloric acid until neutral pH, followed by extraction using an excess amount of dichloromethane. After drying over anhydrous MgSO4, the mixture was concentrated and obtained a brown solid (42 g, Yield: 90%) as an expected intermediate.

[0094] 1.1:1H NMR (400 MHz, CDCl3) 8.73-8.70 (m, 2H), 8.60 (d, 1H, J = 8.6 Hz), 8.26 (d, 1H, J = 8.6 Hz), 7.89-7.84 (m, 1H), 7.50-7.42 (m, 2H), 7.36-7.32 (m, 1H), 7.08 (dd, 1H, J = 7.5, 1.5 Hz), 4.13 (s, 3H)

[0095] b. Synthesis of 2-(pyridin-2-yl)quinolin-8-ol (intermediate 1.2)

[0096] To a pressure vessel 8-(methoxy-2-pyridin-2-yl)quinoline (42 g, 0.18 mol) was added and dissolved in 100 ml of hydrobromic acid (48%). The mixture was stirred at 160°C overnight. Then, the reaction was allowed to cool, and water was added. The obtained yellow solid was filtered, suspended in dichloromethane, and washed with NaHCO3. The combined organic layers were dried over MgSO4and concentrated in vacuo. The crude solid was purified via MPLC eluting with 95:5 dichloromethane:ethyl acetate to give a light-yellow solid (34 g, 86%).

[0097] 1.2:1H NMR (700 MHz, DMSO-d6) 9.80 (s, 1H), 9.09 (d, 1H, J = 8.2 Hz), 8.74-8.73 (m, 1H), 8.59 (d, 1H, J = 8.6 Hz), 8.44 (d, 1H, J = 8.6 Hz), 8.02-8.00 (m, 1H), 7.51-7.42 (m, 3H), 7.15 (dd, 1H, J = 7.5, 1.2 Hz)

[0098] c. Synthesis of sodium 2-(pyridin-2-yl)quinolin-8-olate(Compound 1)

[0099] To the solution of 2-(pyridin-2-yl)quinolin-8-ol (10 g, 45 mmol) in 100 ml of anhydrous dichloromethane sodium hydroxide was added (1.8 g, 45 mmol) under a nitrogen atmosphere. The mixture was stirred at room temperature for 24 hours. The precipitate was filtered, washed with dichloromethane, and dried in vacuo. The yellow solid (10.5 g, 95%) was stored under an inert atmosphere.

[0100] Compound 1:1H NMR (700 MHz, DMSO-d6) 8.58 (d, 1H, J = 4 Hz), 8.38 (d, 1H, J = 7.8 Hz), 8.10 (s, 2H), 7.83 (t, 1H, J = 7.8 Hz), 7.37-7.35 (m, 1H), 7.17 (t, 1H, J = 7.8 Hz), 6.53 (d, 1H, J = 7.8 Hz), 6.48 (d, 1H, J = 7.9 Hz)

[0101] 2.2. Process for the preparation of lithium 2-(pyridin-2-yl)quinolin-8-olate(Compound2).

[0102] To the solution of 2-(pyridin-2-yl)quinolin-8-ol (666 mg, 3 mmol) in 8 ml of anhydrous dichloromethane lithium hydride was added (24 mg, 3 mmol) under a nitrogen atmosphere. The mixture was stirred at room temperature for 24 hours. The precipitate was filtered, washed with dichloromethane, and dried in vacuo. The yellow solid (421 mg, 62%) was stored under an inert atmosphere.

[0103] Compound 2:1H NMR (400 MHz, DMSO-d6) 8.62 (bs, 1H, J = 4 Hz), 8.52 (d, 1H, J = 8.0 Hz), 8.18 (d, 2H, J = 5.9 Hz), 7.71 (bs, 1H), 7.35 (t, 1H, J = 6.0 Hz), 7.22 (t, 1H, J = 7.8 Hz), 6.60 (d, 1H, J = 7.7 Hz), 6.51 (d, 1H, J = 7.4 Hz)

[0104] 2.1. The general procedure for obtaining compounds 5a - 5f is the following:

[0105] 2.2. The procedure for obtainingCompounds3a-3f

[0106] 2-amino-3-methoxybenzaldehyde2a(1 eq) in absolute ethanol, acetyl derivatives1a-1f(1.1 eq), and potassium hydroxide (2 eq) are added into a pressure bottle and kept stirring at 120°C overnight. Then, the crude mixture was allowed to cool down to room temperature and concentrated using a rotary evaporator. The concentrated crude was dissolved in dichloromethane at ambient temperature. Then, transferred to a separation funnel and treated with 1M hydrochloric acid until neutral pH, followed by extraction using an excess amount of dichloromethane. After drying over anhydrous MgSO4the mixture was concentrated and obtained a solid as an expected intermediate.

[0107] 3a8-methoxy-2-(pyrazin-2-yl)quinoline

[0108] Prepared from 2-amino-3-methoxybenzaldehyde2a(20 mmol, 3.0 g, 1.0 eq) and 1-(pyrazin-2-yl)ethan-1-one1a(21 mmol, 2.54 g, 1.05 eq).The crude product was purified by column chromatography (silica gel, dichloromethane / ethyl acetate 1:1, v / v), yellow solid (4.3 g, yield 91%). NMR confirmed the structure.

[0109] 3b2-(furan-2-yl)-8-methoxyquinoline

[0110] Prepared from 2-amino-3-methoxybenzaldehyde2a(6.6 mmol, 1.0 g, 1.0 eq) and 1-(furan-2-yl)ethan-1-one1b(7.0 mmol, 0.76 g, 1.05 eq).The crude product, brown oil, was obtained (1.3 g, yield 88%) and used without purification to the next step of synthesis. NMR confirmed the structure.

[0111] 3c8-methoxy-2-(thiophen-2-yl)quinoline

[0112] Prepared from 2-amino-3-methoxybenzaldehyde2a(13.2 mmol, 2.0 g, 1.1 eq) and 1-(thiophen-2-yl)ethan-1-one1c(12.0 mmol, 1.5 g, 1.01 eq).The crude product, brown oil, was obtained (2.7 g, yield 93%) and used without purification to the next step of synthesis. NMR confirmed the structure.

[0113] 3d8-methoxy-2-(4-(trifluoromethyl)pyridin-2-yl)quinoline

[0114] Prepared from 2-amino-3-methoxybenzaldehyde2a(2.7 mmol, 412 mg, 1.0 eq) and 1-(4-(trifluoromethyl)pyridin-2-yl)ethan-1-one1d(3.0 mmol, 567 mg, 1.1 eq). The crude product was purified by column chromatography (silica gel, dichloromethane) yellow solid (560 mg, yield 68%).1H NMR (DMSO-d6, 400 MHz) 9.03 (d, J = 5.1 Hz, 1H), 8.79 (s, 1 H), 8.58 (d, J = 8.8 Hz, 1H), 8.51 (d, J = 8.8 Hz, 1H), 7.90 (d, J = 5.0 Hz, 1H), 7.62-7.57 (m, 2H), 7.28 (dd, J = 2.8, 6.2 Hz, 1H), 4.05 (s, 3H)

[0115] 3e8-methoxy-2-(5-(trifluoromethyl)pyridin-2-yl)quinoline

[0116] Prepared from 2-amino-3-methoxybenzaldehyde2a(5.82 mmol, 879 mg, 1.1 eq) and 1-(5-(trifluoromethyl)pyridin-2-yl)ethan-1-one1e(5.3 mmol, 1.0 g, 1.1 eq). The crude product was purified by column chromatography (silica gel, dichloromethane) yellow solid (1.6 g, yield 87%). NMR confirmed the structure.

[0117] 3f8-methoxy-2-(1H-pyrrol-2-yl)quinoline

[0118] Prepared from 2-amino-3-methoxybenzaldehyde2a(2.7 mmol, 412 mg, 1.0 eq) and 1-(1H-pyrrol-2-yl)ethan-1-one1f(3.0 mmol, 327 mg, 1.1 eq). The crude product was purified by column chromatography (silica gel, dichloromethane) yellow solid (545 mg, yield 90%).1H NMR (DMSO-d6, 400 MHz) 11.95 (s, 1H), 8.50 (d, J = 5.2 Hz, 1H), 7.67 (m, 1 H), 7.61 (s, 1H), 7.51 (d, J = 8.8 Hz, 2H), 7.12 (d, J = 4.9 Hz, 1H), 6.62 (d, J = 5.0 Hz, 1H), 6.20 (t, J = 8.0 Hz, 1H), 4.12 (s, 3H)

[0119] 2.3. The procedure for obtaining compounds 4a - 4f

[0120] To a pressure vessel derivative3a-3fwas added and dissolved in hydrobromic acid (48%). The mixture was stirred at 160°C overnight. Next, the reaction was allowed to cool, and water was added. The obtained yellow solid was filtered, suspended in dichloromethane and washed with NaHCO3. The combined organic layers were dried over MgSO4and concentrated in vacuo. The crude product4a-4fwas purified via MPLC.

[0121] 4a2-(pyrazin-2-yl)quinolin-8-ol

[0122] Prepared from 8-methoxy-2-(pyrazin-2-yl)quinoline3a. The crude product was dissolved in dichloromethane and a beige solid was precipitated with petroleum ether (1.5 g, 43%).1H NMR (DMSO-d6, 700 MHz) 10.27 (d, J = 1.5 Hz, 1H), 9.92 (s, 1H), 8.78-8.77 (m, 1H), 8.76-8.75 (m, 1H), 8.52-8.49 (m, 2H), 7.51 (t, J = 8.0 Hz, 1H), 7.47 (dd, J = 1.3, 8.1 Hz, 1H), 7.17 (dd, J = 1.2, 7.6 Hz, 1H)

[0123] 4b2-(furan-2-yl)quinolin-8-ol

[0124] Prepared from 2-(furan-2-yl)-8-methoxyquinoline3b. The crude product was purified via MPLC (silica gel) eluting with 1:1 dichloromethane:petroleum ether to give a yellow solid (1.02g, 93%).1H NMR (DMSO-d6, 700 MHz) 9.52 (bs, 1H), 8.36 (d, J = 8.6 Hz, 1H), 7.92-9.89 (m, 1H), 7.60 (d, J = 3.4 Hz, 1H), 7.40-7.35 (m, 2H), 7.10 (d, J = 7.2Hz, 2H), 6.74 (dd, J = 1.7, 3.5, Hz, 1H)

[0125] 4c2-(thiophen-2-yl)quinolin-8-ol

[0126] Prepared from 8-methoxy-2-(thiophen-2-yl)quinoline3c. The crude product was purified via MPLC (silica gel) eluting with 1:1 dichloromethane:petroleum ether to give a white solid (2.72 g, 92%).1H NMR (DMSO-d6, 700 MHz) 9.42 (s, 1H), 8.32 (d, J = 8.6 Hz, 1H), 8.06 (dd, J = 1.2, 3.7 Hz, 1H), 8.04 (d, J = 8,6 Hz, 1H), 7.73 (dd, J = 1.1, 4.8 Hz, 1H), 7.40-7.36 (m, 2H), 7.22 (dd, J = 3.7, 4.8 Hz, 1H), 7.11 (dd, J = 2.1, 6.8, Hz, 1H)

[0127] 4d2-(4-(trifluoromethyl)pyridin-2-yl)quinolin-8-ol

[0128] Prepared from 8-methoxy-2-(4-(trifluoromethyl)pyridin-2-yl)quinoline3d. The crude product was purified via MPLC (silica gel) eluting with 9:1 dichloromethane:ethyl acetate to give a light-yellow solid (254 mg, 50%). NMR confirmed the structure.

[0129] 4e2-(5-(trifluoromethyl)pyridin-2-yl)quinolin-8-ol

[0130] Prepared from 8-methoxy-2-(5-(trifluoromethyl)pyridin-2-yl)quinoline3e. The crude product was purified via MPLC (silica gel) eluting with 7:3 dichloromethane:petroleum ether to give a light-yellow solid (0.9 g, 69%).1H NMR (DMSO-d6, 700 MHz) 10.00 (s, 1H), 9.34 (d, J = 8.3 Hz, 1H), 9.11 (s, 1H), 8.61 (d, J = 8.7 Hz, 1H), 8.50 (d, J = 8.7 Hz, 1H), 8.43 (dd, J = 2.4, 8.4 Hz, 1H), 7.52 (t, J = 7.8 Hz, 1H), 7.47 (d, J = 8.2 Hz, 1H), 7.17 (dd, J = 1.2, 7.8 Hz, 1H)

[0131] 4f2-(1H-pyrrol-2-yl)quinolin-8-ol

[0132] Prepared from 8-methoxy-2-(1H-pyrrol-2-yl)quinoline3f. The crude product was purified via MPLC (silica gel) eluting with 1:1 dichloromethane:petroleum ether to give a yellow solid (0.400 g, 79%).1H NMR (DMSO-d6, 700 MHz) 11.94 (bs, 1H), 9.74 (s, 1H), 8.60 (d, J = 8.5 Hz, 1H), 7.80 (d, J = 3.6 Hz, 1H), 7.62-7.58 (m, 2H), 7.02 (d, J = 3.6 Hz, 1H), 6.74 (dd, J = 1.8, 3.4, Hz, 1H), 6.48 (d, J = 3.7 Hz, 1H), 6.16 (t, J = 7.9 Hz, 1H)

[0133] 2.4. The procedure for obtainingCompounds5a-5f

[0134] To the solution of derivatives4a-4f(1 eq) in 100 ml of anhydrous dichloromethane sodium hydroxide was added (1 eq) under a nitrogen atmosphere. The mixture was stirred at room temperature for 24 hours. The precipitate was filtered, washed with dichloromethane and dried in vacuo. Products5a-5fwere stored under an argon atmosphere and above P2O5.

[0135] 5asodium 2-(pyrazin-2-yl)quinolin-8-olate

[0136] Prepared from 2-(pyrazin-2-yl)quinolin-8-ol4a. Orange solid was obtained 0.24 g (76%).1H NMR (DMSO-d6, 400 MHz) 9.59 (d, J = 1.5 Hz, 1H), 8.59-8.56 (m, 2H), 8.13-8.08 (m, 2H), 7.17 (t, J = 7.9 Hz, 1H), 6.46 (dd, J = 1.2, 7.8 Hz, 1H), 6.41 (dd, J = 1.2, 8.0 Hz, 1H)

[0137] 5bsodium 2-(furan-2-yl)quinolin-8-olate

[0138] Prepared from 2-(furan-2-yl)quinolin-8-ol4b. 0.85 g of a yellow solid was obtained (83%).1H NMR (DMSO-d6, 700 MHz) 7.99 (dd, J = 1.0, 8.7 Hz, 1H), 7.62 (d, J = 8.50 Hz, 1H), 7.60- 7.58 (m, 1H), 7.23 (d, J = 3.5 Hz, 1H), 7.17 (td, J = 1.0, 7.8 Hz, 1H), 6.60 (bs, 1H), 6.40 (d, J = 7.7 Hz, 1H), 6.35 (d, J = 7.7 Hz, 1H)

[0139] 5csodium 2-(thiophen-2-yl)quinolin-8-olate

[0140] Prepared from 2-(thiophen-2-yl)quinolin-8-ol4c. A yellow solid was obtained (1.2 g, 76%).1H NMR (DMSO-d6, 400 MHz) 8.03 (d, J = 8.7 Hz, 1H), 7.81 (d, J = 1.2, 3.7 Hz, 1H), 7.75 (d, J = 8.6 Hz, 1H), 7.58 (dd, J = 1.2, 5.0 Hz, 1H), 7.15 (dd, J = 3.5, 4.6 Hz, 1H), 7.13 (t, J = 7.8 Hz, 1H), 6.67 (dd, J = 1.2, 8.0 Hz, 1H), 6.62 (dd, J = 1.2,7.9 Hz, 1H)

[0141] 5dsodium 2-(4-(trifluoromethyl)pyridin-2-yl)quinolin-8-olate

[0142] Prepared from 2-(4-(trifluoromethyl)pyridin-2-yl)quinolin-8-ol4d. Orange solid was obtained 200 mg (73%).1H NMR (DMSO-d6, 400 MHz) 8.8 (d, J = 5.1 Hz, 1H), 8.70 (s, 1H), 8.19 (d, J = 8.6 Hz, 1H), 8.04 (d, J = 8.8 Hz, 1H), 7.73-7.71 (m, 1H), 7.12 (t, J = 7.8 Hz, 1H), 6.38 (d, J = 7.7 Hz, 1H), 6.32 (dd, J = 1.2, 8.1 Hz, 1H)

[0143] 5esodium 2-(5-(trifluoromethyl)pyridin-2-yl)quinolin-8-olate

[0144] Prepared from 2-(5-(trifluoromethyl)pyridin-2-yl)quinolin-8-ol4e. Orange solid was obtained 680 mg (82%).1H NMR (DMSO-d6, 400 MHz) 8.83 (s, 1H), 8.59 (d, J = 8.3 Hz, 1H), 8.13-8.05 (m, 3H), 7.16 (t, J = 7.8 Hz, 1H), 6.42 (d, J = 7.7 Hz, 1H), 6.39 (d, J = 8.1 Hz, 1H)

[0145] 5fpotassium 2-(1H-pyrrol-2-yl)quinolin-8-olate

[0146] Prepared from 2-(1H-pyrrol-2-yl)quinolin-8-ol5f. A yellow solid was obtained 0.422 g (89%).1H NMR (DMSO-d6, 700 MHz): δ 11.90 (s, 1H), 8.60 (dd, J = 1.1, 8.6 Hz, 1H), 7.80 (d, J = 8.4 Hz, 1H), 7.64- 7.60 (m, 2H), 6.95 (d, J = 3.4 Hz, 1H), 6.75 (d, J = 3.6 Hz, 1H), 6.48 (d, J = 3.6 Hz, 1H), 6.40 (td, J = 1.4, 7.7 Hz, 1H)

[0147] 2.5. The general procedure for obtainingCompounds14a, 14b, 17, and18

[0148] 2.6. The procedure for obtainingCompounds9-11, 13a, 13b, 14a, 14b, 16-19

[0149] 2-amino-3-methoxybenzaldehyde8(30 g, 0.2 mol) in 100 ml of absolute ethanol, 2-acetylpyridine7(24.5 g, 0.21 mol), and potassium hydroxide were added into a pressure bottle and kept stirring at 120°C overnight. Then, the crude mixture was allowed to cool down to room temperature and concentrated using a rotary evaporator. The concentrated crude was dissolved in dichloromethane at ambient temperature. Then, transferred to a separation funnel and treated with 1M hydrochloric acid until neutral pH, followed by extraction using an excess amount of dichloromethane. After drying over anhydrous MgSO4, the mixture was concentrated and obtained a brown solid of9(42 g, yield: 90%) as an expected intermediate.1H NMR (400 MHz, CDCl3) 8.73-8.70 (m, 2H), 8.60 (d, J = 8.6 Hz, 1H), 8.26 (d, J = 8.6 Hz, 1H), 7.88-7.84 (m, 1H), 7.50-7.42 (m, 2H), 7.36-7.32 (m, 1H), 7.08 (dd, J = 1.5, 7.5 Hz, 1H), 4.13 (s, 3H).

[0150] To a pressure vessel 8-(methoxy-2-pyridin-2-yl)quinolone9(42 g, 0.18 mol) was added and dissolved in 100 ml of hydrobromic acid (48%). The mixture was stirred at 160°C overnight. Then, the reaction was allowed to cool, and water was added. The obtained yellow solid was filtered, suspended in dichloromethane and washed with NaHCO3. The combined organic layers were dried over MgSO4and concentrated in vacuo. The crude solid was purified via MPLC eluting with 95:5 dichloromethane:ethyl acetate to give a light-yellow solid of 10 (34 g, 86%).1H NMR (700 MHz, DMSO-d6) 9.80 (s, 1H), 9.09 (dt, J = 1.0, 8.2 Hz, 1H), 8.74-8.73 (m, 1H), 8.59 (d, J = 8.6 Hz, 1H), 8.44 (d, J = 8.6 Hz, 1H), 8.02-8.00 (m, 1H), 7.51-7.42 (m, 3H), 7.15 (dd, J = 1.2, 7.5 Hz, 1H)

[0151] To the solution of 2-(pyridin-2-yl)quinolin-8-ol10(2 g, 9 mmol) in 25 ml of anhydrous dichloromethane NBS (3.2 g, 9.4 mmol) was added under a nitrogen atmosphere. The mixture was stirred overnight at room temperature. The precipitate was filtered, washed with dichloromethane and dried in vacuo. The light orange solid of11(3.2 g, 93%) was obtained.1H NMR (700 MHz, DMSO-d6) 10.82 (s, 1H), 9.19 (d, J = 8 Hz, 1H), 8.77-8.76 (m, 2H), 8.57 (d, J = 8.8 Hz, 1 H), 8.07 (s, 1H), 8.05 (td, J = 1.8, 7.8 Hz, 1H), 7.56-7.54 (m, 1H)

[0152] To the solution of 5,7-dibromo-2-(pyridin-2-yl)quinolin-8-ol11(500 mg, 1.32 mmol) and phenylboronic acid (642 mg, 5.27 mmol) in a mixture of toluene (6 ml), ethanol (2 ml) and water (1 ml), K2CO3(1.09 g, 7.9 mmol) and bis(triphenylphosphine)palladium(II) dichloride (46 mg, 0.07 mmol, 5%mol) were added under a nitrogen atmosphere. The mixture was heated overnight at reflux and then extracted with dichloromethane, washed with brine, and dried over MgSO4. The crude product was purified via flash column chromatography eluting with 99:1 dichloromethane:ethyl acetate to the desired product as a light-yellow solid of13a(350 mg, 71%).1H NMR (400 MHz, DMSO-d6) 9.97 (s, 1H), 9.23-9.20 (m, 1H), 8.76-8.74 (m, 1H), 8.63 (d, J = 8.9 Hz, 1 H), 8.39 (d, J = 8.9 Hz, 1H), 8.03 (td, J = 1.8 7.7 Hz, 1H), 7.86-7.83 (m, 2H), 7.60-7.45 (m, 9H), 7.29 (m, 1H)

[0153] To the solution of 5,7-diphenyl-2-(pyridin-2-yl)quinolin-8-ol13a(280 mg, 0.75 mmol) in 3 ml of anhydrous dichloromethane sodium hydroxide was added (30 mg, 0.75 mmol) under a nitrogen atmosphere. The mixture was stirred at room temperature for 24 hours. Hexane was added to form the precipitate. Solid was filtered, washed with hexane and dried in vacuo. The orange solid of14a(250 mg, 84%) was stored under an inert atmosphere.1H NMR (400 MHz, DMSO-d6) 8.64 (d, J = 4.6 Hz, 1H), 8.46 (d, J = 7.5 Hz, 1H), 8.26 (d, J = 8.8 Hz, 1H), 8.16 (d, J = 8.9 Hz, 1H), 8.05 (d, J = 8.0 Hz, 2H), 7.95 (t, J = 7.9 Hz, 1H), 7.52-7.41 (m, 6H), 7.32 (t, J = 8.0 Hz, 3H), 7.13 (t, J = 7.4 Hz, 1H)

[0154] To the solution of 5,7-dibromo-2-(pyridin-2-yl)quinolin-8-ol 11 (1.0 g, 2.63 mmol) and (4-fluorophenyl)boronic acid12b(0.92 g, 2.5 mmol) in a mixture of toluene (10 ml), ethanol (3 ml), and water (1.5 ml), K2CO3(10.5 g, 4.0 mmol) and bis(triphenylphosphine)palladium(II) dichloride (142 mg, 0.054 mmol, 5% mol) were added under a nitrogen atmosphere. The mixture was heated overnight at reflux and then extracted with dichloromethane, washed with a solution of NH4Cl and dried over MgSO4. The crude product was purified via flash column chromatography eluting with 9:1 petroleum ether:ethyl acetate to the desired product as a white solid of13b(400 mg, 37%).1H NMR (700 MHz, DMSO-d6) 10.05 (s, 1H), 9.22 (d, J = 8.2 Hz, 1H), 8.75-8.74 (m, 1H), 8.63 (d, J = 8.9 Hz, 1H), 8.35 (d, J = 8.9 Hz, 1H), 8.03 (td, J = 2.1, 7.7 Hz, 1H), 7.91-7.88 (m, 2H), 7.64-7.61 (m, 2H), 7.55 (s, 1H), 7.53 (dd, J = 1.3, 4.8 Hz, 1H), 7.40-7.36 (m, 2H), 7.35-7.32 (m, 2H)

[0155] To the solution of 5,7-bis(4-fluorophenyl)-2-(pyridin-2-yl)quinolin-8-ol13b(1.08 g, 2.6 mmol) in 10 ml of anhydrous dichloromethane sodium hydroxide (105 mg, 2.6 mmol) was added under a nitrogen atmosphere. The mixture was stirred at room temperature for 24 hours. Hexane was added to form the precipitate. Solid was filtered, washed with hexane and dried in vacuo. The orange solid of14a(1.02 g, 90%) was stored under an inert atmosphere.1H NMR (700 MHz, DMSO-d6) 8.59 (d, J = 4.5 Hz, 1H), 8.32 (d, J = 8.1 Hz, 1H,), 8.18 (d, J = 8.6 Hz, 1H), 8.14-8.12 (m, 2H), 8.10 (d, J = 9.0 Hz, 1H), 7.91 (td, J = 1.8, 7.7 Hz, 1H) 7.52-7.49 (m, 2H), 7.46 (s, 1H), 7.39 (dd, J = 4.5, 7.9 Hz, 1H), 7.29-7.26 (m, 2H), 7.13-7.09 (m, 2H)

[0156] To the solution of 5,7-dibromo-2-(pyridin-2-yl)quinolin-8-ol11(2.65 g, 6.97 mmol, 1 eq) in 50 ml of DMF, benzyl bromide (1.8 g, 10.46 mmol, 1 eq) and potassium carbonate (1.93 g, 14 mmol, 2 eq) were added under a nitrogen atmosphere. The mixture was stirred at room temperature for 2 hours. The mixture was extracted with dichloromethane, washed with a solution of NH4Cl and dried over MgSO4. The crude product was purified via flash column chromatography eluting with 1:1 petroleum ether:dichloromethane to the desired product as a white solid of16(2.94 g, 90%).1H NMR (400 MHz, DMSO-d6) 8.80 (d, J = 4.8 Hz, 1H), 8.76 (d, J = 8.9 Hz, 1H,), 8.65 (d, J = 8.9 Hz, 1H), 8.52 (d, J = 8.0, 1H), 8.22 (s, 1H), 8.03 (td, J = 1.8, 7.8 Hz, 1H) 7.62-7.56 (m, 3H), 7.45-7.36 (m, 3H), 5.58 (s, 2H)

[0157] A solution of16(0.70 g, 1.50 mmol) in toluene (5 ml), potassium carbonate (0.73 g, 2.23 mmol, 2 eq), palladium acetate (10 mg, 0.045 mmol, 3% mol), tBuXPhos (44 mg, 0.1 mmol, 7% mol) and 5 ml methanol were added to the mixture under a nitrogen atmosphere. The mixture was stirred overnight at 80°C. After cooling to room temperature, the reaction mixture was extracted with dichloromethane, washed with brine and the solvent was removed under reduced pressure. The crude product was purified via flash column chromatography eluting with dichloromethane:ethyl acetate 98:2 to the desired product as a yellow solid of17(310 mg, 56%).1H NMR (400 MHz, DMSO-d6) 8.74 (d, J = 4.7 Hz, 1H), 8.56-8.54 (m, 2H,), 8.39 (d, J = 8.9 Hz, 1H), 7.99 (td, J = 1.8, 7.9 Hz, 1H) 7.63 (d, J = 7.5 Hz, 2H), 7.52-7.49 (m, 1H), 7.42-7.38 (m, 2H), 7.35-7.31 (m, 1H), 7.0 (s, 1H), 5.25 (s, 2H), 4.03 (s, 3H), 4.0 (s, 3H)

[0158] 10% Pd / C (106 mg, 2.3 mmol) was added to a solution of 8-(benzyloxy)-5,7-dimethoxy-2-(pyridin-2-yl)quinolone17in the mixture of EtOH:THF (5ml:20 ml). The inside air was replaced with H2(balloon) by three vacuum / H2cycles. The reaction mixture was stirred at 50°C until the TLC monitoring indicated the complete consumption of the starting material. Then, the reaction mixture was passed through a Celite pad. The reaction mixture was extracted with dichloromethane, washed with brine and the solvent was removed under reduced pressure. The crude product was purified via flash column chromatography eluting with petroleum ether:ethyl acetate 4:1 to the desired product as yellow crystals of17(615 mg, 36%).1H NMR (700 MHz, DMSO-d6) 9.07 (d, J = 8.1 Hz, 1H), 8.78 (s, 1H), 8.72 (d, J = 1.5, 4.6 Hz, 1H), 8.52 (d, J = 8.9, 1H), 8.42 (d, J = 9.0 Hz, 1H), 8.00 (td, J = 1.7, 7.5 Hz, 1H) 7.50 (dd, J = 4.7, 7.5, 1H), 6.98 (s, 1H), 3.99 (s, 3H), 3.98 (s, 3H)

[0159] A mixture of 5,7-dimethoxy-2-(pyridin-2-yl)quinolin-8-ol 18(180 mg, 0.64 mmol) and NaOH (26 mg, 0.64 mmol) in anhydrous dichloromethane was stirred at room temperature for 24h. The precipitate was filtered, washed with dichloromethane and dried in vacuo. The yellow solid (100 mg, 51%) was stored under an inert atmosphere.1H NMR (400 MHz, DMSO-d6) 8.92 (d, J = 8.0 Hz, 1H), 8.65 (d, J = 4.7 Hz, 1H), 8.39 (d, J = 8.3 Hz, 1H), 8.35 (d, J = 8.0 Hz, 1H), 7.7 (td, J = 1.4, 7.8 Hz, 1H), 7.28 (dd, J = 4.5, 7.6 Hz, 1H), 6.88 (s, 1H), 3.98 (s, 3H), 3.95 (s, 3H)

[0160] 2.7. The general procedure for obtainingCompounds25, 29, and32

[0161] 2.8. The procedure for obtainingCompounds21, 23-25, 27-32

[0162] To the solution of 8-methoxy-2-(pyridin-2-yl)quinolone20(2 g, 8.47 mmol) in 25 ml of anhydrous dichloromethane NBS (3.3 g, 18.6 mmol) was added under a nitrogen atmosphere. The mixture was stirred overnight at room temperature. The precipitate was filtered, washed with dichloromethane and dried in vacuo. The crude product was purified via flash column chromatography eluting with 95:5 dichloromethane:ethyl acetate to the desired product as a light orange solid (2.3 g, 85%) was obtained.1H NMR (400 MHz, DMSO-d6) 8.78-8.76 (m, 1H), 8.70 (d, J = 8.8 Hz, 1H), 8.62-8.57 (m, 2H), 8.06 (td, J = 1.8, 7.7 Hz, 1H), 7.89 (d, J = 8.4 Hz, 1H), 7.58-7.54 (m, 1H), 7.21 (d, J = 8.6 Hz, 1H), 4.04 (s, 3H)

[0163] To the solution of 5-bromo-8-methoxy-2-(pyridin-2-yl)quinoline (2.5 g, 7.9 mmol) and phenylboronic acid (1.2 g, 9.9 mmol) in mixture of toluene (25 ml), ethanol (15ml), and water (8 ml), K2CO3(6.6 g, 47.6 mmol) and bis(triphenylphosphine)palladium(II) dichloride (278 mg, 0.4 mmol, 5% mol) were added under a nitrogen atmosphere. The mixture was heated overnight at reflux and then extracted with dichloromethane, washed with brine, and dried over MgSO4. The crude product was used without purification in the next step.

[0164] To a pressure vessel23(2.2g, 7 mmol) was added and dissolved in 20 ml of hydrobromic acid (48%). The mixture was stirred at 160°C overnight. Next, the reaction was allowed to cool, and water was added. The obtained yellow solid was filtered, suspended in dichloromethane and washed with NaHCO3. The combined organic layers were dried over MgSO4and concentrated in vacuo. The crude product was dissolved in dichloromethane, added petroleum ether and light brown solid was obtained (0.84 g, 40%).1H NMR (400 MHz, DMSO-d6) 9.90 (s, 1H), 9.15-9.14 (d, J = 7.9 Hz, 1H), 8.73-8.72 (m, 1H), 8.58 (d, J = 8.9 Hz, 1H), 8.34 (d, J = 9.0 Hz, 1H), 8.02 (td, J = 1.8, 7.8 Hz, 1H), 7.55-7.43 (m, 7H), 7.22 (d, J = 7.8 Hz, 1H)

[0165] To the solution of derivatives 5-phenyl-2-(pyridin-2-yl)quinolin-8-ol24(350 mg, 1.17 mmol) in 10 ml of anhydrous dichloromethane sodium hydroxide was added (47 mg, 1.17 mmol) under a nitrogen atmosphere. The mixture was stirred at room temperature for 24 hours. The precipitate was filtered, washed with dichloromethane and dried in vacuo. Orange solid25(190 mg, 51%) was stored under an argon atmosphere and above P2O5.1H NMR (700 MHz, DMSO-d6) 8.61 (d, J = 4.6 Hz, 1H), 8.31 (d, J = 8.0 Hz, 1H), 8.24 (d, J = 8.8 Hz, 1H), 8.07 (d, J = 8.9 Hz, 1H), 7.90 (td, J = 1.7, 7.7 Hz, 1H), 7.44-7.38 (m, 5H), 7.27-7.24 (m, 1H), 7.17 (d, J = 8.3 Hz, 1H), 6.43 (d, J = 8.3 Hz, 1H)

[0166] 5-bromo-8-methoxy-2-(pyridin-2-yl)quinoline21(315 mg, 1.0 mmol, 1.0 eq), pyrrolidine (85 mg, 1.2 mmol, 1.2 eq), sodium tert-butoxide (384 mg, 4 mmol, 4 eq), (±)-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene (131 mg, 0.21 mmol, 21% mol) and tris(dibenzylideneacetone)dipalladium(0) (92 mg, 0.1 mmol, 10% mol) were dissolved in toluene (3 ml). After that, the solution was heated to 100oC overnight. After this time, the mixture was extracted with dichloromethane, washed with brine, and dried over MgSO4. The crude product was purified via flash column chromatography eluting with 9:1 dichloromethane:ethyl acetate to the desired product as a light orange solid (230 mg, 75%) was obtained. NMR confirmed the structure.

[0167] To a pressure vessel 8-methoxy-2-(pyridin-2-yl)-5-(pyrrolidin-1-yl)quinoline27(2.2g, 7.2 mmol) was added and dissolved in 25 ml of hydrobromic acid (48%). The mixture was stirred at 160°C overnight. Next, the reaction was allowed to cool, and water was added. The obtained yellow solid was filtered, suspended in dichloromethane and washed with NaHCO3. The combined organic layers were dried over MgSO4and concentrated in vacuo. The crude product was purified via flash column chromatography eluting with 95:5 dichloromethane:ethyl acetate to the desired product as a light yellow solid 0.88 g, 42%) was obtained.1H NMR (400 MHz, DMSO-d6) 9.23 (s, 1H), 9.09-9.06 (m, 1H), 8.74-8.72 (m, 1H), 8.64 (d, J = 8.9 Hz, 1H), 8.54 (d, J = 8.9 Hz, 1H), 8.00 (td, J = 1.8, 7.9 Hz, 1H), 7.51-7.48 (m, 1H), 7.02 (s, 1H), 3.20-3.17 (m, 4H), 1.97-1.93 (m, 4H)

[0168] To the solution of derivatives 2-(pyridin-2-yl)-5-(pyrrolidin-1-yl)quinolin-8-ol28(880 mg, 3.02 mmol) in 30 ml of anhydrous dichloromethane sodium hydroxide (121 mg, 3.02 mmol) was added under a nitrogen atmosphere. The mixture was stirred at room temperature for 24 hours. The precipitate was filtered, washed with dichloromethane and dried in vacuo. A yellow solid29(680 mg, 72%) was stored under an argon atmosphere and above P2O5.1H NMR (700 MHz, DMSO-d6) 8.62 (d, J = 4.6 Hz, 1H), 8.39-8.35 (m, 2H), 8.08 (d, J = 8.8 Hz, 1H), 7.90 (td, J = 1.8, 7.7 Hz, 1H), 7.40-7.37 (m, 1H), 7.00 (d, J = 8.5 Hz, 1H), 6.30 (d, J = 8.4 Hz, 1H), 2.98-2.95 (m, 4H), 1.90-1.87 (m, 4H)

[0169] 5-bromo-8-methoxy-2-(pyridin-2-yl)quinoline21(0.5 g, 1.59 mmol) was dissolved in 10 ml of anhydrous THF under a nitrogen atmosphere at -80°C. t-Butyllithium (1.0 ml of 1.6 M solution in pentane) was added slowly. The solution was stirred at -78°C for two hours and then gently warmed to room temperature and stirred overnight. The resulting mixture was quenched with ca. 200 ml of ice water and dichloromethane. The organic layer was separated, washed with 2M HCl and dried over MgSO4. The crude product was purified via flash column chromatography eluting with dichloromethane to produce30as a light-yellow solid (0.2 g, 43%).1H NMR (400 MHz, DMSO-d6) 8.83 (d, J = 4.8 Hz, 1H), 8.65 (d, J = 8.5 Hz, 1H), 8.55-8.58 (m, 2H), 8.12 (t, J = 1.7, 7.5 Hz, 1H), 7.95 (d, J = 8.2 Hz, 1H), 7.65-7.7.68 (m, 1H), 7.23 (d, J = 8.4 Hz, 1H), 4.04 (s, 3H), 1.35 (s, 9H)

[0170] To a pressure vessel 5-(tert-butyl)-8-methoxy-2-(pyridin-2-yl)quinoline30(150 mg, 0.68 mmol) was added and dissolved in 3 ml of hydrobromic acid (48%). The mixture was stirred at 160°C overnight. Then, the reaction was allowed to cool, and water was added. The obtained yellow solid was filtered, suspended in dichloromethane, and washed with NaHCO3. The combined organic layers were dried over MgSO4and concentrated in vacuo. The crude solid was purified via HPLC eluting with 9:1 dichloromethane:ethyl acetate to give a light-yellow solid of31(100 mg, 53%).1H NMR (400 MHz, DMSO-d6) 9.57 (s, 1H), 9.13 (d, J = 7.8 Hz, 1H), 8.68 (d, J = 8.8 Hz, 1H), 8.45 (d, J = 8.7 Hz, 1H), 8.10 (t, J = 7.8 Hz, 1H), 7.75 (m, 1H), 7.31 (t, J = 7.5 Hz, 1H), 1.36 (s, 9H)

[0171] To the solution of 5-(tert-butyl)-2-(pyridin-2-yl)quinolin-8-ol31(100 mg, 0.36 mmol) in 3 ml of anhydrous dichloromethane sodium hydroxide (15 mg, 0.36 mmol) was added under a nitrogen atmosphere. The mixture was stirred at room temperature for 24 hours. Hexane was added to form the precipitate. Solid was filtered, washed with hexane and dried in vacuo. The orange solid32(90 mg, 84%) was stored under an inert atmosphere.1H NMR (400 MHz, DMSO-d6) 8.56 (d, 1H, J = 4.8 Hz), 8.41 (d, J = 7.7 Hz, 1H), 8.24 (d, J = 8.6 Hz, 1H), 8.18 (d, J = 8.8 Hz, 1H), 8.00 (d, J = 8.0 Hz, 1H), 7.89 (t, J = 7.9 Hz, 1H), 7.13 (t, J = 7.4 Hz, 1H), 1.40 (s, 9H)

[0172] 2.9. The general procedure for obtainingCompounds42-45

[0173] 2.10. The procedure for obtainingCompounds36-45

[0174] Compound35was synthesised according to Scheme 2 (General procedure for obtaining compound3a-h). The general procedure for obtaining compounds36and37is the following:

[0175] Solution of concentrated HNO3(5 ml) in glacial acetic acid (45 ml) was added to the solution of 8-methoxy-2-(pyridin-2-yl)quinoline35(5.0 g, 21.2 mmol) in 10 ml acetic anhydride at 0°C. The mixture was stirred overnight at room temperature. Next, water was added and then extracted with dichloromethane, washed with brine and dried over MgSO4. The crude product was purified via flash column chromatography eluting with 95:5 dichloromethane:ethyl acetate to the desired isomers378-methoxy-7-nitro-2-(pyridin-2-yl)quinoline(1.5 g, 25%) and 8-methoxy-5-nitro-2-(pyridin-2-yl)quinoline36(2.40 g, 40%) and as a yellow solid were obtained37.1H NMR (400 MHz, DMSO-d6) 8.80-8.78 (m, 1H), 8.73-8.62 (m, 3H), 8.08 (td, J= 1.8, 7.8 Hz, 1H), 8.00-7.92 (m, 2H), 7.59-7.56 (m, 1H), 4.43 (s, 1H)361H NMR (400 MHz, DMSO-d6) 9.19 (d, J = 9.3 Hz, 1H), 8.82 (d, J = 9.2 Hz, 1H), 8.79-8.77 (m, 1H), 8.61-8.58 (m, 2H), 8.06 (td, J = 1.9, 7.8 Hz, 1H), 7.58-7.55 (m, 1H), 7.40 (d, J = 9.0 Hz, 1H), 4.18 (s, 1H)

[0176] 388-methoxy-2-(pyridin-2-yl)quinolin-5-amine

[0177] 10% Pd / C (300 mg) was added to a solution of 8-methoxy-5-nitro-2-(pyridin-2-yl)quinoline36(3 g, 10.7 mmol) in a mixture of EtOH:THF (20 ml:60ml). The inside air was replaced with H2(balloon) by three vacuum / H2cycles. The reaction mixture was stirred at room temperature until the TLC monitoring indicated the complete consumption of the starting material. Then, the reaction mixture was passed through a celite pad. The reaction mixture was extracted with dichloromethane, washed with brine and the solvent was removed under reduced pressure. The crude product was purified via flash column chromatography eluting with 9:1 dichloromethane:ethyl acetate to the desired product as a yellow solid of38(2.3 g, 86%).1H NMR (400 MHz, DMSO-d6) 8.73 (d, J = 5.1 Hz, 1H), 8.62-8.57 (m, 2H,), 8.42 (d, J = 8.8 Hz, 1H), 8.00 (td, J = 1.8, 7.7 Hz, 1H) 7.51-7.47 (m, 1H), 7.05 (d, J = 8.2 Hz, 1H), 6.71 (d, J = 8.3 Hz, 1H), 5.44 (s, 2H), 3.93 (s, 3H)

[0178] 398-methoxy-2-(pyridin-2-yl)quinolin-7-amine

[0179] 10% Pd / C (150 mg) was added to a solution of 8-methoxy-7-nitro-2-(pyridin-2-yl)quinoline37(1.5 g, 5.3 mmol) in a mixture of EtOH:THF (10 ml:30 ml). The inside air was replaced with H2(balloon) by three vacuum / H2cycles. The reaction mixture was stirred at room temperature until the TLC monitoring indicated the complete consumption of the starting material. Then, the reaction mixture was passed through a celite pad. The reaction mixture was extracted with dichloromethane, washed with brine and the solvent was removed under reduced pressure. The crude product was purified via flash column chromatography eluting with dichloromethane to the desired product as a yellow solid of39(1.2 g, 99%).1H NMR (400 MHz, DMSO-d6) 8.73-8.71 (m, 1H), 8.62-8.60 (m, 1H,), 8.22-8.18 (m, 2H), 8.00 (td, J = 1.8, 7.7 Hz, 1H) 7.50-7.46 (m, 2H), 7.15 (d, J = 8.7 Hz, 1H), 5.55 (s, 2H), 4.07 (s, 3H)

[0180] Solution of NaNO2(1.2 eq) in H2O was added to the solution of amine38or39(1 eq) in 2M HCl at 0°C. The mixture was stirred at 0°C for 10 minutes. After that time, the mixture was added dropwise to the solution of NaBF4(2 eq) in H2O at 0°C. The reaction was stirred overnight at room temperature. The precipitate was formed, next washed with diethyl ether and filtered. The solid was suspended in 1,2-dichlorobenzene and stirred at 180°C overnight. Next, water was added and then extracted with dichloromethane, washed with brine and dried over MgSO4.

[0181] 405-fluoro-8-methoxy-2-(pyridin-2-yl)quinoline

[0182] Prepared from 8-methoxy-2-(pyridin-2-yl)quinolin-5-amine38(3.0 g, 11.95 mmol. The crude product was purified by column chromatography (silica gel, dichloromethane / ethyl acetate 3:1, v / v), yellow solid of40(1.02 g, yield 33%).1H NMR (400 MHz, DMSO-d6) 8.73 (d, J = 4.8 Hz, 1H), 8.66 (d, J = 8.8 Hz, 1H), 8.60 (d, J = 8.1 Hz, 1H), 8.56 (d, J = 8.8 Hz, 1H), 8.04 (td, J = 1.8, 7.7 Hz, 1H), 7.55-7.52 (m, 1H), 7.38 (t, J = 9.0 Hz, 1H), 7.20-7.17 (m, 1H), 4.02 (s, 3H),19H NMR (376 MHz, DMSO-d6) -134 ppm

[0183] 417-fluoro-8-methoxy-2-(pyridin-2-yl)quinoline

[0184] Prepared from 8-methoxy-2-(pyridin-2-yl)quinolin-7-amine39(1.2 g, 4.8 mmol). The crude product was purified by column chromatography (silica gel, dichloromethane / ethyl acetate 3:1, v / v), yellow solid of41(0.45 g, yield 37%).1H NMR (400 MHz, DMSO-d6) 9.25 (d, J = 4.5 Hz, 1H), 8.72 (d, J = 8.6 Hz, 1H), 8.55-8.50 (m, 2H), 8.10 (td, J = 1.8, 7.5 Hz, 1H), 7.75-7.70 (m, 1H), 7.54-7.49 (m, 2H), 4.55 (s, 3H),19F NMR (376 MHz, DMSO-d6) -129 ppm

[0185] To a pressure vessel compound42or43was added and the mixture was dissolved in hydrobromic acid (48%). The mixture was stirred at 160°C overnight. Next, the reaction was allowed to cool, and water was added. The obtained yellow solid was filtered, suspended in dichloromethane and washed with NaHCO3. The combined organic layers were dried over MgSO4and concentrated in vacuo.

[0186] 425-fluoro-2-(pyridin-2-yl)quinolin-8-ol

[0187] Prepared from 5-fluoro-8-methoxy-2-(pyridin-2-yl)quinoline40(0.9 g, 3.54 mmol). The crude product was purified by column chromatography (silica gel, petroleum ether / ethyl acetate 3:1, v / v), yellow solid of42(520 mg, yield 61%).1H NMR (700 MHz, DMSO-d6) 9.80 (s, 1H), 9.08 (d, J = 7.9 Hz, 1H), 8.76-8.75 (m, 1H), 8.68 (d, J = 8.8 Hz, 1H), 8.56 (d, J = 8.9 Hz, 1H), 8.03 (td, J = 1.9, 7.7 Hz, 1H), 7.54-7.52 (m, 1H), 7.33-7.30 (m, 1H), 7.10-7.08 (m, 1H)

[0188] 437-fluoro-2-(pyridin-2-yl)quinolin-8-ol

[0189] Prepared from 7-fluoro-8-methoxy-2-(pyridin-2-yl)quinoline41(1 g, 3.93 mmol). The crude product was purified by column chromatography (silica gel, petroleum ether / ethyl acetate 3:1, v / v), yellow solid of43(450 mg, yield 48%).1H NMR (700 MHz, DMSO-d6) 9.92 (s, 1H), 9.35 (d, J = 7.8 Hz, 1H), 8.78-8.75 (m, 1H), 8.56 (d, J = 8.9 Hz, 1H), 8.45 (d, J = 8.8 Hz, 1H), 8.10 (td, J = 1.9, 7.7 Hz, 1H), 7.65-7.62 (m, 1H), 7.45-7.42 (m, 1H), 7.15-7.10 (m, 1H)

[0190] To the solution of derivatives of42and43(1 eq.) in 5 ml of anhydrous dichloromethane sodium hydroxide (1 eq.) was added under a nitrogen atmosphere. The mixture was stirred at room temperature for 24 hours. The precipitate was filtered, washed with dichloromethane and dried in vacuo.

[0191] 44sodium 5-fluoro-2-(pyridin-2-yl)quinolin-8-olate

[0192] Prepared from 5-fluoro-2-(pyridin-2-yl)quinolin-8-ol42(202 mg, 0.84 mmol). Orange solid of44(190 mg, 87%) was stored under an argon atmosphere and above P2O5.1H NMR (700 MHz, DMSO-d6) 8.66 (d, J = 4.7 Hz, 1H), 8.58-8.57 (m, 1H), 8.28-8.22 (m, 2H), 7.93 (td, J = 1.9, 7.7 Hz, 1H), 7.43-7.41 (m, 1H), 7.00 (t, J = 9.9 Hz, 1H), 6.30-6.28 (m, 1H)

[0193] 45sodium 7-fluoro-2-(pyridin-2-yl)quinolin-8-olate

[0194] Prepared from 7-fluoro-2-(pyridin-2-yl)quinolin-8-ol43(250 mg, 1.04 mmol). Orange solid of45(200 mg, 76%) was stored under an argon atmosphere and above P2O5.1H NMR (700 MHz, DMSO-d6) 8.96 (d, J = 4.78 Hz, 1H), 8.41-8.38 (m, 1H), 8.20-8.18 (m, 2H), 7.83 (td, J = 1.8, 7.7 Hz, 1H), 7.48-7.45 (m, 1H), 7.20 (t, J = 9.8 Hz, 1H), 6.56-6.58 (m, 1H)

[0195] 2.11. Procedure for obtainingCompounds48-51

[0196] 2.12. General procedure for obtainingCompounds48a - b

[0197] 2-methoxybenzene-1,3-diamine46(1.0 eq.) was dissolved in a mixture of HCl (6 M, 10 ml) and water (10 ml), after the addition of α, β ‑unsaturated aldehydes47a-b(1.1 eq.), the mixture was stirred for 1 h at room temperature. Then, toluene (10 mL) was added, and the reaction mixture was heated at reflux temperature and stirred overnight. After cooling down to room temperature, the organic layer was removed. The aqueous layer was neutralized with a solution of 10% NaOH, the solution was extracted with dichloromethane and the organic layer was washed with and brine, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel to give the corresponding derivatives48a-b.

[0198] 48a8-methoxy-2-phenylquinolin-7-amine

[0199] Prepared from 2-methoxybenzene-1,3-diamine46(1.38 g, 10 mmol, 1.0 eq.) and cinnamaldehyde47a(1.45 g, 11 mmol, 1.1 eq.). The crude product was purified by column chromatography (silica gel, dichloromethane / ethyl acetate 95:5, v / v), white solid (1.23 g, yield 49%).1H NMR (DMSO-d6, 700 MHz) 8.33-8.30 (m, 3H), 8.11 (t, J = 2.5 Hz, 1H), 7.55-7.48 (m, 3H),7.03 (d, J = 8.6 Hz, 1H), 6.98 (d, J = 4.2 Hz, 1H), 5.27 (s, 2H), 3.83 (s, 3H)

[0200] 48b2-(cyclopenta-1,3-dien-1-yl)-8-methoxyquinolin-7-amine

[0201] Prepared from 2-methoxybenzene-1,3-diamine46(1.38 g, 10 mmol, 1.0 eq.) and (E)-3-(cyclopenta-1,3-dien-1-yl)acrylaldehyde47b(1.32 g, 11 mmol, 1.1 eq.). The crude product was purified by column chromatography (silica gel, dichloromethane / ethyl acetate 9:1, v / v), white solid (1.12 g, yield 47%).1H NMR (DMSO-d6, 700 MHz) 8.52-8.49 (m, 1H), 8.10-8.12 (m, 1H), 7.49 (m, 1H), 6.96-6.90 (m, 2H), 6.52-6.45 (m, 2H), 5.55 (s, 2H), 3.10 (s, 3H), 3.09 (d, J = 3.2 Hz, 2H)

[0202] 2.13. General procedure for obtainingCompounds49a-d

[0203] 8-methoxy-2-phenylquinolin-7-amine48(1.20 g, 4.8 mmol, 1.0 eq) was dissolved in a mixture of HCl (6 M, 5 ml) and water (5 ml), after the addition of (E)-3-(pyridin-2-yl)acrylaldehyde49(0.70 g, 5.3 mmol, 1.1 eq), the mixture was stirred for 1 h at room temperature. Then, toluene (5 ml) was added, and the reaction mixture was heated at reflux temperature and stirred overnight. After cooling down to room temperature, the organic layer was removed. The aqueous layer was neutralized with solution of 10% NaOH, the solution was extracted with dichloromethane and the organic layer was washed with and brine, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel eluting with 95:5 dichloromethane:ethyl acetate to give the corresponding 10-methoxy-2-phenyl-8-(pyridin-2-yl)pyrido[3,2-g]quinoline50(0.75 g, 43%) as a pale-yellow solid.

[0204] 49a10-methoxy-2-phenyl-8-(pyridin-2-yl)pyrido[3,2-g]quinoline

[0205] Prepared from 8-methoxy-2-phenylquinolin-7-amine48a(2.50 g, 10 mmol, 1.0 eq) and (E)-3-(pyridin-2-yl)acrylaldehyde47c(1.46 g, 11 mmol, 1.1 eq). The crude product was purified by column chromatography (silica gel, dichloromethane / ethyl acetate 9:1, v / v), light yellow solid (1.55 g, yield 43%).1H NMR (DMSO-d6, 700 MHz) 9.18-9.13 (m, 1H), 8.71 (dd, J = 4.5, 6.9 Hz, 1H), 8.45-8.50 (m, 1H), 8.35-8.28 (m, 3H), 8.20 (m, 1H), 7.70 (m, 1H), 7.60-7.45 (m, 3H), 7.28 (dt, J = 2.4, 7.4 Hz, 1H), 7.24 (dt, J = 2.5, 7.5 Hz, 1H), 7.05 (s, 1H), 3.87 (s, 3H)

[0206] 49b2-(cyclopenta-1,3-dien-1-yl)-10-methoxy-8-(pyridin-2-yl)pyrido[3,2-g]quinoline

[0207] Prepared from 2-(cyclopenta-1,3-dien-1-yl)-8-methoxyquinolin-7-amine48b(2.38 g, 10 mmol, 1.0 eq) and (E)-3-(pyridin-2-yl)acrylaldehyde47c(1.46 g, 11 mmol, 1.1 eq). The crude product was purified by column chromatography (silica gel, dichloromethane / ethyl acetate 9:1, v / v), light yellow solid (1.65 g, yield 47%). 1H NMR (DMSO-d6, 700 MHz) 9.25 (d, J = 5.2 Hz 1H), 8.55-8.42 (m, 4H), 7.75 (t, J = 2.5 Hz, 1H), 7.43-7.25 (m, 4H), 6.50-6.43 (m, 2H), 3.11 (s, 3H), 3.07 (d, J = 3.1 Hz, 2H)

[0208] 49c10-methoxy-2-phenyl-8-(1H-pyrrol-2-yl)pyrido[3,2-g]quinoline

[0209] Prepared from 8-methoxy-2-phenylquinolin-7-amine48a(2.51 g, 10 mmol, 1.0 eq) and (E)-3-(1H-pyrrol-2-yl)acrylaldehyde47d(1.33 g, 11 mmol, 1.1 eq). The crude product was purified by column chromatography (silica gel, dichloromethane / ethyl acetate 95:5, v / v), light yellow solid (1.59 g, yield 45%). 1H NMR (DMSO-d6, 700 MHz) 12.11 (s, 1H), 8.72-8.69 (m, 1H), 8.45 (t, J = 3.2 Hz, 1H), 8.30-8.25 (m, 2H), 7.59-7.50 (m, 4H), 7.25 (d, J = 3,2 Hz, 1H), 7.11 (s, 1H), 6.89 (d, J = 3.0 Hz, 1H), 6.45 (d, J = 3.1 Hz, 1H), 6.25 (m, 1H), 3.62 (s, 3H)

[0210] 49d2-(cyclopenta-1,3-dien-1-yl)-8-(1H-pyrrol-2-yl)pyrido[3,2-g]quinolin-10-ol

[0211] Prepared from 2-(cyclopenta-1,3-dien-1-yl)-8-methoxyquinolin-7-amine48b(2.38 g, 10 mmol, 1.0 eq) and (E)-3-(1H-pyrrol-2-yl)acrylaldehyde47d(1.34 g, 11 mmol, 1.1 eq). The crude product was purified by column chromatography (silica gel, dichloromethane / ethyl acetate 9:1, v / v), light yellow solid (1.71 g, yield 50%).1H NMR (DMSO-d6, 700 MHz) 12.2 (s, 1H), 8.62-8.52 (m, 2H), 7.50-7.45 (m, 2H), 7.26 dt, J = 2.7, 7.8 Hz, 1H), 7.18 (s, 1H), 6.96-6.90 (m, 1H), 6.60-6.50 (m, 3H), 6.15-6.10 (m, 1H), 3.85 (s, 3H), 3.1 (d, J = 3.7 Hz, 2H)

[0212] 2.14. General procedure for obtainingCompounds50a - d

[0213] To a pressure vessel derivative50a - dwas added and dissolved in 10 ml of hydrobromic acid (48%). The mixture was stirred at 160°C overnight. Next, the reaction was allowed to cool, and water was added. The obtained yellow solid was filtered, suspended in dichloromethane and washed with NaHCO3. The combined organic layers were dried over MgSO4and concentrated in vacuo. The crude product was purified via flash column chromatography to the desired products50a - d

[0214] 50a2-phenyl-8-(pyridin-2-yl)pyrido[3,2-g]quinolin-10-ol

[0215] Prepared from 10-methoxy-2-phenyl-8-(pyridin-2-yl)pyrido[3,2-g]quinoline49a. The crude solid was purified via MPLC (silica gel) eluting with 95:5 dichloromethane:ethyl acetate to give pale yellow crystals (1.30 g, 87%).1H NMR (DMSO-d6, 700 MHz) 9.75 (s, 1H), 9.20-9.12 (m, 1H), 8.75 (d, J = 2.4 Hz, 1H), 8.55-8.30 (m, 5H), 7.95 (t, J = 7.4 Hz, 1H), 7.60-7.50 (m, 3H), 7.31-7.22 (m, 3H)

[0216] 50b2-(cyclopenta-1,3-dien-1-yl)-8-(pyridin-2-yl)pyrido[3,2-g]quinolin-10-ol

[0217] Prepared from 2-(cyclopenta-1,3-dien-1-yl)-10-methoxy-8-(pyridin-2-yl)pyrido[3,2-g]quinoline49b. The crude solid was purified via MPLC (silica gel) eluting with 9:1 dichloromethane:ethyl acetate to give pale yellow crystals (1.36 g, 86%).1H NMR (DMSO-d6, 700 MHz) 9.71 (s, 1H), 9.18 (d, J = 5.3 Hz 1H), 8.58-8.43 (m, 4H), 7.95 (t, J = 2.9 Hz, 1H), 7.62-7.42 (m, 4H), 6.53-6.47 (m, 2H), 3.08 (d, J = 3.3 Hz, 2H)

[0218] 50c2-phenyl-8-(1H-pyrrol-2-yl)pyrido[3,2-g]quinolin-10-ol

[0219] Prepared from 10-methoxy-2-phenyl-8-(1H-pyrrol-2-yl)pyrido[3,2-g]quinoline49c. The crude solid was purified via MPLC (silica gel) eluting with 9:1 dichloromethane:ethyl acetate to give pale yellow crystals (1.33 g, 90%).1H NMR (DMSO-d6, 700 MHz) 11.95 (s, 1H), 9.85 (s, 1H), 8.69-8.65 (m, 1H), 8.41 (t, J = 3.8 Hz, 1H), 8.25-8.20 (m, 2H), 7.57-7.49 (m, 4H), 7.21 (d, J = 4.1 Hz, 1H), 7.05 (s, 1H), 6.80 (d, J = 3.6 Hz, 1H); 6.40 (d, J = 3.1 Hz, 1H), 6.20 (m, 1H)

[0220] 50d2-(cyclopenta-1,3-dien-1-yl)-8-(1H-pyrrol-2-yl)pyrido[3,2-g]quinolin-10-ol

[0221] Prepared from 2-(cyclopenta-1,3-dien-1-yl)-8-(1H-pyrrol-2-yl)pyrido[3,2-g]quinolin-10-ol49d. The crude solid was purified via MPLC (silica gel) eluting with 4:1 dichloromethane:ethyl acetate to give yellow crystals (1.46 g, 89%).1H NMR (DMSO-d6, 700 MHz) 12.10 (s, 1H), 9.55 (s, 1H), 8.62-8.59 (m, 2H), 7.62-7.52 (m, 2H), 7.24-7.18 (m, 2H), 6.92 (t, J = 2.8 Hz, 1H), 6.52-6.42 (m, 3H), 6.1 (t, J = 1.8 Hz, 1H), 3.1 (d, J = 3.7 Hz, 2H)

[0222] 2.15. General procedure for obtainingCompounds 51a - d

[0223] To the solution of derivative50a - d(1 eq) in 10 ml of anhydrous dichloromethane metal hydroxide (1 eq) was added under a nitrogen atmosphere. The mixture was stirred at room temperature for 24 hours. The precipitate was filtered, washed with dichloromethane and dried in vacuo. Products51a - dwere stored under an argon atmosphere and above P2O5.

[0224] 51alithium 2-phenyl-8-(pyridin-2-yl)pyrido[3,2-g]quinolin-10-olate

[0225] Prepared from 2-phenyl-8-(pyridin-2-yl)pyrido[3,2-g]quinolin-10-ol50a. A yellow solid was obtained 1.04 g (81%).1H NMR (DMSO-d6, 700 MHz) 9.22-9.15 (m, 1H), 8.79 (d, J = 3.2 Hz, 1H), 8.62-8.37 (m, 5H), 8.19 (t, J = 4.2 Hz, 1H), 7.76-7.68 (m, 3H), 7.42-7.30 (m, 3H)

[0226] 51blithium 2-(cyclopenta-1,3-dien-1-yl)-8-(pyridin-2-yl)pyrido[3,2-g]quinolin-10-olate

[0227] Prepared from 2-(cyclopenta-1,3-dien-1-yl)-8-(pyridin-2-yl)pyrido[3,2-g]quinolin-10-ol50b. A yellow solid was obtained 1.12 g (81%).1H NMR (DMSO-d6, 700 MHz) 9.20 (d, J = 5.6 Hz 1H), 8.59-8.47(m, 4H), 8.11 (t, J = 3.5 Hz, 1H), 7.65-7.47 (m, 4H), 6.57-6.49 (m, 2H), 3.08 (d, J = 3.9 Hz, 2H)

[0228] 51ccaesium 2-phenyl-8-(1H-pyrrol-2-yl)pyrido[3,2-g]quinolin-10-olate

[0229] Prepared from 2-phenyl-8-(1H-pyrrol-2-yl)pyrido[3,2-g]quinolin-10-ol50c. A yellow solid was obtained 1.52 g (82%).1H NMR (DMSO-d6, 700 MHz) 11.90 (s, 1H), 8.71-8.68 (m, 1H), 8.45 (t, J = 3.2 Hz, 1H), 8.28-8.22 (m, 2H), 7.60-7.52 (m, 4H), 7.24 (d, J = 3.2 Hz, 1H), 7.21 (s, 1H), 6.89 (d, J = 3.2 Hz, 1H), 6.48 (d, J = 2.3 Hz, 1H), 6.28 (m, 1H)

[0230] 51drubidium 2-(cyclopenta-1,3-dien-1-yl)-8-(1H-pyrrol-2-yl)pyrido[3,2-g]quinolin-10-olate

[0231] Prepared from 2-(cyclopenta-1,3-dien-1-yl)-8-(1H-pyrrol-2-yl)pyrido[3,2-g]quinolin-10-ol50d. A yellow solid was obtained 1.55 g (84%).1H NMR (DMSO-d6, 700 MHz) 12.08 (s, 1H), 8.67-8.62 (m, 2H), 7.68-7.57 (m, 2H), 7.27 (m, 2H), 6.97 (t, J = 2.8 Hz, 1H), 6.58-6.48 (m, 3H), 6.3 (t, J = 1.8 Hz, 1H), 3.20 (d, J = 3.7 Hz, 2H)

[0232] 2.16. General procedure for obtainingCompound 55

[0233] Glycerol56(5 ml, 68 mmol), concentrated sulfuric acid (2 ml), nitrobenzene (2 ml) and amine52(2.51 g, 10 mmol) were sequentially added in a pressure tube. The mixture was heated at 140°C for about 60 min. The mixture was cooled and poured into ice-water. The solid was collected by filtration and purified by column chromatography eluting with dichloromethane to give a light-yellow solid of 10-methoxy-2-(pyridin-2-yl)pyrido[3,2-g]quinoline53(1.12 g, 39%).1H NMR (DMSO-d6, 700 MHz) 9.18 (d, J = 4.9 Hz, 1H), 8.96 (d, J = 5.5 Hz, 1H), 8.50-8.55 (m, 2H), 8.29 (m, 1H), 8.18 (m, 1H), 7.74 (t, J = 2.5, 7.5 Hz, 1H), 7.62 (dt, J = 1.9, 7.4 Hz, 1H), 7.23 (dt, J = 2.4, 7.5 Hz, 1H), 7.13 (s, 1H), 3.83 (s,3H)

[0234] To a pressure vessel 10-methoxy-2-(pyridin-2-yl)pyrido[3,2-g]quinoline53(1.10 g, 3.83 mmol) was added and dissolved in 10 ml of hydrobromic acid (48%). The mixture was stirred at 160°C overnight. Next, the reaction was allowed to cool, and water was added. The obtained yellow solid was filtered, suspended in dichloromethane and washed with NaHCO3. The combined organic layers were dried over MgSO4and concentrated in vacuo. The crude product was purified via flash column chromatography eluting with 4:1 dichloromethane:ethyl acetate to the desired product, 2-(pyridin-2-yl)pyrido[3,2-g]quinolin-10-ol54as light yellow oil(0.72 g, 68%).1H NMR (DMSO-d6, 700 MHz) 9.58 (s, 1H), 9.18 (d, J = 5.6 Hz, 1H), 8.98 (d, J = 5.4 Hz, 1H), 8.50-8.55 (m, 2H), 8.32-8.38 (m, 2H), 7.74 (t, J = 2.4, 7.6 Hz, 1H), 7.62-7.60 (m, 1H), 7.23-7.26 (m, 2H)

[0235] To the solution of 2-(pyridin-2-yl)pyrido[3,2-g]quinolin-10-ol54(0.65 g, 2.38 mmol, 1 eq) in 6 ml of anhydrous dichloromethane rubidium hydroxide (244 mg, 2.38 mmol, 1 eq) was added under a nitrogen atmosphere. The mixture was stirred at room temperature for 24 hours. The precipitate was filtered, washed with dichloromethane and dried in vacuo. Rubidium 2-(pyridin-2-yl)pyrido[3,2-g]quinolin-10-olate55(0.715 g, 84%) was stored under an argon atmosphere and above P2O5.1H NMR (DMSO-d6, 700 MHz) 9.18 (d, J = 5.4 Hz, 1H), 8.98 (d, J = 5.6 Hz, 1H), 8.50-8.55 (m, 2H), 8.32-8.38 (m, 2H), 7.74 (t, J = 2.5, 7.6 Hz, 1H), 7.62 (t, J = 2.4, 7.8 Hz, 1H), 7.23-7.26 (m, 2H)

[0236] 2.17. General procedure for obtainingCompound 63

[0237] Solution of concentrated HNO3(5 ml) in glacial acetic acid (45 ml) was added to the solution of 8-methoxy-2-(1H-pyrrol-2-yl)quinoline58(4.0 g, 17.8 mmol) in 15 ml of acetic anhydride at 0°C. The mixture was stirred overnight at room temperature. Next, water was added and then extracted with dichloromethane, washed with brine and dried over MgSO4. The crude product was purified via flash column chromatography eluting with dichloromethane to the desired 8-methoxy-7-nitro-2-(1H-pyrrol-2-yl)quinoline59(2.12 g, 44%) as a yellow solid was obtained.1H NMR (DMSO-d6) 10.75 (s, 1H), 8.52-8.25 (d, J = 8.2 Hz, 1H), 8.20-8.02 (d, J = 8.5 Hz, 1H), 7.95-7.80 (d, J = 8.0 Hz, 1H), 7.50-7.35 (m, 1H), 7.30-6,90 (d, J = 8.2 Hz, 1H), 6.75-6.35 (m, 2H), 3.92 (s, 3H)

[0238] 10% Pd / C (250 mg) was added to a solution of 8-methoxy-7-nitro-2-(1H-pyrrol-2-yl)quinoline59(2.0 g, 7.43 mmol) in the mixture of EtOH:THF (10 ml:30ml). The inside air was replaced with H2(balloon) by three vacuum / H2cycles. The reaction mixture was stirred at room temperature until the TLC monitoring indicated the complete consumption of the starting material. Then, the reaction mixture was passed through a celite pad. The reaction mixture was extracted with dichloromethane, washed with brine and the solvent was removed under reduced pressure. The crude product was purified via flash column chromatography eluting with 9:1 dichloromethane:ethyl acetate to the desired product as a yellow solid of 8-methoxy-2-(1H-pyrrol-2-yl)quinolin-7-amine60(1.55 g, 87%).1H NMR (DMSO-d6) 10.82 (s, 1H), 8.42-8.25 (d, J = 7.5 Hz, 1H), 8.15-8.00 (d, J = 8.3 Hz, 1H), 7.75-7.50 (d, J = 8.5 Hz, 1H), 7.35-6.5 (m, 4H), 5.55 (s, 2H), 3.90 (s, 3H)

[0239] Glycerol56(5 ml, 68 mmol), concentrated sulfuric acid (2 ml), nitrobenzene (2 ml) and amine60(1.55 g, 6.48 mmol) were sequentially added in a pressure tube. The mixture was heated at 140°C for about 60 min. The mixture was cooled and poured into ice-water. The solid was collected by filtration and purified by column chromatography eluting with dichloromethane to give a light-yellow solid of 10-methoxy-2-(1H-pyrrol-2-yl)pyrido[3,2-g]quinoline61(1.12 g, 63%).1H NMR (DMSO-d6) 10.85 (s, 1H), 8.60-8.42 (d, J = 8.0 Hz, 1H), 8.35-8.10 (d, J = 8.3 Hz, 1H), 8.00-7.85 (d, J = 8.2 Hz, 1H), 7.65-7.45 (d, J = 8.5 Hz, 1H), 7.40-7.20 (d, J = 8.0 Hz, 1H), 7.10-6.90 (d, J = 7.9 Hz, 1H), 6.80-6.35 (m, 3H), 3.85 (s, 3H)

[0240] To a pressure vessel 10-methoxy-2-(1H-pyrrol-2-yl)pyrido[3,2-g]quinoline61(1.10 g, 4.07 mmol) was added and dissolved in 12 ml of hydrobromic acid (48%). The mixture was stirred at 160°C overnight. Next, the reaction was allowed to cool, and water was added. The obtained yellow solid was filtered, suspended in dichloromethane and washed with NaHCO3. The combined organic layers were dried over MgSO4and concentrated in vacuo. The crude product was purified via flash column chromatography eluting with 1:1 dichloromethane:ethyl acetate to the desired product, 2-(1H-pyrrol-2-yl)pyrido[3,2-g]quinolin-10-ol62as light-yellow oil(0.85 g, 80%).1H NMR (DMSO-d6) 10.83 (s, 1H), 9.60 (s, 1H), 8.65-8.44 (d, J = 8.2 Hz, 1H), 8.30-8.15 (d, J = 8.0 Hz, 1H), 8.00-7.80 (d, J = 8.0 Hz, 1H), 7.65-7.35 (d, J = 8.2 Hz, 1H), 7.25-7.10 (d, J = 8.2 Hz, 1H), 7.00-6.80 (d, J = 7.9 Hz, 1H), 6.75-6.30 (m, 3H)

[0241] To the solution of 2-(1H-pyrrol-2-yl)pyrido[3,2-g]quinolin-10-ol62(0.85 g, 3.25 mmol, 1 eq) in 10 ml of anhydrous dichloromethane, caesium hydroxide (0.488 g, 3.25 mmol, 1 eq) was added under a nitrogen atmosphere. The mixture was stirred at room temperature for 24 hours. The precipitate was filtered, washed with dichloromethane and dried in vacuo. Caesium 2-(1H-pyrrol-2-yl)pyrido[3,2-g]quinolin-10-olate63(1.05 g, 81%) was stored under an argon atmosphere and above P2O5.1H NMR (DMSO-d6) 10.90 (s, 1H), 8.55-8.40 (d, J = 8.0 Hz, 1H), 8.30-8.10 (d, J = 8.5 Hz, 1H), 8.00-7.85 (d, J = 8.5 Hz, 1H), 7.55-7.38 (d, J = 7.9 Hz, 1H), 7.27-7.10 (d, J = 8.0 Hz, 1H), 7.00-6.90 (d, J = 8.1 Hz, 1H), 6.80-6.45 (m, 3H)

[0242] 2.18. General procedure for obtainingCompounds 73 - 75

[0243] To the solution of 2-nitronaphthalen-1-ol64(5.68 g, 30.00 mmol, 1.0 eq) and potassium carbonate(12.40 g, 90.00 mmol, 3.0 eq) in anhydrous dimethylformamide (50mL), benzyl bromide65(14.40 g, 84.00 mmol, 2.8 eq) was added under a nitrogen atmosphere. The mixture was heated at 60°C for 4h, after cooling to room temperature, triethylamine (10ml) was added and mixed for 15 minutes. Then, transferred to a separation funnel and treated with 2M hydrochloric acid until neutral pH, followed by extraction using an excess amount of ethyl acetate. After drying over anhydrous MgSO4the mixture was concentrated and obtained a dark red oil, 1-(benzyloxy)-2-nitronaphthalene66(7.42g, 88%).1H NMR (DMSO-d6, 700 MHz), 8.55 (d, J = 8.2 Hz, 1H), 8.25 (dd, J = 2.0, 7.5 Hz, 1H), 7.95-7.45 (m, 4H),7.40-7.05 (m, 5H), 5.35 (s, 2H)

[0244] To the solution of 1-(benzyloxy)-2-nitronaphthalene66(4.45 g, 14.98 mmol, 1.0 eq) in ethanol (80 ml) and water (25 ml), iron (8.36 g, 149.80 mmol, 10.0 eq) and ammonium chloride (4.81g, 89.90 mmol, 6.0 eq) were added, under a nitrogen atmosphere. The mixture was heated overnight at reflux. After cooling to room temperature, the crude mixture was filtered through celite, and washed with THF (200 ml). The mixture was concentrated, followed by extraction using an excess amount of ethyl acetate. After drying over anhydrous MgSO4the mixture was concentrated and purified via flash column chromatography eluting with 99:1 petroleum ether:ethyl acetate to the desired product as a dark red oil, 1-(benzyloxy)naphthalen-2-amine67(3.40 g, 91%).1H NMR (DMSO-d6, 700 MHz) 8.10-7.75 (m, 4H), 7.45-7.18 (m, 5H), 7.10 (dd, J = 2.0, 7.5 Hz, 1H), 6.91 (d, J = 8.1 Hz, 1H), 5.38 (s, 2H), 5.05 (s, 2H)

[0245] To the solution of 1-(benzyloxy)naphthalen-2-amine67(800 mg, 3.02 mmol, 1.0 eq) in anhydrous THF (15 ml), di-tert-butyl dicarbonate (1.32 g, 6.04 mmol, 2.0 eq) and potassium carbonate (1.25 g, 9.05 mmol, 3.0 eq) were added, under a nitrogen atmosphere. The mixture was heated overnight at reflux. After cooling to room temperature, the mixture was concentrated followed by extraction using an excess amount of ethyl acetate. After drying over anhydrous MgSO4the mixture was concentrated and purified via flash column chromatography eluting with 99:1 petroleum ether:ethyl acetate to the desired product as a dark red oil,tert-butyl-(1-(benzyloxy)naphthalen-2-yl)carbamate (900 mg, 82%).1H NMR (DMSO-d6, 700 MHz) 8.95 (s, 1H), 8.00-7.60 (m, 4H), 7.45 (d, J = 8.5 Hz, 1H), 7.39-7.25 (m, 5H), 7.20 (d, J = 8.1 Hz, 1H), 5.25 (s, 2H), 1.45 (s, 9H)

[0246] The solution oftert-butyl-(1-(benzyloxy)naphthalen-2-yl)carbamate68(1.04 g, 2.98 mmol, 1.0 eq) in anhydrous THF (10 ml) was cooled to 0°C. Next,N-bromosuccinimide (640 mg, 3.57 mmol, 1.2 eq) was slowly added under a nitrogen atmosphere. The mixture was stirred overnight allowed to warm to room temperature. The mixture was concentrated followed by extraction using an excess amount of ethyl acetate. After drying over anhydrous MgSO4the mixture was concentrated and purified via flash column chromatography eluting with 99:1 petroleum ether:ethyl acetate to the desired product as a dark red oil,tert-butyl-(1-(benzyloxy)-3-bromonaphthalen-2-yl)carbamate69(578 mg, 45%).1H NMR (DMSO-d6, 700 MHz) 8.92 (s, 1H), 8.00-7.66 (m, 4H), 7.40 (s, 1H), 7.37-7.22 (m, 5H), 5.23 (s, 2H), 1.47 (s, 9H)

[0247] The solution oftert-butyl-(1-(benzyloxy)-3-bromonaphthalen-2-yl)carbamate69(700 mg, 1.21 mmol, 1.0 eq) in anhydrous THF (5 ml) was cooled to -78°C. Next, 2.5M nBuLi in hexane (388 mg, 6.05 mmol, 5.0 eq) was slowly added under a nitrogen atmosphere. After 15 minutes, dimethylformamide (442 mg, 6.05 mmol, 5.0 eq) was slowly added and the mixture was stirred for 1h allowed to warm up. Next, 2M hydrochloric acid (3 ml) was added and stirring was continued for 15 minutes. Then, it was transferred to a separation funnel and treated with 10% NaOH until neutral pH, followed by extraction using an excess amount of ethyl acetate. After drying over anhydrous MgSO4the mixture was concentrated and purified via flash column chromatography eluting with 99:1 petroleum ether:ethyl acetate to the desired product as a dark red oil,tert-butyl-(1-(benzyloxy)-3-formylnaphthalen-2-yl)carbamate70(340 mg, 75%).1H NMR (DMSO-d6, 700 MHz) 9.99 (s, 1H), 8.90 (s, 1H), 8.05 (s, 1H), 7.96-7.57 (m, 4H), 7.42-7.26 (m, 5H), 5.25 (s, 2H), 1.47 (s, 9H)

[0248] To the solution oftert-butyl-(1-(benzyloxy)-3-formylnaphthalen-2-yl)carbamate70(330 mg, 0.848 mmol, 1.0 eq) in DCM (5 ml), trifluoroacetic acid (2 ml) was added. The mixture was stirred for 2h at room temperature. The crude mixture after concentrated, was transferred to a separation funnel and treated with saturated NaHCO3until neutral pH, followed by extraction using an excess amount of ethyl acetate. After drying over anhydrous MgSO4the mixture was concentrated and purified via flash column chromatography eluting with 95:5 dichloromethane:ethyl acetate to the desired product as a dark red oil, 3-amino-4-(benzyloxy)-2-naphthaldehyde71(200 mg, 85%).1H NMR (DMSO-d6, 700 MHz) 10.05 (s, 1H), 7.95-7.49 (m, 4H), 7.35-7.22 (m, 5H), 7.27 (s, 1H), 5.25 (s, 2H), 5.10 (s, 2H)

[0249] 2.19. General procedure for obtainingCompounds 73a - b

[0250] 3-amino-4-(benzyloxy)-2-naphthaldehyde71(1 eq) in absolute ethanol, acetyl derivatives72a-b(1.0 eq), and potassium hydroxide (2 eq) were added into a pressure bottle and kept stirring at 120°C overnight. Then, the crude mixture was allowed to cool down to room temperature and concentrated using a rotary evaporator. The concentrated crude product was dissolved in dichloromethane at ambient temperature. Then, transferred to a separation funnel and treated with 1M hydrochloric acid until neutral pH, followed by extraction using an excess amount of dichloromethane. After drying over anhydrous MgSO4the mixture was concentrated and obtained the expected intermediates73a-b.

[0251] 73a10-(benzyloxy)-2-(pyridin-2-yl)benzo[g]quinoline

[0252] Prepared from 3-amino-4-(benzyloxy)-2-naphthaldehyde71(200 mg, 0.72 mmol, 1.0 eq), 1-(pyridin-2-yl)ethan-1-one72a(87 mg, 0.72 mmol, 1.0 eq).The crude product was purified by a column chromatography (silica gel, dichloromethane), dark red oil, (190 mg, 73%).1H NMR (DMSO-d6, 700 MHz) 8.75 (d, J = 4.8 Hz, 1H), 8.52 (d, J = 5.5 Hz, 1H), 7.92-7.56 (m, 5H), 7.82 (s, 1H),7.50 (s, 1H), 7.42-7.23 (m, 5H), 7.42 (ddd, J = 1.9, 4.4, 7.5, 4.4 Hz, 1H), 7.25 (d, J = 4.9 Hz, 1H), 5.30 (s, 2H)

[0253] 73b10-(benzyloxy)-2-(1H-pyrrol-2-yl)benzo[g]quinolone

[0254] Prepared from 3-amino-4-(benzyloxy)-2-naphthaldehyde71(1.0 g, 3.60 mmol, 1.0 eq), 1-(1H-pyrrol-2-yl)ethan-1-one72b(0.393 g, 3.60 mmol, 1.0 eq).The crude product was purified by column chromatography (silica gel, dichloromethane:ethyl acetate 99:1, v / v), orange oil, (0.85 g, 67%).1H NMR (DMSO-d6, 700 MHz) 11.00 (s, 1H), 8.55 (d, J = 5.2 Hz, 1H), 7.90-7.50 (m, 6H), 7.43-7.25 (m, 5H), 6.90-6.40 (m, 3H), 5.32 (s, 2H)

[0255] 2.20. General procedure for obtainingCompounds74a - b

[0256] To the solution of benzyl derivatives73a - b(1.0 eq) in mixture of THF and DMSO (2:1), potassiumtert-butoxide (10 eq) was added and saturated with oxygen. After stirring at room temperature for 2h. Then, the crude mixture was extracted with dichloromethane. After drying over anhydrous MgSO4the mixture was concentrated and purified via flash column chromatography eluting with ethyl acetate to the desired products74a - b.

[0257] 74a2-(pyridin-2-yl)benzo[g]quinolin-10-ol

[0258] Prepared from 10-(benzyloxy)-2-(pyridin-2-yl)benzo[g]quinolone73a(190 mg, 0.52 mmol, 1.0 eq) and potassium tert-butoxide (582 mg, 5.20 mmol, 10 eq). The crude product was purified by column chromatography (silica gel, dichloromethane:ethyl acetate 99:1, v / v), orange solid (110 mg, 78%).1H NMR (DMSO-d6, 700 MHz) 10.35 (s,1H), 8.65 (d, J = 4.9 Hz, 1H), 7.90 (d, J = 7.0 Hz, 1H), 7.82 (s, 1H), 7.80-7.47 (m, 5H), 7.39 (ddd, J = 1.9, 4.8, 7.9 Hz, 1H), 7.30 (ddd, J = 1.9, 4.8, 7.9 Hz, 1H), 7.10 (s, 1H)

[0259] 74b2-(1H-pyrrol-2-yl)benzo[g]quinolin-10-ol

[0260] Prepared from 10-(benzyloxy)-2-(1H-pyrrol-2-yl)benzo[g]quinolone73b(0.82g, 2.34 mmol, 1.0 eq) and potassium tert-butoxide (2.63 g, 23.4 mmol, 10 eq). The crude product was purified by column chromatography (silica gel, dichloromenthane:ethyl acetate 9:1, v / v), orange solid (0.50 g, 82%).1H NMR (DMSO-d6, 700 MHz) 10.90 (s, 1H),9.5 (s, 1H), 8.2 (d, J = 8.0 Hz,1H), 8.0-7.35 (m, 6H), 7.00-6.85 (m, 1H), 6.60-6.50 (m, 1H), 6.35-6.15 (m, 1H)

[0261] 2.21. General procedure for obtainingCompound75a - b

[0262] To the solution of derivatives74a - b(1 eq) in 10 ml of anhydrous dichloromethane metal hydroxide (1 eq) was added under a nitrogen atmosphere. The mixture was stirred at room temperature for 24 hours. The precipitate was filtered, washed with dichloromethane and dried in vacuo. Products75a - bwere stored under an argon atmosphere and above P2O5.

[0263] 75apotassium 2-(pyridin-2-yl)benzo[g]quinolin-10-olate

[0264] Prepared from 2-(pyridin-2-yl)benzo[g]quinolin-10-ol74a. Orange solid was obtained (100 mg, 88%).1H NMR (DMSO-d6, 700 MHz) 8.60 (d, J = 5.2 Hz, 1H), 7.87 (d, J = 7.8 Hz, 1H), 7.82 (s, 1H), 7.80-7.45 (m, 5H), 7.32 (ddd, J = 1.8, 4.7, 7.8 Hz, 1H), 7.30 (d, J = 4.8 Hz, 1H), 7.10 (s, 1H)

[0265] 75bpotassium 2-(1H-pyrrol-2-yl)benzo[g]quinolin-10-olate

[0266] Prepared from 2-(1H-pyrrol-2-yl)benzo[g]quinolin-10-ol74b.Orange solid was obtained 0.537 g (94%).1H NMR (DMSO-d6, 700 MHz)10.95 (s, 1H), 8.2 (d, J = 8.0 Hz; 1H), 8.0-7.29 (m, 6H), 6.90-6.85 (m, 1H), 6.57-6.48 (m, 1H), 6.35-6.10 (m, 1H)

[0267] Example 3:A diode comprisingCompound 1

[0268] The electroluminescent device comprises an anode, a cathode, andCompound 1andCompound 2disposed between the anode and cathode. The electroluminescent device, i.e. diode, can comprise an electrode 1 and electrode 2 that can be made of aluminium (Al) and ITO. The diode can comprise at least one layer, i.e. electron transport layer comprisingCompound 1andCompound 2and / or an electron injection layer comprisingCompound 1andCompound 2. Constructed exemplary diodes 1 (reference), 2, and 3 comprise ITO, HATCN as HIL, PCBBiF as HTL, PCzAc as EBL, 2CzPy: 20% 4CzIPN as an emissive layer, DDBFT as HBL and BPPB:Compound1(2:1) as ETL. Reference diode 1 comprises Liq as EIL and diodes 2 and 3 compriseCompound 1as EIL. Constructed exemplary diodes 4 (reference), 5, 6 and 7 comprise ITO, HATCN as HIL, PCBBiF as HTL, DPFAn:5% BD-06 as an emissive layer, and BPPB:Compound1(2:1) as ETL. Reference diode 4 comprises Liq as EIL and diodes 5 - 7 compriseCompound 1andCompound 2as EIL. Exemplary electroluminescent diodes are presented inTable 1.

[0269] Table1.Exemplary electroluminescent diodes according to the inventionNo. of diodeAnode layerHILHTLEBLEmissive layer(weight ratio)HBLETL (weight ratio)EILCathode layer1. Ref.ITOHATCNPCBBiFPCzAc2CzPy: 20% 4CzIPNDDBFTBPPB:Comp. 1(2:1)Liq1.5 nmAl2.ITOHATCNPCBBiFPCzAc2CzPy: 20% 4CzIPNDDBFTBPPB:Comp. 1(2:1)Comp. 1 1.0 nmAl3.ITOHATCNPCBBiFPCzAc2CzPy: 20% 4CzIPNDDBFTBPPB:Comp. 1(2:1)Comp. 1 1.5 nmAl4.Ref.ITOHATCNPCBBiF-DPFAn:5% BD-06-BPPB:Comp. 1(2:1)Liq1.5 nmAl5.ITOHATCNPCBBiF-DPFAn:5% BD-06-BPPB:Comp. 1(2:1)Comp. 1 1.0 nmAl6.ITOHATCNPCBBiF-DPFAn:5% BD-06BPPB:Comp. 1(2:1)Comp. 1 1.5 nmAl7.ITOHATCNPCBBiF-DPFAn:5% BD-06-BPPB:Comp. 2(2:1)Comp. 2 1.5 nmAl

[0270] Abbreviations: ITO - indium tin oxide; HIL - hole injection layer; HTL - hole transport layer; EBL - electron blocking layer; HBL - hole blocking layer; ETL - electron transport layer; EIL - electron injection layer; Comp. - compound.

[0271] The compounds used in exemplary diodes presented inTable 1are:

[0272] Compound 1andCompound 2are characterized by high crystallinity, confirmed by XRD measurements (Table 3), and strong π-π interactions, both π-π stacking and edge-to-face, which lead to well-ordered films in the EIL and ETL and thus enhance electron transport and electron injection efficiency in the device, leading to a significantly longer lifetime of the electroluminescent device. No significant defects of the crystal structure are present, thus no local temperature increase occurs in the ETL and EIL and no electron traps appear. This has a significant effect on the prolonged lifetime of the device. Reference diode 1 comprising Liq as an electron injection material exhibits a shorter lifetime (LT90= 16 h) than analogous diodes 2 (LT90= 56 h) and 3 (LT90= 65 h) comprisingCompound 1as electron injection material. Diodes 5 and 6 comprisingCompound 1as an electron injection material show an even longer lifetime (LT90= 110.2 h and 122.5 h, respectively) than reference diode 4 (LT90= 8 h). At the same time, current-spectral properties (i.e. VON, EQE, C.E., ELmax, FWHM, CIE) of such devices are not significantly changed. Exemplary current-spectral measurements for exemplary electroluminescent diodes are presented in Table 2.

[0273] Table 2.Current-spectral measurements for the diodes according to the inventionNo. of diodeVon@1 cd / m2[V]EQE(max / 5 000cd / m2)[%]C.E.(max / 1 000 cd / m2 / 5 000 cd / m2)[cd / A]ELmax[nm]FWHM[nm]LT90(@1 000nits / 5 000 nits)[h]Colour coordinatesCIE[x / y]1. Ref.3.320.7 / 18.459.2 / - / 52.753991- / 160.38 / 0.572.3.216.1 / 15.346.0 / - / 44.154594- / 560.39 / 0.563.3.218.2 / 16.251.6 / - 46.454497- / 650.39 / 0.574. Ref.2.677.96 / 7.727.22 / 7.17 / -457458 / -0.14 / 0.125.2.678.03 / 7.727.36 / 7.17 / -45744110.2 / -0.14 / 0.136.2.678.51 / 8.377.62 / 7.58 / -45744122.5 / -0.14 / 0.127.2.6712.2 / 8.810.8 / 7.7 / -457453 / -0.14 / 0.12

[0274] Abbreviations: Ref. - reference diode; Von- turn-on voltage; EQE - external quantum efficiency; C.E. - current efficiency; ELmax- a maximum wavelength of the diode emission; FWHM - full width at half maximum; LT90- operational lifetime of diode, wherein luminance decreases to 90% of the original; CIE - CIE 1931 colour spaces.

[0275] InTable 3crystallographic parameters ofCompound 1are presented. The single-crystal XRD method confirms a monoclinic crystal system and Cc space group ofCompound 1with low R1 parameter (0.0878). R(int)factor is low, thus confirming high crystallinity. No significant structural defects are confirmed by Δρ max parameter equal to 0.489, which is less than one electron. This characteristic influences the prolonged device lifetime.

[0276] Table 3.Crystallographic parameters ofCompound 1T[K]Λ[Å]Crystal systemSpace groupUCDInd. refl.Ref.R indicesΔρ max, Δρ max [eÅ-3]1001.54184ÅmonoclinicCca=15.9006 Åα=90°b=15.1699 Åβ=95.095°c=19.9635 Åγ=90°6460R(int)=0.0244Full-matrix least-squares on F2R1=0.08780.489 and-0.795

[0277] Abbreviations: T - temperature of the measurement; Λ - wavelength; UCD - unit cell dimensions; Ind. refl. - independent reflections; R(int)- reliability factor; Ref. - refinement method; Δρ max, Δρ max - largest difference peak and hole.

[0278] Example 4:A diode comprising the electron injecting layer and electron transport layer according to the invention

[0279] The electroluminescent device comprises an anode, a cathode, and the electron injecting layer according to the invention disposed between the anode and cathode. The electroluminescent device, i.e. diode, can comprise an electrode 1 and electrode 2 that can be made of aluminium (Al) and ITO. The diode can comprise at least one layer, i.e. electron injecting layer comprising the compound according to the invention. The constructed exemplary diodes and the reference diode (1 Ref.) comprise ITO, HATCN as HIL, PCBBiF as HTL, PCzAc as EBL, DPFAn:5% BD-06 as an emissive layer and BPPB as ETL. Reference diode 1 comprises Liq as EIL and exemplary diodes comprise exemplary compounds according to the invention as EIL. Exemplary electroluminescent diodes are presented inTable 4.

[0280] Table 4.Exemplary diodes comprising according to the invention  No. of diode Anode layer HIL HTL EML ETL EIL Cathode layer Ref 1 ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Liq Al 8ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 5c Al 9ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 5d Al 10ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 5e Al 11ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 5f Al 12ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 6Al 13ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 14a Al 14ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 15Al 15ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 16Al 16ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 14b Al 17 ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 19 Al 18ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 25 Al 19 ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 29 Al 20 ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 32 Al 21 ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 44 Al 22 ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 45 Al 23ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 2Al 24ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 39Al 25ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 63Al 26ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 75aAl 27ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 75bAl 28ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 51dAl 29ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 58Al 30ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 24Al 31ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 51aAl

[0281] The diodes comprising the electron injecting layer according to the invention exhibit a similar emission maximum in a blue region. Low turn-on voltage (2.66 - 2.70 V) indicates uniform electron injection characteristics. The highest EQE is observed for Compound14areaching 11.3%, followed by14b, 19, and45with EQE exceeding 10%. Compound14aalso demonstrates the longest operational stability with LT90of 123 hours, followed by6and44, showing lifetimes of 83 and 82 hours, respectively, and Compounds19and14b, with LT90of 90 and 81 hours. When compared with reference diodes, all exemplary diodes according to the invention exhibit prolonged lifetime. The current-spectral measurement for the diodes comprising the electron injecting layer according to the invention is presented inTable 5.

[0282] Table 5.Current-spectral measurements for the diodes according to the invention No. of diode Von@1cd / m2[V] EQE (max / 1000 cd / m2) [%] CE (max / 1000 cd / m2) [cd / A] ELmax [nm] LT90(@1000 nits) [h] Colour coordinates CIE[x / y] 8 2.688.9 / 7.58.0 / 6.8457220.13; 0.129  2.689.3 / 8.58.4 / 7.7457600.13; 0.1310  2.709.6 / 9.18.6 / 8.245764 0.14; 0.14112.67 10.6 / 10.3 9.6 / 9.4 457 - 0.13, 0.13 122.668.5 / 8.17.7 / 7.3457830.13; 0.1313 2.67 11.3 / 10.8 10.3 / 9.8 457 123 0.13, 0.13 142.689.0 / 6.17.7 / 5.2457180.14; 0.14152.679.5 / 7.88.6 / 7.1457370.13; 0.1316 2.6710.2 / 9.8 8.7 / 8.345781  0.14; 0.1217  2.66 10.4 / 10.0 9.4 / 9.0457900.14; 0.1318 2.689.5 / 9.18.6 / 8.2456720.13; 0.1119 2.678.7 / 8.27.8 / 7.4457700.14; 0.1220  2.678.4 / 7.57.6 / 6.8457550.14; 0.1421 2.689.8 / 9.48.8 / 8.5457820.14; 0.1222  2.6810.1 / 9.5 9.1 / 8.6457680.14; 0.14232.679.6 / 8.17.7 / 7.3457400.13; 0.13242.669.9 / 9.28.9 / 8.3457290.14; 0.13252.6710.1 / 9.69.1 / 8.6457580.13; 0.13262.709.7 / 8.98.7 / 8.0457360.14; 0.14272.6810.1 / 9.49.1 / 8.5457520.14; 0.13282.6810.3 / 9.79.3 / 8.7457400.13; 0.13292.679.7 / 9.08.7 / 8.1457210.13; 0.13302.679.7 / 9.18.2 / 7.7457380.14; 0.14312.6810.2 / 9.88.7 / 8.3457800.14; 0.13

[0283] The electroluminescent device comprises an anode, a cathode, andthe electron injecting and / or electron transport layer according to the inventiondisposed between the anode and cathode. The electroluminescent device, i.e. diode, can comprise an electrode 1 and electrode 2 that can be made of aluminium (Al) and ITO. The diode can comprise at least one layer, i.e. electron transport layer comprisingthe compoundand / or an electron injection layer comprisingthe compound. Constructed exemplary diodes and thereference diode (1 Ref.)comprise ITO, HATCN as HIL, PCBBiF as HTL and DPFAn:5% BD-06 as an emissive layer. Reference diode 1 comprises Liq as EIL and BPPB:Liq as ETL, and exemplary diodes comprise BPPB:Compound (2:1) as ETL and the compound according to the invention as EIL. Exemplary diodes are presented inTable 6.

[0284] Table 6.Exemplary diodes according to the invention No. of diode Anode layer HIL HTL EML ETL EIL Cathode layer Ref 1 ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB:Liq (1:1) Liq Al 32ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 5c (2:1) Compound 5c Al 33 ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 5d (2:1) Compound 5d Al 34 ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 5e (2:1) Compound 5e Al 35 ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 5f (2:1) Compound 5f Al 36ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 6 (2:1) Compound 6Al37ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 14a (2:1) Compound 14a Al 38ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 15 (2:1) Compound 15Al39ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 16 (2:1) Compound 16Al40 ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 14b (2:1) Compound 14b Al 41ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 19 (2:1) Compound 19 Al 42ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 25 (2:1) Compound 25 Al 43ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 29 (2:1) Compound 29 Al 44 ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 32 (2:1) Compound 32 Al 45 ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 44 (2:1) Compound 44 Al 46ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB Compound 45 (2:1) Compound 45 Al 47ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 2Compound 2Al48ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 39Compound 39Al 49ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 63Compound 63Al 50ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 75aCompound 75aAl 51ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 75bCompound 75bAl52ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 51d51dAl 53ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 58Compound 58Al 54ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 24Compound 24Al 55ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB: Compound 51aCompound 51aAl

[0285] The diodes comprising the electron injecting layer and electron transport layer according to the invention continue to exhibit consistent optical properties exhibiting an emission maximum in the blue region. Low turn-on voltage (2.66 - 2.70 V) indicates uniform electron injection and transport characteristics. The highest EQE is observed forCompound 14areaching 10.8%, followed by51a,24, 45 and 5fwith EQE exceeding 10%. Compound14aalso demonstrates the longest operational stability with LT90of 173 hours, followed by5e,6,14b,19, 44,75b,58and51awith LT90over 100 hours. When compared with reference diodes and with exemplary diodes comprising the electron injecting layer according to the invention (Table 5) all exemplary diodes comprising both layers according to the invention exhibit prolonged lifetime. The current-spectral measurement for the diodes according to the invention are presented inTable 7.

[0286] Table 7.Current-spectral measurements for the diodes according to the invention No. of diode Von@1cd / m2[V] EQE (max / 1000 cd / m2) [%] CE (max / 1000 cd / m2) [cd / A] ELmax [nm] LT90(@1000 nits) [h] Colour coordinates CIE[x / y] 32 2.688.0 / 6.87.2 / 6.1457280.13; 0.1333 2.688.4 / 7.78.0 / 7.3457780.13; 0.1334  2.678.6 / 8.28.2 / 7.8457120 0.13; 0.14352.67 10.3 / 10.0 8.7 / 8.6 457 93 0.14, 0.12 362.677.7 / 7.37.3 / 6.94571040.13; 0.1337 2.67 10.8 / 10.4 9.3 / 8.8 457 173 0.14, 0.12 382.688.1 / 5.57.2 / 4.9457250.14; 0.14392.679.0 / 7.48.2 / 6.7457480.13; 0.1340 2.679.5 / 9.1 8.3 / 7.9457125 0.14; 0.1441 2.66 9.6 / 9.0 8.5 / 8.04571080.14; 0.1442 2.668.6 / 8.27.7 / 7.3457920.13; 0.14432.677.8 / 7.47.4 / 7.1457860.14; 0.1344 2.677.6 / 6.87.2 / 6.4457650.13; 0.14452.689.0 / 8.57.9 / 7.54571120.14; 0.1446  2.6710.5 / 9.7 9.1 / 8.4457920.14; 0.14472.679.2 / 8.37.4 / 6.6457840.13; 0.13482.669.4 / 8.77.1 / 5.7457720.14; 0.13492.679.7 / 9.28.6 / 8.3457750.14; 0.13502.678.4 / 7.76.3 / 4.4457480.14; 0.14512.689.7 / 9.08.7 / 8.14571040.13; 0.13522.689.8 / 8.78.8 / 7.8457980.13; 0.12532.678.7 / 8.58.4 / 8.24571340.13; 0.13542.6710.2 / 9.59.2 / 8.3457750.13; 0.14552.6810.0 / 9.48.1 / 7.64571020.13; 0.13

[0287] The electroluminescent device comprises an anode, a cathode, andthe electron transport layer according to the inventiondisposed between the anode and cathode. The electroluminescent device, i.e. diode, can comprise an electrode 1 and electrode 2 that can be made of aluminium (Al) and ITO. The diode can comprise at least one layer, i.e. electron transport layer comprisingthe compound. Constructed exemplary diodes and thereference diode (1 Ref.)comprise ITO, HATCN as HIL, PCBBiF as HTL and DPFAn:5% BD-06 as an emissive layer and Liq as EIL. Reference diode 1 comprises BPPB:Liq (1:1) as ETL, and exemplary diodes comprise the Compound according to the invention as ETL. Exemplary diodes are presented inTable 8.

[0288] Table 8.Exemplary diodes according to the invention No. of diode Anode layer HIL HTL EML ETL EIL Cathode layer Ref 1 ITO HATCN PCBBiF DPFAn:5% BD-06 BPPB:Liq (1:1) Liq Al 56ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 5cLiq Al 57ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 5dLiq Al 58ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 5eLiq Al 59ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 5fLiq Al 60ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 6Liq Al61ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 14aLiq Al 62ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 15Liq Al63ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 16Liq Al64ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 14bLiq Al 65ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 19Liq Al 66ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 25Liq Al 67ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 29Liq Al 68ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 32Liq Al 69ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 44Liq Al 70 ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 45Liq Al 71ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 2Liq Al72ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 39Liq Al 73ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 63aLiq Al 74ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 75aLiq Al 75ITO HATCN PCBBiF DPFAn:5% BD-06 75bLiq Al76ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 51dLiq Al 77ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 58Liq Al 78ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 24Liq Al 79ITO HATCN PCBBiF DPFAn:5% BD-06 Compound 51aLiq Al

[0289] The diodes comprising the electron transport layer according to the invention continue to exhibit consistent optical properties exhibiting an emission maximum in the blue region. Higher turn-on voltage (3.50 - 3.74 V) is observed. The highest EQE is observed forCompound 14areaching 7.3%, followed by5d,14b and 19with EQE exceeding 6%. Compound2demonstrates the longest operational stability with LT90of 22 hours, followed by63a,45 and 75awith LT9020 hours or longer. When compared with reference diodes and with exemplary diodes comprising the electron injecting layer according to the invention and diodes comprising both electron injecting and transport layers (Table5 and Table 7) all exemplary diodes comprising electron transport according to the invention exhibit shorter lifetime. The current-spectral measurement for the diodes according to the invention are presented inTable9.

[0290] Table 9.Current-spectral measurements for the diodes according to the invention No. of diode Von@1cd / m2[V] EQE (max / 1000 cd / m2) [%] CE (max / 1000 cd / m2) [cd / A] ELmax [nm] LT90(@1000 nits) [h] Colour coordinates CIE[x / y] 56  3.525.0 / 3.04.5 / 2.746790.15; 0.1457  3.646.2 / 2.85.0 / 2.246720.15; 0.1358  3.594.5 / 2.53.8 / 2.146512 0.15; 0.1559 3.505.2 / 1.93.1 / 1.546550.15, 0.14 603.633.4 / 2.23.1 / 2.0467140.14; 0.1561 3.547.3 / 3.76.6 / 3.3467180.15, 0.14 623.584.5 / 2.03.6 / 1.6467120.14; 0.14633.565.6 / 1.84.5 / 1.646720.15; 0.1464  3.626.1 / 3.4 5.5 / 3.146616 0.15; 0.1465  3.60 6.2 / 2.5 5.6 / 2.2467140.14; 0.14663.535.8 / 1.55.2 / 1.446730.15; 0.15673.624.4 / 2.24.0 / 1.9467130.15; 0.1468  3.614.2 / 2.53.4 / 2.0467110.14; 0.14693.523.2 / 1.32.6 / 0.9467100.15; 0.1570 3.503.4 / 2.0 3.1 / 1.8467200.14; 0.15713.645.0 / 2.14.0 / 1.7467220.14; 0.15723.604.5 / 2.34.1 / 2.146790.16; 0.15733.744.6 / 1.83.7 / 1.4466210.15; 0.13743.673.8 / 2.73.4 / 2.3467200.15; 0.14753.605.6 / 2.05.0 / 1.8467180.15; 0.15763.625.2 / 2.94.2 / 2.3467190.14; 0.14773.484.0 / 1.93.6 / 1.746740.15; 0.15783.494.6 / 1.64.1 / 1.3467120.15; 0.14793.604.3 / 2.83.9 / 2.5467140.14; 0.15

Claims

An electron injecting layer (EIL) or electron transport layer (ETL) comprises a compound according to Formula 1,wherein:M+is Li+, Na+, K+, Rb+, or Cs+;R1- R2, together or independently, are hydrogen, deuterium, halogen, cyano, nitro, hydrazine, hydrazone, C1-C60alkyl, C2-C60alkenyl, C1-C60haloalkanyl, C2-C60haloalkenyl, C2-C60haloalkynyl, C2-C60alkynyl, C1-C60alkoxy group, C3-C60cycloalkyl, C3-C60cycloalkenyl, C1-C60heterocycloalkyl, C1-C60heterocycloalkenyl group, C3-C60cycloalkynyl group, C1-C60heterocycloalkynyl group, C6-C60aryl, C1-C60heteroaryl group, C5-C60aryloxy, C1-C60heteroaryloxy group, C2-C60ether group, C6-C60thioaryl, C1-C60heterothioaryl, C1-C60amino, C1-C60alkylamino, C1-C60dialkylamino, C6-C60arylamino, C6-C60diarylamino, C6-C60heteroarylamino group, C6-C60heterodiarylamino group, C4-C60non-aromatic fused polycyclic group, C1-C60non-aromatic fused heteropolycyclic group or deuterated analogues thereof;HAis, together with the carbon atom explicitly drawn in, a group of Formula 2 or Formula 3:wherein:Q1- Q4, together or independently, are C(R8) or -N;X1- X3, together or independently, C(R8) or -N;Y1is N;Y2is N(R8), O, S, or Se;where the dashed bonds in Formula 2 and Formula 3 denote the linking of this group in Formula 1;R8is hydrogen, deuterium, halogen, cyano, nitro, hydrazine, hydrazone, C1-C60alkyl, C2-C60alkenyl, C2-C60alkynyl, C1-C60haloalkanyl, C2-C60haloalkenyl, C2-C60haloalkynyl, C1-C60alkoxy group, C3-C60cycloalkyl, C3-C60cycloalkenyl, C1-C60heterocycloalkyl, C1-C60heterocycloalkenyl group, C3-C60cycloalkynyl group, C1-C60heterocycloalkynyl group, C6-C60aryl, C1-C60heteroaryl group, C5-C60aryloxy, C1-C60heteroaryloxy group, C2-C60ether group, C6-C60thioaryl, C1-C60heterothioaryl, C1-C60amino, C1-C60alkylamino, C1-C60dialkylamino, C6-C60arylamino, C6-C60diarylamino, C6-C60heteroarylamino group, C6-C60heterodiarylamino group, C4-C60non-aromatic fused polycyclic group, C1-C60non-aromatic fused heteropolycyclic group or deuterated analogues thereof;A is, together with the two carbon atoms explicitly drawn in, a group of Formula 4, Formula 5, Formula 6, or Formula 7:wherein:R3- R7, together or independently, are hydrogen, deuterium, halogen, cyano, nitro, hydrazine, hydrazone, C1-C60alkyl, C2-C60alkenyl, C2-C60alkynyl, C1-C60haloalkanyl, C2-C60haloalkenyl, C2-C60haloalkynyl, C1-C60alkoxy group, C3-C60cycloalkyl, C3-C60cycloalkenyl, C1-C60heterocycloalkyl, C1-C60heterocycloalkenyl group, C3-C60cycloalkynyl group, C1-C60heterocycloalkynyl group, C6-C60aryl, C1-C60heteroaryl group, C5-C60aryloxy, C1-C60heteroaryloxy group, C2-C60ether group, C6-C60thioaryl, C1-C60heterothioaryl, C1-C60amino, C1-C60alkylamino, C1-C60dialkylamino, C6-C60arylamino, C6-C60diarylamino, C6-C60heteroarylamino group, C6-C60heterodiarylamino group, C4-C60non-aromatic fused polycyclic group, C1-C60non-aromatic fused heteropolycyclic group or deuterated analogues thereof;where the dashed bonds in Formula 4, Formula 5, Formula 6 and Formula 7 denote the linking of this group in Formula 1;HBis, together with the carbon atom explicitly drawn in, a group of Formula 8 or Formula 9:wherein:Z1- Z5, together or independently, are C(R9) or N, O, S, Se;Z6-Z8, together or independently, are C(R9) or N;Z9is C(R9)(R10) or N(R9), O, S, Se;R9-R10, together or independently, are hydrogen, deuterium, halogen, cyano, nitro, hydrazine, hydrazone, C1-C60alkyl, C2-C60alkenyl, C2-C60alkynyl, C1-C60alkoxy group, C3-C60cycloalkyl, C3-C60cycloalkenyl, C1-C60heterocycloalkyl, C1-C60heterocycloalkenyl group, C3-C60cycloalkynyl group, C1-C60heterocycloalkynyl group, C6-C60aryl, C1-C60heteroaryl group, C5-C60aryloxy, C1-C60heteroaryloxy group, C2-C60ether group, C6-C60thioaryl, C1-C60heterothioaryl, C1-C60amino, C1-C60alkylamino, C1-C60dialkylamino, C6-C60arylamino, C6-C60diarylamino, C6-C60heteroarylamino group, C6-C60heterodiarylamino group, C4-C60non-aromatic fused polycyclic group, C1-C60non-aromatic fused heteropolycyclic group or deuterated analogues thereof;where the dashed bonds in Formula 8 and Formula 9 denote the linking of this group in Formula 7.The EIL or ETL according to claim 1, wherein the compound according to Formula 1 is selected from Formula 10 - Formula 19:wherein:Y1, Y2, X1- X3, Q1- Q4, Z1- Z9, R1- R10, M+are the same as described in claim 1.The EIL or ETL according to claim 1 or claim 2, wherein the compound according to Formula 1 is selected from:An electroluminescent device comprising an anode, a cathode, and a compound according to Formula 1 disposed between the anode and cathode.The device according to claim 4, wherein the electron injecting layer is according to claim 1 or / and the electron transport layer is according to claim 1.The device according to claim 4 or 5, wherein comprises at least one layer selected from: a hole injection layer, hole transport layer, electron blocking layer, hole blocking layer, and emissive layer.The use of a compound according to Formula 1 as the compound intermediating a transport or injection of electrons in an electroluminescent device.

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