CN116178402A - Boron-containing hydrogenated carbazole organic compound and application thereof - Google Patents

Boron-containing hydrogenated carbazole organic compound and application thereof Download PDF

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CN116178402A
CN116178402A CN202111403739.3A CN202111403739A CN116178402A CN 116178402 A CN116178402 A CN 116178402A CN 202111403739 A CN202111403739 A CN 202111403739A CN 116178402 A CN116178402 A CN 116178402A
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boron
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宋鑫龙
肖志华
何锐锋
宋晶尧
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Abstract

The application discloses a boron-containing hydrogenated carbazole organic compound, a mixture, a composition and an organic electronic device comprising the same, wherein the boron-containing hydrogenated carbazole organic compound has a structure shown as a general formula (1):
Figure DDA0003371996970000011
the boron-containing hydrogenated carbazole organic compound is used in organic electronic devices, particularly used as a luminescent material in a luminescent layer of an organic electronic device, and is used for improving the efficiency and the service life of the organic electronic device.

Description

Boron-containing hydrogenated carbazole organic compound and application thereof
Technical Field
The application relates to the technical field of luminescent materials, in particular to a boron-containing hydrogenated carbazole organic compound, and a mixture, a composition and an organic electronic device comprising the same.
Background
Organic semiconductor materials are synthetically diverse, relatively low in cost to manufacture, and excellent in optical and electrical properties. Organic Light Emitting Diodes (OLEDs) have advantages of wide viewing angle, fast reaction time, low operating voltage, thin panel thickness, etc. in applications of optoelectronic devices such as flat panel displays and illumination, and thus have a wide development potential.
In order to improve the luminous efficiency of the organic light emitting diode, various luminescent material systems based on fluorescence and phosphorescence have been developed. Among them, the organic light emitting diode using the fluorescent material has a characteristic of high reliability, but its internal electroluminescent quantum efficiency is limited to 25% under electrical excitation because the branching ratio of the singlet excited state and the triplet excited state of excitons is 1:3. Organic light emitting diodes using phosphorescent materials have achieved almost 100% internal electroluminescent quantum efficiency, but phosphorescent OLEDs have a Roll-off effect, i.e., the luminous efficiency decreases rapidly with increasing current or brightness, which is particularly disadvantageous for high brightness applications.
To date, conventional phosphorescent materials having practical use values are iridium-and platinum-containing complexes, however, such raw materials are rare and expensive, and the synthesis of the complexes is complicated, so that the cost is quite high. In order to overcome the above problems, adachi proposes the concept of reverse internal conversion, so that high efficiency comparable to phosphorescent OLEDs can be achieved with organic compounds, i.e. without using metal complexes. This concept has been achieved by various combinations of materials, such as: 1) Utilizing a composite excited state material; 2) Thermally excited delayed fluorescence (TADF) materials are utilized. Whereas conventional organic compounds with TADF mostly employ a means of electron donating (Donor) groups to electron withdrawing (accepter) groups, resulting in complete separation of the highest occupied orbital (HOMO) from the lowest unoccupied orbital (LUMO) electron cloud distribution, shrinking the differences (Δest) between the organic compound singlet (S1) and triplet (T1). The performance of the traditional blue light TADF material is still different from that of the phosphorescent luminescent material in terms of efficiency and service life.
Therefore, there is a need to develop new blue light TADF materials to improve the performance of organic electronic devices.
Disclosure of Invention
In view of the above, the present application provides a blue-light fluorescent boron-containing hydrogenated carbazole organic compound, which is used as a novel luminescent material in organic electronic devices, and aims to solve the problems of low luminous efficiency and short service life of organic electronic devices.
The technical scheme of the application is as follows:
a boron-containing hydrogenated carbazole organic compound has a structure shown in a general formula (1):
Figure BDA0003371996950000011
wherein:
n1 is selected from 0, 1, 2 or 3; n2 is selected from 0, 1, 2 or 3; n3 is selected from 0, 1, 2 or 3;
R 1 、R 2 、R 3 each occurrence is independently selected from the group consisting of-D (deuterium), or a linear alkyl group having 1 to 20C atoms, a linear alkoxy group having 1 to 20C atoms, or a linear thioalkoxy group having 1 to 20C atoms, or a branched alkyl group having 3 to 20C atoms, or a branched alkoxy group having 3 to 20C atoms, or a branched thioalkoxy group having 3 to 20C atoms, or a cyclic alkyl group having 3 to 20C atoms, or a cyclic alkoxy group having 3 to 20C atoms, or a cyclic thioalkoxy group having 3 to 20C atoms, or a silyl group, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, or isothiocyanate, hydroxyl, nitro, substituted or unsubstituted amine, -CF 3 -Cl, -Br, -F, -I, or a substituted or unsubstituted alkenyl group having 1 to 20C atoms, or a substituted or unsubstituted aryl group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, or a substituted or unsubstituted aryloxy group having 5 to 60 ring atoms,Or a substituted or unsubstituted heteroaryloxy group having 5 to 60 ring atoms, or a combination of such groups;
adjacent R 1 With or without each other being cyclic;
adjacent R 2 With or without each other being cyclic;
adjacent R 3 With or without each other.
Correspondingly, the application also provides a mixture which comprises the boron-containing hydrogenated carbazole organic compound and at least one organic functional material, wherein the organic functional material is selected from hole injection materials, hole transport materials, electron injection materials, electron blocking materials, hole blocking materials, luminophores, host materials or organic dyes.
Correspondingly, the application also provides a composition which comprises the boron-containing hydrogenated carbazole organic compound or the mixture and at least one organic solvent.
Correspondingly, the application also provides an organic electronic device, which comprises at least one functional layer, wherein the functional layer comprises the boron-containing hydrogenated carbazole organic compound or the mixture, or the functional layer is prepared from the composition.
Compared with the prior art, the boron-containing hydrogenated carbazole organic compound has the following beneficial effects:
the boron-containing hydrogenated carbazole organic compound has the advantages that the hydrogenated carbazole formed by the condensed benzene ring and the six-membered aliphatic ring enables the whole molecular structure to have better conjugation and flatness, the rigidity and stability of organic compound molecules are improved, the introduction of the aliphatic ring further improves the solubility of the molecules, the compound is easier to purify, the purity of the compound is improved, and the purposes of prolonging the luminous efficiency and the service life of the organic electronic device are further achieved. In addition, the boron-containing hydrogenated carbazole organic compound can be used as a blue light guest material, and can improve the luminous efficiency and the service life of an organic electronic device by being matched with a proper host material.
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In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly introduced below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of an organic electronic device according to an embodiment of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, based on the embodiments herein, which are obtained by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present application. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and explanation only and is not intended to limit the present application. In this application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used to generally refer to the upper and lower directions of the device in actual use or operation, and in particular, the directions of the drawings in the drawings. In addition, in the description of the present application, the term "comprising" means "including but not limited to," the term "plurality" means "two or more," and the term "and/or" includes any and all combinations of one or more of the associated listed items. Various embodiments of the present application may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be interpreted as a rigid limitation on the scope of the application. It is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In the present application, aromatic groups, aromatic ring systems have the same meaning and are interchangeable.
In the present application, heteroaromatic groups, heteroaromatic ring systems have the same meaning and can be interchanged.
In the present application, "substituted" means that a hydrogen atom in a substituted group is substituted with a substituent.
In this application, the same substituent, when present multiple times, may be independently selected from different groups. If the general formula contains a plurality of R, R can be independently selected from different groups.
In the present application, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood that the defined group may be substituted with one or more substituents R selected from, but not limited to: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1 to 20C atoms, heterocyclyl containing 3 to 20 ring atoms, aromatic containing 6 to 20 ring atoms, heteroaromatic containing 5 to 20 ring atoms, -NR' R ", silane, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl, and which may be further substituted with substituents acceptable in the art; it is understood that R 'and R "in-NR' R" are each independently selected from, but not limited to: H. deuterium atoms, cyano groups, isocyano groups, nitro groups or halogen groups, alkyl groups containing 1 to 10C atoms, heterocyclic groups containing 3 to 20 ring atoms, aromatic groups containing 6 to 20 ring atoms, heteroaromatic groups containing 5 to 20 ring atoms. Preferably, R is selected from, but not limited to: deuterium atoms, cyano groups, isocyano groups, nitro groups or halogen groups, alkyl groups containing 1 to 10C atoms, heterocyclic groups containing 3 to 10 ring atoms, aromatic groups containing 6 to 20 ring atoms, heteroaromatic groups containing 5 to 20 ring atoms, silane groups, carbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, haloformyl groups, formyl groups, isocyanate groups, thiocyanate groups, isothiocyanate groups, hydroxyl groups, trifluoromethyl groups, and which may be further substituted with substituents acceptable in the art.
In the present application, the "number of ring atoms" means the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below, unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
In the present application, "aryl or aromatic group" means an aromatic hydrocarbon group derived by removing one hydrogen atom on the basis of an aromatic ring compound, and may be a monocyclic aryl group, or a condensed ring aryl group, or a polycyclic aryl group, at least one of which is an aromatic ring system. For example, "substituted or unsubstituted aryl group having 6 to 40 ring atoms" means an aryl group having 6 to 40 ring atoms, preferably a substituted or unsubstituted aryl group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aryl group having 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted aryl group having 6 to 14 ring atoms, and the aryl group is optionally further substituted; suitable examples include, but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluoranthryl, triphenylenyl, pyrenyl, perylenyl, tetracenyl, fluorenyl, perylenyl, acenaphthylenyl and derivatives thereof. It will be appreciated that a plurality of aryl groups may also be interrupted by short non-aromatic units (e.g. <10% of non-H atoms, such as C, N or O atoms), such as acenaphthene, fluorene, or 9, 9-diaryl fluorene, triarylamine, diaryl ether systems in particular should also be included in the definition of aryl groups.
In the present application, "heteroaryl or heteroaromatic group" means that at least one carbon atom is replaced by a non-carbon atom on the basis of an aryl group, which may be an N atom, an O atom, an S atom, etc. For example, "substituted or unsubstituted heteroaryl having 5 to 40 ring atoms" refers to heteroaryl having 5 to 40 ring atoms, preferably substituted or unsubstituted heteroaryl having 6 to 30 ring atoms, more preferably substituted or unsubstituted heteroaryl having 6 to 18 ring atoms, particularly preferably substituted or unsubstituted heteroaryl having 6 to 14 ring atoms, and the heteroaryl is optionally further substituted, suitable examples include, but are not limited to: thienyl, furyl, pyrrolyl, imidazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, triazolyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzothienyl, benzofuranyl, indolyl, carbazolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothiothienyl, furopyrrolyl, furofuranyl, thienofuranyl, benzofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, quinolinyl, isoquinolinyl, phthalazinyl, phenanthridinyl, primary pyridyl, quinazolinyl, quinazolinonyl, dibenzothienyl, dibenzofuranyl, carbazolyl, and derivatives thereof.
In this application, "alkyl" may mean straight, branched, and/or cyclic alkyl. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Phrases containing this term, e.g., "C 1-9 Alkyl "means an alkyl group containing 1 to 9 carbon atoms, which at each occurrence may be, independently of one another, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, C 7 Alkyl, C 8 Alkyl or C 9 An alkyl group. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexylHexyl, 4-t-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, t-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3, 7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylcetyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, n-eicosyl, n-triceicosyl, n-tetraeicosyl, n-tetraceicosyl, n-pentaceicosyl, n-eicosyl, n-heptacosyl, n-eicosyl, etc.
In the present application, the abbreviations for substituents correspond to: n-n, sec-sec, i-iso, t-tert, o-o, m-m, p-pair, memethyl, et ethyl, pr propyl, bu butyl, am-n-pentyl, hx hexyl, cy cyclohexyl.
In the present application, "amine group" means a derivative of an amine having the formula-N (X) 2 Wherein each "X" is independently H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, or the like. Non-limiting types of amine groups include-NH 2 -N (alkyl) 2 -NH (alkyl), -N (cycloalkyl) 2 -NH (cycloalkyl), -N (heterocyclyl) 2 -NH (heterocyclyl), -N (aryl) 2 -NH (aryl), -N (alkyl) (heterocyclyl), -N (cycloalkyl) (heterocyclyl), -N (aryl) (heteroaryl), -N (alkyl) (heteroaryl), and the like.
In this application "×" attached to a single bond represents a linking or fusing site.
In this application, where no attachment site is specified in a group, an optionally attachable site in the group is meant as an attachment site.
In this application, where no fused site is indicated in a group, it is meant that an optionally fused site in the group is taken as a fused site, preferably two or more sites in the group that are ortho to each other are fused sites.
In the present application, when the same group contains a plurality of substituents of the same symbol, each substituent may be the same or different from each other, for example
Figure BDA0003371996950000041
The 6R groups on the benzene ring may be the same or different from each other.
In the present application, a single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached to an optional position on the ring, e.g
Figure BDA0003371996950000042
R in (2) is attached to any substitutable site of the benzene ring, e.g.>
Figure BDA0003371996950000043
Representation->
Figure BDA0003371996950000044
Can be combined with->
Figure BDA0003371996950000045
Optionally substituted positions on the substrate form a fused ring.
In this application, "adjacent group" refers to a site where there is no substitutable between two substituents.
In the present application, "two adjacent R are mutually cyclic" means one ring system formed by connecting two adjacent R to each other, which ring system may be selected from aliphatic hydrocarbon ring, aliphatic heterocyclic ring, aromatic hydrocarbon ring or aromatic heterocyclic ring. Preferably, can be formed into
Figure BDA0003371996950000046
In the examples of the present application, the energy level structure of the organic material, the triplet energy level ET, HOMO, LUMO plays a key role. These energy levels are described below:
HOMO and LUMO energy levels can be measured by photoelectric effects such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet electron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as density functional theory (hereinafter abbreviated as DFT), have also become effective methods for calculating molecular orbital energy levels.
The triplet energy level ET1 of the organic material can be measured by low temperature Time resolved luminescence spectroscopy or obtained by quantum simulation calculations (e.g. by Time-dependent DFT), such as by commercial software Gaussian 03W (Gaussian inc.), specific simulation methods can be seen in WO2011141110 or in the examples below.
It should be noted that the absolute value of HOMO, LUMO, ET1 depends on the measurement or calculation method used, and even for the same method, different evaluation methods, e.g. starting and peak points on the CV curve, may give different HOMO/LUMO values. Thus, a reasonable and meaningful comparison should be made with the same measurement method and the same evaluation method. In the description of the embodiments of the present application, the value of HOMO, LUMO, ET1 is based on a simulation of the Time-dependent DFT, but does not affect the application of other measurement or calculation methods.
In this application, (HOMO-1) is defined as the second highest occupied orbital level, (HOMO-2) is the third highest occupied orbital level, and so on. (lumo+1) is defined as the second lowest unoccupied orbital level, (lumo+2) is the third lowest occupied orbital level, and so on.
Cyclic alkyl or cycloalkyl groups as described herein have the same meaning and are interchangeable.
The technical scheme of the application is as follows:
a boron-containing hydrogenated carbazole organic compound has a structure shown in a general formula (1):
Figure BDA0003371996950000047
wherein:
n1 is selected from 0, 1, 2 or 3; n2 is selected from 0, 1, 2 or 3; n3 is selected from 0, 1, 2 or 3;
R 1 、R 2 、R 3 each occurrence is independently selected from the group consisting of-D (deuterium), or a linear alkyl group having 1 to 20C atoms, a linear alkoxy group having 1 to 20C atoms, or a linear thioalkoxy group having 1 to 20C atoms, or a branched alkyl group having 3 to 20C atoms, or a branched alkoxy group having 3 to 20C atoms, or a branched thioalkoxy group having 3 to 20C atoms, or a cyclic alkyl group having 3 to 20C atoms, or a cyclic alkoxy group having 3 to 20C atoms, or a cyclic thioalkoxy group having 3 to 20C atoms, or a silyl group, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, or isothiocyanate, hydroxyl, nitro, substituted or unsubstituted amine, -CF 3 -Cl, -Br, -F, -I, or a substituted or unsubstituted alkenyl group having 1 to 20C atoms, or a substituted or unsubstituted aryl group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, or a substituted or unsubstituted aryloxy group having 5 to 60 ring atoms, or a substituted or unsubstituted heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;
Adjacent R 1 With or without each other being cyclic;
adjacent R 2 With or without each other being cyclic;
adjacent R 3 With or without each other.
In one embodiment, the "inter-ring" is the formation of a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 10 ring atoms; in a particular embodiment, the "inter-rings" are substituted or unsubstituted aromatic or heteroaromatic groups having 6 ring atoms.
In one embodiment, adjacent R 3 Are not looped; further, the saidThe boron-containing hydrogenated carbazole organic compound is selected from structures shown in formulas (2-1) - (2-4):
Figure BDA0003371996950000051
in one embodiment, adjacent R 1 Forms a substituted or unsubstituted aromatic or heteroaromatic group having 6 ring atoms, or adjacent R 1 Are not looped.
In one embodiment, adjacent R 2 Forms a substituted or unsubstituted aromatic or heteroaromatic group having 6 ring atoms, or adjacent R 2 Are not looped.
In one embodiment, the boron-containing hydrogenated carbazole organic compound is selected from the following structures:
Figure BDA0003371996950000052
in a specific embodiment, the boron-containing hydrogenated carbazole organic compound is selected from structures represented by formulas (3-1) - (3-18):
Figure BDA0003371996950000053
/>
Figure BDA0003371996950000061
In one embodiment, R 1 、R 2 、R 3 Each occurrence is independently selected from the group consisting of-D, or a linear alkyl group having 1 to 10C atoms, a linear alkoxy group having 1 to 10C atoms, or a linear thioalkoxy group having 1 to 10C atoms, or a branched alkyl group having 3 to 10C atoms, or a branched alkoxy group having 3 to 10C atoms, or a branched thioalkoxy group having 3 to 10C atoms, or a cyclic alkyl group having 3 to 10C atoms, or a cyclic alkoxy group having 3 to 10C atoms, orCyclic thioalkoxy having 3 to 10C atoms, or silyl, or keto having 1 to 10C atoms, or alkoxycarbonyl having 2 to 10C atoms, or aryloxycarbonyl having 7 to 10C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, thiocyanate, or isothiocyanate, hydroxy, nitro, substituted or unsubstituted amino, -CF 3 -Cl, -Br, -F, -I, or a substituted or unsubstituted alkenyl group having 1 to 10C atoms, or a substituted or unsubstituted aryl group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, or a substituted or unsubstituted aryloxy group having 5 to 30 ring atoms, or a substituted or unsubstituted heteroaryloxy group having 5 to 30 ring atoms, or a combination of these groups.
In one embodiment, R 1 、R 2 、R 3 Independently at each occurrence selected from-D, or a straight chain alkyl group having 1 to 8C atoms, or a branched alkyl group having 3 to 8C atoms, or a cyclic alkyl group having 3 to 8C atoms, or a silyl group,
Figure BDA0003371996950000062
Or by R 0 Substituted or unsubstituted aromatic groups having 6 to 20 ring atoms, or substituted by R 0 A substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, or a combination of these groups.
Wherein:
R 4 、R 5 independently selected from a linear alkyl group having 1 to 8C atoms, or a branched alkyl group having 3 to 8C atoms, or a cyclic alkyl group having 3 to 8C atoms, or R 0 Substituted or unsubstituted aromatic groups having 6 to 20 ring atoms, or substituted by R 0 A substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, or a combination of such groups;
R 0 independently at each occurrence selected from-D, or a straight chain alkyl group having 1 to 10C atoms, or a branched alkyl group having 3 to 10C atoms, or a cyclic alkyl group having 3 to 10C atoms, or methylA silane group, or an aromatic group having 6 to 20 ring atoms, or a heteroaromatic group having 6 to 20 ring atoms, or a combination of these groups;
* Representing the ligation site.
In one embodiment, R 1 、R 2 、R 3 Independently at each occurrence is selected from a straight chain alkyl group having 1 to 8C atoms, or a branched alkyl group having 3 to 8C atoms, or a cyclic alkyl group having 3 to 8C atoms,
Figure BDA0003371996950000071
Or the following groups:
Figure BDA0003371996950000072
wherein:
y is selected from CR 6 R 7 ，NR 8 O or S;
R 6 、R 7 、R 8 each occurrence is independently selected from the group consisting of-H, -D, or a linear alkyl group having 1 to 10C atoms, a linear alkoxy group having 1 to 10C atoms, or a linear thioalkoxy group having 1 to 10C atoms, or a branched alkyl group having 3 to 10C atoms, or a branched alkoxy group having 3 to 10C atoms, or a branched thioalkoxy group having 3 to 10C atoms, or a cyclic alkyl group having 3 to 10C atoms, or a cyclic alkoxy group having 3 to 10C atoms, or a cyclic thioalkoxy group having 3 to 10C atoms, or a silyl group, or a keto group having 1 to 10C atoms, or an alkoxycarbonyl group having 2 to 10C atoms, or an aryloxycarbonyl group having 7 to 10C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, or isothiocyanate, hydroxyl, nitro, substituted or unsubstituted amine, -CF 3 -Cl, -Br, -F, -I, or a substituted or unsubstituted alkenyl group having 1 to 10C atoms, or a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, or a substituted or unsubstituted aromatic group having 5 to 20 ring atoms An aryloxy group of 20 ring atoms, or a substituted or unsubstituted heteroaryloxy group having 5 to 20 ring atoms, or a combination of these groups.
m1 is selected from 0, 1, 2, 3 or 4; m2 is selected from 0, 1, 2 or 3; m3 is selected from 0, 1, 2, 3, 4 or 5.
In a particular embodiment, R 6 、R 7 、R 8 Each occurrence is independently selected from-H, -D, a linear alkyl group having 1 to 4C atoms, or a branched alkyl group having 3 to 4C atoms, or a cyclic alkyl group having 3 to 4C atoms, or a substituted or unsubstituted aromatic group having 6 to 10 ring atoms, or a substituted or unsubstituted heteroaromatic group having 6 to 10 ring atoms, or a combination of such groups.
In one embodiment, the
Figure BDA0003371996950000073
Selected from the following groups: />
Figure BDA0003371996950000074
Wherein: m4 is selected from 0, 1, 2, 3, 4 or 5; m5 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; m6 is selected from 0, 1, 2, 3 or 4; m7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.
In one embodiment, R as referred to above 0 Independently for each occurrence selected from-D, methyl, ethyl, iPr, tBu, tAm, et, phenyl, biphenyl, naphthyl, phenanthryl, pyridyl, pyrimidinyl, or phenyl substituted with an alkyl group having 1 to 6C atoms.
In a particular embodiment, R 3 Each occurrence is independently selected from methyl, ethyl, iPr, tBu, tAm, et, or the following groups:
Figure BDA0003371996950000075
/>
Figure BDA0003371996950000081
Figure BDA0003371996950000091
in one embodiment, R 3 At multiple occurrences, selected from the same group; preferably, R 3 At multiple occurrences, selected from
Figure BDA0003371996950000092
Or a group represented by (A-1) or a group represented by (A-2) or a group represented by (A-3). Preferably, R in the structure represented by the formula (2-3), (3-5) or (3-9) 3 Selected from->
Figure BDA0003371996950000093
Or a group represented by (A-1) or a group represented by (A-2) or a group represented by (A-3).
In a particular embodiment, R 1 、R 2 Independently for each occurrence a straight chain alkyl group having 1 to 8C atoms, or a branched alkyl group having 3 to 8C atoms; further, R 1 、R 2 Each occurrence is independently selected from methyl, ethyl, iPr, tBu, tAm, or Et.
The iPr is isopropyl; tBu is tert-butyl; tAm is tert-amyl; et ethyl; ph is phenyl.
As an example, in one embodiment, the boron-containing hydrogenated carbazole organic compound of the present application may be selected from, but is not limited to, any of the following structures:
Figure BDA0003371996950000094
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Figure BDA0003371996950000101
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Figure BDA0003371996950000111
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Figure BDA0003371996950000121
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Figure BDA0003371996950000131
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Figure BDA0003371996950000141
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Figure BDA0003371996950000151
it is understood that H in the structural formula of the boron-containing hydrogenated carbazole organic compound described above may be further substituted.
In one embodiment, the boron-containing hydrogenated carbazole organic compound can be used as an organic functional material in a functional layer of an organic electronic device, particularly a functional layer of an OLED device. The organic functional material may be, but is not limited to, a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), an Emitter (Emitter), a Host material (Host Emitter), and an organic dye.
In an embodiment, the boron-containing hydrogenated carbazole organic compound is used in a light emitting layer, preferably, the boron-containing hydrogenated carbazole organic compound is used as a guest material of the light emitting layer.
In a specific embodiment, a boron-containing hydrogenated carbazole-containing organic compound according to the present application is used as a blue light emitting material in the light emitting layer.
The present application further relates to a mixture comprising at least one boron-containing hydrogenated carbazole organic compound as described above and at least one other organic functional material. The another organic functional material is selected from the group consisting of a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a light emitting body (Emitter), a host material, and an organic dye. Wherein the luminophore is selected from singlet luminophores (fluorescent luminophores) or triplet luminophores (phosphorescent luminophores) grade organic thermal excitation delayed fluorescence material (TADF material). Details of various organic functional materials are found in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of which 3 patent documents are hereby incorporated by reference. It is understood that the other organic functional material may be a small molecule organic material and a high polymer material.
In an embodiment, the another organic functional material is selected from a host material; further, the another organic functional material is selected from blue host materials.
The present application also relates to a composition comprising at least one boron-containing hydrogenated carbazole organic compound or mixture as described above, and at least one organic solvent.
The organic solvent is at least one selected from aromatic or heteroaromatic based solvents, ester based solvents, aromatic ketone based solvents, aromatic ether based solvents, aliphatic ketones, aliphatic ethers, alicyclic compounds, olefin compounds, boric acid ester compounds and phosphoric acid ester compounds.
In at least one embodiment, the organic solvent is selected from aromatic or heteroaromatic based solvents in the composition.
The aromatic or heteroaromatic based solvent may be selected from, but is not limited to, p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluenes, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenylmethane, 4- (3-phenylpropylpyridine, 1, 3-dimethylquinoline, 2-dimethylquinoline, and at least one of the ethyl esters of furan.
The ester-based solvent may be selected from, but is not limited to, alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. At least one of octyl octanoate, diethyl sebacate, diallyl phthalate and isononyl isononanoate is particularly preferable.
The aromatic ketone-based solvent may be selected from, but is not limited to, 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof. Among them, the derivative may be selected from, but not limited to, at least one of 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropophenone, 3-methylpropophenone, and 2-methylpropophenone, as an example.
The aromatic ether-based solvent may be selected from, but is not limited to, at least one of 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxane, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylben-ther, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-t-butyl anisole, trans-p-propenyl anisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran and ethyl-2-naphthyl ether.
The aliphatic ketone-based solvent may be selected from, but is not limited to, 2-nonene, 3-nonene, 5-nonene, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonene, fenchyl ketone, phorone, isophorone, di-n-amyl ketone, and the like; or aliphatic ethers such as at least one of amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
It is understood that the organic solvents may be used alone or as a mixed solvent of two or more organic solvents.
In one embodiment, the composition of the present application comprises at least one organic compound or mixture as described above, and at least one organic solvent, and may further comprise another organic solvent.
The other organic solvent may be selected from, but is not limited to, at least one of methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1-trichloroethane, 1, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide (DMSO), tetrahydronaphthalene, decalin, and indene.
In one embodiment, suitable organic solvents for the present application are solvents having Hansen (Hansen) solubility parameters within the following ranges:
δd (dispersion force) is in the range of 17.0 to 23.2MPa1/2, particularly in the range of 18.5 to 21.0MPa 1/2;
δp (polar force) is in the range of 0.2-12.5MPa1/2, especially in the range of 2.0-6.0MPa 1/2;
δh (hydrogen bonding force) is in the range of 0.9 to 14.2MPa1/2, particularly in the range of 2.0 to 6.0MPa 1/2.
In one embodiment, the organic solvent is selected in accordance with the compositions of the present application taking into account boiling point. In at least some embodiments, the organic solvent has a boiling point of ∈deg.C or greater; preferably not less than 180 ℃; preferably not less than 200 ℃; more preferably not less than 250 ℃; the optimal temperature is more than or equal to 300 ℃. Boiling points in these ranges are beneficial in preventing nozzle clogging of inkjet printheads.
It is understood that the organic solvent may be evaporated from the solvent system to form a film comprising the organic compound.
In one embodiment, the composition is a solution. In still other embodiments, the composition is a suspension. The solution or suspension may additionally include additives for adjusting viscosity, adjusting film forming properties, improving adhesion, etc. The additive may be selected from at least one of, but not limited to, a surface active compound, a lubricant, a wetting agent, a dispersing agent, a hydrophobizing agent, and a binder.
The composition may also be referred to as an ink.
When used in the printing process, the viscosity and surface tension of the ink are important parameters. The surface tension parameters of a suitable ink are suitable for a particular substrate and a particular printing method.
In one embodiment, an ink according to the present application has a surface tension at an operating temperature or at 25 ℃ in the range of about 19dyne/cm to 50dyne/cm; more preferably 22dyne/cm to 35dyne/cm; preferably from 25dyne/cm to 33dyne/cm.
In one embodiment, the ink according to the present application has a viscosity in the range of 1cps to 100cps at the operating temperature or 25 ℃; preferably 1cps to 50cps; more preferably 1.5cps to 20cps; and preferably from 4.0cps to 20cps.
It will be appreciated that inks having the surface tension and viscosity described above will facilitate inkjet printing.
It will be appreciated that the viscosity of the ink may be adjusted by different methods, such as by appropriate solvent selection and concentration of functional material in the ink. The inks comprising the boron-containing hydrogenated carbazole organic compounds according to the present application can be conveniently adjusted to the printing ink in the appropriate range according to the printing method used. Generally, the compositions according to the present application comprise the boron-containing hydrogenated carbazole organic compound or mixture in an amount of 0.3 to 30wt%, preferably 0.5 to 20wt%, more preferably 0.5 to 15wt%, most preferably 0.5 to 10wt%, most preferably 1 to 5wt% of the composition.
The application also relates to the use of the composition as a coating or printing ink in the preparation of an organic electronic device. In one embodiment, the composition is used in the preparation of organic electronic devices by a print or coating preparation method. The printing or coating may be prepared by, but is not limited to, ink jet printing, gravure printing, spray printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roll printing, twist roller printing, offset printing, flexography, rotary printing, spray coating, brush coating, pad printing, slot die coating, and the like. Preferred are gravure printing, inkjet printing and inkjet printing.
The present application also relates to the use of an organic compound, mixture or composition as described above in an organic electronic device. The specific scheme is as follows:
an organic electronic device includes at least one functional layer. The functional layer comprises at least one boron-containing hydrogenated carbazole organic compound or mixture as described above, or is prepared from the composition as described above.
Further, the organic electronic device includes a cathode, an anode, and at least one functional layer. The functional layer comprises at least one boron-containing hydrogenated carbazole organic compound or mixture as described above, or is prepared from the composition as described above.
The functional layer may be, but is not limited to, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), a light emitting layer, an electron blocking layer, an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), or a hole blocking layer. Preferably, the functional layer is a light emitting layer.
The organic electronic device may be, but is not limited to, an Organic Light Emitting Diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an Organic Field Effect Transistor (OFET), an organic light emitting field effect transistor, an organic laser, an organic spintronic device, an organic sensor, an organic plasmon emitting diode (Organic Plasmon Emitting Diode), and the like. Organic electroluminescent devices such as OLEDs, oleccs, organic light emitting field effect transistors, etc. are particularly preferred. Further particularly preferred are OLEDs.
In one embodiment, the organic electronic device comprises a substrate, and an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode which are sequentially stacked on the substrate. The luminescent layer comprises at least one boron-containing hydrogenated carbazole organic compound or mixture, or is prepared from the composition. It is understood that the structure of the organic electronic device is not limited thereto.
The substrate may be transparent or opaque. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, bulovic et al Nature 1996,380, p29, and Gu et al, appl. Phys. Lett.1996,68, p2606. The substrate may also be rigid or elastic. In one embodiment, the substrate is plastic, metal, semiconductor wafer, or glass. Preferably, the substrate has a smooth surface, and a substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150℃or higher, preferably over 200℃and more preferably over 250℃and most preferably over 300 ℃. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).
The anode is an electrode that injects holes, and the anode can easily inject holes into a hole injection layer, or a hole transport layer, or a light emitting layer. The anode may comprise a conductive metal, conductive metal oxide, or conductive polymer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or of the p-type semiconductor material as HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. Examples of anode materials include, but are not limited to: al, cu, au, ag, mg, fe, co, ni, mn, pd, pt, ITO aluminum doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present application. The cathode is an electrode injecting electrons, and the cathode can easily inject electrons into an electron injection layer, or an electron transport layer, or a light emitting layer. The cathode may comprise a conductive metal or conductive metal oxide. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO or conduction band level of the light-emitting body in the light-emitting layer or of the n-type semiconductor material as an Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, and most preferably less than 0.2eV. In principle, all materials that can be used as cathodes of the organic electronic devices are possible as cathode materials for the organic electronic devices of the present application. Examples of cathode materials include, but are not limited to: al, au, ag, ca, ba, mg, liF/Al, mgAg alloy, baF2/Al, cu, fe, co, ni, mn, pd, pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
The hole injection layer is a layer for promoting injection of holes from the anode to the light emitting layer, and the hole injection material is a material that can receive holes injected from the positive electrode proficiently at a low voltage, and it is preferable that the Highest Occupied Molecular Orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazabenzophenanthrene-based organic material, quinacridone-based organic material, perylene-based organic material, anthraquinone, polyaniline-based and polythiophene-based conductive polymer, and the like, but are not limited thereto.
The hole transport layer may be used to smoothly transport holes. The hole transport material for the hole transport layer known in the art is suitably a material having high hole mobility, which can receive holes transported from the anode or the hole injection layer and transfer the holes to the light emitting layer. Specific examples thereof include an arylamine-based organic material, a conductive polymer, a block copolymer having both conjugated and non-conjugated portions, and the like, but are not limited thereto.
The electron blocking layer may be disposed between the hole transport layer and the light emitting layer. As the electron blocking layer, a spiroindoloacridine-based compound or a material known in the art may be used.
Examples of the host material for the light-emitting layer include a condensed aromatic ring derivative or a heterocyclic ring-containing compound, and the like. Specifically, examples of the condensed aromatic ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and examples of the heterocycle-containing compound include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but examples thereof are not limited thereto.
The electron transport layer may be used to smoothly transport electrons. The electron transport material is suitably a material having high electron mobility, which can be proficiently receiving electrons injected from the negative electrode and transferring the electrons to the light emitting layer. Specific examples thereof may include, but are not limited to: at least one of Al complexes of 8-hydroxyquinoline, complexes comprising Alq3, organic radical compounds, hydroxyflavone-metal complexes, lithium 8-hydroxyquinoline (Liq), and benzimidazole-based compounds.
The electron injection layer may be used to smoothly inject electrons. The electron injection material is preferably: has an ability to transport electrons, has an effect of injecting electrons from the negative electrode, has an excellent effect of injecting electrons into the light emitting layer or the light emitting material, prevents excitons generated by the light emitting layer from moving to the hole injecting layer, and also has an excellent ability to form a thin film. Specific examples thereof include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, oxazole, diazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone and the like and derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives and the like, but are not limited thereto.
The hole blocking layer is a layer that blocks holes from reaching the negative electrode, and may be generally formed under the same conditions as those of the hole injection layer. Specific examples thereof include, but are not limited to, diazole derivatives or triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, and the like.
The organic electronic device has a luminescence wavelength of between 300 and 1000nm, preferably between 350 and 900nm, more preferably between 400 and 800 nm.
In one embodiment, the organic electronic device described herein is a solution-type organic electronic device, one or more functional layers of which are prepared by printing; further, the solution-type organic electronic device is a solution-type OLED.
The present application also relates to the use of an organic electronic device according to the present application in various electronic devices, which may be, but are not limited to, display devices, lighting devices, light sources, sensors, etc.
The application also relates to an electronic device comprising said electronic device. The electronic device may be, but is not limited to, a display device, a lighting device, a light source, a sensor, etc.
The present application is specifically illustrated by the following examples, which are only some of the examples of the present application and are not limiting of the present application.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
The synthetic route for the organic compound 1 of this example is as follows:
Figure BDA0003371996950000181
synthesis of intermediates 1-3
In a dry three-neck flask under nitrogen protection atmosphere, 10mmol of compound 1-1 and 20mmol of compound 1-2 are respectively added, 100ml of DMSO (dimethyl sulfoxide) is poured as a solvent, and dry Cs is added 2 CO 3 Taking alkali as a reaction for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for a plurality of times, simultaneously extracting the water phase for a plurality of times by using the dichloromethane, merging organic phases, and using anhydrous Na 2 CO 3 Drying, filtering, spin-drying the reaction solution to obtain a crude product, and recrystallizing with ethyl acetate to obtainIntermediate 1-3, molar amount 8.43mmol, reaction yield 84.3%, MS (ASAP) = 494.5.
Synthesis of organic Compound 1
Into a 250ml three-necked flask, 10mmol of the intermediate 1-3 and 100ml of dry tert-butylbenzene were charged, followed by N 2 In the atmosphere, cooling to-30℃and adding 21mmol of t-BuLi n-hexane solution dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 21mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 42mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted by ethyl acetate and the organic phases are combined, the solvent in the aqueous phase is distilled off in a rotary way to obtain a crude product, the crude product is purified by a rapid silica gel column to obtain a pure product, and the pure product is recrystallized by toluene and ethyl acetate to obtain a yellowish solid powder of the product, namely the organic compound 1, the yield is 78.4%, and MS (ASAP) =424.6.
Example 2
The synthetic route for the organic compound 2 of this example is as follows:
Figure BDA0003371996950000182
synthesis of intermediate 2-2
In a dry three-neck flask under the protection of nitrogen, 10mmol of compound 1-1 and 20mmol of compound 2-1 are respectively added, 100ml of DMSO is poured as a solvent, and dry Cs is added 2 CO 3 Taking alkali as a reaction for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for a plurality of times, simultaneously extracting the water phase for a plurality of times by using the dichloromethane, merging organic phases, and using anhydrous Na 2 CO 3 Drying, filtering, spin-drying the reaction solution to obtain a crude product, recrystallizing with ethyl acetate to obtain an intermediate 2-2, wherein the molar weight is 8.59mmol, the reaction yield is 85.9%, and MS(ASAP)＝594.3。
Synthesis of organic Compound 2
Into a 250ml three-necked flask, 10mmol of intermediate 2-2 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooling to-30℃and adding 21mmol of t-BuLi n-hexane solution dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 21mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 42mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted by ethyl acetate and the organic phases are combined, the solvent in the organic phases is distilled off in a rotating way, crude products are obtained, the crude products are purified by a rapid silica gel column, the pure products are obtained by recrystallization by toluene and ethyl acetate, and the product is pale yellow solid powder, namely the organic compound 2, the yield is 59.4%, and MS (ASAP) =524.5.
Example 3
The synthetic route for the organic compound 3 of this example is as follows:
Figure BDA0003371996950000191
synthesis of intermediate 3-3
Compound 3-1 (10 mmol), compound 3-2 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 6h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 3-3 in a molar amount of 8.33mmol, yield 83.3%, MS (ASAP) = 359.3.
Synthesis of intermediate 3-4
In a dry three-neck flask under the protection of nitrogen, 10mmol of intermediate 3-3 and 20mmol of compound 1-2 are respectively added, 100ml of DMSO is poured into the flask as a solvent, and dry Cs is added 2 CO 3 As alkali at 120 DEG CAfter the reaction was completed, the reaction solution was cooled to room temperature, water and methylene chloride were sequentially added, the reaction solution was washed with water several times, the aqueous phase was extracted with methylene chloride several times, the organic phase was combined, and anhydrous Na was used 2 CO 3 Drying, filtering, spin-drying the reaction solution to obtain a crude product, and recrystallizing with ethyl acetate to obtain an intermediate 3-4, wherein the molar amount is 7.59mmol, the reaction yield is 75.9%, and MS (ASAP) = 661.3.
Synthesis of organic Compound 3
Into a 250ml three-necked flask, 10mmol of intermediate 3-4 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooling to-30℃and adding 21mmol of t-BuLi n-hexane solution dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 21mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 42mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the organic phases are combined, the solvent in the organic phases is distilled off in a rotating way, crude products are obtained, the crude products are purified by a rapid silica gel column, pure products are obtained, toluene and ethyl acetate are used for recrystallization, and light yellow solid powder of the products, namely the organic compound 3, is obtained, the yield is 71.7%, and MS (ASAP) = 591.5.
Example 4
The synthetic route for the organic compound 4 of this example is as follows:
Figure BDA0003371996950000192
synthesis of intermediate 4-2
Compound 3-1 (10 mmol), compound 4-1 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 6h. Cooling, rotary evaporating to remove solvent, extracting, washing with water, collecting organic phase, drying, concentrating under reduced pressure, and purifying with column Chromatography gave intermediate 4-2 in a molar amount of 8.75mmol in a yield of 87.5%, MS (ASAP) = 471.4.
Synthesis of intermediate 4-3
In a dry three-neck flask under the protection of nitrogen, 10mmol of intermediate 4-2 and 20mmol of compound 1-2 are respectively added, 100ml of DMSO is poured into the flask as a solvent, and dry Cs is added 2 CO 3 Taking alkali as a reaction for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for a plurality of times, simultaneously extracting the water phase for a plurality of times by using the dichloromethane, merging organic phases, and using anhydrous Na 2 CO 3 Drying, filtering, spin-drying the reaction solution to obtain a crude product, and recrystallizing with ethyl acetate to obtain an intermediate 4-3, wherein the molar quantity is 6.54mmol, the reaction yield is 65.4%, and MS (ASAP) = 773.5.
Synthesis of organic Compound 4
Into a 250ml three-necked flask, 10mmol of intermediate 4-3 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooling to-30℃and adding 21mmol of t-BuLi n-hexane solution dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 21mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 42mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the organic phases are combined, the solvent in the organic phases is distilled off in a rotating way, crude products are obtained, the crude products are purified by a rapid silica gel column, the pure products are obtained by recrystallization of toluene and ethyl acetate, and the product is pale yellow solid powder, namely organic compound 4, the yield is 69.3%, and MS (ASAP) = 703.6.
Example 5
The synthetic route for the organic compound 5 of this example is as follows:
Figure BDA0003371996950000201
synthesis of intermediate 5-3
Compound 5-1 (10 mmol), compound 5-2 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium t-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 12h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 5-3 in a molar amount of 7.18mmol and a yield of 71.8%, MS (ASAP) = 337.2.
Synthesis of intermediate 5-4
Compound 3-1 (10 mmol), intermediate 5-3 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 6h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 5-4 in a molar amount of 8.14mmol and a yield of 81.4%, MS (ASAP) = 527.3.
Synthesis of intermediate 5-5
In a dry three-neck flask under the protection of nitrogen, 10mmol of intermediate 5-4 and 20mmol of compound 1-2 are respectively added, 100ml of DMSO is poured in as a solvent, and dry Cs is added 2 CO 3 The reaction is carried out for 8 hours at 120 ℃ as alkali, TLC monitors the reaction, after the reaction is completed, the reaction liquid is cooled to room temperature, water and methylene dichloride are sequentially added, the reaction liquid is washed for a plurality of times, meanwhile, the methylene dichloride is used for extracting the water phase for a plurality of times, the organic phases are combined, dried by anhydrous Na2CO3, filtered and spin-dried to obtain a crude product, the crude product is recrystallized by ethyl acetate, thus obtaining an intermediate 5-5 with the molar quantity of 5.96mmol, the reaction yield is 59.6 percent, and MS (ASAP) = 829.6.
Synthesis of organic Compound 5
Into a 250ml three-necked flask, 10mmol of intermediate 5-5 and 100ml of dried tert-butylbenzene were charged in N 2 In the atmosphere, cooling to-30℃and adding 21mmol of t-BuLi n-hexane solution dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction mixture was cooled again to-30℃and 21mmol of boron tribromide solution was added thereto, and the mixture was warmedStirring for 0.5 hours at room temperature, then cooling the reaction solution to 0 ℃, adding 42mmol of N, N-diisopropylethylamine, heating to room temperature and stirring after the dripping is finished, continuously heating to 120 ℃ and stirring for 3 hours, and cooling the reaction solution to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the organic phases are combined, the solvent in the organic phases is distilled off in a rotating way, crude products are obtained, the crude products are purified by a rapid silica gel column, the pure products are obtained by recrystallization of toluene and ethyl acetate, and the product is pale yellow solid powder, namely the organic compound 5, the yield is 70.8%, and MS (ASAP) = 759.6.
Example 6
The synthetic route for the organic compound 6 of this example is as follows:
Figure BDA0003371996950000211
synthesis of intermediate 6-2
Compound 5-1 (10 mmol), compound 6-1 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium t-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 12h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 6-2 in a molar amount of 6.54mmol, yield 65.4%, MS (ASAP) = 357.4.
Synthesis of intermediate 6-3
Compound 3-1 (10 mmol), intermediate 6-2 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 6h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 6-3 in a molar amount of 7.51mmol, yield 75.1%, MS (ASAP) = 547.5.
Synthesis of intermediate 6-4
In a dry three-neck flask under the protection of nitrogen, 10mmol of intermediate 6-3 and 20mmol of compound 1-2 are respectively added, 100ml of DMSO is poured into the flask as a solvent, and dry Cs is added 2 CO 3 Taking alkali as a reaction for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for a plurality of times, simultaneously extracting the water phase for a plurality of times by using the dichloromethane, merging organic phases, and using anhydrous Na 2 CO 3 Drying, filtering, spin-drying the reaction solution to obtain a crude product, and recrystallizing with ethyl acetate to obtain an intermediate 6-4, wherein the molar amount is 6.71mmol, the reaction yield is 67.1%, and MS (ASAP) = 849.5.
Synthesis of organic Compound 6
Into a 250ml three-necked flask, 10mmol of intermediate 6-4 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooling to-30℃and adding 21mmol of t-BuLi n-hexane solution dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 21mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 42mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the organic phases are combined, the solvent in the organic phases is distilled off in a rotating way, crude products are obtained, the crude products are purified by a rapid silica gel column, the pure products are obtained by recrystallization of toluene and ethyl acetate, and the product is pale yellow solid powder, namely organic compound 6, the yield is 69.4%, and MS (ASAP) =779.6.
Example 7
The synthetic route for the organic compound 7 of this example is as follows:
Figure BDA0003371996950000221
synthesis of intermediate 7-3
Compound 7-1 (10 mmol), compound 7-2 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium t-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 12h. Cooling, rotary evaporating to remove solvent, extracting, washing with water, separating liquid, collecting organic phase, and standing Drying, concentration under reduced pressure and column chromatography gave intermediate 7-3, molar amount of 6.32mmol, yield 63.2%, MS (ASAP) = 329.3.
Synthesis of intermediate 7-4
Compound 3-1 (10 mmol), intermediate 7-3 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 6h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 7-4 in a molar amount of 8.83mmol, yield 88.3%, MS (ASAP) =519.5.
Synthesis of intermediate 7-5
In a dry three-neck flask under the protection of nitrogen, 10mmol of intermediate 7-4 and 20mmol of compound 1-2 are respectively added, 100ml of DMSO is poured in as a solvent, and dry Cs is added 2 CO 3 Taking alkali as a reaction for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for a plurality of times, simultaneously extracting the water phase for a plurality of times by using the dichloromethane, merging organic phases, and using anhydrous Na 2 CO 3 Drying, filtering, spin-drying the reaction solution to obtain a crude product, and recrystallizing with ethyl acetate to obtain an intermediate 7-5, wherein the molar quantity is 6.43mmol, the reaction yield is 64.3%, and MS (ASAP) = 821.4.
Synthesis of organic Compound 7
Into a 250ml three-necked flask, 10mmol of intermediate 7-5 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooling to-30℃and adding 21mmol of t-BuLi n-hexane solution dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 21mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 42mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined and the solvent was distilled offThe crude product is obtained, purified by a rapid silica gel column to obtain a pure product, and recrystallized by toluene and ethyl acetate to obtain yellowish solid powder of the product, namely organic compound 7, with the yield of 54.3 percent, and MS (ASAP) = 751.6.
Example 8
The synthetic route for the organic compound 8 of this example is as follows:
Figure BDA0003371996950000222
synthesis of intermediate 8-3
Compound 8-1 (10 mmol), compound 8-2 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium t-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 12h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 8-3 in a molar amount of 7.48mmol, yield 74.8%, MS (ASAP) = 401.4.
Synthesis of intermediate 8-4
Compound 3-1 (10 mmol), intermediate 8-3 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 6h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 8-4 in a molar amount of 8.19mmol in a yield of 81.9% MS (ASAP) = 591.5.
Synthesis of intermediate 8-5
In a dry three-neck flask under the protection of nitrogen, 10mmol of intermediate 8-4 and 20mmol of compound 1-2 are respectively added, 100ml of DMSO is poured in as a solvent, and dry Cs is added 2 CO 3 Taking alkali as a reaction for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for a plurality of times, simultaneously extracting the water phase for a plurality of times by using the dichloromethane, merging organic phases, and using anhydrous Na 2 CO 3 Drying, filtering, spin-drying the reaction solution to obtain a crude product, and re-using ethyl acetateCrystallization gave intermediate 8-5, molar mass 6.32mmol, reaction yield 63.2%, MS (ASAP) = 893.5.
Synthesis of organic Compound 8
Into a 250ml three-necked flask, 10mmol of intermediate 8-5 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooling to-30℃and adding 21mmol of t-BuLi n-hexane solution dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 21mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 42mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the organic phases are combined, the solvent in the organic phases is distilled off in a rotating way, crude products are obtained, the crude products are purified by a rapid silica gel column, the pure products are obtained by recrystallization of toluene and ethyl acetate, and the product is pale yellow solid powder, namely the organic compound 8, the yield is 68.4%, and MS (ASAP) = 823.7.
Example 9
The synthetic route for the organic compound 9 of this example is as follows:
Figure BDA0003371996950000231
synthesis of intermediate 9-3
Compound 9-1 (10 mmol), compound 9-2 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium t-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 12h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 9-3 in a molar amount of 8.56mmol, yield 85.6%, MS (ASAP) =499.7.
Synthesis of intermediate 9-4
Compound 3-1 (10 mmol), intermediate 9-3 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in tolueneStirring is carried out for 6h at 100℃under nitrogen. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 9-4 in a molar amount of 7.42mmol, yield 74.2%, MS (ASAP) = 689.6.
Synthesis of intermediate 9-5
In a dry three-neck flask under the protection of nitrogen, 10mmol of intermediate 9-4 and 20mmol of compound 1-2 are respectively added, 100ml of DMSO is poured in as a solvent, and dry Cs is added 2 CO 3 Taking alkali as a reaction for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for a plurality of times, simultaneously extracting the water phase for a plurality of times by using the dichloromethane, merging organic phases, and using anhydrous Na 2 CO 3 Drying, filtering, spin-drying the reaction solution to obtain a crude product, and recrystallizing with ethyl acetate to obtain an intermediate 9-5, wherein the molar amount is 5.48mmol, the reaction yield is 54.8%, and MS (ASAP) = 991.7.
Synthesis of organic Compound 9
Into a 250ml three-necked flask, 10mmol of intermediate 9-5 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooling to-30℃and adding 21mmol of t-BuLi n-hexane solution dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 21mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 42mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the organic phases are combined, the solvent in the organic phases is distilled off in a rotating way, crude products are obtained, the crude products are purified by a rapid silica gel column, the pure products are obtained by recrystallization of toluene and ethyl acetate, and the product is pale yellow solid powder, namely the organic compound 9, the yield is 50.4%, and MS (ASAP) =921.6.
Example 10
The synthetic route for the organic compound 10 of this example is as follows:
Figure BDA0003371996950000241
synthesis of intermediate 10-3
Compound 10-1 (10 mmol), compound 10-2 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium t-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 12h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 10-3 in a molar amount of 7.41mmol, yield 74.1%, MS (ASAP) =365.5.
Synthesis of intermediate 10-4
Compound 3-1 (10 mmol), intermediate 10-3 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 6h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 10-4 in a molar amount of 8.46mmol, yield 84.6%, MS (ASAP) = 555.3.
Synthesis of intermediate 10-5
In a dry three-neck flask under the protection of nitrogen, 10mmol of intermediate 10-4 and 20mmol of compound 1-2 are respectively added, 100ml of DMSO is poured into the flask as a solvent, and dry Cs is added 2 CO 3 Taking alkali as a reaction for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for a plurality of times, simultaneously extracting the water phase for a plurality of times by using the dichloromethane, merging organic phases, and using anhydrous Na 2 CO 3 Drying, filtering, spin-drying the reaction solution to obtain a crude product, and recrystallizing with ethyl acetate to obtain an intermediate 10-5, wherein the molar quantity is 3.89mmol, the reaction yield is 38.9%, and MS (ASAP) = 857.4.
Synthesis of organic Compound 10
Into a 250ml three-necked flask, 10mmol of intermediate 10-5 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 Cooling to-30deg.C in the atmosphere, and dropwise adding21mmol of t-BuLi in n-hexane are introduced. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 21mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 42mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined, the solvent was distilled off in vacuo to give crude product, which was purified by flash column chromatography to give pure product, which was recrystallized from toluene and ethyl acetate to give the product as pale yellow solid powder, organic compound 10, yield 79.6%, MS (ASAP) = 787.5.
Example 11
The synthetic route for the organic compound 11 of this example is as follows:
Figure BDA0003371996950000242
synthesis of intermediate 11-3
Compound 11-1 (20 mmol), compound 11-2 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium t-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 12h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 11-3 in a molar amount of 8.45mmol, yield 84.5%, MS (ASAP) = 390.4.
Synthesis of intermediate 11-4
In a dry three-neck flask under the protection of nitrogen, 10mmol of intermediate 11-3 and 20mmol of compound 1-2 are respectively added, 100ml of DMSO is poured into the flask as a solvent, and dry Cs is added 2 CO 3 Taking alkali as a reaction for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for a plurality of times, simultaneously extracting the water phase for a plurality of times by using the dichloromethane, merging organic phases, and using anhydrous Na 2 CO 3 Drying, filtering, spin-drying the reaction solution to obtain a crude product, and recrystallizing with ethyl acetate to obtain intermediate 11-4 with a molar mass of 6.58mmol and a reaction yield of 65.8%, MS (ASAP) = 692.5.
Synthesis of organic Compound 11
Into a 250ml three-necked flask, 10mmol of intermediate 11-4 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooling to-30℃and adding 21mmol of t-BuLi n-hexane solution dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 21mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 42mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the organic phases are combined, the solvent in the organic phases is distilled off in a rotating way, crude products are obtained, the crude products are purified by a rapid silica gel column, the pure products are obtained by recrystallization of toluene and ethyl acetate, and the product is pale yellow solid powder, namely the organic compound 11, the yield is 46.3%, and MS (ASAP) =622.8.
Example 12
The synthetic route for the organic compound 12 of this example is as follows:
Figure BDA0003371996950000251
synthesis of intermediate 12-2
Compound 12-1 (20 mmol), compound 11-2 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium t-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 12h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 12-2 in a molar amount of 7.05mmol, yield 70.5%, MS (ASAP) =526.3.
Synthesis of intermediate 12-3
Under the protection of nitrogen, in a dry three-port atmosphereIn a flask, 10mmol of intermediate 12-2 and 20mmol of compound 1-2 were added, respectively, 100ml of DMSO was poured as a solvent, and dried Cs was added 2 CO 3 Taking alkali as a reaction for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for a plurality of times, simultaneously extracting the water phase for a plurality of times by using the dichloromethane, merging organic phases, and using anhydrous Na 2 CO 3 Drying, filtering, spin-drying the reaction solution to obtain a crude product, and recrystallizing with ethyl acetate to obtain intermediate 12-3, wherein the molar amount is 7.49mmol, the reaction yield is 74.9%, and MS (ASAP) = 828.4.
Synthesis of organic Compound 12
Into a 250ml three-necked flask, 10mmol of intermediate 12-3 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooling to-30℃and adding 21mmol of t-BuLi n-hexane solution dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 21mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 42mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the organic phases are combined, the solvent in the organic phases is distilled off in a rotating way, crude products are obtained, the crude products are purified by a rapid silica gel column, pure products are obtained, toluene and ethyl acetate are used for recrystallization, and light yellow solid powder of the products, namely the organic compound 12, is obtained, the yield is 55.7%, and MS (ASAP) = 758.8.
Example 13
The synthetic route for the organic compound 13 of this example is as follows:
Figure BDA0003371996950000261
synthesis of intermediate 13-3
Intermediate 13-1 (10 mmol) and intermediate 13-2 (10 mmol) were dissolved in a mixed solvent of 1, 4-dioxane and water (21/2 ml) Pd (PPh) was added 3 ) 4 (tetrakis (triphenylphosphine) palladium 0.1 mmol) and potassium carbonate (30 mmol). Stirring is carried out for 6h at 80℃under nitrogen. After cooling, most of the solvent was removed by rotary evaporation, followed by extraction and water washing, and the organic phase was subjected to column chromatography and recrystallized to give intermediate 13-3 in a molar amount of 8.46mmol, yield 84.6%, MS (ASAP) = 407.4.
Synthesis of intermediate 13-5
Intermediate 13-3 (10 mmol), compound 13-4 (10 mmol) were dissolved in a mixed solvent of 1, 4-dioxane and water (21/2 ml), and Pd (PPh) was added 3 ) 4 (0.1 mmol) and potassium carbonate (30 mmol). Stirring is carried out for 6h at 100℃under nitrogen. After cooling, most of the solvent was removed by rotary evaporation, followed by extraction and water washing, and the organic phase column chromatography and recrystallization gave intermediate 13-5 in a molar amount of 6.98mmol, yield 69.8%, MS (ASAP) =496.1.
Synthesis of intermediate 13-6
In a dry three-neck flask under the protection of nitrogen, 10mmol of intermediate 13-5 and 20mmol of compound 1-2 are respectively added, 100ml of DMSO is poured into the flask as a solvent, and dry Cs is added 2 CO 3 Taking alkali as a reaction for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for a plurality of times, simultaneously extracting the water phase for a plurality of times by using the dichloromethane, merging organic phases, and using anhydrous Na 2 CO 3 Drying, filtering, spin-drying the reaction solution to obtain a crude product, and recrystallizing with ethyl acetate to obtain an intermediate 13-6, wherein the molar amount is 5.91mmol, the reaction yield is 59.1%, and MS (ASAP) = 798.5.
Synthesis of organic Compound 13
Into a 250ml three-necked flask, 10mmol of intermediate 13-6 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooling to-30℃and dropwise adding 32mmol of t-BuLi n-hexane solution. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30℃and 21mmol of boron tribromide solution was added thereto, stirred at room temperature for 0.5 hours, and then the reaction solution was cooled to 0℃and 42mmol of N, N-diisopropylethyl was added theretoAnd (3) after the amine is added dropwise, heating to room temperature and stirring, continuously heating to 120 ℃ and stirring for 3 hours, and cooling the reaction solution to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined, the solvent was distilled off in vacuo to give crude product, which was purified by flash column chromatography to give pure product, which was recrystallized from toluene and ethyl acetate to give the product as pale yellow solid powder, organic compound 13, yield 29.3%, MS (ASAP) = 772.7.
Example 14
The synthetic route for the organic compound 14 of this example is as follows:
Figure BDA0003371996950000262
synthesis of intermediate 14-2
In a dry three-neck flask under the protection of nitrogen, 10mmol of compound 1-1 and 20mmol of compound 14-1 are respectively added, 100ml of DMSO is poured as a solvent, and dry Cs is added 2 CO 3 Taking alkali as a reaction for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for a plurality of times, simultaneously extracting the water phase for a plurality of times by using the dichloromethane, merging organic phases, and using anhydrous Na 2 CO 3 Drying, filtering, spin-drying the reaction solution to obtain a crude product, and recrystallizing with ethyl acetate to obtain intermediate 14-2 with a molar mass of 8.11mmol and a reaction yield of 81.1%, MS (ASAP) = 606.8.
Synthesis of organic Compound 14
Into a 250ml three-necked flask, 10mmol of intermediate 14-2 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooling to-30℃and adding 21mmol of t-BuLi n-hexane solution dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. Cooling the reaction solution to-30 ℃ again, adding 21mmol of boron tribromide solution, stirring for 0.5 hour at room temperature, cooling the reaction solution to 0 ℃, adding 42mmol of N, N-diisopropylethylamine, after the dropwise addition is completed, heating to room temperature, stirring, and continuing The temperature was raised to 120℃and stirred for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined, the solvent was distilled off in vacuo to give crude product, which was purified by flash column chromatography to give pure product, which was recrystallized from toluene and ethyl acetate to give the product as pale yellow solid powder, organic compound 14, yield 73.1%, MS (ASAP) =536.9.
Example 15
The synthetic route for the organic compound 15 of this example is as follows:
Figure BDA0003371996950000271
synthesis of intermediate 15-2
Compound 15-1 (20 mmol), compound 11-2 (10 mmol) were dissolved in a mixed solvent of 1, 4-dioxane and water (21/2 ml), and Pd (PPh 3) 4 (0.1 mmol) and potassium carbonate (30 mmol) were added. Stirring is carried out for 3h at 80℃under nitrogen. After cooling, most of the solvent was removed by rotary evaporation, followed by extraction and water washing, and the organic phase was subjected to column chromatography and recrystallized to give intermediate 15-2 in a molar amount of 7.35mmol, yield 73.5%, MS (ASAP) = 484.7.
Synthesis of intermediate 15-4
In a dry three-neck flask under the protection of nitrogen, 10mmol of intermediate 15-2 and 20mmol of compound 15-3 are respectively added, 100ml of DMSO is poured into the flask as a solvent, and dry Cs is added 2 CO 3 Taking alkali as a reaction for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for a plurality of times, simultaneously extracting the water phase for a plurality of times by using the dichloromethane, merging organic phases, and using anhydrous Na 2 CO 3 Drying, filtering, spin-drying the reaction solution to obtain a crude product, and recrystallizing with ethyl acetate to obtain intermediate 15-4 with a molar mass of 6.39mmol and a reaction yield of 63.9%, MS (ASAP) = 871.3.
Synthesis of organic Compound 15
Into a 250ml three-necked flask, 10mmol of intermediate 15-4 and 100ml were chargedDried tert-butylbenzene, in N 2 In the atmosphere, cooling to-30℃and adding 21mmol of t-BuLi n-hexane solution dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 21mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 42mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the organic phases are combined, the solvent in the organic phases is distilled off in a rotating way, crude products are obtained, the crude products are purified by a rapid silica gel column, the pure products are obtained by recrystallization of toluene and ethyl acetate, and light yellow solid powder of the products, namely the organic compound 15, is obtained, the yield is 53.1%, and MS (ASAP) =800.8.
Example 16
The synthetic route for the organic compound 16 of this example is as follows:
Figure BDA0003371996950000272
synthesis of intermediate 16-2
Compound 16-1 (20 mmol) and compound 11-2 (10 mmol) were dissolved in a mixed solvent of 1, 4-dioxane and water (21/2 ml), and Pd (PPh) was added 3 ) 4 (0.1 mmol) and potassium carbonate (30 mmol). Stirring is carried out for 3h at 80℃under nitrogen. After cooling, most of the solvent was removed by rotary evaporation, followed by extraction and water washing, and the organic phase was subjected to column chromatography and recrystallized to give intermediate 16-2 in a molar amount of 7.18mmol, yield 71.8%, MS (ASAP) = 524.9.
Synthesis of intermediate 16-3
In a dry three-neck flask under the protection of nitrogen, 10mmol of intermediate 16-2 and 20mmol of compound 14-1 are respectively added, 100ml of DMSO is poured into the flask as a solvent, and dry Cs is added 2 CO 3 Taking alkali as a reaction for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing with waterWashing the reaction solution multiple times while extracting the aqueous phase multiple times with dichloromethane, combining the organic phases, and using anhydrous Na 2 CO 3 Drying, filtering, spin-drying the reaction solution to obtain a crude product, and recrystallizing with ethyl acetate to obtain an intermediate 16-3 with a molar amount of 6.15mmol and a reaction yield of 61.5%, MS (ASAP) = 938.4.
Synthesis of organic Compound 16
Into a 250ml three-necked flask, 10mmol of intermediate 16-3 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooling to-30℃and adding 21mmol of t-BuLi n-hexane solution dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 21mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 42mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined, the solvent was distilled off in vacuo to give crude product, which was purified by flash column chromatography to give pure product, which was recrystallized from toluene and ethyl acetate to give the product as pale yellow solid powder, organic compound 16, yield 57.5%, MS (ASAP) = 868.7.
Example 17
The synthetic route for the organic compound 17 of this example is as follows:
Figure BDA0003371996950000281
synthesis of intermediate 17-3
Compound 17-1 (10 mmol), compound 17-2 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium t-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 12h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 17-3 in a molar amount of 7.27mmol and a yield of 72.7%, MS (ASAP) =259.8.
Synthesis of intermediate 17-4
Compound 3-1 (10 mmol), intermediate 17-3 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 6h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 17-4 in a molar amount of 7.59mmol and a yield of 75.9%, MS (ASAP) = 449.9.
Synthesis of intermediate 17-6
In a dry three-neck flask under the protection of nitrogen, 10mmol of intermediate 17-4 and 20mmol of compound 17-5 are respectively added, 100ml of DMSO is poured into the flask as a solvent, and dry Cs is added 2 CO 3 Taking alkali as a reaction for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for a plurality of times, simultaneously extracting the water phase for a plurality of times by using the dichloromethane, merging organic phases, and using anhydrous Na 2 CO 3 Drying, filtering, spin-drying the reaction solution to obtain a crude product, and recrystallizing with ethyl acetate to obtain an intermediate 17-6, wherein the molar quantity is 5.89mmol, the reaction yield is 58.9%, and MS (ASAP) =779.6.
Synthesis of organic Compound 17
Into a 250ml three-necked flask, 10mmol of intermediate 17-6 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooling to-30℃and adding 21mmol of t-BuLi n-hexane solution dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 21mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 42mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. Extracting the water phase with ethyl acetate, mixing the organic phases, evaporating solvent to obtain crude product, purifying with rapid silica gel column to obtain pure product, recrystallizing with toluene and ethyl acetate to obtain yellowish solid powder, i.e. organizedCompound 17, yield 64.5%, MS (ASAP) =710.1.
Example 18
The synthetic route for the organic compound 18 of this example is as follows:
Figure BDA0003371996950000291
synthesis of intermediate 18-2
Compound 3-1 (10 mmol), compound 18-1 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 6h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 18-2 in a molar amount of 8.25mmol, yield 82.5%, MS (ASAP) = 385.5.
Synthesis of intermediate 18-3
In a dry three-neck flask under the protection of nitrogen, 10mmol of intermediate 18-2 and 20mmol of compound 15-3 are respectively added, 100ml of DMSO is poured into the flask as a solvent, and dry Cs is added 2 CO 3 Taking alkali as a reaction for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for a plurality of times, simultaneously extracting the water phase for a plurality of times by using the dichloromethane, merging organic phases, and using anhydrous Na 2 CO 3 Drying, filtering, spin-drying the reaction solution to obtain a crude product, and recrystallizing with ethyl acetate to obtain an intermediate 18-3, wherein the molar amount is 7.59mmol, the reaction yield is 75.9%, and MS (ASAP) = 771.7.
Synthesis of organic Compound 18
Into a 250ml three-necked flask, 10mmol of intermediate 18-3 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooling to-30℃and adding 21mmol of t-BuLi n-hexane solution dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30℃and 21mmol of boron tribromide solution was added thereto, stirred at room temperature for 0.5 hours, and then the reaction solution was cooled to 0℃and 42mmo ofl N N-diisopropylethylamine, after the completion of the dropwise addition, was stirred at room temperature, and then was stirred at 120℃for 3 hours, and the reaction mixture was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the organic phases are combined, the solvent in the organic phases is distilled off in a rotating way, crude products are obtained, the crude products are purified by a rapid silica gel column, pure products are obtained, toluene and ethyl acetate are used for recrystallization, and light yellow solid powder of the products, namely the organic compound 18, is obtained, the yield is 54.2%, and MS (ASAP) = 701.7.
Example 19
The synthetic route for the organic compound 19 of this example is as follows:
Figure BDA0003371996950000292
synthesis of intermediate 19-3
Compound 19-1 (10 mmol), compound 19-2 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 6h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 19-3 in a molar amount of 7.27mmol and a yield of 72.7% MS (ASAP) =408.1.
Synthesis of intermediate 19-5
Intermediate 19-3 (10 mmol), compound 19-4 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 6h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 19-5 in a molar amount of 8.11mmol in a yield of 81.1% MS (ASAP) = 634.5.
Synthesis of organic Compound 19
Into a 250ml three-necked flask, 10mmol of intermediate 19-5 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooling to-30℃and adding 21mmol of t-BuLi n-hexane solution dropwise. Raising the temperature to 60 ℃ for reaction for 2 hours, and evaporating n-hexane in the mixture under reduced pressure And (3) an agent. The reaction solution was cooled again to-30 ℃, 21mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 42mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined, the solvent was distilled off in vacuo to give crude product, which was purified by flash column chromatography to give pure product, which was recrystallized from toluene and ethyl acetate to give the product as pale yellow solid powder, organic compound 19, yield 45.9%, MS (ASAP) = 608.1.
Example 20
The synthetic route of the organic compound 20 of this example is as follows:
Figure BDA0003371996950000301
synthesis of intermediate 20-3
Compound 20-1 (10 mmol), compound 20-2 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 6h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 20-3 in a molar amount of 8.35mmol, yield 83.5%, MS (ASAP) = 491.4.
Synthesis of intermediate 20-4
Intermediate 20-3 (10 mmol), compound 1-2 (10 mmol), pd (dba) 2 (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100deg.C for 6h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 20-4 in a molar amount of 6.52mmol, yield 65.2%, MS (ASAP) = 582.7.
Synthesis of intermediate 20-6
Intermediate 20-4 (10 mmol), compound 20-5 (10 mmol), pd (dba) 2 (0.1mmol)、TTBP(0.2mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred under nitrogen at 100℃for 6h. After cooling, the solvent was removed by rotary evaporation, extracted and the organic phase was collected by water washing, dried, concentrated under reduced pressure and column chromatographed to give intermediate 20-6 in a molar amount of 6.17mmol in 61.7% yield, MS (ASAP) = 767.9.
Synthesis of organic Compound 20
Into a 250ml three-necked flask, 10mmol of intermediate 20-6 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooling to-30℃and adding 21mmol of t-BuLi n-hexane solution dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 21mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 42mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined, the solvent was distilled off in vacuo to give crude product, which was purified by flash column chromatography to give pure product, which was recrystallized from toluene and ethyl acetate to give the product as pale yellow solid powder, organic compound 20, yield 37.9%, MS (ASAP) = 741.9.
Comparative example
The organic compound of this comparative example is BD-Ref1, which has the following chemical structural formula:
Figure BDA0003371996950000311
organic compound energy level calculation
The energy levels HOMO, LUMO, T1 and S1 of the organic compounds of examples 1 to 20 and comparative examples were calculated. Specifically, using TD-DFT (time-density functional theory) and passing through Gaussian 09W (Gaussian inc.), a specific simulation method can be seen in WO2011141110, first, using a Semi-empirical method "group State/Semi-empirical/Default Spin/AM1" (Charge 0/Spin single let) to optimize the molecular geometry, and then using the TD-DFT (time-density functional theory) method to calculate the energy structure of the organic molecule as "TD-SCF/DFT/Default Spin/B3PW91" and the group "6-31G (d)" (Charge 0/Spin single let). HOMO and LUMO energy levels were calculated according to the following calibration formula, S1 and T1 being used directly:
HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206；
LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385。
wherein HOMO, LUMO, T and S1 are direct calculations of Gaussian 09W in Hartree. The results are given in Table I below.
Table one:
compounds of formula (I) HOMO[eV] LUMO[eV] T1[eV] S1[eV]
Example 1 Organic Compound 1 -5.45 -2.70 2.33 2.95
Example 2 Organic Compound 2 -5.35 -2.68 2.35 3.04
Example 3 Organic Compound 3 -5.30 -2.54 2.41 2.95
Example 4 Organic Compound 4 -5.35 -2.54 2.38 2.93
Example 5 Organic Compound 5 -5.29 -2.51 2.39 3.07
Example 6 Organic Compound 6 -5.15 -2.41 2.43 3.05
Example 7 Organic Compound 7 -5.28 -2.49 2.41 2.97
Example 8 Organic Compound 8 -5.17 -2.45 2.48 3,05
Example 9 Organic Compound 9 -5.40 -2.63 2.41 3.04
Example 10 Organic Compound 10 -5.29 -2.56 2.38 3.01
Example 11 Organic Compound 11 -5.21 -2.51 2.37 3.09
Example 12 Organic Compound 12 -5.24 -2.46 2.39 2.93
Example 13 Organic Compound 13 -5.18 -2.47 2.35 3.06
Example 14 Organic Compound 14 -5.12 -2.38 2.41 3.01
Example 15 Organic Compound 15 -5.15 -2.41 2.35 2.96
Example 16 Organic Compound 16 -5.20 -2.45 2.32 2.98
Example 17 Organic Compound 17 -5.22 -2.49 2.46 2.93
Example 18 Organic Compound 18 -5.15 -2.51 2.38 2.98
Example 19 Organic Compound 19 -5.14 -2.43 2.41 2.96
Example 20 Organic Compound 20 -5.16 -2.51 2.43 3.05
Comparative example BD-Ref1 -5.17 -2.32 2.31 2.81
As can be seen from table one, the organic compounds of the present application have suitable HOMO, LUMO, T and S1 energy levels and can be used as blue guest materials.
Preparation and characterization of OLED devices
This practice isIn the OLED device of the example, ITO is used as an anode, and PEDOT (polyethylene dioxythiophene, clevelos TM AI 4083) as a hole injection layer material, PVK (Sigma Aldrich, average Mn 25,000-50,000) as a hole transport material, BH as a host material for a light emitting material, the organic compounds in examples 1-20 and comparative examples as guest materials (BD) for a light emitting material, ET and Liq as electron transport materials, al as a cathode, and the constitution device structure was ITO/PEDOT/PVK/BH: BD/ET: liq/Al.
The chemical structural formula of BH, ET, liq is as follows:
Figure BDA0003371996950000321
the above materials BH, ET, liq are all commercially available or their methods of synthesis are all known in the art.
A schematic diagram of an OLED device is shown in fig. 1. Wherein 10 is a substrate, 20 is an anode, 30 is a Hole Injection Layer (HIL), 40 is a Hole Transport Layer (HTL), 50 is a light emitting layer, 60 is an Electron Transport Layer (ETL), and 70 is a cathode.
The process of manufacturing an OLED device using the above materials is described in detail below by way of specific examples.
Device example 1
The method for manufacturing the OLED device of the present embodiment includes the steps of:
a. cleaning an ITO (indium tin oxide) conductive glass substrate: cleaning with various solvents (such as chloroform, acetone or isopropanol, or both), and performing ultraviolet ozone treatment;
b. HIL (hole injection layer, 40 nm): PEDOT (polyethylene dioxythiophenes, clevelos) TM AI 4083) as HIL in a clean room and processed for 10 minutes on a hot plate at 180 ℃;
c. HTL (hole transport layer, 20 nm): PVK solution (Sigma Aldrich, average Mn 25,000-50,000) of PVK added to toluene solvent at a solution solubility of 5mg/ml was spin-coated in a nitrogen glove box, followed by treatment on a hot plate at 180deg.C for 60 minutes;
d. EML (organic light emitting layer, 40 nm): EML is prepared by spin coating in a nitrogen glove box, wherein the used solution is methyl benzoate solution of different hosts (the weight ratio of the hosts is 95:5), the solution solubility is 15mg/ml, and then the mixture is treated on a hot plate at 140 ℃ for 10 minutes, wherein the host material is BH, the organic compound of example 1 is adopted as the host, and other embodiments are the same;
e. An electron transport layer and a cathode: transferring the heat-treated substrate into a vacuum chamber, then placing ET and Liq in different evaporation units under high vacuum (1×10) -6 Mbar) were co-deposited in a proportion of 50wt% respectively, forming an electron transport layer of 20nm on the light-emitting layer, followed by redeposition of an Al cathode having a thickness of 100 nm;
f. and (3) packaging: encapsulation with ultraviolet curable resin was performed in a nitrogen glove box.
Device examples 2 to 20
Substantially the same as device example 1, except that the guest materials of the light-emitting layers of device examples 2 to 20 were selected from the organic compounds of examples 2 to 20, respectively.
Device comparative example
Substantially the same as in device example 1, except that the guest material of the light-emitting layer of the device comparative example was BD-Ref1.
Performance detection and results
The current-voltage (J-V) characteristics of the OLED devices of device examples 1-20 and device comparative examples were tested using a characterization apparatus while recording important parameters such as color coordinates, voltage, luminous efficacy CE, and lifetime LT90.
Table one:
Figure BDA0003371996950000322
Figure BDA0003371996950000331
from Table one can see:
the organic compounds of examples 1-20 produced blue OLED devices with better color coordinates than blue OLED devices produced with the organic compound of the comparative example.
The blue OLED devices prepared using the organic compounds of examples 1-20 as guest materials in the light emitting layer all had light emitting efficiencies in the range of 5.3-6.4cd/a, with more excellent light emitting efficiencies.
The blue OLED devices prepared by using the organic compounds of examples 1, 3, 11, and 12 as guest materials in the light-emitting layers all have light-emitting efficiencies in the range of 6.0-6.4cd/A, and have lifetimes of about 160-170h, and have the most excellent light-emitting efficiencies and lifetimes. The possible reasons are: the device of example 1 has better luminous efficiency and lifetime than other examples, indicating that the most basic structure itself has excellent properties and is suitable for use as a blue guest material; in the embodiments 3, 11 and 12, the para-position and meta-position of the boron atom in the molecular structure are introduced with the diphenylamino group and the diisopropylamine group, so that the organic compound molecule has a large triarylamine structure, and the luminous efficiency and the service life of the device are slightly improved on the basis of the embodiment 1; in addition, the introduction of the hydrogenated carbazole enables the organic compound to have better molecular solubility and is easy to purify, so that the purity of the compound can be effectively improved, and the luminous efficiency and the service life of the device are further improved.
In addition, the lifetime of blue OLED devices prepared using the organic compounds of examples 1 to 20 as guest materials in the light emitting layer is generally improved by 50% to 70% as compared to blue OLED devices prepared using the organic compounds of comparative examples as guest materials in the light emitting layer.
The boron-containing hydrogenated carbazole organic compound has the advantages that the hydrogenated carbazole formed by the condensed benzene ring and the six-membered aliphatic ring enables the whole molecular structure to have better conjugation and flatness, the rigidity and stability of organic compound molecules are improved, the introduction of the aliphatic ring further improves the solubility of the molecules, the compound is easier to purify, the purity of the compound is improved, and the purposes of prolonging the luminous efficiency and the service life of the organic electronic device are further achieved. In addition, the boron-containing hydrogenated carbazole organic compound can be used as a blue light guest material, and can improve the luminous efficiency and the service life of an organic electronic device by being matched with a proper host material.
The organic compounds, mixtures, compositions and organic electronic devices provided in the examples of the present application are described in detail, and specific examples are used herein to illustrate the principles and embodiments of the present application, the description of the examples above being only for aiding in the understanding of the methods of the present application and the core ideas thereof; meanwhile, those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, and the present description should not be construed as limiting the present application in view of the above.

Claims (12)

1. A boron-containing hydrogenated carbazole organic compound is characterized by having a structure shown in a general formula (1):
Figure FDA0003371996940000011
wherein:
n1 is selected from 0, 1, 2 or 3; n2 is selected from 0, 1, 2 or 3; n3 is selected from 0, 1, 2 or 3;
R 1 、R 2 、R 3 each occurrence is independently selected from the group consisting of-D (deuterium), or a linear alkyl group having 1 to 20C atoms, a linear alkoxy group having 1 to 20C atoms, or a linear thioalkoxy group having 1 to 20C atoms, or a branched alkyl group having 3 to 20C atoms, or a branched alkoxy group having 3 to 20C atoms, or a branched thioalkoxy group having 3 to 20C atoms, or a cyclic alkyl group having 3 to 20C atoms, or a cyclic alkoxy group having 3 to 20C atoms, or a cyclic thioalkoxy group having 3 to 20C atoms, or a silyl group, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, or isothiocyanate, hydroxyl, nitro, substituted or unsubstituted amine, -CF 3 -Cl, -Br, -F, -I, orSubstituted or unsubstituted alkenyl having 1 to 20C atoms, or substituted or unsubstituted aryl having 6 to 60 ring atoms, or substituted or unsubstituted heteroaryl having 5 to 60 ring atoms, or substituted or unsubstituted aryloxy having 5 to 60 ring atoms, or substituted or unsubstituted heteroaryloxy having 5 to 60 ring atoms, or a combination of these groups;
Adjacent R 1 With or without each other being cyclic;
adjacent R 2 With or without each other being cyclic;
adjacent R 3 With or without each other.
2. The boron-containing hydrogenated carbazole organic compound according to claim 1, wherein the boron-containing hydrogenated carbazole organic compound is selected from structures represented by formulae (2-1) to (2-4):
Figure FDA0003371996940000012
3. the boron-containing hydrogenated carbazole organic compound according to claim 1, characterized by a structure as shown below:
Figure FDA0003371996940000013
Figure FDA0003371996940000021
4. the boron-containing hydrogenated carbazole organic compound according to claim 1, wherein the boron-containing hydrogenated carbazole organic compound is selected from structures represented by formulae (3-1) to (3-18):
Figure FDA0003371996940000022
/>
Figure FDA0003371996940000031
5. the boron-containing hydrogenated carbazole organic compound as claimed in claim 1 or 2 or 3 or 4, characterized in that: r is R 1 、R 2 、R 3 Independently at each occurrence selected from-D, or a straight chain alkyl group having 1 to 8C atoms, or a branched alkyl group having 3 to 8C atoms, or a cyclic alkyl group having 3 to 8C atoms, or a silyl group,
Figure FDA0003371996940000032
Or by R 0 Substituted or unsubstituted aromatic groups having 6 to 20 ring atoms, or substituted by R 0 A substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, or a combination of such groups;
Wherein R is 4 、R 5 Independently selected from a linear alkyl group having 1 to 8C atoms, or a branched alkyl group having 3 to 8C atoms, or a cyclic alkyl group having 3 to 8C atoms, or R 0 Substituted or unsubstituted aromatic groups having 6 to 20 ring atoms, or substituted by R 0 A substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, or a combination of such groups;
R 0 independently selected for each occurrence from-D, or a linear alkyl group having 1 to 10C atoms, or a branched alkyl group having 3 to 10C atoms, or a cyclic alkyl group having 3 to 10C atoms, or a silyl group, or an aromatic group having 6 to 20 ring atoms, or a heteroaromatic group having 6 to 20 ring atoms, or a combination of these groups;
* Representing the ligation site.
6. The boron-containing hydrogenated carbazole organic compound as claimed in claim 5, wherein: r is R 1 、R 2 、R 3 Each occurrence ofIndependently selected from a straight chain alkyl group having 1 to 8C atoms, or a branched alkyl group having 3 to 8C atoms, or a cyclic alkyl group having 3 to 8C atoms,
Figure FDA0003371996940000033
Or the following groups:
Figure FDA0003371996940000034
wherein:
y is selected from CR 6 R 7 ，NR 8 O or S;
R 6 、R 7 、R 8 each occurrence is independently selected from the group consisting of-H, -D, or a linear alkyl group having 1 to 10C atoms, a linear alkoxy group having 1 to 10C atoms, or a linear thioalkoxy group having 1 to 10C atoms, or a branched alkyl group having 3 to 10C atoms, or a branched alkoxy group having 3 to 10C atoms, or a branched thioalkoxy group having 3 to 10C atoms, or a cyclic alkyl group having 3 to 10C atoms, or a cyclic alkoxy group having 3 to 10C atoms, or a cyclic thioalkoxy group having 3 to 10C atoms, or a silyl group, or a keto group having 1 to 10C atoms, or an alkoxycarbonyl group having 2 to 10C atoms, or an aryloxycarbonyl group having 7 to 10C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, or isothiocyanate, hydroxyl, nitro, substituted or unsubstituted amine, -CF 3 -Cl, -Br, -F, -I, or a substituted or unsubstituted alkenyl group having 1 to 10C atoms, or a substituted or unsubstituted aryl group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaryl group having 5 to 20 ring atoms, or a substituted or unsubstituted aryloxy group having 5 to 20 ring atoms, or a substituted or unsubstituted heteroaryloxy group having 5 to 20 ring atoms, or a combination of these groups;
m1 is selected from 0, 1, 2, 3 or 4; m2 is selected from 0, 1, 2 or 3; m3 is selected from 0, 1, 2, 3, 4 or 5.
7. The boron-containing hydrogenated carbazole organic compound as claimed in claim 1 or 2 or 3 or 4, wherein R 3 Each occurrence is independently selected from methyl, ethyl, iPr, tBu, tAm, et, or the following groups:
Figure FDA0003371996940000035
/>
Figure FDA0003371996940000041
Figure FDA0003371996940000051
wherein: * Representing the ligation site.
8. The boron-containing hydrogenated carbazole organic compound as claimed in claim 1 or 2 or 3 or 4, wherein R 1 、R 2 Each occurrence is independently selected from methyl, ethyl, iPr, tBu, tAm, or Et.
9. The boron-containing hydrogenated carbazole organic compound according to claim 1, wherein the boron-containing hydrogenated carbazole organic compound is selected from the following structures:
Figure FDA0003371996940000052
/>
Figure FDA0003371996940000061
/>
Figure FDA0003371996940000071
/>
Figure FDA0003371996940000081
/>
Figure FDA0003371996940000091
/>
Figure FDA0003371996940000101
/>
Figure FDA0003371996940000111
10. a mixture characterized by: the mixture comprising the boron-containing hydrogenated carbazole organic compound according to any one of claims 1 to 9 and at least one organic functional material selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitter, a host material, or an organic dye.
11. A composition characterized by: the composition comprising the boron-containing hydrogenated carbazole organic compound or the mixture of claim 10, and at least one organic solvent.
12. An organic electronic device comprising at least one functional layer, characterized in that: the functional layer comprises the boron-containing hydrogenated carbazole organic compound according to any one of claims 1 to 9, or the mixture according to claim 10, or is prepared from the composition according to claim 11.
CN202111403739.3A 2021-11-24 2021-11-24 Boron-containing hydrogenated carbazole organic compound and application thereof Pending CN116178402A (en)

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