CN115605469A - Novel compound and organic light emitting device comprising same - Google Patents

Novel compound and organic light emitting device comprising same Download PDF

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CN115605469A
CN115605469A CN202180034282.5A CN202180034282A CN115605469A CN 115605469 A CN115605469 A CN 115605469A CN 202180034282 A CN202180034282 A CN 202180034282A CN 115605469 A CN115605469 A CN 115605469A
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金旼俊
李东勋
车龙范
金曙渊
崔乘源
沈在勋
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LG Chem Ltd
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Abstract

The invention provides a novel compound and an organic light emitting device using the same.

Description

Novel compound and organic light emitting device comprising same
Technical Field
Cross reference to related applications
This application claims priority based on korean patent application No. 10-2020-0057324, on year 2020, month 5, and day 13, and korean patent application No. 10-2021-0062165, on year 2021, month 5, and day 13, and the entire contents disclosed in the documents of this korean patent application are incorporated as part of this specification.
The present invention relates to a novel compound and an organic light emitting device comprising the same.
Background
Generally, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic substance. An organic light emitting device using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, a fast response time, and excellent luminance, driving voltage, and response speed characteristics, and thus a great deal of research is being conducted.
An organic light emitting device generally has a structure including an anode and a cathode, and an organic layer between the anode and the cathode. In order to improve efficiency and stability of the organic light emitting device, the organic layer is often formed of a multilayer structure formed of different materials, and may be formed of, for example, a hole injection layer, a hole transport layer, an electron suppression layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, or the like. With the structure of such an organic light emitting device, if a voltage is applied between the two electrodes, holes are injected from the anode into the organic layer, electrons are injected from the cathode into the organic layer, and when the injected holes and electrons meet, excitons (exiton) are formed, which emit light when they transition to the ground state again.
For organic materials used for the organic light emitting devices as described above, development of new materials is continuously demanded.
Documents of the prior art
Patent document
(patent document 0001) Korean patent laid-open publication No. 10-2000-0051826
Disclosure of Invention
Technical subject
The present invention relates to a novel compound and an organic light emitting device including the same.
Means for solving the problems
The present invention provides a compound represented by the following chemical formula 1:
[ chemical formula 1]
Figure BDA0003935930440000021
In the above-mentioned chemical formula 1,
each Y is independently a single bond, or is O or S, with the proviso that at least one of Y is O or S,
R 1 each independently is hydrogen; deuterium; a halogen; a cyano group; substituted or unsubstituted C 1-60 An alkyl group; substituted or unsubstituted C 1-60 An alkoxy group; substituted or unsubstituted C 2-60 An alkenyl group; substituted or unsubstituted C 2-60 An alkynyl group; substituted or unsubstituted C 3-60 A cycloalkyl group; substituted or unsubstituted C 6-60 An aryl group; substituted or unsubstituted C containing one or more heteroatoms selected from N, O and S 2-60 (ii) a heteroaryl group, wherein,
n1 and n2 are integers from 0 to 4,
n3 is an integer of 0 to 3,
R 2 represented by the following chemical formula 2,
[ chemical formula 2]
Figure BDA0003935930440000031
In the above-described chemical formula 2,
l is a single bond, or substituted or unsubstituted C 6-60 An arylene group, a cyclic or cyclic alkylene group,
x is N or CH, at least 2 or more of X are N,
Ar 1 and Ar 2 Each independently substituted or unsubstituted C 6-60 An aryl group; get theSubstituted or unsubstituted C containing one or more heteroatoms selected from N, O and S 2-60 A heteroaryl group.
In addition, the present invention provides an organic light emitting device, comprising: the organic light emitting device includes a first electrode, a second electrode disposed to face the first electrode, and 1 or more organic layers disposed between the first electrode and the second electrode, wherein 1 or more of the organic layers include a compound represented by the chemical formula 1.
Effects of the invention
The compound represented by the above chemical formula 1 may be used as a material for an organic layer of an organic light emitting device in which improvement in efficiency, lower driving voltage, and/or improvement in lifetime characteristics may be achieved. In particular, the compound represented by the above chemical formula 1 may be used as a material for hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection.
Drawings
Fig. 1 illustrates an example of an organic light-emitting device composed of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.
Fig. 2 illustrates an example of an organic light-emitting device composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron suppression layer 6, a light-emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4.
Detailed Description
Hereinafter, the present invention will be described in more detail to assist understanding thereof.
In the context of the present specification,
Figure BDA0003935930440000041
or
Figure BDA0003935930440000042
Represents a bond to other substituents.
In the present specification, the term "substituted or unsubstituted" means substituted with a substituent selected from deuterium; a halogen group; a nitrile group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amino group; phosphine oxideA group; an alkoxy group; an aryloxy group; alkylthio(s) of (A), (B) and (C)
Figure BDA0003935930440000043
) (ii) a Aryl radicals thio group (S)
Figure BDA0003935930440000044
) (ii) a Alkylsulfonyl (
Figure BDA0003935930440000045
) (ii) a Arylsulfonyl (C)
Figure BDA0003935930440000046
) (ii) a A silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; aralkyl group; an aralkenyl group; an alkylaryl group; an alkylamino group; an aralkylamino group; a heteroaryl amino group; an arylamine group; an aryl phosphine group; or 1 or more substituents of 1 or more heterocyclic groups containing N, O and S atoms, or substituents formed by connecting 2 or more substituents of the above-exemplified substituents. For example, "a substituent in which 2 or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which 2 phenyl groups are linked.
In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the compound may have the following structure, but is not limited thereto.
Figure BDA0003935930440000047
In the present specification, in the ester group, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 25 carbon atoms. Specifically, the compound may be represented by the following structural formula, but is not limited thereto.
Figure BDA0003935930440000051
In the present specification, the number of carbon atoms in the imide group is not particularly limited, but is preferably 1 to 25. Specifically, the compound may have the following structure, but is not limited thereto.
Figure BDA0003935930440000052
In the present specification, specific examples of the silyl group include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, and a phenylsilyl group.
In the present specification, the boron group specifically includes a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like, but is not limited thereto.
In the present specification, as examples of the halogen group, there are fluorine, chlorine, bromine or iodine.
In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the number of carbon atoms of the alkyl group is 1 to 10. According to another embodiment, the number of carbon atoms of the alkyl group is 1 to 6. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, and 5-methylhexyl.
In the present specification, the alkenyl group may be a linear or branched one, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the number of carbon atoms of the alkenyl group is 2 to 20. According to another embodiment, the number of carbon atoms of the alkenyl group is 2 to 10. According to another embodiment, the number of carbon atoms of the above alkenyl group is 2 to 6. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylethen-1-yl, 2-diphenylethen-1-yl, 2-phenyl-2- (naphthalen-1-yl) ethen-1-yl, 2-bis (biphenyl-1-yl) ethen-1-yl, stilbenyl, styryl and the like, but the present invention is not limited thereto.
In the present specification, the cycloalkyl group is not particularly limited, but is preferably a cycloalkyl group having 3 to 60 carbon atoms, and according to an embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. Specifically, there may be mentioned, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like.
In the present specification, the aryl group is not particularly limited, but is preferably an aryl group having 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aromatic group may be a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a perylene group,
Figure BDA0003935930440000061
And a fluorenyl group, but is not limited thereto.
In the present specification, the fluorenyl group may be substituted, and 2 substituents may be combined with each other to form a spiro structure. When the fluorenyl group is substituted, the substituted fluorenyl group may be
Figure BDA0003935930440000071
And so on. But is not limited thereto.
In the present specification, the heterocyclic group is a heterocyclic group containing 1 or more of O, N, si and S as a hetero element, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60. Examples of the heterocyclic group include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, thienyl,
Figure BDA0003935930440000072
Azole group,
Figure BDA0003935930440000073
Oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzobenzoxazinyl
Figure BDA0003935930440000074
Azolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuranyl, phenanthrolinyl (phenanthroline), and isooxazolyl
Figure BDA0003935930440000075
Oxazolyl, thiadiazolyl, phenothiazinyl, dibenzofuranyl, and the like, but is not limited thereto.
In the present specification, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the aryl group described above. In the present specification, the alkyl group in the aralkyl group, alkylaryl group, and alkylamino group is the same as the above-mentioned alkyl group. In the present specification, the heteroaryl group in the heteroarylamine can be applied to the above description about the heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as exemplified above for the alkenyl group. In the present specification, the arylene group is a 2-valent group, and the above description of the aryl group can be applied thereto. In the present specification, a heteroarylene group is a 2-valent group, and in addition to this, the above description about a heterocyclic group can be applied. In the present specification, the hydrocarbon ring is not a 1-valent group but is formed by combining 2 substituents, and in addition to this, the above description about the aryl group or the cycloalkyl group can be applied. In the present specification, the heterocyclic group is not a 1-valent group but a combination of 2 substituents, and the above description of the heterocyclic group can be applied.
The present invention provides a compound represented by the above chemical formula 1.
The compound represented by chemical formula 1 may be improved in characteristics of an organic light emitting device using the same by bonding a heterocyclic ring containing 2 or more N at a specific position of a mother nucleus structure in which a fluoranthene (fluoranthene) ring and a bicyclic heterocyclic ring containing O or S are fused. In particular, the compound represented by the above chemical formula 1 can improve quantum efficiency and lifetime by increasing the binding force (rigidity) of molecules, increasing the stability of electrons and holes, and exhibiting better light emission characteristics by using a polycyclic aromatic nucleus in which a plurality of aromatic rings are linked.
In the above chemical formula 1, the compound represented by the above chemical formula 1 may be represented by any one of the following chemical formulas 1-1 to 1-8, depending on a specific position to which a heterocyclic ring containing 2 or more N is bound:
[ chemical formula 1-1]
Figure BDA0003935930440000081
[ chemical formulas 1-2]
Figure BDA0003935930440000082
[ chemical formulas 1-3]
Figure BDA0003935930440000091
[ chemical formulas 1 to 4]
Figure BDA0003935930440000092
[ chemical formulas 1-5]
Figure BDA0003935930440000093
[ chemical formulas 1 to 6]
Figure BDA0003935930440000094
[ chemical formulas 1 to 7]
Figure BDA0003935930440000101
[ chemical formulas 1 to 8]
Figure BDA0003935930440000102
In the above chemical formulas 1-1 to 1-8,
z is O or S, and the compound is a linear or branched compound,
R 1 、n1、n2、n3、L、X、Ar 1 and Ar 2 The same as defined in the above chemical formula 1.
Specifically, in chemical formula 1, one of Y is O or S, and the others are single bonds.
Specifically, in the above chemical formula 1 and chemical formulae 1-1 to 1-8, R 1 Each may be hydrogen, deuterium, halogen or cyano; or substituted or unsubstituted C 1-20 Alkyl, or C 1-12 Alkyl, or C 1-6 An alkyl group; or substituted or unsubstituted C 1-20 Alkoxy, or C 1-12 Alkoxy, or C 1-6 An alkoxy group; or substituted or unsubstituted C 2-20 Alkenyl, or C 2-12 Alkenyl, or C 2-6 An alkenyl group; or substituted or unsubstituted C 2-20 Alkynyl, or C 2-12 Alkynyl, or C 2-6 Alkynyl; or substituted or unsubstituted C 3-30 Cycloalkyl, or C 3-25 Cycloalkyl, or C 3-20 A cycloalkyl group; or substituted or unsubstituted C 6-30 Aryl, or C 6-28 Aryl, or C 6-25 Aryl, or C 6-20 An aryl group; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O and S 3-30 Heteroaryl, or C 5-28 Heteroaryl, or C 5-25 Heteroaryl, or C 6-20 Heteroaryl, or C 12-18 A heteroaryl group.
As an example, R 1 Each may be hydrogen or deuterium. Furthermore, R 1 May all be hydrogen.
Specifically, in the above chemical formula 1 and chemical formulae 1-1 to 1-8, n1, n2, and n3 may each be an integer of 0 to 2, or 0 or 1.
Specifically, in the above chemical formula 1 and chemical formulae 1-1 to 1-8, L may be a single bond; or substituted or unsubstituted C 6-30 Arylene, or C 6-28 Arylene, or C 6-25 Arylene radical, or C 6-20 An arylene group. Preferably, L may be a single bond; or phenylene, biphenylene, terphenylene, tetrabiphenylene, or naphthylene.
As an example, L may be a single bond or represented by any one selected from the following groups.
Figure BDA0003935930440000111
Specifically, in the above chemical formula 1 and chemical formulae 1-1 to 1-8, two of X may be N, and the rest may be CH, or X may be N.
Specifically, in the above chemical formula 1 and chemical formulae 1-1 to 1-8, ar 1 And Ar 2 Each of which may be substituted or unsubstituted C 6-30 Aryl radicalOr C 6-28 Aryl, or C 6-25 Aryl, or C 6-20 An aryl group; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O and S 3-30 Heteroaryl, or C 5-28 Heteroaryl, or C 5-25 Heteroaryl, or C 6-20 Heteroaryl, or C 12-18 A heteroaryl group.
More specifically, ar 1 And Ar 2 Each may be phenyl, naphthyl-substituted phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, phenanthryl, dibenzofuranyl, dibenzothienyl, carbazolyl, or phenyl-substituted carbazolyl.
In particular, ar 1 And Ar 2 At least one of them may be phenyl, naphthyl-substituted phenyl, biphenyl, naphthyl, or phenyl-substituted naphthyl, and preferably, it may be phenyl, biphenyl, or naphthyl.
Representative examples of the compound represented by the above chemical formula 1 are shown below.
Figure BDA0003935930440000131
Figure BDA0003935930440000141
Figure BDA0003935930440000151
Figure BDA0003935930440000161
Figure BDA0003935930440000171
Figure BDA0003935930440000181
Figure BDA0003935930440000191
Figure BDA0003935930440000201
Figure BDA0003935930440000211
Figure BDA0003935930440000221
On the other hand, the compound represented by the above chemical formula 1 can be produced by a production method as shown in the following reaction formula 1. The above-described production method can be further embodied in the synthesis examples described later.
[ reaction formula 1]
Figure BDA0003935930440000222
In the above reaction formula 1, Y and R 1 、R 2 N1 and n2 are as defined in the above chemical formula 1, and Q 1 Is BO 2 C 2 (CH 3 ) 4 Or B (OH) 2 ，Q 2 Is a halogen group, preferably Cl, br or I, more preferably Cl.
Specifically, the reaction formula 1 is a reaction in which a heteroaryl substituent having at least 2 or more N atoms is introduced into a specific position in a parent structure in which a fluoranthene ring and a bicyclic heterocycle containing O or S are fused.
As an example, the above reaction formula 1 is performed as follows: make Q 1 Is pinacolborane (pinacolborane) group or BO 2 C 2 (CH 3 ) 4 Or boric acid (boric ac)id) radical, i.e. B (OH) 2 And a polycyclic compound in which a fluoranthene ring is fused with a bicyclic heterocycle containing O or S and Q is contained as a halogen group 2 And a heterocyclic compound containing at least 2 or more N is reacted with a palladium catalyst (Pd catalyst) in the presence of a base (base). By such a reaction, pinacolboronic acid alkyl BO in which a heteroaryl group containing at least 2 or more N is introduced into a polycyclic compound in which a fluoranthene ring and a bicyclic heterocycle containing O or S are fused 2 C 2 (CH 3 ) 4 Or B (OH) 2 At position Q 1 Location. Preferably, in the above reaction formula 1, Q 1 Can be BO 2 C 2 (CH 3 ) 4 、Q 2 May be chlorine. The specific reaction conditions of such reaction formula 1 may be carried out with reference to known reactions known in the art. The above-described production method can be further embodied in the synthesis examples described later.
Further, as the alkali component, potassium carbonate (K) can be used 2 CO 3 ) Sodium bicarbonate (NaHCO) 3 ) Cesium carbonate (Cs) 2 CO 3 ) Sodium acetate (NaOAc), potassium acetate (KOAc), sodium tert-butoxide (NaOtBu), sodium ethoxide (NaOEt), or triethylamine (triethylamine, et) 3 N), N-diisopropylethylamine (N, N-diisopropropylethylamine, etN (iPr) 2 ) And the like. Preferably, the alkali component may be potassium carbonate (K) 2 CO 3 ) Cesium carbonate (Cs) 2 CO 3 ) Potassium acetate (KOAc), sodium tert-butoxide (NaOtBu), or N, N-diisopropylethylamine (EtN (iPr) 2 )。
Further, as the palladium catalyst, bis (tri (tert-butyl) phosphine) palladium (0) (bis (tri-butyl) phosphine) palladium (0), pd (P-tBu) may be used 3 ) 2 ) Tetrakis (triphenylphosphine) palladium (0) (tetrakis (triphenylphosphine) palladium (0)), tris (dibenzylideneacetone) -dipalladium (0), pd 2 (dba) 3 ) Bis (dibenzylideneacetone) palladium (0) (bis (dibenzylideneacetone) palladium (0), pd (A), (B)dba) 2 )、Pd(PPh 3 ) 4 ) Or palladium (II) acetate (palladium (II) acetate, pd (OAc) 2 ) And the like. Preferably, the above palladium catalyst may be bis (tri (tert-butyl) phosphine) palladium (0) (Pd (P-tBu) 3 ) 2 ) Tetrakis (triphenylphosphine) palladium (0) (Pd (PPh) 3 ) 4 ) Or bis (dibenzylideneacetone) palladium (0) (Pd (dba) 2 ). In particular, in the above reaction formula 1, bis (tri (t-butyl) phosphine) palladium (0) (Pd (P-tBu) may be used 3 ) 2 ) As a catalyst.
In the present specification, an equivalent (eq.) refers to a molar equivalent.
In another aspect, the present invention provides an organic light emitting device comprising the compound represented by the above chemical formula 1. As an example, the present invention provides an organic light emitting device, comprising: the organic light emitting device includes a first electrode, a second electrode disposed to face the first electrode, and 1 or more organic layers disposed between the first electrode and the second electrode, wherein 1 or more of the organic layers include a compound represented by the chemical formula 1.
The organic layer of the organic light-emitting device of the present invention may have a single-layer structure, or may have a multilayer structure in which 2 or more organic layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron suppression layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like as an organic layer. However, the structure of the organic light emitting device is not limited thereto, and a smaller number of organic layers may be included.
In addition, the organic layer may include a hole injection layer, a hole transport layer, or a layer simultaneously performing hole injection and transport, and the hole injection layer, the hole transport layer, or the layer simultaneously performing hole injection and transport includes the compound represented by the above chemical formula 1.
In addition, the organic layer may include an electron inhibiting layer including the compound represented by the chemical formula 1.
In addition, the organic layer may include a light emitting layer including the compound represented by the chemical formula 1.
In addition, the light-emitting layer further contains a dopant compound.
In addition, the light emitting layer includes the compound of chemical formula 1 and a dopant.
As an example, the above light emitting layer includes the compound of chemical formula 1 and a dopant, and includes the compound of chemical formula 1 and the dopant at a content ratio of 100.
In addition, the light emitting layer includes the compound of chemical formula 1 and a dopant, and includes the compound of chemical formula 1 and the dopant at a content ratio of 100.
In addition, the light emitting layer includes the compound of chemical formula 1 and a dopant, and includes the compound of chemical formula 1 and the dopant at a content ratio of 100.
As an example, the dopant is a metal complex.
Specifically, the dopant is an iridium-based metal complex.
The organic layer includes a light-emitting layer, the light-emitting layer contains a dopant, and the dopant is selected from the following structural formulae.
Figure BDA0003935930440000261
Figure BDA0003935930440000271
Figure BDA0003935930440000281
The above-mentioned explicit structure is a dopant compound, and is not limited thereto.
In addition, the organic layer may include a hole blocking layer including the compound represented by the chemical formula 1.
In addition, the organic layer may include an electron transport layer, an electron injection layer, or a layer simultaneously performing electron injection and transport, and the electron transport layer, the electron injection layer, or the layer simultaneously performing electron injection and transport includes the compound represented by the above chemical formula 1.
In addition, the organic layer may include a light emitting layer and a hole transport layer, and the light emitting layer or the hole transport layer may include the compound represented by the chemical formula 1.
In addition, the organic light emitting device according to the present invention may be an organic light emitting device of a structure (normal type) in which an anode, 1 or more organic layers, and a cathode are sequentially stacked on a substrate. Further, the organic light emitting device according to the present invention may be an inverted (inverted type) organic light emitting device in which a cathode, 1 or more organic layers, and an anode are sequentially stacked on a substrate. For example, a structure of an organic light emitting device according to an embodiment of the present invention is illustrated in fig. 1 and 2.
Fig. 1 illustrates an example of an organic light-emitting device composed of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. In the structure as described above, the compound represented by the above chemical formula 1 may be contained in the above light emitting layer.
Fig. 2 illustrates an example of an organic light-emitting device composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron suppression layer 6, a light-emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4. In the structure as described above, the compound represented by the above chemical formula 1 may be contained in 1 or more of the above hole injection layer, hole transport layer, electron suppression layer, light emitting layer, hole blocking layer, and electron injection and transport layer. Specifically, the compound represented by the above chemical formula 1 may be contained in the above light emitting layer or hole transport layer, for example, may be contained as a host material of the light emitting layer.
The organic light emitting device according to the present invention may be manufactured using materials and methods known in the art, except that 1 or more of the above organic layers include the compound represented by the above chemical formula 1. In addition, when the organic light emitting device includes a plurality of organic layers, the organic layers may be formed of the same substance or different substances.
For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic layer, and a second electrode on a substrate. This can be produced as follows: the organic el device is manufactured by depositing a metal, a metal oxide having conductivity, or an alloy thereof on a substrate by a Physical Vapor Deposition (PVD) method such as a sputtering method or an electron beam evaporation method, forming an anode, forming an organic layer including a hole injection layer, a hole transport layer, an electron suppression layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer on the anode, and then depositing a substance that can be used as a cathode on the organic layer. In addition to this method, a cathode material, an organic layer, and an anode material may be sequentially deposited on a substrate to manufacture an organic light-emitting device.
In addition, the compound represented by the above chemical formula 1 may be formed into an organic layer not only by a vacuum evaporation method but also by a solution coating method in the manufacture of an organic light emitting device. In particular, the compound represented by the above chemical formula 1 has excellent solubility in a solvent used in a solution coating method, and thus the solution coating method is easily applicable. Here, the solution coating method refers to spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.
Here, the present invention provides a coating composition comprising the compound represented by the above chemical formula 1 and a solvent.
The solvent is not particularly limited as long as it can dissolve or disperse the compound according to the present invention, and examples thereof include chlorine-based solvents such as chloroform, dichloromethane, 1, 2-dichloroethane, 1, 2-trichloroethane, chlorobenzene, and o-dichlorobenzene; tetrahydrofuran, di
Figure BDA0003935930440000301
Ether solvents such as alkanes; aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene and mesitylene; cyclohexaneAliphatic hydrocarbon solvents such as alkane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ester-based solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; polyhydric alcohols such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerol, and 1, 2-hexanediol, and derivatives thereof; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; sulfoxide solvents such as dimethyl sulfoxide; and amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide; benzoate solvents such as butyl benzoate and methyl 2-methoxybenzoate; tetrahydronaphthalene; 3-phenoxy-toluene (3-phenoxy-toluene) and the like. Further, 1 or more of the above solvents may be used alone or 2 or more of the solvents may be used in combination.
The viscosity of the coating composition is preferably 1cP to 10cP, and the coating composition can be easily applied within the above range. Furthermore, the concentration of the compound according to the present invention in the above-mentioned coating composition is preferably 0.1 to 20wt/v%.
In addition, the present invention provides a method of forming a functional layer using the above coating composition. Specifically, the method comprises the following steps: a step of coating the above-described coating composition according to the present invention through a solution process; and a step of heat-treating the coated coating composition.
In the above heat treatment step, the heat treatment temperature is preferably 150 to 230 ℃. Further, the above heat treatment time is 1 minute to 3 hours, more preferably 10 minutes to 1 hour. The heat treatment is preferably performed in an inert gas atmosphere such as argon or nitrogen.
As an example, the first electrode is an anode, and the second electrode is a cathode; or the first electrode is a cathode and the second electrode is an anode.
The anode material is preferably a material having a large work function in order to smoothly inject holes into the organic layer. Specific examples of the above-mentioned anode material include vanadium, chromium and copperMetals such as zinc and gold, or alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); znO-Al or SnO 2 A combination of a metal such as Sb and an oxide; poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxythiophene) thiophene]Conductive polymers such as (PEDOT), polypyrrole, and polyaniline, but the present invention is not limited thereto.
The cathode material is preferably a material having a small work function in order to easily inject electrons into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, and alloys thereof; liF/Al or LiO 2 And a multilayer structure material such as Al, but not limited thereto.
The hole injection layer is a layer for injecting holes from the electrode, and the following compounds are preferable as the hole injection substance: a compound having an ability to transport holes, having an effect of injecting holes from an anode, having an excellent hole injection effect for a light-emitting layer or a light-emitting material, preventing excitons generated in the light-emitting layer from migrating to an electron-injecting layer or an electron-injecting material, and having an excellent thin film-forming ability. Preferably, the HOMO (highest occupied molecular orbital) of the hole injecting substance is between the work function of the anode substance and the HOMO of the surrounding organic layer. Specific examples of the hole injecting substance include, but are not limited to, metalloporphyrins (porphyrins), oligothiophenes, arylamine-based organic substances, hexanenitrile-based organic substances, quinacridone-based organic substances, perylene-based organic substances, anthraquinone-based and polyaniline-based and polythiophene-based conductive polymers, and the like.
The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light-emitting layer, and the hole transport substance is a substance that can receive holes from the anode or the hole injection layer and transport the holes to the light-emitting layer, and is suitable for a substance having a high mobility for holes. Specific examples thereof include, but are not limited to, arylamine organic substances, conductive polymers, and block copolymers having both conjugated portions and non-conjugated portions.
The light-emitting substance is a substance that can emit light in the visible light region by receiving holes and electrons from the hole-transporting layer and the electron-transporting layer, respectively, and is preferably a substance having high quantum efficiency with respect to fluorescence or phosphorescence. As an example, there is 8-hydroxy-quinoline aluminum complex (Alq) 3 ) (ii) a A carbazole-based compound; dimeric styryl (dimerized styryl) compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzo (b) is
Figure BDA0003935930440000321
Azole, benzothiazole and benzimidazole-based compounds; poly (p-phenylene vinylene) (PPV) polymers; spiro (spiroo) compounds; polyfluorene, rubrene, and the like, but are not limited thereto.
The light emitting layer may include a host material and a dopant material. The host material includes aromatic fused ring derivatives, heterocyclic compounds, and the like. Specifically, as the aromatic condensed ring derivative, there are an anthracene derivative, a pyrene derivative, a naphthalene derivative, a pentacene derivative, a phenanthrene compound, a fluoranthene compound and the like, and as the heterocycle-containing compound, there are a carbazole derivative, a dibenzofuran derivative, a ladder furan compound: (
Figure BDA0003935930440000331
) And pyrimidine derivatives, but are not limited thereto. Preferably, the compounds according to the invention are used as the above-mentioned host materials.
As the dopant material, there are an aromatic amine derivative, a styryl amine compound, a boron complex, a fluoranthene compound, a metal complex, and the like. Specifically, the aromatic amine derivative is an aromatic fused ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, or the like having an arylamino group,
Figure BDA0003935930440000332
And diindenopyrene, the styrylamine compound is a compound having at least 1 arylvinyl group substituted on a substituted or unsubstituted arylamine, and is substituted with 1 or 2 or more groups selected from aryl, silyl, alkyl, cycloalkyl and arylaminoThe radicals being substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltrriamine, and styryltretraamine. The metal complex includes, but is not limited to, iridium complexes and platinum complexes. Preferably, an iridium-based metal complex is used as the dopant material.
The light emitting layer may be a red light emitting layer, and when the compound according to the present invention is used as a host material, the stability with respect to electrons and holes is increased, energy transfer from the host to the red dopant is well realized, and driving voltage, light emitting efficiency, and life span characteristics of the organic light emitting device can be improved.
The electron transporting layer is a layer that receives electrons from the electron injecting layer and transports the electrons to the light emitting layer, and the electron transporting substance is a substance that can favorably receive electrons from the cathode and transfer the electrons to the light emitting layer, and is suitable for a substance having a high electron mobility. Specific examples thereof include an Al complex of 8-hydroxyquinoline and an Al complex containing Alq 3 The complex of (a), an organic radical compound, a hydroxyflavone-metal complex, etc., but are not limited thereto. The electron transport layer may be used with any desired cathode (cathode) material as used in the art. Examples of suitable cathode substances are, in particular, the customary substances having a low work function and associated with an aluminum layer or a silver layer. In particular cesium, barium, calcium, ytterbium and samarium, in each case accompanied by an aluminum layer or a silver layer.
The electron injection layer is a layer for injecting electrons from the electrode, and is preferably a compound of: a compound having an ability to transport electrons, having an effect of injecting electrons from a cathode, having an excellent electron injection effect with respect to a light-emitting layer or a light-emitting material, preventing excitons generated in the light-emitting layer from migrating to a hole-injecting layer, and having an excellent thin-film-forming ability. Specifically, fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, and the like,
Figure BDA0003935930440000341
Azole,
Figure BDA0003935930440000342
Oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like, and derivatives thereof, metal complex compounds, nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto.
Examples of the metal complex include, but are not limited to, lithium 8-quinolinolato, zinc bis (8-quinolinolato), copper bis (8-quinolinolato), manganese bis (8-quinolinolato), aluminum tris (2-methyl-8-quinolinolato), gallium tris (8-quinolinolato), beryllium bis (10-hydroxybenzo [ h ] quinoline), zinc bis (10-hydroxybenzo [ h ] quinoline), gallium bis (2-methyl-8-quinolinolato) chloride, gallium bis (2-methyl-8-quinolinolato) (o) gallium, bis (2-methyl-8-quinolinolato) (1-naphthol) aluminum, and gallium bis (2-methyl-8-quinolinolato) (2-naphthol) gallium.
The organic light emitting device according to the present invention may be a bottom emission (bottom emission) device, a top emission (top emission) device, or a bi-directional light emitting device, and particularly, may be a bottom emission device requiring relatively high light emitting efficiency.
In addition, the compound according to the present invention may be included in an organic solar cell or an organic transistor, in addition to the organic light emitting device.
The manufacture of the compound represented by the above chemical formula 1 and the organic light emitting device including the same is specifically illustrated in the following examples. However, the following examples are provided to illustrate the present invention, and the scope of the present invention is not limited thereto.
Production example 1 production of intermediate Compound AA
Figure BDA0003935930440000343
Compound substance (sub) A (20g, 91.6mmol), N-bromosuccinimide (N-bromosuccinimide) (NBS, 17.1g, 96.2mmol) was added to 400mL of chloroform (chloroform) (CHCl) under a nitrogen atmosphere 3 ) And stirring at normal temperature. After 6 hours of reaction, the reaction mixture was washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 20.3g of compound A-1. (yield 75%, MS: [ M + H ]] + ＝297)。
Compound A-1 (10g, 33.7mmol) and compound 1 (6.5g, 37mmol) were added to 200mL of Tetrahydrofuran (THF) under a nitrogen atmosphere, and stirred and refluxed. Then, potassium carbonate (K) 2 CO 3 14g, 101mmol) was dissolved in 42mL of water and introduced, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (Pd (P-tBu) 3 ) 2 ) (0.2g, 0.3mmol). After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 7.8g of compound AA _ P1. (yield 67%, MS: [ M + H ]] + ＝347)。
Under nitrogen, compound AA _ P1 (10g, 28.8mmol) and potassium carbonate (12g, 86.5mmol) were added to 200mL of N, N-Dimethylacetamide (N, N-Dimethylacetamide) (DMAc), stirred and refluxed. After 9 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic solvent was distilled under reduced pressure. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 7g of compound AA _ P2. (yield 74%, MS: [ M + H ]] + ＝327)。
Under a nitrogen atmosphere, compound AA _ P2 (15g, 45.9mmol) and bis (pinacolato) diboron (12.8g, 50.5mmol) were added to 300mL of 1, 4-bis
Figure BDA0003935930440000351
The mixture was refluxed in an alkane (1, 4-dioxane) and stirred. Then, potassium acetate (KOAc, 6.8g, 68.9mmol) was charged, and after sufficiently stirring, bis (dibenzylideneacetone) palladium (0) (Pd (dba) was charged 2 ) (0.8g, 1.4mmol) and tricyclohexylphosphine (PCy) 3 0.8g, 2.8mmol). Reacting for 10 hours, cooling to normal temperature, and utilizingThe organic layer was separated with chloroform and water, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.9g of compound AA. (yield 67%, MS: [ M + H ]] + ＝419)。
Production example 2 production of intermediate Compound AB
Figure BDA0003935930440000361
12.7g of compound AB was produced in the same manner as in production example 1, except that compound substance 2 was used as a starting material in place of compound substance 1 in production example 1. (yield 66%, MS: [ M + H ]] + ＝419)。
Production example 3 production of intermediate Compound AC
Figure BDA0003935930440000362
13.2g of compound AC was produced by the same method as in production example 1, except that in production example 1, compound substance 3 was used instead of compound substance 1 as a starting material. (yield 69%, MS: [ M + H ]] + ＝419)。
Production example 4 production of intermediate Compound AD
Figure BDA0003935930440000371
13.6g of Compound AD (yield 71%, MS: [ M + H ] was prepared in the same manner as in preparation example 1, except that in preparation example 1, compound 4 was used as a starting material in place of Compound 1] + ＝419)。
Production example 5 production of intermediate Compound BA
Figure BDA0003935930440000372
Compound B (10g, 35.6mmol) and compound 5 (7.9g, 39.1mmol) were added to 200mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (14.7g, 106.7mmol) was dissolved in 44mL of water and charged, and after stirring sufficiently, bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.4mmol) was charged. After 11 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.1g of compound BA — P1. (yield 79%, MS: [ M + H ]] + ＝359)。
Under a nitrogen atmosphere, compound BA _ P1 (10g, 27.9mmol) and hydrogen peroxide (Hyd rogen peroxide) (H) 2 O 2 1g,30.7 mmol) was added to 200mL of acetic acid (AcOH), stirred and refluxed. After 3 hours, the reaction was poured into water, the crystals were allowed to fall, and filtered. The filtered solid was dissolved in chloroform, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 7.6g of compound BA _ P2. (yield 73%, MS: [ M + H ]] + ＝375)。
Compound BA _ P2 (10g, 26.7mmol) was added to 200mL of H under nitrogen atmosphere 2 SO 4 In (1), stirring is performed. After 2 hours, at the end of the reaction, the reaction was poured into water, the crystals were allowed to fall and filtered. The filtered solid was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 6.1g of compound BA _ P3. (yield 67%, MS: [ M + H ]] + ＝343)。
Under nitrogen atmosphere, compound BA P3 (15g, 43.8mmol) and bis (pinacolato) diboron (12.2g, 48.1mmo) were placed in 300mL of 1, 4-bis
Figure BDA0003935930440000381
Refluxing in alkane and stirring. Then, potassium acetate (6.4g, 65.6 mmol) was charged, and after sufficiently stirring, bis (dibenzylideneacetone) palladium (0) (0.8g, 1.3mmol) and tricyclohexylphosphine (0.7g, 2.6 mmol) were charged. After the reaction was carried out for 10 hours, the reaction mixture was cooled to normal temperature, and the organic layer was separated with chloroform and water and then distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.2g of compound BA. (yield 80%, MS: [ M + H ]] + ＝435)。
Production example 6 production of intermediate Compound BB
Figure BDA0003935930440000391
12.9g of compound BB was produced in the same manner as in production example 5, except that compound substance 6 was used as a starting material in place of compound substance 5 in production example 5. (yield 68%, MS: [ M + H ]] + ＝435)。
Production example 7 production of intermediate Compound BC
Figure BDA0003935930440000392
13.9g of compound BC was produced by the same method as in production example 5, except that compound substance 7 was used as a starting material in place of compound substance 5 in production example 5. (yield 73%, MS: [ M + H ]] + ＝435)。
Production example 8 production of intermediate Compound BD
Figure BDA0003935930440000401
In production example 5, compound 8 was used instead of14.2g of compound BD was produced in the same manner as in production example 5, except that compound 5 was used as a starting material. (yield 75%, MS: [ M + H ]] + ＝435)。
Production example 9 production of intermediate Compound C
Figure BDA0003935930440000402
13.8g of compound CA was produced in the same manner as in production example 1, except that the compound substance C was used as a starting material in place of the compound substance A in production example 1. (yield 72%, MS: [ M + H ]] + ＝419)。
Production example 10 production of intermediate Compound CB
Figure BDA0003935930440000411
13.6g of Compound CB was produced in the same manner as in production example 1, except that in production example 1, compound C was used in place of Compound A as a starting material, and Compound 2 was used in place of Compound 1. (yield 71%, MS: [ M + H ]] + ＝419)。
Production example 11 production of intermediate Compound CC
Figure BDA0003935930440000412
13.6g of Compound CC was prepared in the same manner as in preparation example 1, except that Compound C was used as a starting material in place of Compound A in preparation example 1 and substance 3 was used in place of substance 1. (yield 71%, MS: [ M + H ]] + ＝419)。
PREPARATION EXAMPLE 12 preparation of intermediate Compound CD
Figure BDA0003935930440000421
13.6g of compound CD was produced in the same manner as in production example 1, except that in production example 1, compound C was used as a starting material in place of compound A, and substance 4 was used in place of substance 1. (yield 71%, MS: [ M + H ]] + ＝419)。
Production example 13 production of intermediate Compound DA
Figure BDA0003935930440000422
12.9g of compound DA was produced in the same manner as in production example 5, except that the compound substance D was used as a starting material in place of the compound substance B in production example 5. (yield 68%, MS: [ M + H ]] + ＝435)。
Production example 14 production of intermediate Compound DB
Figure BDA0003935930440000431
14.1g of compound DB was produced by the same method as in production example 5, except that in production example 5, compound D was used instead of compound B as a starting material, and compound 6 was used instead of substance 5. (yield 74%, MS: [ M + H ]] + ＝435)。
Production example 15 production of intermediate Compound DC
Figure BDA0003935930440000432
14.4g of compound DC was produced in the same manner as in production example 5, except that in production example 5, compound D was used in place of compound B as a starting material, and compound 7 was used in place of compound 5. (yield 76%, MS: [ M + H ]] + ＝435)。
Production example 16 production of intermediate Compound DD
Figure BDA0003935930440000441
13.3g of compound DD was produced in the same manner as in production example 5, except that the compound substance D was used instead of the compound substance B as a starting material and the compound substance 8 was used instead of the compound substance 5 in production example 5. (yield 70%, MS: [ M + H ]] + ＝435)。
Synthesis example 1 Synthesis of Compound 1
Figure BDA0003935930440000442
Under a nitrogen atmosphere, compound AA (10g, 23.9mmol) and compound Trz1 (8.4g, 24.4mmol) were added to 200mL of THF, stirred, and refluxed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.2g of compound 1. (yield 78%, MS: [ M + H ]] + ＝600)。
Synthesis example 2 Synthesis of Compound 2
Figure BDA0003935930440000451
Under a nitrogen atmosphere, compound AA (10g, 23.9mmol) and compound Trz2 (9.1g, 24.4mmol) were added to 200mL of THF, stirred, and refluxed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 11 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. Dissolving in chloroform again, washing with water for 2 times, separating organic layer, addingAnhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.8g of compound 2. (yield 65%, MS: [ M + H ]] + ＝630)。
Synthesis example 3 Synthesis of Compound 3
Figure BDA0003935930440000452
Compound AA (10g, 23.9mmol) and compound Trz3 (9.6g, 24.4mmol) are added to 200mL of THF under nitrogen atmosphere, and the mixture is stirred and refluxed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.6g of compound 3. (yield 75%, MS: [ M + H ]] + ＝650)。
Synthesis example 4 Synthesis of Compound 4
Figure BDA0003935930440000461
Under a nitrogen atmosphere, compound AA (10g, 23.9mmol) and compound Trz4 (12.1g, 24.4mmol) were added to 200mL of THF, stirred and refluxed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14g of compound 4. (yield 78%, MS: [ M + H ]] + ＝752)。
Synthesis example 5 Synthesis of Compound 5
Figure BDA0003935930440000462
Compound AB (10g, 23.9mmol) and compound Trz5 (7.7g, 24.4mmol) were added to 200mL of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.3g of compound 5. (yield 75%, MS: [ M + H ]] + ＝574)。
Synthesis example 6 Synthesis of Compound 6
Figure BDA0003935930440000471
Compound AB (10g, 23.9mmol) and compound Trz6 (10.2g, 24.4mmol) were added to 200mL of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.9g of compound 6. (yield 74%, MS: [ M + H ]] + ＝676)。
Synthesis example 7 Synthesis of Compound 7
Figure BDA0003935930440000472
Compound AB (10g, 23.9mmol) and compound Trz7 (10.6g, 24.4mmol) were added to 200mL of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.2g of compound 7. (yield 68%, MS: [ M + H ]] + ＝690)。
Synthesis example 8 Synthesis of Compound 8
Figure BDA0003935930440000481
Under a nitrogen atmosphere, compound AC (10g, 23.9mmol) and compound Trz8 (9.6g, 24.4mmol) were added to 200mL of THF, stirred, and refluxed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.3g of compound 8. (yield 73%, MS: [ M + H ]] + ＝650)。
Synthesis example 9 Synthesis of Compound 9
Figure BDA0003935930440000482
Under a nitrogen atmosphere, compound AC (10g, 23.9mmol) and Compound Trz9 (8.4g, 24.4mmol) were added to 200mL of THF, stirred, and refluxed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11g of compound 9. (yield 77%, MS: [ M + H ]] + ＝600)。
Synthesis example 10 Synthesis of Compound 10
Figure BDA0003935930440000491
Compound AC (10g, 23.9mmol) and compound Trz10 (111g, 24.4mmol) were added to 200mL of THF under a nitrogen atmosphere, stirred, and refluxed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.3g of compound 10. (yield 73%, MS: [ M + H ]] + ＝706)。
Synthesis example 11 Synthesis of Compound 11
Figure BDA0003935930440000492
Compound AC (10g, 23.9mmol) and compound Trz11 (8.7g, 24.4mmol) are added to 200mL of THF under a nitrogen atmosphere, and stirring and refluxing are performed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. Dissolving it againAfter washing the mixture with chloroform for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.1g of compound 11. (yield 76%, MS: [ M + H ]] + ＝613)。
Synthesis example 12 Synthesis of Compound 12
Figure BDA0003935930440000501
Under a nitrogen atmosphere, compound AD (10g, 23.9mmol) and compound Trz12 (9.6g, 24.4mmol) were added to 200mL of THF, stirred, and refluxed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.8g of compound 12. (yield 63%, MS: [ M + H ]] + ＝650)。
Synthesis example 13 Synthesis of Compound 13
Figure BDA0003935930440000502
Under a nitrogen atmosphere, compound AD (10g, 23.9mmol) and compound Trz13 (9.1g, 24.4mmol) were added to 200mL of THF, stirred, and refluxed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 11 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.2g of compound 13.(yield 68%, MS: [ M + H ]] + ＝630)。
Synthesis example 14 Synthesis of Compound 14
Figure BDA0003935930440000511
Compound BA (10g, 23mmol) and compound Trz14 (8.4g, 23.5mmol) were added to 200mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.3g of compound 14. (yield 71%, MS: [ M + H ]] + ＝630)。
Synthesis example 15 Synthesis of Compound 15
Figure BDA0003935930440000512
Compound BA (10g, 23mmol) and compound Trz15 (9.2g, 23.5mmol) were added to 200mL of THF under a nitrogen atmosphere, and stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 11 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.2g of compound 15. (yield 60%, MS: [ M + H ]] + ＝666)。
Synthesis example 16 Synthesis of Compound 16
Figure BDA0003935930440000521
Compound BA (10g, 23mmol) and compound Trz16 (8.6g, 23.5mmol) were added to 200mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.9g of compound 16. (yield 67%, MS: [ M + H ]] + ＝640)。
Synthesis example 17 Synthesis of Compound 17
Figure BDA0003935930440000522
Under a nitrogen atmosphere, compound BA (10g, 23mmol) and compound Trz17 (6.3g, 23.5mmol) were added to 200mL of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.8g of compound 17. (yield 79%, MS: [ M + H ]] + ＝540)。
Synthesis example 18 Synthesis of Compound 18
Figure BDA0003935930440000531
Under a nitrogen atmosphere, compound BB (10g, 23mmol) and compound Trz18 (9.9g, 23.5mmol) were added200mL of THF were stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.5g of compound 18. (yield 72%, MS: [ M + H ]] + ＝692)。
Synthesis example 19 Synthesis of Compound 19
Figure BDA0003935930440000532
Under a nitrogen atmosphere, compound BB (10g, 23mmol) and compound Trz19 (9.2g, 23.5mmol) were added to 200mL of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11g of compound 19. (yield 72%, MS: [ M + H ]] + ＝666)。
Synthesis example 20 Synthesis of Compound 20
Figure BDA0003935930440000541
Under a nitrogen atmosphere, compound BB (10g, 23mmol) and compound Trz20 (9.2g, 23.5mmol) were added to 200mL of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 10 hours of reaction, cooling to normal temperature to obtainAfter the organic layer and the aqueous layer were separated, the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.3g of compound 20. (yield 67%, MS: [ M + H ]] + ＝666)。
Synthesis example 21 Synthesis of Compound 21
Figure BDA0003935930440000542
Under a nitrogen atmosphere, the compound BC (10g, 23mmol) and the compound Trz3 (9.2g, 23.5mmol) were added to 200mL of THF, stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.5g of compound 21. (yield 62%, MS: [ M + H ]] + ＝666)。
Synthesis example 22 Synthesis of Compound 22
Figure BDA0003935930440000551
Compound BC (10g, 23mmol) and compound Trz11 (8.4g, 23.5mmol) were added to 200mL of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. Subjecting the concentrated compound to silica gel column chromatographyThe resulting solution was purified to give 9.4g of Compound 22. (yield 65%, MS: [ M + H ]] + ＝629)。
Synthesis example 23 Synthesis of Compound 23
Figure BDA0003935930440000552
Under a nitrogen atmosphere, compound BD (10g, 23mmol) and compound Trz12 (9.2g, 23.5mmol) were added to 200mL of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.6g of compound 23. (yield 76%, MS: [ M + H ]] + ＝666)。
Synthesis example 24 Synthesis of Compound 24
Figure BDA0003935930440000561
Under a nitrogen atmosphere, compound BD (10g, 23mmol) and compound Trz21 (9.2g, 23.5mmol) were added to 200mL of THF, stirred, and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.6g of compound 24. (yield 76%, MS: [ M + H ]] + ＝666)。
Synthesis example 25 Synthesis of Compound 25
Figure BDA0003935930440000562
Under a nitrogen atmosphere, compound BD (10g, 23mmol) and compound Trz22 (8.1g, 23.5mmol) were added to 200mL of THF, stirred, and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 11 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.6g of compound 25. (yield 68%, MS: [ M + H ]] + ＝616)。
Synthesis example 26 Synthesis of Compound 26
Figure BDA0003935930440000571
Under a nitrogen atmosphere, compound BD (10g, 23mmol) and Compound Trz23 (10.4g, 23.5mmol) were added to 200mL of THF, stirred, and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.3g of compound 26. (yield 75%, MS: [ M + H ]] + ＝716)。
Synthesis example 27 Synthesis of Compound 27
Figure BDA0003935930440000572
Under nitrogen atmosphere, the compoundCA (10g, 23.9mmol) and compound Trz24 (10.8g, 24.4mmol) were added to 200mL of THF, stirred and refluxed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.2g of compound 27. (yield 79%, MS: [ M + H ]] + ＝700)。
Synthesis example 28 Synthesis of Compound 28
Figure BDA0003935930440000581
Compound CA (10g, 23.9mmol) and compound Trz25 (9.1g, 24.4mmol) are added to 200mL of THF under nitrogen atmosphere, and the mixture is stirred and refluxed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.7g of compound 28. (yield 71%, MS: [ M + H ]] + ＝630)。
Synthesis example 29 Synthesis of Compound 29
Figure BDA0003935930440000582
Compound CB (10g, 23.9mmol) and compound Trz8 (9.6g, 24.4mmol) are added to 200mL of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) was chargedPalladium (0) (0.1g, 0.2mmol). After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11g of compound 29. (yield 71%, MS: [ M + H ]] + ＝650)。
Synthesis example 30 Synthesis of Compound 30
Figure BDA0003935930440000591
Compound CB (10g, 23.9mmol) and compound Trz11 (8.7g, 24.4mmol) are added to 200mL of THF under a nitrogen atmosphere, and stirring and refluxing are performed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.7g of compound 30. (yield 66%, MS: [ M + H ]] + ＝613)。
Synthesis example 31 Synthesis of Compound 31
Figure BDA0003935930440000592
Compound CB (10g, 23.9mmol) and compound Trz26 (9.6g, 24.4mmol) are added to 200mL of THF under a nitrogen atmosphere, and stirring and refluxing are carried out. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. Dissolving in chloroform again, washing with water for 2 times, separating organic layer, adding anhydrous magnesium sulfate, stirringStirring, filtering, and distilling the filtrate under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.3g of compound 31. (yield 73%, MS: [ M + H ]] + ＝650)。
Synthesis example 32 Synthesis of Compound 32
Figure BDA0003935930440000601
Compound CB (10g, 23.9mmol) and compound Trz27 (12.4g, 24.4mmol) are added to 200mL of THF under a nitrogen atmosphere, and stirring and refluxing are performed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.5g of compound 32. (yield 74%, MS: [ M + H ]] + ＝765)。
Synthesis example 33 Synthesis of Compound 33
Figure BDA0003935930440000602
Under a nitrogen atmosphere, compound CC (10g, 23.9mmol) and Compound Trz17 (6.5g, 24.4mmol) were added to 200mL of THF, stirred, and refluxed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.8g of compound 33. (yield 78%, MS: [ M + H ]] + ＝524)。
Synthesis example 34 Synthesis of Compound 34
Figure BDA0003935930440000611
Compound CC (10g, 23.9mmol) and compound Trz28 (8.7g, 24.4mmol) are added to 200mL of THF under a nitrogen atmosphere, and stirring and refluxing are performed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10g of compound 34. (yield 68%, MS: [ M + H ]] + ＝614)。
Synthesis example 35 Synthesis of Compound 35
Figure BDA0003935930440000612
Compound CD (10g, 23.9mmol) and compound Trz14 (8.7g, 24.4mmol) were added to 200mL of THF under a nitrogen atmosphere, stirred, and refluxed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10g of compound 35. (yield 68%, MS: [ M + H ]] + ＝614)。
Synthesis example 36 Synthesis of Compound 36
Figure BDA0003935930440000621
Under a nitrogen atmosphere, compound CD (10g, 23.9mmol) and compound Trz29 (9g, 24.4mmol) were added to 200mL of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 11 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11g of compound 36. (yield 74%, MS: [ M + H ]] + ＝624)。
Synthesis example 37 Synthesis of Compound 37
Figure BDA0003935930440000622
Compound CD (10g, 23.9mmol) and compound Trz30 (9.6g, 24.4mmol) are added to 200mL of THF under nitrogen atmosphere, and stirring and refluxing are carried out. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.5g of compound 37. (yield 74%, MS: [ M + H ]] + ＝650)。
Synthesis example 38 Synthesis of Compound 38
Figure BDA0003935930440000631
Compound CD (10g, 23.9mmol) and compound Trz17 (6.5g, 24.4mmol) are added to 200mL of THF under a nitrogen atmosphere, and the mixture is stirred and refluxed. Then, potassium carbonate (9.9g, 71.7mmol) was added) Dissolved in 30mL of water, was added, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was added. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10g of compound 38. (yield 80%, MS: [ M + H ]] + ＝524)。
Synthesis example 39 Synthesis of Compound 39
Figure BDA0003935930440000632
Compound CD (10g, 23.9mmol) and compound Trz31 (8.4g, 24.4mmol) are added to 200mL of THF under nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (9.9 g,71.7 mmol) was dissolved in 30mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10g of compound 39. (yield 70%, MS: [ M + H ]] + ＝600)。
Synthesis example 40 Synthesis of Compound 40
Figure BDA0003935930440000641
Compound DA (10g, 23mmol) and compound Trz21 (9.2g, 23.5mmol) were added to 200mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. Redissolving it in chloroformAfter washing with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.2g of compound 40. (yield 73%, MS: [ M + H ]] + ＝666)。
Synthesis example 41 Synthesis of Compound 41
Figure BDA0003935930440000642
Compound DA (10g, 23mmol) and compound Trz30 (9.2g, 23.5mmol) were added to 200mL of THF under a nitrogen atmosphere, and stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.2g of compound 41. (yield 60%, MS: [ M + H ]] + ＝666)。
Synthesis example 42 Synthesis of Compound 42
Figure BDA0003935930440000651
Compound DA (10g, 23mmol) and compound Trz5 (7.5g, 23.5mmol) were added to 200mL of THF under a nitrogen atmosphere, and stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 11 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.9g of compound 42. (the yield thereof was found to be 80%,MS:[M+H] + ＝590)。
synthesis example 43 Synthesis of Compound 43
Figure BDA0003935930440000652
Under a nitrogen atmosphere, compound DB (10g, 23mmol) and compound Trz32 (10.4g, 23.5mmol) were added to 200mL of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12g of compound 43. (yield 73%, MS: [ M + H ]] + ＝716)。
Synthesis example 44 Synthesis of Compound 44
Figure BDA0003935930440000661
Under a nitrogen atmosphere, compound DB (10g, 23mmol) and compound Trz33 (9.9g, 23.5mmol) were added to 200mL of THF, stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 11 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.4g of compound 44. (yield 78%, MS: [ M + H ]] + ＝692)。
Synthesis example 45 Synthesis of Compound 45
Figure BDA0003935930440000662
Under a nitrogen atmosphere, compound DB (10g, 23mmol) and compound Trz34 (11g, 23.5mmol) were added to 200mL of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.6g of compound 45. (yield 68%, MS: [ M + H ]] + ＝742)。
Synthesis example 46 Synthesis of Compound 46
Figure BDA0003935930440000671
Under a nitrogen atmosphere, compound DB (10g, 23mmol) and compound Trz1 (8.1g, 23.5mmol) were added to 200mL of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11g of compound 46. (yield 78%, MS: [ M + H ]] + ＝616)。
Synthesis example 47 Synthesis of Compound 47
Figure BDA0003935930440000672
Under a nitrogen atmosphere, compound DC (10g, 23mmol) and compound Trz35 (10.2g, 23.5mmol) were added to 200mL of THF,stirring and refluxing. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12g of compound 47. (yield 74%, MS: [ M + H ]] + ＝705)。
Synthesis example 48 Synthesis of Compound 48
Figure BDA0003935930440000681
Under a nitrogen atmosphere, compound DC (10g, 23mmol) and compound Trz36 (10.2g, 23.5mmol) were added to 200mL of THF, stirred, and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.3g of compound 48. (yield 76%, MS: [ M + H ]] + ＝705)。
Synthesis example 49 Synthesis of Compound 49
Figure BDA0003935930440000682
Compound DC (10g, 23mmol) and compound Trz28 (8.4g, 23.5mmol) were added to 200mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer and the aqueous layer were separatedAfter separation, the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.4g of compound 49. (yield 79%, MS: [ M + H ]] + ＝630)。
Synthesis example 50 Synthesis of Compound 50
Figure BDA0003935930440000691
Under a nitrogen atmosphere, compound DD (10g, 23mmol) and compound Trz22 (8.1g, 23.5mmol) were added to 200mL of THF, and stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.9g of compound 50. (yield 77%, MS: [ M + H ]] + ＝616)。
Synthesis example 51 Synthesis of Compound 51
Figure BDA0003935930440000692
Compound DD (10g, 23mmol) and compound Trz14 (8.4g, 23.5mmol) were added to 200mL of THF under a nitrogen atmosphere, and stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. Purifying the concentrated compound by silica gel column chromatographyThereby, 10g of compound 51 was produced. (yield 69%, MS: [ M + H ]] + ＝630)。
Synthesis example 52 Synthesis of Compound 52
Figure BDA0003935930440000701
Under a nitrogen atmosphere, the compound DD (10g, 23mmol) and the compound Trz29 (8.6g, 23.5mmol) were added to 200mL of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.6g of compound 52. (yield 72%, MS: [ M + H ]] + ＝640)。
Synthesis example 53 Synthesis of Compound 53
Figure BDA0003935930440000702
Under a nitrogen atmosphere, compound DD (10g, 23mmol) and compound Trz5 (7.5g, 23.5mmol) were added to 200mL of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.5g, 69.1mmol) was dissolved in 29mL of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.6g of compound 53. (yield 71%, MS: [ M + H ]] + ＝590)。
Example 1
Indium Tin Oxide (ITO) was added at 1000. ANG(
Figure BDA0003935930440000703
angstrom) was put in distilled water in which a detergent was dissolved, and the glass substrate coated with a thin film was cleaned by ultrasonic waves. In this case, the detergent was prepared by Fischer co, and the distilled water was filtered twice by a Filter (Filter) manufactured by Millipore co. After washing the ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After the completion of the distilled water washing, the resultant was ultrasonically washed with a solvent of isopropyl alcohol, acetone, or methanol, dried, and then transported to a plasma cleaning machine. After the substrate was cleaned with oxygen plasma for 5 minutes, the substrate was transported to a vacuum evaporator.
On the ITO transparent electrode thus prepared, as a hole injection layer, the following compound HI-1 was added
Figure BDA0003935930440000711
The hole injection layer was formed by thermal vacuum deposition, and the following compound a-1 was p-doped (p-doping) at a concentration of 1.5%. On the hole injection layer, the following compound HT-1 was vacuum-deposited to form a film having a thickness
Figure BDA0003935930440000712
The hole transport layer of (1). Then, on the hole transport layer, the film thickness
Figure BDA0003935930440000713
The following compound EB-1 was vacuum-deposited to form an electron inhibiting layer. Then, the following compound 1 and the following compound Dp-7 were vacuum-deposited on the EB-1 deposited film at a weight ratio of 98
Figure BDA0003935930440000714
A thick red light emitting layer. On the light-emitting layer, the thickness of the film
Figure BDA0003935930440000715
The following compound HB-1 was vacuum-deposited to form a hole-blocking layer. Next, on the hole blocking layer, the following compound ET-1 and the following compound LiQ were vacuum-evaporated at a weight ratio of 2
Figure BDA0003935930440000716
The thickness of (a) forms an electron injection and transport layer. On the above electron injecting and transporting layer, lithium fluoride (LiF) is sequentially added
Figure BDA0003935930440000717
Thickness of aluminum and
Figure BDA0003935930440000718
is deposited to form a cathode.
Figure BDA0003935930440000721
In the above process, the evaporation speed of the organic material is maintained
Figure BDA0003935930440000722
Per second to
Figure BDA0003935930440000723
Second, maintenance of lithium fluoride at the cathode
Figure BDA0003935930440000724
Vapor deposition rate per second, aluminum maintenance
Figure BDA0003935930440000725
A vapor deposition rate of 2X 10/sec, and a degree of vacuum maintained during vapor deposition -7 To 5X 10 -6 And supporting to thereby fabricate the organic light emitting device.
Examples 2 to 53
An organic light-emitting device was produced in the same manner as in example 1 above, except that compounds 2 to 53 described in table 1 below were each used instead of compound 1 in the organic light-emitting device of example 1.
Figure BDA0003935930440000731
Figure BDA0003935930440000741
Figure BDA0003935930440000751
Figure BDA0003935930440000761
Comparative examples 1 to 13
An organic light-emitting device was produced in the same manner as in example 1 above, except that the compound described in table 1 below was used instead of compound 1 in the organic light-emitting device of example 1. The compounds of C-1 to C-13 used in the following Table 1 are shown below.
Figure BDA0003935930440000771
When a current was applied to the organic light-emitting devices manufactured in the above examples and comparative examples, the voltage and efficiency (15 mA/cm) 2 ) The results are shown in table 1 below. The lifetime T95 refers to the time required for the luminance to decrease from the initial luminance (6000 nit) to 95%.
[ Table 1]
Figure BDA0003935930440000781
Figure BDA0003935930440000791
Figure BDA0003935930440000801
When a current was applied to the organic light emitting devices fabricated according to examples 1 to 53 and comparative examples 1 to 13, the results of table 1 above were obtained. The red organic light-emitting device of example 1 described above uses a conventionally widely used substance as described above, and has a structure in which the compound EB-1 is used as an electron-inhibiting layer and the compound 1 and the compound Dp-7 are used as a red light-emitting layer. In addition, comparative examples 1 to 13 manufactured organic light emitting devices using compounds C-1 to C-13 instead of compound 1.
As shown in table 1 above, according to the present invention, it is understood that the organic light emitting devices of examples 1 to 22, in which the compound represented by chemical formula 1, i.e., the compound having a specific polycyclic structure including 2 or more heteroaryl substituents containing N at specific positions of a parent nucleus structure formed by fusing a fluoranthene ring and a bicyclic heterocycle including O or S, are used for the light emitting layer, have a significantly lower driving voltage and a significantly improved efficiency compared to the organic light emitting devices of comparative examples 1 to 13 manufactured using the above-described C-1 to C-13 compounds, and thus, the energy transfer from the host to the red dopant is favorably realized. In addition, it is known that the organic light emitting devices of embodiments 1 to 53 can greatly improve the lifetime characteristics while maintaining high efficiency. This can be finally judged to be due to the high stability of the compounds according to the examples of the present invention with respect to electrons and holes, as compared with the compounds of the comparative examples. As described above, it was confirmed that when the compound of the present invention is used as a host of a red light emitting layer, driving voltage, light emitting efficiency and life characteristics of an organic light emitting device can be improved.
[ description of symbols ]
1: substrate 2: anode
3: light-emitting layer 4: cathode electrode
5: hole injection layer 6: hole transport layer
7: electron suppression layer 8: hole blocking layer
9: an electron injection and transport layer.

Claims (11)

1. A compound represented by the following chemical formula 1:
chemical formula 1
Figure FDA0003935930430000011
In the chemical formula 1, the first and second organic solvents,
each Y is independently a single bond, or is O or S, with the proviso that at least one of Y is O or S,
R 1 each independently is hydrogen; deuterium; a halogen; a cyano group; substituted or unsubstituted C 1-60 An alkyl group; substituted or unsubstituted C 1-60 An alkoxy group; substituted or unsubstituted C 2-60 An alkenyl group; substituted or unsubstituted C 2-60 Alkynyl; substituted or unsubstituted C 3-60 A cycloalkyl group; substituted or unsubstituted C 6-60 An aryl group; substituted or unsubstituted C containing one or more heteroatoms selected from N, O and S 2-60 (ii) a heteroaryl group, wherein,
n1 and n2 are integers from 0 to 4,
n3 is an integer of 0 to 3,
R 2 represented by the following chemical formula 2,
chemical formula 2
Figure FDA0003935930430000012
In the chemical formula 2,
l is a single bond, or substituted or unsubstituted C 6-60 An arylene group, a cyclic or cyclic alkylene group,
x is N or CH, at least 2 or more of X are N,
Ar 1 and Ar 2 Each independently substituted or unsubstituted C 6-60 An aryl group; substituted or unsubstituted C containing one or more heteroatoms selected from N, O and S 2-60 A heteroaryl group.
2. The compound according to claim 1, wherein the compound represented by the chemical formula 1 is one of compounds represented by any one of the following chemical formulae 1-1 to 1-8:
chemical formula 1-1
Figure FDA0003935930430000021
Chemical formula 1-2
Figure FDA0003935930430000022
Chemical formula 1-3
Figure FDA0003935930430000023
Chemical formulas 1 to 4
Figure FDA0003935930430000031
Chemical formulas 1 to 5
Figure FDA0003935930430000032
Chemical formulas 1 to 6
Figure FDA0003935930430000033
Chemical formulas 1 to 7
Figure FDA0003935930430000041
Chemical formulas 1 to 8
Figure FDA0003935930430000042
In the chemical formulas 1-1 to 1-8,
z is O or S, and the compound is a linear or branched compound,
R 1 、n1、n2、n3、L、X、Ar 1 and Ar 2 As defined in claim 1.
3. The compound of claim 1, wherein R 1 Each hydrogen or deuterium.
4. The compound of claim 1, wherein L is a single bond; or phenylene, biphenylene, terphenylene, tetraphenylene, or naphthylene.
5. The compound according to claim 1, wherein L is a single bond, or is represented by any one selected from the group consisting of:
Figure FDA0003935930430000051
6. the compound of claim 1, wherein X is N.
7. The compound of claim 1, wherein Ar 1 And Ar 2 Each being substituted or unsubstituted C 6-30 An aryl group; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O and S 5-30 A heteroaryl group.
8. The compound of claim 1, wherein Ar 1 And Ar 2 Each phenyl, naphthyl-substituted phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, phenanthryl, dibenzofuranyl, dibenzothienyl, carbazolyl, or phenyl-substituted carbazolyl.
9. The compound according to claim 1, wherein the compound represented by the chemical formula 1 is any one selected from the group consisting of:
Figure FDA0003935930430000061
Figure FDA0003935930430000071
Figure FDA0003935930430000081
Figure FDA0003935930430000091
Figure FDA0003935930430000101
Figure FDA0003935930430000111
Figure FDA0003935930430000121
Figure FDA0003935930430000131
Figure FDA0003935930430000141
Figure FDA0003935930430000151
10. an organic light emitting device, comprising: a first electrode, a second electrode provided so as to face the first electrode, and 1 or more organic layers provided between the first electrode and the second electrode, wherein 1 or more of the organic layers contain the compound according to any one of claims 1 to 9.
11. The organic light emitting device according to claim 10, wherein the organic layer containing the compound is a light emitting layer.
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