KR20180008279A - Novel hetero-cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

Provided are a novel heterocyclic compound and an organic light emitting device using the same. A compound represented by chemical formula 1 to 5 can be used as a material for an organic layer in an organic light emitting device, thereby being capable of improving efficiency, having low driving voltage and/or improving lifespan properties of an organic light emitting device.

Description

[0001] The present invention relates to novel heterocyclic compounds and organic light emitting devices using the same. More particularly,

The present invention relates to a novel heterocyclic compound and an organic light emitting device comprising the same.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, excellent characteristics of luminance, driving voltage and response speed, and much research has been conducted.

The 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 increase the efficiency and stability of the organic light emitting device, the organic material layer may have a multilayer structure composed of different materials. For example, the organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out.

There is a continuing need for the development of new materials for the organic materials used in such organic light emitting devices.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to a novel heterocyclic compound and an organic light emitting device comprising the same.

The present invention provides a compound represented by any one of the following formulas (1) to (5):

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above Formulas 1 to 5,

X ₁ to X ₃ are each independently N or CR ₁₁ , at least one of X ₁ to X ₃ is N,

Y ₁ is O or S,

L ₁ is combined with any one of the positions * 1 to * 3,

L ₁ is a single bond; Substituted or unsubstituted C _6-60 arylene; Or a substituted or unsubstituted O, N, C _1-60 heteroaryl containing 1 or more heteroatoms selected from the group consisting of Si and S arylene,

a1 is an integer of 0 to 3,

Ar ₁ To Ar ₃ is, each independently, a substituted or unsubstituted C _6-60 aryl; Or a substituted or unsubstituted N, O, and C _1-60 heteroaryl comprising 1 to 3 heteroatoms selected from the group consisting of S aryl,

R ₁ to R ₃ and R ₁₁ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-6 alkyl; C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Or a substituted or unsubstituted C _1-60 heterocyclic group containing at least one heteroatom selected from the group consisting of N, O and S,

b1 is an integer of 0 to 4,

b2 is an integer of 0 to 2,

b3 is an integer of 0 to 3;

The present invention also provides a plasma display panel comprising: a first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers includes a compound represented by any one of Chemical Formulas 1 to 5, Device.

The compound represented by any one of the above-described formulas (1) to (5) can be used as a material of an organic material layer of an organic light emitting device and can improve the efficiency, the driving voltage and / or the lifetime characteristics of the organic light emitting device. In particular, the compound represented by any one of the above-mentioned formulas (1) to (5) can be used as a host material for the light emitting layer.

Fig. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3 and a cathode 4. Fig.
2 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 7, an electron transporting layer 8 and a cathode 4 It is.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The present invention provides a compound represented by any one of the above formulas (1) to (5).

는 다른 치환기에 연결되는 결합을 의미하고, 단일 결합은 L₁으로 표시되는 부분에 별도의 원자가 존재하지 않은 경우를 의미한다. In the present specification,

Means a bond connected to another substituent, and a single bond means a case where no separate atom exists in a portion represented by L < _{1 &} gt ;.

As used herein, the term " substituted or unsubstituted " A halogen group; Cyano; A nitro group; A hydroxy group; A carbonyl group; An ester group; Imide; An amino group; Phosphine oxide groups; An alkoxy group; An aryloxy group; An alkyloxy group; Arylthioxy group; An alkylsulfoxy group; Arylsulfoxy group; Silyl group; Boron group; An alkyl group; Cycloalkyl groups; An alkenyl group; An aryl group; Aralkyl groups; An aralkenyl group; An alkylaryl group; An alkylamine group; An aralkylamine group; A heteroarylamine group; An arylamine group; Arylphosphine groups; Or a heterocyclic group containing at least one of N, O and S atoms, or a substituted or unsubstituted group in which at least two of the above-exemplified substituents are connected to each other . For example, "a substituent to which at least two substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, or may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the carbon number of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with a straight-chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms in the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, But are not limited thereto.

In the present specification, the boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, and a phenylboron group.

In the present specification, examples of the halogen group include 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 alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, But are not limited to, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, But are not limited to, dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl and 5-methylhexyl.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3- 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 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 phenyl group, a biphenyl group, a terphenyl group or the like as the monocyclic aryl group, but is not limited thereto. Examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, a fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

And the like. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a hetero ring group containing at least one of O, N, Si and S as a hetero atom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furane group, a furyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, A pyridazinyl group, a pyrazinopyrazinyl group, an isoquinoline group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, , An indole group, a carbazole group, a benzoxazole group, a benzoimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline, An isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group and the arylamine group is the same as the aforementioned aryl group. In the present specification, the alkyl group in the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the alkyl group described above. In the present specification, the heteroaryl among the heteroarylamines can be applied to the aforementioned heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the above-mentioned alkenyl group. In the present specification, the description of the aryl group described above can be applied except that arylene is a divalent group. In the present specification, the description of the above-mentioned heterocyclic group can be applied except that the heteroarylene is a divalent group. In the present specification, the description of the above-mentioned aryl group or cycloalkyl group can be applied except that the hydrocarbon ring is not a monovalent group and two substituents are bonded to each other. In the present specification, the description of the above-mentioned heterocyclic group can be applied except that the heterocyclic ring is not a monovalent group and two substituents are bonded to each other.

When L ₁ is bonded to the * 1, * 2, or * 3 positions in the formula 1, the compound may be represented by the following formula 1-1, 1-2, or 1-3, respectively:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 through 1-3,

X ₁ to X ₃ , Y ₁ , L ₁ , a ₁ , Ar ₁ To Ar ₃ , R ₁ to R ₃ , R ₁₁ and b 1 to b ₃ are as defined in the above formula (1).

In the above formula (2), when L ₁ is bonded to the * 1, * 2, or * 3 position, the compound may be represented by the following formula 2-1, 2-2,

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In the above formulas (2-1) to (2-3)

X ₁ to X ₃ , Y ₁ , L ₁ , a ₁ , Ar ₁ To Ar ₃ , R ₁ to R ₃ , R ₁₁ and b 1 to b ₃ are the same as defined in the above formula (2).

In the above formula (3), when L ₁ is bonded to the * 1, * 2, or * 3 position, the compound may be represented by the following formula 3-1, 3-2,

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

In the above formulas (3-1) to (3-3)

X ₁ to X ₃ , Y ₁ , L ₁ , a ₁ , Ar ₁ To Ar ₃ , R ₁ to R ₃ , R ₁₁ and b 1 to b 3 are the same as defined in the above formula (3).

In the above formula (4), when L ₁ is bonded to the * 1, * 2, or * 3 positions, the compound may be represented by the following formula 4-1, 4-2 or 4-3, respectively:

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

In Formulas 4-1 to 4-3,

X ₁ to X ₃ , Y ₁ , L ₁ , a ₁ , Ar ₁ To Ar ₃ , R ₁ to R ₃ , R ₁₁ and b 1 to b 3 are as defined in the above formula (4).

When L ₁ is bonded to the * 1, * 2, or * 3 position in Formula 5, the compound may be represented by the following Formula 5-1, 5-2, or 5-3, respectively:

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

In formulas (5-1) to (5-3)

X ₁ to X ₃ , Y ₁ , L ₁ , a ₁ , Ar ₁ To Ar ₃ , R ₁ to R ₃ , R ₁₁ and b 1 to b ₃ are the same as defined in the above formula (5).

When L ₁ is bonded to the * 1, * 2, or * 3 positions in the formulas (1) to (5), the compound improves the efficiency of the organic light emitting device, And / or the lifetime characteristics can be improved.

On the other hand, in the above formulas (1) to (5), a compound in which L ₁ is bonded to a position other than the * 1, * 2 or * 3 position (for example, * 4 position) There is a limit that the lifetime characteristic of the device is drastically reduced.

This is because the oxygen atom of the indolodibenzofurane corresponding to the HOMO and the aromatic functional group (including Ar ₂ and Ar ₃ ) linked to L ₁ corresponding to LUMO are located in the same direction, the dipole moment of the compound Dipole moment of the light emitting layer increases, and as a result, the balance of holes and electrons in the light emitting layer decreases. Further, the stability of the compound is deteriorated due to the repulsive force of non-covalent electrons of the oxygen atom of indolodibenzofuran and the non-covalent electrons of the aromatic group connected to L ₁ or adjacent hydrogen atoms. .

In the above Formulas 1 to 5,

X ₁ is N, X ₂ is N, and X ₃ is N;

X ₁ is N, X ₂ is N, and X ₃ is CR ₁₁ ;

X ₁ is N, X ₂ is CR ₁₁ , and X ₃ is N;

X ₁ is CR ₁₁ , X ₂ is N, and X ₃ is N;

X ₁ is N, X ₂ is CR ₁₁ , and X ₃ is CR ₁₁ ;

X ₁ is CR ₁₁ , X ₂ is N, and X ₃ is CR ₁₁ ; or

X ₁ is CR ₁₁ , X ₂ is CR ₁₁ , and X ₃ is N.

According to one embodiment, Y < ₁ >

According to one embodiment, L ₁ may be combined with the * 1 position. Accordingly, the compound may be a compound represented by the above formula (1-1), (2-1), or (3-1).

According to one embodiment, L &_lt; ₁ > is a single bond; Substituted or unsubstituted C _6-20 arylene; Or C _1-20 heteroarylene containing one or two substituted or unsubstituted N atoms.

For example, L &_lt; ₁ > is a single bond; C _6-20 arylene unsubstituted or substituted by deuterium, fluoro, or cyano; Or C _1-20 heteroarylene unsubstituted or substituted with deuterium, fluoro, or cyano.

Specifically, for example, L < ₁ > may be a single bond, or any one selected from the group consisting of:

.

.

More specifically, for example, L < ₁ > may be a single bond, or any one selected from the group consisting of:

.

.

According to one embodiment, al may be 0, 1, or 2. In this case, a1 represents the number of L ₁ , and when a ₁ is 2 or more, L 2 of 2 or more may be the same or different from each other. When a1 is 0, it means that L ₁ is a single bond.

According to one embodiment, Ar ₁ may be substituted or unsubstituted C _6-60 aryl.

For example, Ar ₁ is substituted or unsubstituted phenyl; Substituted or unsubstituted biphenyl; Substituted or unsubstituted naphthyl; Substituted or unsubstituted fluorenyl; Substituted or unsubstituted phenanthrenyl; Substituted or unsubstituted anthracenyl; Substituted or unsubstituted fluoranthenyl; Substituted or unsubstituted triphenylenyl; Substituted or unsubstituted pyrenyl; Or a substituted or unsubstituted crysinyl.

Specifically, for example, Ar < ₁ > may be any one selected from the group consisting of:

In the above,

Z ₁ to Z ₄ each independently represent hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; C _1-20 alkyl; C _1-20 haloalkyl; Or C _6-20 aryl,

c1 is an integer of 0 to 5,

c2 is an integer of 0 to 7,

c3 is an integer of 0 to 9,

c4 is an integer of 0 to 4,

and c5 is an integer of 0 to 3.

In the above, Z ₁ to Z ₄ each independently may be hydrogen or phenyl, and c 1 to c 5 each independently may be 0 or 1.

More specifically, for example, Ar ₁ may be any one selected from the group consisting of

.

.

According to one embodiment, Ar < _{2 >} And Ar ₃ is independently, substituted or unsubstituted C _6-20 aryl; Or substituted or unsubstituted C _1-20 heteroaryl containing one heteroatom selected from the group consisting of N, O and S.

For example, Ar ₂ And Ar ₃ is independently selected from substituted or unsubstituted phenyl; Substituted or unsubstituted biphenyl; Substituted or unsubstituted naphthyl; Substituted or unsubstituted fluorenyl; Substituted or unsubstituted phenanthrenyl; Substituted or unsubstituted anthracenyl; Substituted or unsubstituted fluoranthenyl; Substituted or unsubstituted triphenylenyl; Substituted or unsubstituted pyrenyl; Substituted or unsubstituted chlorenyl; Substituted or unsubstituted carbazolyl; Substituted or unsubstituted dibenzofuranyl; Substituted or unsubstituted dibenzothiophenyl; Substituted or unsubstituted pyridinyl; Substituted or unsubstituted pyrazinyl; Substituted or unsubstituted pyrimidinyl; Substituted or unsubstituted pyridazinyl; Or substituted or unsubstituted triazolyl.

Specifically, for example, Ar ₂ And Ar ₃ may each independently be selected from the group consisting of:

In the above,

Z ₁₁ to Z ₁₄ each independently represent hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; C _1-20 alkyl; C _6-20 aryl; Or C _1-20 heteroaryl containing 1 to 3 N,

c11 is an integer of 0 to 5,

c12 is an integer of 0 to 7,

c13 is an integer of 0 to 3,

and c14 is an integer of 0 to 4.

In the above, Z ₁₁ to Z ₁₄ each independently represent hydrogen; Fluoro; Cyano; methyl; Phenyl; Naphthyl; Or pyridinyl, and c11 to c14 each independently may be 0, 1, or 2.

More specifically, for example, Ar ₂ And Ar ₃ may each independently be selected from the group consisting of:

According to one embodiment, R ₁ to R ₃ and R ₁₁ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; C _1-20 alkyl; Or C _6-20 aryl.

For example, R ₁ to R ₃ and R ₁₁ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; methyl; Or phenyl.

Specifically, for example, R ₁ to R ₃ may be hydrogen, and b 1 to b 3 may each independently be 0 or 1.

R < ₁₁ > is hydrogen; heavy hydrogen; Fluoro; Or cyano.

Herein, b1 represents the number of R < _{1 &} gt ;, and when b1 is 2 or more, two or more R < ₁ > b2 and b3 can be understood with reference to the description of b1 and the structures of the above formulas (1) to (5).

Also, c1 is indicated as the number of Z _1, the case c1 is 2 or more, two or more of Z ₁ may be the same or different from each other. c2 to c5 and c11 to c14 can be understood with reference to the description of c1 and the structure of the above formula.

On the other hand, the compound may be any one selected from the compounds represented by the following formulas 1-1-1 to 5-1-1:

[Formula 1-1-1]

[Formula 2-1-1]

[Formula 3-1-1]

[Formula 4-1-1]

[Formula 5-1-1]

In the above formulas 1-1-1 to 5-1-1,

X ₁ to X ₃ , R ₁ , L ₁ , a ₁ , b ₁ and Ar ₁ To The definition of Ar ₃ is the same as defined in claim 1.

For example, the compound may be selected from the group consisting of the following compounds:

Wherein the compound represented by any one of Chemical Formulas 1 to 5 is a structure in which an N-atom-containing heteroaryl substituent such as a pyridinyl group, a pyrimidinyl group, or a triazinyl group is connected to a specific position of indolodibenzofuran or indolodibenzothiophene core The organic light emitting device using the organic light emitting device can have a high efficiency, a low driving voltage, a high brightness and a long life.

The compound represented by the above formula (1-1-1) can be prepared, for example, according to the following reaction scheme 1.

[Reaction Scheme 1]

In the above Reaction Scheme 1, X ₁ to X ₃ , L ₁ , a ₁ , and Ar ₁ To The definition of Ar ₃ is as defined in the above formula (1), and X represents halogen.

The compounds represented by any one of formulas (1) to (5) may be prepared by appropriately substituting a starting material according to the structure of a compound to be prepared with reference to Scheme 1.

Meanwhile, the present invention provides an organic light emitting device comprising a compound represented by any one of Chemical Formulas 1 to 5. In one embodiment, the present invention provides a liquid crystal display comprising: a first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers includes a compound represented by any one of Chemical Formulas 1 to 5, Device.

In addition, the organic layer may include a light emitting layer, and the light emitting layer may include a compound represented by any one of Chemical Formulas 1 to 5. In the light emitting layer, the compound represented by any one of Chemical Formulas 1 to 5 may serve as a host.

The light emitting layer may further include a known dopant. In the light emitting layer, the dopant may be included in an amount of about 0.01 to about 15 parts by weight based on about 100 parts by weight of the compound represented by any one of formulas 1 to 5, But is not limited thereto.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, in the organic light emitting device of the present invention, in addition to the light emitting layer as the organic material layer, a hole injecting layer and a hole transporting layer between the first electrode and the light emitting layer, and an electron transporting layer and an electron injecting layer between the light emitting layer and the second electrode are further included . ≪ / RTI > However, the structure of the organic light emitting device is not limited thereto, and may include fewer or more organic layers.

The organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, at least one organic layer, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an inverted type organic light emitting device in which an anode, one or more organic compound layers and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting diode according to an embodiment of the present invention is illustrated in FIGS.

Fig. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3 and a cathode 4. Fig. In such a structure, the compound represented by any one of Chemical Formulas 1 to 5 may be included in the light emitting layer.

2 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 7, an electron transporting layer 8 and a cathode 4 It is. In such a structure, the compound represented by any one of Chemical Formulas 1 to 5 may be contained in at least one of the hole injecting layer, the hole transporting layer, the light emitting layer, and the electron transporting layer.

The organic light emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one of the organic layers includes a compound represented by one of the above Chemical Formulas 1 to 5. In addition, when the organic light emitting diode includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention can be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form an anode Forming an organic material layer including a hole injection layer, a hole transporting layer, a light emitting layer and an electron transporting layer on the organic material layer, and then depositing a material usable as a cathode on the organic material layer. In addition to such a method, an organic light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

In addition, the compound represented by any one of Chemical Formulas 1 to 5 may be formed into an organic material layer by a solution coating method as well as a vacuum evaporation method in the production of an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating and the like, but is not limited thereto.

In addition to such a method, an organic light emitting device can be manufactured by sequentially depositing an organic material layer and a cathode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.

In one example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode and the second electrode is a cathode.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SNO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

The hole injecting material is a layer for injecting holes from the electrode. The hole injecting material has a hole injecting effect, a hole injecting effect in the anode, and an excellent hole injecting effect in the light emitting layer or the light emitting material. A compound which prevents the exciton from migrating to the electron injection layer or the electron injection material and is also excellent in the thin film forming ability is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer and transports holes from the anode or the hole injection layer to the light emitting layer by using a hole transport material. Is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material as described above. The host material may further include a condensed aromatic ring derivative or a heterocyclic compound in addition to the compound represented by any one of the above formulas (1) to (5). Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds. Examples of the heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specific examples of the aromatic amine derivatives include condensed aromatic ring derivatives having substituted or unsubstituted arylamino groups, and examples thereof include pyrene, anthracene, chrysene, and peripherrhene having an arylamino group. Examples of the styrylamine compound include substituted or unsubstituted Wherein at least one aryl vinyl group is substituted with at least one aryl vinyl group, and at least one substituent selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group is substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. Examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto.

The electron transporting material is a layer that receives electrons from the electron injecting layer and transports electrons to the light emitting layer. The electron transporting material is a material capable of transferring electrons from the cathode well to the light emitting layer. Is suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transporting layer can be used with any desired cathode material as used according to the prior art. In particular, an example of a suitable cathode material is a conventional material having a low work function followed by an aluminum layer or a silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer for injecting electrons from the electrode. The electron injection layer has the ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron injection effect with respect to the light emitting layer or the light emitting material. A compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A nitrogen-containing 5-membered ring derivative, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.

The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

In addition, the compound represented by any one of Chemical Formulas 1 to 5 may be included in an organic solar cell or an organic transistor in addition to an organic light emitting device.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

< Synthetic example >

Synthetic example  1: Preparation of Compound 1-1

Compound 1-1 was prepared through the following steps 1) to 6).

1) Preparation of Compound 1-1-1

(100 g, 546 mmol) was dissolved in 1 L of tetrahydrofuran (THF), and the temperature was lowered to 0 캜. N-Bromosuccinimide (97 g, 546 mmol) was added little by little. After about 1 hour, 500 mL of a saturated ammonium chloride aqueous solution was added, and the mixture was stirred. The water layer was separated, and the organic layer was concentrated under reduced pressure. A small amount of ethyl acetate and an excess amount of hexane were added to the concentrated compound, followed by slurry filtration to obtain Compound 1-1-1 as a gray solid. (112 g, yield 78%).

2) Preparation of Compound 1-1-2

The compound 1-1-1 (50 g, 190 mmol) and (2-chloro-6-fluorophenyl) boronic acid (99 g, 570 mmol) were dispersed in tetrahydrofuran (400 ml) aqueous (aq. K ₂ CO ₃₎ was added (190 ml, 380 mmol) and tetrakis triphenyl phosphino palladium _{[Pd (PPh 3) 4]} (2.2 g, 1 mol%) was stirred under reflux for 6 hours, after inserting the Respectively. The temperature was lowered to room temperature, the water layer was separated, and the organic layer was further washed with water once more to separate the layers. Anhydrous magnesium sulfate was added to the collected organic layer, followed by slurry filtration and concentration under reduced pressure. The oily compound was separated through a silica column with a combination of hexane and ethyl acetate to give Compound 1-1-2 (48.1 g, 81%) as a white solid.

3) Preparation of Compound 1-1-3

Compound 1-1-2 (59 g, 189 mmol) was diluted in 400 mL of N-methyl-2-pyrrolidone, and potassium carbonate (52 g, 190 mmol) was added and the mixture was heated to 140 占 폚. After about 1 hour, the reaction was cooled to room temperature and slowly added to 1.6 L of water. The precipitated solid was filtered, dissolved in tetrahydrofuran, treated with anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The concentrated compound was slurried with a small amount of tetrahydrofuran and excess amount of hexane and filtered. The filtered compound was separated through a silica column with hexane and ethyl acetate to purify Compound 1-1-3 (38.6 g, 70%).

4) Preparation of Compound 1-1-4

Bis (pinacolato) diborone (38.2 g, 133 mmol) and potassium acetate (21.8 g, 222 mmol) were added to a solution of Compound 1-1-3 (32 g, 111 mmol) Was added to 370 mL of 1,4-dioxane, and 1.9 g (3.3 mmol) of dibenzylidene acetone palladium and 1.8 g (6.7 mmol) of tricyclohexylphosphine were added under reflux and stirring, followed by stirring under reflux for 12 hours. When the reaction is complete, the mixture is cooled to room temperature and filtered through celite. The filtrate was concentrated under reduced pressure, and the residue was dissolved in ethyl acetate. The organic layer was washed with water, and dried over anhydrous magnesium sulfate. This was distilled under reduced pressure, and the mixture was stirred with ethyl acetate and ethanol to prepare Compound 1-1-4 (27.6 g, yield 65%).

5) Preparation of Compound 1-1-5

(15.5 g, 39 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (10.5 g, 39 mmol) were dispersed in tetrahydrofuran was then added a 2M aqueous solution of potassium carbonate _{(aq. K 2 CO 3)} (58 ml, 117 mmol) and tetrakis triphenyl phosphino palladium into the _{[Pd (PPh 3) 4]} (0.45 g, 1 mol%) The mixture was refluxed with stirring for 6 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtrate was concentrated and re-dissolved in ethyl acetate, washed twice with water, and then dried over anhydrous magnesium sulfate, filtered and concentrated. The concentrated residue was slurried in a small amount of ethyl acetate and an excess of hexane and ethanol to obtain a dark yellow Compound 1-1-5 (5.2 g, yield 27%).

6) Preparation of Compound 1-1

The compound 1-1-5 (20 g, 41 mmol) and iodobenzene (25 g, 123 mmol) were dissolved in toluene (150 mL) and sodium tert-butoxide (7.9 g, 82 mmol) . (Tris (tert-butylphosphine) palladium (0.21 g, 1 mol%) was added thereto, and the mixture was stirred under reflux for 12 hours. When the reaction was completed, the temperature was lowered to room temperature and the resulting solid was filtered. The yellow solid was dissolved in 700 mL of chloroform and washed twice with water. The organic layer was separated, and anhydrous magnesium sulfate was added thereto, followed by stirring, followed by filtration, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using ethyl acetate and hexane to prepare a dark yellow solid compound (1-1) (17.8 g, 77%, MS: [M + H] ⁺ = 565).

Synthetic example  2: Preparation of Compound 1-2

Was obtained in the same manner as in step 6) of the above compound 1-1 except that 2-bromo-9-phenyl-9H-carbazole (13 g, 41 mmol) was used instead of iodobenzene (25 g, 123 mmol) Compound 1-2 (21.8 g, 73%, MS: [M + H] &lt; ⁺ &gt; = 730) was prepared by proceeding the reaction.

Synthetic example  3: Preparation of compound 2-1

Compound 2-1 was prepared through the following steps 1) to 7).

1) Preparation of compound 2-1-1

3-chloro-2-iodophenol (100 g, 393 mmol) and (3-bromo-2-fluorophenyl) boronic acid (86 g, 393 mmol) was dispersed in tetrahydrofuran (1000 ml), followed by the addition of a 2M aqueous potassium carbonate solution (aq. K ₂ CO ₃ ) (400 ml, 786 mmol) and tetrakistriphenylphosphino after loading of palladium _{[Pd (PPh 3) 4]} (4.5 g, 1 mol%) was refluxed with stirring for 6 hours. The temperature was lowered to room temperature, the water layer was separated, and anhydrous magnesium sulfate was added to the organic layer, followed by slurry filtration and concentration under reduced pressure. The oily compound was separated by silica column chromatography using a combination of hexane and ethyl acetate to give Compound 2-1-1 (90 g, 76%) as a white solid.

2) Preparation of compound 2-1-2

Compound 2-1-1 (90 g, 298 mmol) was used in the same manner as in the synthesis example of Compound 1-1-3 to prepare Compound 2-1-2 (61 g, yield 73%).

3) Preparation of compound 2-1-3

Compound 2-1-2 (61 g, 217 mmol) and 2-chloroaniline (30 g, 238 mmol) were dissolved in 750 mL of toluene and potassium phosphate (138 g, 650 mmol) was added and warmed. And palladium (0.6 g, 0.5 mol%) of bis (tritiated-butylphosphine) was added thereto, and the mixture was refluxed and stirred for 3 hours. When the reaction was completed, 500 mL of toluene was removed under reflux, the temperature was lowered to room temperature, and the precipitated solid was filtered. The filtered solid was dissolved in 500 mL of chloroform and washed twice with water. The organic layer was separated, and anhydrous magnesium sulfate was added thereto, followed by stirring, followed by filtration, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica column chromatography using ethyl acetate and hexane to obtain a solid compound of Formula 2-1-3 (48.3 g, yield 68%).

4) Preparation of compound 2-1-4

Compound 2-1-3 (45 g, 137 mmol) was dissolved in 450 mL of diethylacetamide (DMAc), and then potassium phosphate (43.6 g, 206 mmol) was added thereto. 1.58 g (2.74 mmol) of dibenzylidene acetone palladium and 3.85 (13.7 mmol) of tricyclohexylphosphine were added and the mixture was stirred under reflux for 6 hours. When the reaction was completed, the reaction product was cooled to room temperature, and the reactant was added to 1.8 L of water. After stirring, the resulting solid was filtered. The filtered solid was completely dissolved in ethyl acetate and washed with water. The separated organic layer was treated with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The concentrated compound was purified by silica column chromatography using ethyl acetate and hexane to obtain a solid compound (2-1-4) (32.4 g, yield 81%).

5) Preparation of compound 2-1-5

Compound 2-1-5 (32.7 g, yield 83%) was prepared using Compound 2-1-4 (30 g, 103 mmol) in the same manner as in the synthesis example of Compound 1-1-4.

6) Preparation of compound 2-1-6

Compound 2-1-5 (30 g, 78 mmol) and 2 - ([1,1'-biphenyl] -4-chloro-6-phenyl-1,3,5-triazine (26.9 g, 78 mmol), the same procedure as in the synthesis example of the compound 1-1-5 was conducted to prepare a compound 2-1-6 (38 g, yield 86%).

7) Preparation of Compound 2-1

Compound 2-1 (12.8 g, yield 75%, MS: [M + H] &lt; ⁺ &gt; = 641 (75%) was obtained in the same manner as in the synthesis example 1-1 using Compound 2-1-6 ).

Synthetic example  4: Preparation of compound 3-1

Compound 3-1 was prepared by the following steps 1) to 7).

1) Preparation of compound 3-1-1

Using the compound 3-bromo-2-iodophenol (50 g, 167 mmol) and (2-chloro-6-fluorophenyl) boronic acid (44 g, 251 mmol) The compound 3-1-1 (41 g, yield 82%) was prepared.

2) Preparation of compound 3-1-2

Compound 3-1-1 (41 g, 136 mmol) was used in the same manner as in the synthesis example of Compound 1-1-3 to prepare Compound 3-1-2 (29 g, yield 76%).

3) Preparation of compound 3-1-3

Using Compound 3-1-2 (25 g, 89 mmol) and 2-chloro-4- (9-phenyl-9H-carbazol-3-yl) aniline (33 g, 89 mmol) , The compound 3-1-3 (37 g, yield 73%) was prepared.

4) Preparation of compound 3-1-4

Compound 3-1-4 (25 g, yield 81%) was prepared using Compound 3-1-3 (33 g, 58 mmol) in the same manner as in the synthesis example of Compound 2-1-4.

5) Preparation of compound 3-1-5

Compound 3-1-5 (22 g, yield 75%) was prepared using Compound 3-1-4 (25 g, 47 mmol) in the same manner as in the synthesis example of Compound 1-1-4.

6) Preparation of compound 3-1-6

Compound 3-1-5 (20 g, 32 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (8.8 g, 32 mmol) Compound 3-1-6 (18.7 g, yield 80%) was prepared in the same manner as in Synthesis Example.

7) Preparation of Compound 3-1

Compound 3-1-6 (15 g, 21 mmol) was added to iodobenzene (75 mL, 5 vol), and then potassium phosphate (8.7 g, 41 mmol) was added and warmed. CuI (3.9 g, 21 mmol) is slowly added at about 60 &lt; 0 &gt; C. When the reaction is complete at reflux, cool the reaction to room temperature and add 100 mL of water. The precipitated solid was filtered and dissolved in 1 L of chloroform, and washed twice with 2M HCl aqueous solution. The organic layer was separated, and the resulting mixture was slurry-filtered using anhydrous magnesium sulfate and acidic white clay, followed by concentration under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to obtain Compound 3-1 (11.6 g, yield 70%, MS: [M + H] ⁺ = 806).

Synthesis Example 5: Preparation of Compound 4-1

Compound 4-1 was prepared through the following steps 1) to 8).

1) Preparation of compound 4-1-1

The compound 1-1-2 was obtained by using 3-bromo-4-nitrophenol (50 g, 229 mmol) and ([1,1'- biphenyl] -4-yl) boronic acid (54 g, 275 mmol) , The compound 4-1-1 (58.8 g, yield 88%) was prepared.

2) Preparation of compound 4-1-2

Compound 4-1-2 (58 g, yield 83%) was prepared using Compound 4-1-1 (55 g, 189 mmol) in the same manner as in the synthesis example of Compound 1-1-1.

3) Preparation of compound 4-1-3

Using the compound 4-1-2 (50 g, 135 mmol) and (2-chloro-6-fluorophenyl) boronic acid (29 g, 162 mmol) To obtain Compound 4-1-3 (46.0 g, yield 81%).

4) Preparation of compound 4-1-4

Compound 4-1-4 (32.6 g, yield 76%) was prepared using Compound 4-1-3 (45 g, 107 mmol) in the same manner as in the synthesis example of Compound 1-1-3.

5) Preparation of compound 4-1-5

Triethyl phosphite (P (OEt) ₃ ) (21.3 g, 128 mmol) was added to the compound 4-1-4 (45 g, 107 mmol), and the mixture was warmed and stirred. When the reaction is complete, the remaining triethyl phosphite is removed by distillation in vacuo, and the mixture is cooled to room temperature and stirred. The resulting solid is filtered by adding hexane and ethyl acetate, and the filtered solid is washed with hexane. The solid was dissolved again in chloroform and washed twice with water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The compound was recrystallized from ethanol and ethyl acetate to give compound 4-1-5 (30.0 g, yield 76%).

6) Preparation of compound 4-1-6

Compound 4-1-6 (33.0 g, yield 88%) was prepared using Compound 4-1-5 (30 g, 82 mmol) in the same manner as in the synthesis example of Compound 1-1-4.

7) Preparation of compound 4-1-7

Compound 4-1-6 (30 g, 65 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (12.0 g, 68.6 mmol) Compound 4-1-7 (28.4 g, yield 77%) was prepared in the same manner as in Synthesis Example.

8) Preparation of compound 4-1

Compound 4-1 (11.0 g, yield 65%, MS: [M + H] &lt; ⁺ &gt; = 641 (Yield: 65%) was obtained in the same manner as in the synthesis example 3-1 using 4-1-7 ).

Synthetic example  6: Preparation of compound 5-1

Compound 5-1 was prepared through the following steps 1) to 7).

1) Preparation of compound 5-1-1

2-bromobenzene-1,3-diol (50 g, 265 mmol) and (2-chloro-6-fluorophenyl) -fluorophenyl) boronic acid (55.3 g, 317 mmol) was used in the same manner as in the synthesis example of Compound 1-1-2 to prepare Compound 5-1-1 (42.9 g, yield 68%).

2) Preparation of compound 5-1-2

Compound 5-1-2 (32.6 g, yield 76%) was prepared using Compound 5-1-1 (41 g, 172 mmol) in the same manner as in the synthesis example of Compound 1-1-3.

3) Preparation of compound 5-1-3

Compound 5-1-2 (41 g, 172 mmol) and (2-nitrophenyl) boronic acid (34.4 g, 206 mmol) were tested in the same manner as in the synthesis example of Compound 1-1-2, -4 (46 g, yield 81%).

4) Preparation of compound 5-1-4

Compound 5-1-3 (40 g, 131 mmol) was used in the same manner as in the synthesis example 4-1-5 to give compound 5-1-5 (27 g, yield 76%).

5) Preparation of compound 5-1-5

Compound 5-1-4 (25 g, 91.5 mmol) was diluted in 200 mL of acetonitrile and an aqueous solution of 30 mL of perfluorobutanesulfonyl fluoride (30.3 g, 100.6 mmol) and potassium carbonate (25 g, 183 mmol) I put it together. After warming to 40 ° C and stirring, when the reaction is complete, cool to room temperature. The water layer is separated, and the organic layer is concentrated under reduced pressure. The concentrated compound was separated by silica column chromatography with hexane and ethyl acetate to obtain a white solid compound 5-1-5 (37 g, yield 73%).

6) Preparation of compound 5-1-6

Compound 5-1-5 (35 g, 63 mmol) and 2,4-diphenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- -1,3,5-triazine (28.8 g, 66 mmol) was used in the same manner as in the synthesis example of the compound 1-1-5 to give 28.4 g (yield 80%) of the compound 5-1-6.

7) Preparation of compound 5-1

3-iodo-1,1'-biphenyl (14.9 g, 53 mmol) was added to 100 mL of toluene, and a solution of the compound 5-1-6 (20 g, Compound 5-1 (15 g, yield 75%, MS: [M + H] &lt; ⁺ &gt; = 717) was prepared in the same manner as in the synthesis example 3-1,

Synthetic example  7: Preparation of compound 2-2

Compound 2-2 was prepared through the following steps 1) to 7).

1) Preparation of compound 2-2-1

4-chloro-2-iodophenol (80 g, 314 mmol) and (3-bromo-2-fluorophenyl) boronic acid (72 g, 330 mmol), the compound 2-2-1 (69 g, yield 73%) was prepared in the same manner as in the synthesis example 2-1-1.

2) Preparation of compound 2-2-2

Compound 2-2-2 (50 g, yield 82%) was prepared in the same manner as in the synthesis example of Compound 1-1-3, using Compound 2-2-1 (65 g, 215 mmol).

3) Preparation of compound 2-2-3

Compound 2-2-3 (53 g, yield 76%) was prepared in the same manner as in the synthesis example 2-1-3, using the compound 2-2-2 (60 g, 213 mmol).

4) Preparation of compound 2-2-4

Compound 2-2-4 (37 g, yield 80%) was prepared in the same manner as in the synthesis example 2-1-4, using the compound 2-2-3 (52 g, 158 mmol).

5) Preparation of compound 2-2-5

Compound 2-2-5 (33.5 g, yield 73%) was prepared using Compound 2-2-4 (35 g, 120 mmol) in the same manner as in the synthesis example of Compound 1-1-4.

6) Preparation of compound 2-2-6

Compound 2-2-5 (30 g, 78 mmol) and 2 - ([1,1'-biphenyl] -3-yl) -4-chloro-6-phenyl-1,3,5-triazine Synthesis of Compound 1-1-5 Using (26.9 g, 78 mmol) of (1-1, biphenyl-3-yl) -4-chloro-6- To give Compound 2-2-6 (35 g, yield 80%).

7) Preparation of compound 2-2

Compound 2-2 (14.8 g, yield 77%, MS: [M + H] &lt; ⁺ &gt; = 641 (Yield: 77%) was used in the same manner as in the synthesis example 3-1, ).

Synthetic example  8: Preparation of compound 4-2

Compound 4-2 was prepared through the following steps 1) to 8).

1) Preparation of compound 4-2-1

A solution of 3-bromo-4-nitrophenol (50 g, 229 mmol) and (3- (9H-carbazol-9- carbazol-9-yl) phenyl) boronic acid (66 g, 229 mmol) was used in the same manner as in the synthesis example of Compound 1-1-2 to give Compound 4-2-1 (71 g, yield 81% .

2) Preparation of compound 4-2-2

Compound 4-2-2 (73 g, yield 86%) was prepared using Compound 4-2-1 (70 g, 184 mmol) in the same manner as in the synthesis example of Compound 1-1-1.

3) Preparation of compound 4-2-3

Using the compound 4-2-2 (72 g, 157 mmol) and (4-chloro-2-fluorophenyl) boronic acid (32.8 g, 188 mmol) To obtain Compound 4-2-3 (58 g, yield 73%).

4) Preparation of compound 4-2-4

Compound 4-2-4 (44 g, yield 83%) was prepared by conducting the same procedure as in the synthesis example of Compound 1-1-3, using Compound 4-2-3 (55 g, 108 mmol).

5) Preparation of compound 4-2-5

Compound 4-2-5 (27.7 g, yield 74%) was prepared by the same procedure as in the synthesis example 4-1-5 using 4-2-4 (40 g, 82 mmol).

6) Preparation of compound 4-2-6

Compound 4-2-6 (24.6 g, yield 82%) was prepared using Compound 4-2-5 (25 g, 54 mmol) in the same manner as in the synthesis example of Compound 1-1-4.

7) Preparation of compound 4-2-7

Compound 4-2-6 (24 g, 44 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (12.3 g, 46 mmol) Compound 4-2-7 (25 g, yield 88%) was prepared in the same manner as in Synthesis Example.

8) Preparation of compound 4-2

Compound 4-2 (17 g, yield 75%, MS: [M + H] &lt; ⁺ &gt; = 730 (75%) was obtained in the same manner as in the synthesis example 3-1 using compound 4-2-7 ).

<Examples>

Example 1

A thin glass substrate coated with ITO (indium tin oxide) at a thickness of 1,300 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, a Fischer Co. product was used as a detergent, and distilled water, which was filtered with a filter of Millipore Co., was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

The following HI-1 compound was thermally vacuum deposited on the ITO transparent electrode prepared above to a thickness of 50 Å to form a hole injection layer.

The HT-1 compound was thermally vacuum-deposited on the hole injection layer to a thickness of 250 Å to form a hole transport layer, and an HT-2 compound was vacuum deposited on the HT-1 deposition layer to a thickness of 50 Å to form an electron blocking layer.

Next, Compound 1-1 prepared in Synthesis Example 1 was deposited on the HT-2 deposited film to a thickness of 400 Å, and a phosphorescent dopant GD-1 was co-deposited at a weight ratio of 6 to 15% to form a light emitting layer.

An ET-1 material was vacuum deposited on the light-emitting layer to a thickness of 250 ANGSTROM and an ET-2 material was co-deposited with a 2% weight ratio Li to a thickness of 100 ANGSTROM to form an electron transport layer and an electron injection layer. Aluminum was deposited on the electron injecting layer to a thickness of 1000 to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å / sec, the deposition rate of aluminum was maintained at 2 Å / sec, and the vacuum degree during deposition was maintained at 1 × 10 ^-7 to 5 × 10 ^-8 torr Respectively.

Examples 2 to 8

The organic light emitting devices of Examples 2 to 8 were fabricated in the same manner as in Example 1, except that the phosphorescent host material and the dopant content in the light emitting layer were changed as shown in Table 1 below.

<Comparative Example>

Comparative Examples 1 to 5

The organic light emitting devices of Comparative Examples 1 to 5 were fabricated in the same manner as in Example 1, except that the phosphorescent host material and the dopant content in the light emitting layer were changed as shown in Table 1 below. Here, the host material compounds A to C used in the comparative example are as follows.

[Compound A]

[Compound B]

[Compound C]

<Experimental Example>

The current, voltage, efficiency, color coordinates and lifetime of the organic light-emitting device fabricated in Examples 1 to 8 and Comparative Examples 1 to 5 were measured, and the results are shown in Table 1 below. In this case, T95 is the optical density of 20mA / cm ² Is the time required for the luminance to be reduced to 95% when the initial luminance is 100%.

division Host: dopant
(Thickness, A) dopant content Voltage (V)
(@ 10 mA / cm ² ) EQE (%)
(@ 10 mA / cm ² ) Color coordinates
(x, y) Life (T ₉₅ , h)
(@ 20 mA / cm ² ) Example 1 Compound 1-2: GD-1
(400) 12% 3.03 18.2 (0.33, 0.63) 64.5 Example 2 Compound 2-2: GD-1
(400) 12% 3.13 17.9 (0.34, 0.62) 60.2 Example 3 Compound 3-1: GD-1
(400) 12% 3.01 18.5 (0.34, 0.62) 59.8 Example 4 Compound 4-2: GD-1
(400) 12% 3.15 19.5 (0.34, 0.62) 48.2 Example 5 Compound 1-1: PH-1: GD-1
(200: 200) 6% 3.22 19.5 (0.34, 0.62) 80.3 Example 6 Compound 2-1: PH-1: GD-1
(240: 160) 12% 3.20 20.1 (0.33, 0.63) 88.1 Example 7 Compound 4-1: PH-1: GD-1
(200: 200) 10% 3.28 19.7 (0.32, 0.63) 90.4 Example 8 Compound 5-1: PH-2: GD-1
(280: 120) 10% 3.25 21.1 (0.33, 0.63) 79.5 Comparative Example 1 Compound A: GD-1
(400) 12% 3.10 17.3 (0.33, 0.63) 26.6 Comparative Example 2 Compound A: PH-1: GD-1
(200: 200) 12% 3.43 18.1 (0.34, 0.62) 45.3 Comparative Example 3 Compound B: GD-1
(400) 10% 3.20 16.8 (0.32, 0.63) 17.1 Comparative Example 4 Compound C: GD-1
(400) 12% 3.30 17.1 (0.32, 0.62) 20.3 Comparative Example 5 Compound B: PH-2: GD-1
(240: 160) 12% 3.40 17.5 (0.33, 0.62) 28.8

As shown in Table 1, in the case of the organic luminescent devices of Examples 1 to 8, when a compound satisfying one of the formulas (1) to (5) is used as a host of the luminescent layer, And at the same time, the time required for luminance reduction was as high as 48.2 hours or more, thus realizing excellent lifetime characteristics.

On the other hand, the organic light emitting devices of Comparative Examples 1 and 2 using a compound A having a completely different structure from the general formulas (1) to (5) had a problem that the driving voltage was higher or the efficiency was lowered, Which is shorter than that in the Examples.

Compared with Examples 1 to 5 in which functional groups were introduced at positions 1 to 3 of indolodibenzofuran, in Comparative Examples 3 to 5 using compounds B and C into which a functional group was introduced at position 4, There was a problem that the driving voltage was high or the efficiency was inferior. In particular, it was confirmed that the time required for the luminance reduction sharply shortened to less than 30 hours.

1: substrate 2: anode
3: light emitting layer 4: cathode
5: Hole injection layer 6: Hole transport layer
7: light emitting layer 8: electron transporting layer

Claims (6)

A compound represented by any one of the following formulas (1) to (5):
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above Formulas 1 to 5,
X ₁ to X ₃ are each independently N or CR ₁₁ , at least one of X ₁ to X ₃ is N,
Y ₁ is O or S,
L ₁ is combined with any one of the positions * 1 to * 3,
L ₁ is a single bond; Substituted or unsubstituted C _6-60 arylene; Or a substituted or unsubstituted O, N, C _1-60 heteroaryl containing 1 or more heteroatoms selected from the group consisting of Si and S arylene,
a1 is an integer of 0 to 3,
Ar ₁ To Ar ₃ is, each independently, a substituted or unsubstituted C _6-60 aryl; Or a substituted or unsubstituted N, O, and C _1-60 heteroaryl comprising 1 to 3 heteroatoms selected from the group consisting of S aryl,
R ₁ to R ₃ and R ₁₁ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-6 alkyl; C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Or a substituted or unsubstituted C _1-60 heterocyclic group containing at least one heteroatom selected from the group consisting of N, O and S,
b1 is an integer of 0 to 4,
b2 is an integer of 0 to 2,
b3 is an integer of 0 to 3;
The method according to claim 1,
Ar ₁ is any one selected from the group consisting of:

Ar ₂ And And Ar &lt; ₃ &gt; are each independently selected from the group consisting of:

.
The method according to claim 1,
Wherein said compound is any one selected from the compounds represented by the following formulas (1-1) to (5-1-1):
[Formula 1-1-1]

[Formula 2-1-1]

[Formula 3-1-1]

[Formula 4-1-1]

[Formula 5-1-1]

In the above formulas 1-1-1 to 5-1-1,
X ₁ to X ₃ , R ₁ , L ₁ , a ₁ , b ₁ and Ar ₁ To The definition of Ar ₃ is the same as defined in claim 1.
The method according to claim 1,
Wherein said compound is any one selected from the group consisting of the following compounds:

.
A first electrode; A second electrode facing the first electrode; And at least one organic compound layer provided between the first electrode and the second electrode, wherein at least one of the organic compound layers comprises the compound according to any one of claims 1 to 4 The organic light-emitting device.
6. The method of claim 5,
Wherein the organic compound layer containing the compound is a light emitting layer.

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