TWI770328B - Compounds having boron as spiro atoms, polymer compounds thereof, materials for organic elements, organic electroluminescence elements, display devices and lighting devices - Google Patents

Abstract

A環～D環為可被取代的芳基環或雜芳基環等，其中，作為針對A環單獨及D環單獨的取代基，將吖啶系取代基去除，X¹ ～X⁴ 分別獨立地為C或N，Z¹ 及Z² 為單鍵、或可被部分取代的伸烷基等連結基，其中，Z¹ 及Z² 不會同時為單鍵，式（1）所表示的化合物中的至少一個氫可由氰基、鹵素或重氫取代。The present invention provides a novel compound having boron as a spiro ring atom and an organic EL device using the same. An excellent organic EL device is provided by a novel compound having boron as a spiro ring attachment atom represented by the following general formula (1) and a polymer compound thereof.

Rings A to D are substituted aryl rings, heteroaryl rings, etc., wherein, as the substituents for the A ring alone and the D ring alone, the acridine-based substituent is removed, and X ¹ to X ⁴ are each independently Ground is C or N, Z ¹ and Z ² are single bonds, or linking groups such as alkylene groups that can be partially substituted, wherein Z ¹ and Z ² cannot be single bonds at the same time, the compound represented by formula (1) At least one hydrogen in can be replaced by cyano, halogen or deuterium.

Description

Compounds having boron as spiro atoms, polymer compounds thereof, materials for organic elements, organic electroluminescence elements, display devices and lighting devices

The present invention relates to a compound having boron as a spiro ring atom, a polymer compound using the same as a repeating unit, an organic electroluminescence device, an organic field-effect transistor, an organic thin-film solar cell, and a display device using these compounds fixtures and lighting fixtures.

Conventionally, various studies have been conducted on display devices using light-emitting elements that perform electroluminescence to achieve power saving and thinning. Furthermore, organic electroluminescence elements including organic materials can be easily reduced in weight or in size. Active research. In particular, development of organic materials having light-emitting properties such as blue, which is one of the three primary colors of light, and development of organic materials having charge transport capabilities such as holes and electrons (possibly becoming semiconductors or superconductors) , So far, regardless of high molecular compounds, low molecular compounds have been actively researched.

An organic electroluminescence (EL) element has the following structure, and the structure includes a pair of electrodes including an anode and a cathode, and one or more layers disposed between the pair of electrodes and including an organic compound. Among the layers containing organic compounds, there are light-emitting layers, charge transport/injection layers for transporting or injecting charges such as holes and electrons, and the like, and various organic materials suitable for these layers have been developed.

As a material for a light-emitting layer, for example, a benzoyl compound or the like has been developed (International Publication No. 2004/061047). In addition, as a hole transport material, for example, triphenylamine-based compounds and the like have been developed (Japanese Patent Laid-Open No. 2001-172232). Moreover, as an electron transport material, an anthracene type compound etc. are developed, for example (Japanese Unexamined-Japanese-Patent No. 2005-170911).

In recent years, as a material used for an organic EL element or an organic thin-film solar cell, an improved triphenylamine derivative has also been reported (International Publication No. 2012/118164). This material is a material characterized by combining N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4 which has been put into practical use ,4'-diamine (TPD) was used as a reference and the aromatic rings constituting triphenylamine were linked to each other, thereby improving the planarity thereof. In addition, examples of such compounds have been found (International Publication No. 2011/107186, International Publication No. 2015/102118), and compounds having a conjugated structure with a large triplet exciton energy (T1) can emit a shorter wavelength. Therefore, it is beneficial as a material for a blue light-emitting layer. In addition, there is also a report that a compound having a Heteraborin ring including a boron atom, an oxygen atom, or a sulfur atom has been similarly investigated (International Publication No. 2015/072537). [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2004/061047 [Patent Document 2] Japanese Patent Laid-Open No. 2001-172232 [Patent Document 3] Japanese Patent Laid-Open No. 2005-170911 [Patent Document 4] International Publication No. 2012/118164 [Patent Document 5] International Publication No. 2011/107186 [Patent Document 6] International Publication No. 2015/102118 [Patent Document 7] International Publication No. 2015/072537

[The problem to be solved by the invention] As described above, various materials have been developed as materials used in organic elements such as organic EL elements, and in order to increase the selection of materials for organic elements, it is desired to develop materials containing compounds different from those previously used. [Means of Solving Problems]

The inventors of the present invention have made diligent studies in order to solve the above-mentioned problems, and as a result, they have found and succeeded in producing a novel compound having boron as a spiro ring attachment atom. In addition, the inventors found that an excellent organic EL element can be obtained by arranging a layer containing the compound between a pair of electrodes to constitute an organic EL element, and completed the present invention. That is, the present invention provides the following compounds or a polymer compound using the same as a repeating unit, and a material for organic elements containing these compounds.

（所述式（1）中， A環、C環及D環分別獨立地為芳基環或雜芳基環，B環為雜芳基環，A環與B環及/或C環與D環可鍵結而形成環結構，該些環中的至少一個氫可被取代，其中，作為針對A環單獨及D環單獨的取代基，將吖啶系取代基去除， X¹ ～X⁴ 分別獨立地為C或N， Z¹ 及Z² 分別獨立地為單鍵、伸烷基、伸烯基、伸炔基或伸芳基，該些中的任意的-CH₂ -可由-C(=CR₂ )-、-C(=C(=O))-、-C(=O)-、-C(=S)-、-C(=O)O-、-C(=S)O-、-C(=O)S-、-C(=S)S-、-C(=O)NR-、-O-、-S-、-Se-、-Po-、-P(=O)-、-P(=S)-、-S(=O)-、-S(=O)₂ -、-SiR₂ -、-NR-、或-N=N-取代，此處，R分別獨立地為氫、芳基、雜芳基、二芳基胺基、二雜芳基胺基、芳基雜芳基胺基、烷基、環烷基、烯基、炔基、烷氧基或芳氧基，R中的至少一個氫可由芳基、雜芳基、烷基或環烷基取代，鄰接的R、與A環、B環、C環及/或D環可鍵結而形成環結構，其中，Z¹ 及Z² 不會同時為單鍵， 式（1）所表示的化合物或結構中的至少一個氫可由氰基、鹵素或重氫取代）。Item 1. A compound or a polymer compound, wherein the compound is represented by the following general formula (1), and the polymer compound has a structure represented by the general formula (1) as a repeating unit;

(In the formula (1), A ring, C ring and D ring are independently an aryl ring or a heteroaryl ring, B ring is a heteroaryl ring, A ring and B ring and/or C ring and D Rings can be bonded to form a ring structure, and at least one hydrogen in these rings can be substituted, wherein, as the substituents for the A ring alone and the D ring alone, the acridine-based substituent is removed, and X ¹ to X ⁴ are respectively independently C or N, Z ¹ and Z ² are each independently a single bond, an alkylene group, an alkenylene group, an alkynylene group or an aryl group, and any -CH ₂ - among them can be represented by -C(= CR ₂ )-, -C(=C(=O))-, -C(=O)-, -C(=S)-, -C(=O)O-, -C(=S)O- , -C(=O)S-, -C(=S)S-, -C(=O)NR-, -O-, -S-, -Se-, -Po-, -P(=O) -, -P(=S)-, -S(=O)-, -S(=O) ₂ -, -SiR ₂ -, -NR-, or -N=N- substitution, where R is independent of each other is hydrogen, aryl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, or aryl Oxygen, at least one hydrogen in R can be substituted by aryl, heteroaryl, alkyl or cycloalkyl, the adjacent R, and ring A, ring B, ring C and/or ring D can be bonded to form a ring structure , wherein Z ¹ and Z ² will not be single bonds at the same time, and at least one hydrogen in the compound or structure represented by formula (1) can be substituted by cyano, halogen or deuterium).

Item 2. The compound or polymer compound according to Item 1, wherein the A ring, the C ring and the D ring are each independently an aryl ring having 6 to 30 carbon atoms or a heteroaryl ring having 2 to 30 carbon atoms, and B The ring is a heteroaryl ring with 2 to 30 carbon atoms, A ring and B ring and/or C ring and D ring can be bonded to form a ring structure, and at least one hydrogen in these rings can be substituted, wherein, as a The acridine-based substituents are removed from the substituents of the A ring alone and the D ring alone, X ¹ to X ⁴ are each independently C or N, and Z ¹ and Z ² are each independently a single bond, -(CR ₂ ) _n -(n is 1 to 12), -CR=CR-, -C≡C-, -(CR=CR-CR ₂ ) _n -(n is 1 to 4), -C(=CR ₂ )-, - C(=C(=O))-, -C(=O)-, -C(=S)-, -C(=O)O-, -C(=S)O-, -C(=O )S-, -C(=S)S-, -C(=O)NR-, -C(=O)C(=O)-, -C(=O)OC(=O)-, -( CR ₂ -O) _n - (n is 1 to 12), -(CR ₂ ) _n -O- (n is 1 to 12), -(CR ₂ -CR ₂ -O) _n - (n is 1 to 6 ), -O-, -S-, -SS-, -Se-, -Po-, -P(=O)-, -P(=S)-, -S(=O)-, -S(= O) ₂ -, -SiR ₂ -, -NR-, -N=N-, or phenylene, where R is independently hydrogen, aryl, heteroaryl, diarylamine, dihetero Arylamine, arylheteroarylamine, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, at least one hydrogen in R can be aryl, heteroaryl, alkyl Or cycloalkyl substitution, the adjacent R, and A ring, B ring, C ring and/or D ring can be bonded to form a ring structure, wherein, Z ¹ and Z ² will not be a single bond at the same time, formula (1) At least one hydrogen in the represented compound or structure can be replaced by cyano, halogen or deuterium.

Item 3. The compound according to Item 1 or Item 2, wherein A ring, C ring and D ring are each independently a benzene ring, a naphthalene ring, an indane ring, an indene ring, a furan ring, a thiophene ring, a benzofuran ring Or benzothiophene ring, B ring is pyrrole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, quinoline ring or isoquinoline ring, A ring and B ring and/or C ring and D ring can bond junction to form a ring structure, at least one hydrogen in these rings can be substituted, wherein, as the substituent for the A ring alone and the D ring alone, the acridine-based substituent is removed, X ¹ to X ⁴ are C, Z ¹ and Z ² are each independently a single bond, -CR ₂ -, -CR=CR-, -C(=O)-, -C(=S)-, -O-, -S-, -Se-, -P(=O)-, -P(=S)-, -S(=O)-, -SiR ₂ -, -NR-, or phenylene, where R is independently hydrogen, aryl, respectively , heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, in R At least one hydrogen can be substituted by aryl, heteroaryl, alkyl or cycloalkyl, and adjacent R, and A ring, B ring, C ring and/or D ring can be bonded to form a ring structure, wherein Z ¹ and Z ² is not a single bond at the same time, and at least one hydrogen in the compound represented by the formula (1) may be substituted with a cyano group, a halogen group or a deuterium group.

（所述式（2）中， Z¹ 及Z² 分別獨立地為單鍵、-O-、-S-、-Se-、-NR-、或1,2-伸苯基，此處，R為氫、芳基、雜芳基、二芳基胺基、二雜芳基胺基、芳基雜芳基胺基、烷基、環烷基、烯基、炔基、烷氧基或芳氧基，R中的至少一個氫可由芳基、雜芳基、烷基或環烷基取代，其中，Z¹ 及Z² 不會同時為單鍵， R¹ ～R¹⁶ 分別獨立地為氫、芳基、雜芳基、二芳基胺基、二雜芳基胺基、芳基雜芳基胺基、烷基、環烷基、烯基、炔基、烷氧基或芳氧基，該些中的至少一個氫可由芳基、雜芳基、烷基或環烷基取代，其中，作為R¹ ～R⁴ 及R¹³ ～R¹⁶ ，將吖啶系取代基去除， 另外，R¹ ～R⁴ 及R⁹ ～R¹⁶ 中的鄰接的基彼此可鍵結而與a環、c環或d環一同形成碳數9～30的芳基環或碳數6～30的雜芳基環，R⁵ ～R⁸ 中的鄰接的基彼此可鍵結而與b環一同形成碳數6～30的雜芳基環，所形成的環中的至少一個氫可由芳基、雜芳基、二芳基胺基、二雜芳基胺基、芳基雜芳基胺基、烷基、環烷基、烷氧基或芳氧基取代，該些中的至少一個氫可由芳基、雜芳基、烷基或環烷基取代，其中，作為針對包含a環或d環而形成的環的取代基，將吖啶系取代基去除， 式（2）所表示的化合物中的至少一個氫可由氰基、鹵素或重氫取代）。Item 4. The compound according to any one of Items 1 to 3, which is represented by the following general formula (2);

(In the formula (2), Z ¹ and Z ² are each independently a single bond, -O-, -S-, -Se-, -NR-, or 1,2-phenylene, where R is hydrogen, aryl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, or aryloxy group, at least one hydrogen in R can be substituted by an aryl group, a heteroaryl group, an alkyl group or a cycloalkyl group, wherein Z ¹ and Z ² cannot be a single bond at the same time, and R ¹ to R ¹⁶ are independently hydrogen, aryl alkynyl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, these At least one of the hydrogens may be substituted by an aryl group, a heteroaryl group, an alkyl group or a cycloalkyl group, wherein, as R ¹ to R ⁴ and R ¹³ to R ¹⁶ , an acridine-based substituent is removed, and R ¹ to R Adjacent groups in ⁴ and R ⁹ to R ¹⁶ may be bonded to each other to form an aryl ring with 9 to 30 carbon atoms or a heteroaryl ring with 6 to 30 carbon atoms together with a ring, c ring or d ring, and R The adjacent groups in ⁵ to R ⁸ can be bonded to each other to form a heteroaryl ring with a carbon number of 6 to 30 together with the b ring, and at least one hydrogen in the formed ring can be an aryl group, a heteroaryl group, or a diaryl group. amine, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkoxy or aryloxy substituted at least one of these hydrogens can be aryl, heteroaryl, alkane group or cycloalkyl group, wherein, as the substituent for the ring formed by the a ring or the d ring, the acridine-based substituent is removed, and at least one hydrogen in the compound represented by the formula (2) can be cyano group, halogen or deuterium substitution).

Item 5. The compound according to Item 4, wherein in the formula (2), Z ¹ and Z ² are each independently a single bond, -O-, -S-, -Se-, -NR-, or 1 ,2-phenylene, where R is hydrogen, aryl, heteroaryl, alkyl or cycloalkyl, wherein Z ¹ and Z ² cannot be single bonds at the same time, and R ¹ to R ¹⁶ are each independently is hydrogen, aryl, heteroaryl, diarylamine, alkyl, cycloalkyl, alkoxy, or aryloxy, at least one of these hydrogens may be aryl, heteroaryl, alkyl, or cyclic Alkyl-substituted in which, as R ¹ to R ⁴ and R ¹³ to R ¹⁶ , an acridine-based substituent is removed, and the adjacent groups among R ¹ to R ⁴ and R ⁹ to R ¹⁶ may be bonded to each other to form Together with ring a, ring c, or ring d, it forms an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms, and adjacent groups in R ⁵ to R ⁸ may be bonded to each other to form a ring with b Together to form a heteroaryl ring with 6 to 15 carbon atoms, at least one hydrogen in the formed ring can be aryl, heteroaryl, diarylamine, alkyl, cycloalkyl, alkoxy or aryloxy Substituted, at least one of these hydrogens may be substituted by an aryl group, a heteroaryl group, an alkyl group or a cycloalkyl group, wherein the acridine-based substituent is removed as the substituent for the ring formed by the a ring or the d ring , at least one hydrogen in the compound represented by formula (2) may be substituted by cyano, halogen or deuterium.

Item 6. The compound according to Item 4 or Item 5, wherein in the formula (2), Z ¹ and Z ² are each independently a single bond, -O-, -S-, -Se-, -NR- , or 1,2-phenylene, where R is hydrogen, an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 3 to 12 carbon atoms. cycloalkyl, wherein Z ¹ and Z ² cannot be single bonds at the same time, and R ¹ to R ¹⁶ are independently hydrogen, aryl with 6 to 16 carbons, heteroaryl with 2 to 15 carbons, two Arylamino group (wherein the aryl group is an aryl group with 6 to 12 carbon atoms), an alkyl group with 1 to 6 carbon atoms, a cycloalkyl group with 3 to 12 carbon atoms, an alkoxy group with 1 to 6 carbon atoms or a carbon Aryloxy with 6-16 carbons, at least one hydrogen in these can be aryl with 6-16 carbons, heteroaryl with 2-15 carbons, alkyl with 1-6 carbons or alkyl with 3-12 carbons wherein, as R ¹ to R ⁴ and R ¹³ to R ¹⁶ , the acridine-based substituent is removed, and the adjacent groups among R ¹ to R ⁴ and R ⁹ to R ¹⁶ may be bonded to each other together with a ring, c ring or d ring to form an aryl ring having 9 to 12 carbon atoms or a heteroaryl ring having 6 to 10 carbon atoms, and adjacent groups in R ⁵ to R ⁸ may be bonded to each other to form The b rings together form a heteroaryl ring with a carbon number of 6-10, and at least one hydrogen in the formed ring can be an aryl group with a carbon number of 6-16, a heteroaryl group with a carbon number of 2-15, a diarylamine group ( Among them, the aryl group is an aryl group having 6 to 12 carbon atoms), an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 6 to 16 carbon atoms. Aryloxy is substituted, and at least one of these hydrogens can be aryl with 6-16 carbons, heteroaryl with 2-15 carbons, alkyl with 1-6 carbons or cycloalkyl with 3-12 carbons Substituted, wherein the acridine-based substituent is removed as a substituent for the ring formed by the a ring or the d ring, and at least one hydrogen in the compound represented by the formula (2) may be replaced by a cyano group, a halogen or a deuterium group .

Item 7. The compound according to any one of Items 4 to 6, wherein in the formula (2), Z ¹ and Z ² are each independently a single bond, -O-, -S-, -Se- , -NR-, or 1,2-phenylene, where R is hydrogen, an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a carbon A cycloalkyl group having 3 to 12 numbers, wherein Z ¹ and Z ² cannot be a single bond at the same time, R ¹ to R ⁴ and R ⁹ to R ¹⁶ are hydrogen, and R ⁵ to R ⁸ are independently hydrogen and carbon number. Aryl with 6-16, heteroaryl with 2-15 carbons, diarylamine group (wherein, aryl is aryl with 6-12 carbons), alkyl with 1-6 carbons, and alkyl with 3-carbons -12 cycloalkyl, alkoxy with 1-6 carbons or aryloxy with 6-16 carbons, at least one hydrogen in these can be aryl with 6-16 carbons, aryl with 2-15 carbons Heteroaryl group, alkyl group having 1 to 6 carbon atoms, or cycloalkyl group having 3 to 12 carbon atoms is substituted, and the adjacent groups among R ⁵ to R ⁸ may be bonded to each other to form a ring having 6 to carbon atoms together with the b ring. 10 of the heteroaryl ring, at least one hydrogen in the formed ring can be an aryl group with a carbon number of 6-16, a heteroaryl group with a carbon number of 2-15, a diarylamine group (wherein, the aryl group is a carbon number of 6 -12 aryl), alkyl with 1-6 carbons, cycloalkyl with 3-12 carbons, alkoxy with 1-6 carbons or aryloxy with 6-16 carbons, among these At least one hydrogen of can be substituted by an aryl group with 6-16 carbon atoms, a heteroaryl group with 2-15 carbon atoms, an alkyl group with 1-6 carbon atoms or a cycloalkyl group with 3-12 carbon atoms, represented by formula (2) At least one hydrogen in the compound can be replaced by cyano, halogen or deuterium.

[化18]

[化19]

[化20]

。Item 8. The compound according to Item 1, which is represented by the following chemical structural formula;

[Chemical 18]

[Chemical 19]

[hua 20]

.

Item 9. The compound according to Item 4, wherein in the formula (2), Z ¹ and Z ² are each independently a single bond, -O-, -S-, -Se-, -NR-, or 1 ,2-phenylene, where R is aryl, heteroaryl or cycloalkyl, and at least one hydrogen in R can be substituted by aryl, heteroaryl, alkyl or cycloalkyl, wherein Z ¹ or Any one or more of Z ² is -NR-, the R and R ¹ , R ⁸ , R ⁹ and/or R ¹⁶ are connected by a single bond, -CR ₂ -, -CR=CR-, -C(=O) -, -C(=S)-, -O-, -S-, -Se-, -P(=O)-, -P(=S)-, -S(=O)-, -SiR ₂ - , -NR-, or extended phenyl groups are bonded to form a ring structure, where R is independently hydrogen, aryl, heteroaryl, diarylamine, diheteroarylamine, arylhetero Arylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, at least one hydrogen in R can be substituted by aryl, heteroaryl, alkyl or cycloalkyl, R ¹ ~R ¹⁶ is each independently hydrogen, aryl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkenyl, alkynyl, An alkoxy group or an aryloxy group in which at least one hydrogen may be substituted by an aryl group, a heteroaryl group, an alkyl group or a cycloalkyl group, wherein, as R ¹ to R ⁴ and R ¹³ to R ¹⁶ , an acridine-based Substituents are removed, and adjacent groups among R ¹ to R ⁴ and R ⁹ to R ¹⁶ may be bonded to each other to form an aryl ring or a carbon number of 9 to 30 together with a ring, c ring or d ring. 6-30 heteroaryl ring, adjacent groups in R ⁵ -R ⁸ may be bonded to each other to form a heteroaryl ring with 6-30 carbon atoms together with the b ring, and at least one hydrogen in the formed ring may be Aryl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkoxy, or aryloxy substituted, at least one of these Hydrogen may be substituted by an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, wherein the acridine-based substituent is removed as a substituent for the ring formed by the a ring or the d ring, and represented by formula (2) At least one hydrogen in the compound can be replaced by cyano, halogen or deuterium.

Item 10. The compound according to Item 4, wherein in the formula (2), Z ¹ and Z ² are each independently a single bond, -O-, -S-, -Se- or -NR-, where , R is an aryl group, and at least one hydrogen in R can be substituted by an aryl group, a heteroaryl group, an alkyl group or a cycloalkyl group, wherein any one of Z ¹ or Z ² or more is -NR-, and the R and R ¹ , R ⁸ , R ⁹ and/or R ¹⁶ are bonded by a single bond, -CR ₂ -, -O-, -S- or -NR- to form a ring structure, where R is independently hydrogen, Aryl, alkyl or cycloalkyl, at least one hydrogen in R can be substituted by aryl, alkyl or cycloalkyl, R ¹ to R ¹⁶ are independently hydrogen, aryl, heteroaryl, diarylamine R ¹ to R ⁴ and R ¹³ to R ¹⁶ , the acridine-based substituent is removed, and the adjacent groups among R ¹ to R ⁴ and R ⁹ to R ¹⁶ may be bonded to each other to form a carbon number of 9 together with a ring, c ring or d ring. ～16 aryl ring or carbon number 6～15 heteroaryl ring, the adjacent groups in R ⁵ ～R ⁸ can be bonded to each other to form a carbon number 6～15 heteroaryl ring together with b ring, so At least one hydrogen in the formed ring can be substituted by aryl, heteroaryl, diarylamine, alkyl, cycloalkyl, alkoxy or aryloxy, and at least one hydrogen in these can be substituted by aryl, hetero Aryl, alkyl or cycloalkyl substitution, wherein the acridine-based substituent is removed as a substituent for the ring formed including the a ring or the d ring, and at least one hydrogen in the compound represented by the formula (2) Can be substituted by cyano, halogen or deuterium.

Item 11. The compound according to Item 4, wherein in the formula (2), Z ¹ and Z ² are each independently a single bond, -O-, -S-, -Se- or -NR-, where , R is an aryl group with carbon number 6-16, at least one hydrogen in R can be an aryl group with carbon number 6-16, a heteroaryl group with carbon number 2-15, an alkyl group with carbon number 1-6 or an alkyl group with carbon number 3 Cycloalkyl substitution of ~12, wherein any one or more of Z ¹ or Z ² is -NR-, and the R and R ¹ , R ⁸ , R ⁹ and/or R ¹⁶ are connected by a single bond, -CR ₂ - , -O-, -S- or -NR- are bonded to form a ring structure, where R is independently hydrogen, an aryl group having 6 to 16 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. Cycloalkyl of 3-12, at least one hydrogen in R can be substituted by aryl with 6-16 carbons, alkyl with 1-6 carbons or cycloalkyl with 3-12 carbons, R ¹ to R ¹⁶ are respectively independently hydrogen, an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, a diarylamine group (wherein, the aryl group is an aryl group having 6 to 12 carbon atoms), and an aryl group having 1 to 6 carbon atoms. alkyl, cycloalkyl with 3 to 12 carbons, alkoxy with 1 to 6 carbons or aryloxy with 6 to 16 carbons, at least one of these hydrogens can be aryl with 6 to 16 carbons , a heteroaryl group with 2 to 15 carbon atoms, an alkyl group with 1 to 6 carbon atoms or a cycloalkyl group with 3 to 12 carbon atoms, wherein, as R ¹ to R ⁴ and R ¹³ to R ¹⁶ , the acridine-based Substituents are removed, and adjacent groups among R ¹ to R ⁴ and R ⁹ to R ¹⁶ may be bonded to each other to form an aryl ring having 9 to 12 carbon atoms or a carbon number together with a ring, c ring or d ring. 6-10 heteroaryl ring, adjacent groups in R ⁵ -R ⁸ may be bonded to each other to form a heteroaryl ring with 6-10 carbon atoms together with the b ring, and at least one hydrogen in the formed ring may be Aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 15 carbon atoms, diarylamine group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms), alkyl group having 1 to 6 carbon atoms, carbon atoms Cycloalkyl with 3 to 12 carbons, alkoxy with 1 to 6 carbons, or aryloxy with 6 to 16 carbons, at least one hydrogen in these -15 heteroaryl group, C1-6 alkyl group or C3-12 cycloalkyl group, wherein, as the substituent for the ring formed by including a ring or d ring, an acridine is substituted group is removed, and at least one hydrogen in the compound represented by the formula (2) may be substituted with a cyano group, a halogen group or a deuterium group.

Item 12. The compound according to any one of Items 9 to 11, wherein in the formula (2), Z ¹ is a single bond, -O-, -S-, -Se- or -NR-, Z ² is -NR-, where R is an aryl group with 6 to 16 carbon atoms, and at least one hydrogen in R can be an aryl group with 6 to 16 carbon atoms, a heteroaryl group with 2 to 15 carbon atoms, or a heteroaryl group with 1 to 15 carbon atoms. Alkyl group of 6 or cycloalkyl group having 3 to 12 carbon atoms is substituted, and R and R ⁸ or R ⁹ in -NR- of Z ² are substituted by a single bond, -CR ₂ -, -O-, -S- or - NR- is bonded to form a ring structure, where R is each independently hydrogen, an aryl group having 6 to 16 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms.

[化22]

[化23]

。Item 13. The compound according to Item 1, which is represented by the following chemical structural formula;

[Chemical 22]

[Chemical 23]

.

所述式（TSG1）所表示的基中的至少一個氫可由芳基、雜芳基、二芳基胺基、烷基、環烷基、烷氧基或芳氧基取代， Y為單鍵、-O-、-S-、-Se-、-NR-、＞CR₂ 、或＞SiR₂ ，此處，R分別獨立地為氫、芳基、雜芳基、二芳基胺基、烷基、環烷基、烷氧基或芳氧基，R中的鄰接的基彼此可鍵結而形成碳數6～15的芳基環。Item 14. The compound or polymer compound according to any one of Items 1 to 13, wherein the substituent for the C ring or at least one of R ⁹ to R ¹² is represented by the following partial structural formula (TSG1) base; [Chemical 24]

At least one hydrogen in the group represented by the formula (TSG1) can be substituted by an aryl group, a heteroaryl group, a diarylamine group, an alkyl group, a cycloalkyl group, an alkoxy group or an aryloxy group, Y is a single bond, -O-, -S-, -Se-, -NR-, >CR ₂ , or >SiR ₂ , where R is independently hydrogen, aryl, heteroaryl, diarylamine, alkyl , a cycloalkyl group, an alkoxy group or an aryloxy group, and adjacent groups in R may be bonded to each other to form an aryl ring having 6 to 15 carbon atoms.

所述結構式中的至少一個氫可由芳基、雜芳基、二芳基胺基、烷基、環烷基、烷氧基或芳氧基取代。Item 15. The compound or polymer compound according to Item 14, wherein the group represented by the partial structural formula (TSG1) is the following partial structural formula (TSG100), formula (TSG110), formula (TSG111), formula (TSG112) ), formula (TSG113), formula (TSG120) or base represented by formula (TSG121);

At least one hydrogen in the structural formula can be substituted by an aryl, heteroaryl, diarylamine, alkyl, cycloalkyl, alkoxy, or aryloxy group.

[化27]

。Item 16. The compound according to Item 14, which is represented by the following chemical structural formula;

[Chemical 27]

.

Item 17. The compound or polymer compound according to any one of Items 14 to 16, which satisfies the following formula: ΔE _ST ≦0.20 eV.

Item 18. A material for an organic element containing the compound or polymer compound according to any one of Items 1 to 17.

Item 19. The material for an organic element according to item 18, wherein the material for an organic element is a material for an organic electroluminescence element, a material for an organic field effect transistor, or a material for an organic thin film solar cell.

Item 20. An organic electroluminescence element comprising a pair of electrodes including an anode and a cathode, and an organic layer disposed between the pair of electrodes and containing the material for an organic electroluminescence element according to item 19.

Item 21. The organic electroluminescence device according to item 20, further comprising an electron transport layer and/or an electron injection layer, and at least one of the electron transport layer and the electron injection layer contains a metal complex selected from the group consisting of quinoline-based metal complexes, pyridine At least one of the group consisting of derivatives, phenanthroline derivatives, borane derivatives and benzimidazole derivatives.

Item 22. The organic electroluminescence element according to item 21, wherein the electron transport layer and/or the electron injection layer further contains a material selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, alkaline earth metals The group consisting of metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes at least one of the group.

（所述式（1）中， A環、C環及D環分別獨立地為芳基環或雜芳基環，B環為雜芳基環，A環與B環及/或C環與D環可鍵結而形成環結構，該些環中的至少一個氫可被取代，其中，作為針對A環單獨及D環單獨的取代基，將吖啶系取代基去除， X¹ ～X⁴ 分別獨立地為C或N， Z¹ 及Z² 分別獨立地為單鍵、伸烷基、伸烯基、伸炔基或伸芳基，該些中的任意的-CH₂ -可由-C(=CR₂ )-、-C(=C(=O))-、-C(=O)-、-C(=S)-、-C(=O)O-、-C(=S)O-、-C(=O)S-、-C(=S)S-、-C(=O)NR-、-O-、-S-、-Se-、-Po-、-P(=O)-、-P(=S)-、-S(=O)-、-S(=O)₂ -、-SiR₂ -、-NR-、或-N=N-取代，此處，R分別獨立地為氫、芳基、雜芳基、二芳基胺基、二雜芳基胺基、芳基雜芳基胺基、烷基、環烷基、烯基、炔基、烷氧基或芳氧基，R中的至少一個氫可由芳基、雜芳基、烷基或環烷基取代，鄰接的R、與A環、B環、C環及/或D環可鍵結而形成環結構，其中，Z¹ 及Z² 不會同時為單鍵， 式（1）所表示的化合物或結構中的至少一個氫可由氰基、鹵素或重氫取代）。Item 23. An organic electroluminescent element having a light-emitting layer comprising at least one host compound as a first component and at least one thermally activated retarder as a second component A phosphor, and has a compound represented by the following general formula (1), or a polymer compound having a structure represented by the general formula (1) as a repeating unit as the first component or the second component, [Chemical 28 ]

(In the formula (1), A ring, C ring and D ring are independently an aryl ring or a heteroaryl ring, B ring is a heteroaryl ring, A ring and B ring and/or C ring and D Rings can be bonded to form a ring structure, and at least one hydrogen in these rings can be substituted, wherein, as the substituents for the A ring alone and the D ring alone, the acridine-based substituent is removed, and X ¹ to X ⁴ are respectively independently C or N, Z ¹ and Z ² are each independently a single bond, an alkylene group, an alkenylene group, an alkynylene group or an aryl group, and any -CH ₂ - among them can be represented by -C(= CR ₂ )-, -C(=C(=O))-, -C(=O)-, -C(=S)-, -C(=O)O-, -C(=S)O- , -C(=O)S-, -C(=S)S-, -C(=O)NR-, -O-, -S-, -Se-, -Po-, -P(=O) -, -P(=S)-, -S(=O)-, -S(=O) ₂ -, -SiR ₂ -, -NR-, or -N=N- substitution, where R is independent of each other is hydrogen, aryl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, or aryl Oxygen, at least one hydrogen in R can be substituted by aryl, heteroaryl, alkyl or cycloalkyl, the adjacent R, and ring A, ring B, ring C and/or ring D can be bonded to form a ring structure , wherein Z ¹ and Z ² will not be single bonds at the same time, and at least one hydrogen in the compound or structure represented by formula (1) can be substituted by cyano, halogen or deuterium).

Item 24. The organic electroluminescence device according to item 23, comprising a compound represented by general formula (1) or a polymer compound having a structure represented by general formula (1) as a repeating unit as a first component.

Item 25. The organic electroluminescence element according to item 23, comprising a compound represented by the general formula (1) or a polymer compound having the structure represented by the general formula (1) as a repeating unit as a second component.

Item 26. A display device comprising the organic electroluminescent element according to any one of items 20 to 25.

Item 27. A lighting device comprising the organic electroluminescence element according to any one of items 20 to 25. [Effect of invention]

According to a preferred aspect of the present invention, there can be provided a novel compound having boron as a spiro ring atom, which can be used as a material for organic devices such as organic EL devices, or a polymer compound having it as a repeating unit, And by using these compounds, an excellent organic EL device can be provided.

1. A compound having boron as a spiro ring atom and its polymer compound The present invention is a compound represented by the following general formula (1), or a polymer compound having a structure represented by the general formula (1) as a repeating unit, A compound represented by the following general formula (2) or a polymer compound having a structure represented by the general formula (2) as a repeating unit is preferable. Hereinafter, the polymer compound is also simply referred to as a "compound". [Chemical 29]

In the compound represented by the general formula (1) of the present invention, the donor structure and the acceptor structure are separated in the molecule by a spiro ring structure having a boron atom as a center or by bridging the C ring and the D ring of the boron atom. , thereby having a high triplet energy.

In particular, in the case of completely separating the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) by the separation of the donor structure and the acceptor structure , and the high triplet energy can be used in the host or the peripheral material of the light-emitting layer. In this case, for example, HOMO and LUMO take a spiro ring structure with a boron atom as the center, HOMO is localized on the A ring and/or D ring, and LUMO is localized on the B ring and/or C ring molecular orbitals. When used as a host, it can be used as one component of a host compound using two or more types of host compounds, and can also be used as one component of a host compound that can be used in an adjacent multilayer light-emitting layer.

In addition, in particular, in the case of a molecule with thermally activated delayed fluorescence (referred to as a "D-A-type TADF (Thermally Activated Delayed Fluorescence) compound"), it can be used as a luminescent material of TADF (luminescent dopant). Dopant (emitting dopant) or TAF (TADF Assisting Fluorescence (TADF Assisting Fluorescence)) components used in assisting dopant (assisting dopant). In this case, for example, HOMO and LUMO are localized on the donor structure in which the HOMO is localized on the C ring and/or the C ring is substituted by bridging the C ring and the D ring by the boron atom, and the LUMO is localized on the B ring. The molecular orbital that exists locally on the upper part of the LUMO sometimes escapes to the C ring. When used as an auxiliary dopant, it may be included in a different layer adjacent to the light-emitting dopant and the auxiliary dopant.

In addition, in the case of not having thermally activated delayed fluorescence (referred to as "fluorescent light-emitting compounds"), light-emitting materials (dopants) that can be triplet-triplet fusion (TTF) ) or light-emitting dopants in TAF (TADF Assisting Fluorescence) elements. In this case, for example, the substituents of Z ¹ and/or Z ² are molecules that form a cyclic structure with ring A, ring B, ring C and/or ring D, and HOMO and LUMO are locally relatively large and overlapping molecules. track. When used as a light-emitting dopant, the light-emitting dopant and the auxiliary dopant may be contained in different layers adjacent to each other.

First, in the formula (1), ring A, ring C and ring D are independently an aryl ring or a heteroaryl ring, ring B is a heteroaryl ring, ring A and ring B and/or ring C and The D ring may be bonded to form a ring structure, and at least one hydrogen in these rings may be substituted, wherein, as the substituent for the A ring alone and the D ring alone, the acridine-based substituent is removed, and X ¹ to X ⁴ are independently C or N, Z ¹ and Z ² are each independently a single bond, an alkylene group, an alkenylene group, an alkynylene group or an aryl group, and any of these -CH ₂ - can be selected from -C( =CR ₂ )-, -C(=C(=O))-, -C(=O)-, -C(=S)-, -C(=O)O-, -C(=S)O -, -C(=O)S-, -C(=S)S-, -C(=O)NR-, -O-, -S-, -Se-, -Po-, -P(=O )-, -P(=S)-, -S(=O)-, -S(=O) ₂ -, -SiR ₂ -, -NR-, or -N=N- substitution, where R respectively is independently hydrogen, aryl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, or Aryloxy, at least one hydrogen in R can be substituted by aryl, heteroaryl, alkyl or cycloalkyl, adjacent R, and ring A, ring B, ring C and/or ring D can be bonded to form a ring structure, wherein Z ¹ and Z ² cannot be single bonds at the same time, and at least one hydrogen in the compound or structure represented by formula (1) may be substituted by cyano, halogen or deuterium.

In addition, in the above formula (2), Z ¹ and Z ² are each independently a single bond, -O-, -S-, -Se-, -NR-, or 1,2-phenylene, and here, R is hydrogen, aryl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, or aryl Oxygen, at least one hydrogen in R can be substituted by aryl, heteroaryl, alkyl or cycloalkyl, wherein Z ¹ and Z ² cannot be a single bond at the same time, and R ¹ to R ¹⁶ are independently hydrogen, Aryl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, the Among them, at least one hydrogen may be substituted by an aryl group, a heteroaryl group, an alkyl group or a cycloalkyl group, wherein, as R ¹ to R ⁴ and R ¹³ to R ¹⁶ , the acridine-based substituent is removed, and R 1 to R ¹ to Adjacent groups among R ⁴ and R ⁹ to R ¹⁶ may be bonded to each other to form an aryl ring having 9 to 30 carbon atoms or a heteroaryl ring having 6 to 30 carbon atoms together with a ring, c ring or d ring, Adjacent groups in R ⁵ to R ⁸ may be bonded to each other to form a heteroaryl ring having 6 to 30 carbon atoms together with ring b, and at least one hydrogen in the formed ring may be an aryl group, a heteroaryl group, a diaryl group amino, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkoxy or aryloxy substituted at least one hydrogen of which may be aryl, heteroaryl, Alkyl or cycloalkyl substitution, in which at least one hydrogen in the compound represented by formula (2) may be cyano group by removing an acridine-based substituent as a substituent for a ring formed by a ring or a ring d , halogen or deuterium substitution. Furthermore, in the above formula (2), any one or more of Z ¹ or Z ² is -NR-, and the R and R ¹ , R ⁸ , R ⁹ and/or R ¹⁶ are connected by a single bond, -CR ₂ -, -CR=CR-, -C(=O)-, -C(=S)-, -O-, -S-, -Se-, -P(=O)-, -P(=S) -, -S(=O)-, -SiR ₂ -, -NR-, or phenylene are bonded to form a ring structure, where R is independently hydrogen, aryl, heteroaryl, diaryl amino, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, at least one hydrogen in R can be aryl, Heteroaryl, alkyl or cycloalkyl substitution.

Hereinafter, since the general formula (2) is a preferred form contained in the general formula (1), the description common to the two formulas is represented by the description of the general formula (1), and the general formula (2) may be omitted. ) in the case of the description.

Ring A, ring C, and ring D are each independently an aryl ring or a heteroaryl ring. Ring B is a heteroaryl ring containing at least one nitrogen.

Examples of the "aryl ring" of the A ring, the C ring and the D ring include an aryl ring having 6 to 30 carbon atoms, preferably an aryl ring having 6 to 16 carbon atoms, and more preferably an aryl ring having 6 to 12 carbon atoms. The aryl ring is particularly preferably an aryl ring having 6 to 10 carbon atoms. In addition, this "aryl ring" corresponds to "R ¹ to R ⁴ and R ⁹ to R ¹⁶ in the adjacent groups defined in the general formula (2) are bonded to each other to a ring, c ring or d ring. "Aryl ring with 9 to 30 carbon atoms formed together", in addition, the a ring (or the c ring, the d ring) already contains a benzene ring with a carbon number of 6, so the total number of condensed rings formed by condensing a 5-membered ring therein The carbon number of 9 becomes the lower limit carbon number.

Specific examples of the "aryl ring" include a benzene ring as a monocyclic ring, a biphenyl ring as a bicyclic ring, a naphthalene ring as a condensed bicyclic ring, and a triphenyl ring as a tricyclic ring (inter- Triphenyl, o-triphenyl, p-triphenyl), acenaphthylene ring, perylene ring, phenanthrene ring, phenanthrene ring as condensed tricyclic ring system, triphenylene ring, pyrene ring, condensed tetraphenyl ring as condensed tetracyclic ring system A benzene ring (naphthacene ring), a benzopyridine ring, a perylene ring as a condensed pentacyclic ring system, a condensed pentabenzene ring, and the like. In addition, the perylene ring or the benzopyridine ring also includes a structure in which the perylene ring or the benzopyridine ring is spiro-bonded.

Examples of the "heteroaryl ring" of rings A to D include a heteroaryl ring having 2 to 30 carbon atoms, preferably a heteroaryl ring having 2 to 25 carbon atoms, and more preferably a heteroaryl ring having 2 to 20 carbon atoms. The heteroaryl ring is more preferably a heteroaryl ring having 2 to 15 carbon atoms, and particularly preferably a heteroaryl ring having 2 to 10 carbon atoms. Moreover, as a "heteroaryl ring", the heterocyclic ring etc. which contain 1-5 heteroatoms selected from oxygen, sulfur, and nitrogen as ring constituent atoms other than carbon are mentioned, for example. In addition, this "heteroaryl ring" corresponds to "R ¹ to R ⁴ and R ⁹ to R ¹⁶ adjacent groups in the general formula (2) are bound to each other to form a ring, c ring or d ring. A heteroaryl ring with 6 to 30 carbon atoms formed together" or "a heteroaryl ring with 6 to 30 carbon atoms formed together with ring b by bonding adjacent groups in R ⁵ to R ⁸ ", and, The ring b already includes a pyridine ring having 5 carbon atoms, so the total number of carbon atoms in the condensed ring in which the 5-membered ring is condensed is 6, which is the lower limit of the number of carbon atoms.

Specific examples of the "heteroaryl ring" include a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring (unsubstituted, substituted with an alkyl group such as methyl, or substituted with a benzene ring) substituted by aryl groups such as base), oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring , isoindole, 1H-indazole, benzimidazole, benzoxazole, benzothiazole, 1H-benzotriazole, quinoline, isoquinoline, cinnoline ring, quinazoline ring, quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, pteridine ring, carbazole ring, acridine ring, phenothiazine ring, phenothiazine ring, phenothiazine ring, Phanazine ring, indolizine ring, furan ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, naphthobenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, naphthalene benzothiophene ring, benzophosphazene, dibenzophosphazene, benzophosphazene oxide ring, dibenzophosphazene oxide ring, furazan ring, oxadiazole ring, thianthracene, etc.

The A ring and the B ring and/or the C ring and the D ring may be bonded to form a ring structure, and the bonding group in this case includes the same groups as Z ¹ and Z ² , and may be a single bond.

At least one hydrogen in the "aryl ring" or "heteroaryl ring" as the A ring to the D ring, and the ring structure formed by the bonding between the A ring and the B ring and/or the C ring and the D ring may be the first Substituents are substituted, and the first substituent may be further substituted by the second substituent. Examples of the first substituent include an aryl group, a heteroaryl group, a diarylamino group, a diheteroarylamino group, an arylheteroarylamino group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, and an alkane group. An oxy group, an aryloxy group, etc., and an aryl group, a heteroaryl group, an alkyl group, a cycloalkyl group, etc. are mentioned as a 2nd substituent. The first substituent also corresponds to the substituents “R ¹ to R ¹⁶ ” in the general formula (2), or the groups adjacent to “R ¹ to R ¹⁶ are bonded to each other to a ring, b ring, and c ring. Or the substituent of the aryl ring or heteroaryl ring formed together with the d ring, and the second substituent also corresponds to the further substituent for these.

"Aryl" or "heteroaryl" as the first substituent, aryl of "diarylamino", heteroaryl of "diheteroarylamino", "arylheteroarylamino" The aryl group and heteroaryl group, the aryl group of the "aryloxy group", the "aryl group" and the "heteroaryl group" as the second substituent include the above-mentioned "aryl ring" or "heteroaryl ring". One price basis.

The "alkyl group" as the first substituent and the second substituent may be either straight chain or branched chain, for example, a straight chain alkyl group having 1 to 24 carbon atoms or a branched chain alkyl group having 3 to 24 carbon atoms can be mentioned. . Preferably, it is an alkyl group having 1 to 18 carbon atoms (branched chain alkyl group having 3 to 18 carbon atoms), more preferably an alkyl group having 1 to 12 carbon atoms (branched chain alkyl group having 3 to 12 carbon atoms), and even more preferably It is an alkyl group having 1 to 6 carbon atoms (branched alkyl group having 3 to 6 carbon atoms), particularly preferably an alkyl group having 1 to 4 carbon atoms (branched alkyl group having 3 to 4 carbon atoms).

Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isoamyl, neo- Pentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1 -Methylhexyl, n-octyl, third octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,2, 6-Dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1- Hexyl heptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptyl, n-octadecyl, n-twenty, etc.

The "cycloalkyl group" as the first substituent and the second substituent may be a cycloalkyl group containing one ring, a cycloalkyl group containing a plurality of rings, or a cycloalkyl group containing an unconjugated double bond in the ring As for any cycloalkyl group having a branch outside the ring, for example, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a cycloalkyl group having 5 carbon atoms to 5 carbon atoms may be mentioned. -10 cycloalkyl, cycloalkyl with 6-10 carbon atoms, etc. Among these, a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable.

Specific cycloalkyl groups include cyclopropyl, methylcyclopropyl, cyclobutyl, methylcyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, and cycloheptyl yl, methylcycloheptyl, cyclooctyl, methylcyclooctyl, cyclononyl, methylcyclononyl, cyclodecyl, methylcyclodecyl, bicyclo[1.0.1]butyl, bicyclo[1.1 .1]pentyl, bicyclo[2.0.1]pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[2.2.1]heptyl, bicyclo[2.1.2]heptyl, bicyclo [2.2.2] Octyl, decalinyl, adamantyl, diadamantyl, decahydroazulene, etc.

The "alkenyl group" as the first substituent includes one or more -CH ₂ -CH ₂ - substituted by -C═C- in the above-mentioned "alkyl group", preferably one or two substituted, more preferably a substituted group.

Examples of the "alkynyl group" as the first substituent include one or more -CH ₂ -CH ₂ - substituted with -C≡C- in the "alkyl group", preferably one or two. substituted, more preferably a substituted group.

Examples of the "alkoxy group" as the first substituent include a linear alkoxy group having 1 to 24 carbon atoms or a branched chain alkoxy group having 3 to 24 carbon atoms. Preferably it is an alkoxy group having 1 to 18 carbon atoms (branched alkoxy group having 3 to 18 carbon atoms), more preferably an alkoxy group having 1 to 12 carbon atoms (branched alkoxy group having 3 to 12 carbon atoms) ), more preferably an alkoxy group having 1 to 6 carbon atoms (branched alkoxy group having 3 to 6 carbon atoms), particularly preferably an alkoxy group having 1 to 4 carbon atoms (branched alkoxy group having 3 to 4 carbon atoms) oxy).

Specific alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, 2nd butoxy, 3rd butoxy, pentoxy group, hexyloxy, heptyloxy, octyloxy, etc.

Here, the acridine-based substituent is removed as the substituent for the A ring (a ring) alone and the D ring (d ring) alone. The acridine-based substituent refers to a monovalent group of acridine and an acridine derivative. The acridine derivative refers to acridine having a substituent, and examples of the substituent include an alkyl group, an aryl group, and the like. In addition, as the substituent for the A ring (a ring) alone and the D ring (d ring) alone, it is preferable not only to remove the acridine-based substituent, but also to replace the substituent having a nitrogen atom with the nitrogen atom directly on A The group (for example, amine group, etc.) to which the ring (a ring) alone and the D ring (d ring) are independently bonded are removed, and it is more preferable to remove the substituent having a nitrogen atom.

In addition, it is preferable that the substituent for the C ring or at least one of R ⁹ to R ¹² is a group represented by the following partial structural formula (TSG1). [Chemical 30]

At least one hydrogen in the group represented by the formula (TSG1) may be substituted by an aryl group, a heteroaryl group, a diarylamine group, an alkyl group, a cycloalkyl group, an alkoxy group or an aryloxy group, and the For details, the description of the first substituent and the second substituent can be cited.

Y in the group represented by the formula (TSG1) is a single bond, -O-, -S-, -Se-, -NR-, >CR ₂ , or >SiR ₂ , where R is each independently Hydrogen, aryl, heteroaryl, diarylamine, alkyl, cycloalkyl, alkoxy or aryloxy, for details of these groups, the first substituent and the second substituent can be cited base description. In addition, adjacent groups in R may be bonded to each other to form an aryl ring having 6 to 15 carbon atoms, and the description of the above-mentioned A ring to D ring can be cited for the details of the aryl ring.

所述結構式中的至少一個氫可由芳基、雜芳基、二芳基胺基、烷基、環烷基、烷氧基或芳氧基取代，關於該些基的詳細情況，可引用所述第1取代基及第2取代基的說明。Specific examples of the group represented by the partial structural formula (TSG1) include the following partial structural formula (TSG100), formula (TSG110), formula (TSG111), formula (TSG112), formula (TSG113), and formula (TSG120) or the base represented by the formula (TSG121). "Me" in the formula is a methyl group. [Chemical 31]

At least one hydrogen in the structural formula can be substituted by an aryl group, a heteroaryl group, a diarylamine group, an alkyl group, a cycloalkyl group, an alkoxy group or an aryloxy group. Description of the first substituent and the second substituent.

Examples of the alkylene group, alkenylene group, alkynylene group, or arylidene group for Z ¹ and Z ² include "alkyl", "alkenyl", "alkynyl" or "aryl" described above as a monovalent group. base" of the bivalent base. Any -CH ₂ - among these can be -CR ₂ -, -C(=CR ₂ )-, -CR=CR-, -C(=C(=O))-, -C(=O)- , -C(=S)-, -C(=O)O-, -C(=S)O-, -C(=O)S-, -C(=S)S-, -C(=O )NR-, -O-, -S-, -Se-, -Po-, -P(=O)-, -P(=R)-, -P(=O)(-R)-, -P (=S)-, -S(=O)-, -S(=O) _2- , _-SiR2- , -NR-, or -N=N- substituted.

"-CR ₂ -", "-C(=CR ₂ )-", "-CR=CR-", "-C(=O)NR-", "-P(=R-" in Z ¹ and Z ² R in "-", "-P(=O)(-R)-", "-SiR ₂ -" or "-NR-" are independently hydrogen, aryl, heteroaryl, diarylamine aryl, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, at least one hydrogen in R can be aryl, heteroaryl group, alkyl or cycloalkyl substitution. The description of these groups can refer to the description of the first substituent and the second substituent.

In addition, when the above R is adjacent to A ring, B ring, C ring and/or D ring (a ring, b ring, c ring and/or (d ring)), these may be bonded to form Ring structure, as the bonding group, in addition to the single bond, an alkylene bond, etc. can also be mentioned, and a part of -CH ₂ - in the bonding group can be substituted by -NR-, -O- or -S-, and When the neighbor of -CH ₂ - or -CH= is not a hetero atom, -CH ₂ - or -CH= may be substituted by a hetero atom. The details of the "-NR-" can be referred to the description.

Furthermore, specifically, for example, in the above formula (2), the R (preferably R of "-NR-") and R ¹ , R ⁸ , R ⁹ and/or R ¹⁶ are connected by a single bond, -CR ₂ -, -CR=CR-, -C(=O)-, -C(=S)-, -O-, -S-, -Se-, -P(=O)-, -P( =S)-, -S(=O)-, -SiR ₂ -, -NR-, or phenylene are bonded to form a ring structure, where R is independently hydrogen, aryl, heteroaryl , diarylamine, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy (descriptions of these groups may be cited The description of the first substituent and the second substituent), at least one hydrogen in R can be aryl, heteroaryl, alkyl or cycloalkyl (the description of these groups can refer to the first substituent and Explanation of the 2nd substituent) substituted. Preferably, the R (preferably R of "-NR-") and R ¹ , R ⁸ , R ⁹ and/or R ¹⁶ are via a single bond, -CR ₂ -, -O-, -S- or -NR- is bonded to form a ring structure, where R is independently hydrogen, aryl, alkyl or cycloalkyl (the description of these groups can refer to the description of the first substituent and the second substituent description), at least one hydrogen in R can be substituted by an aryl group, an alkyl group or a cycloalkyl group (the description of these groups can refer to the description of the first substituent and the second substituent). The specific ring structure formed will be described later.

Furthermore, in the compound of the present invention, Z ¹ and Z ² are not simultaneously a single bond.

In addition, all or a part of hydrogen in the chemical structure of the compound of the present invention and its polymer compound may be substituted with a cyano group, halogen or deuterium. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine.

Next, the structure of the compound of this invention is demonstrated more concretely. In addition, the symbols in all the structural formulas used in the following description are as defined above unless otherwise specified.

1-1. Changes in the basic skeleton of the compound The compound of the present invention is a condensed ring site including A ring and D ring (a ring and d ring) and a condensed ring including B ring and C ring (b ring and c ring). A compound having boron as a spiro-ring bonding atom at the site and performing a spiro-ring bond. A substituent may be bonded to each ring or Z ¹ and Z ² . First, the basic skeleton of the spiro compound will be described below. Hereinafter, only the basic skeleton and matters attached thereto will be described, and therefore descriptions of substituents (R ¹ to R ¹⁶ and the like when referring to formula (2)) that do not participate in the change in the structural formula are basically omitted. Or explain, and describe or explain only when necessary. In addition, since the general formula (2) is a preferred form contained in the general formula (1), the description common to the two formulas is represented by the description of the general formula (1), and the general formula (2) may be omitted. ) in the case of the description.

In the compound or repeating structure represented by the general formula (1) (hereinafter, also abbreviated as "compound"), boron "B" as a spiro ring connecting atom is respectively associated with carbon ( In the formula, the expression of "C" is omitted) bond, and it is coordinately bonded to one nitrogen "N" in the B ring. X ¹ to X ⁴ are each independently C (carbon) or N (nitrogen), Z ¹ is a linking group for A ring and D ring, and Z ² is a linking group for B ring and C ring.

As an example, the following general formula (1-C) is a structural formula in which X ¹ to X ⁴ are C (carbon), and the general formula (1-N) is a structural formula in which X ¹ to X ⁴ are N (nitrogen). X ¹ to X ⁴ may be independently selected from C or N, and forms other than the following structural formula may be present.

[Chemical 32]

Examples of Z ¹ and Z ² include the following partial structural formulae (a) to (v).

[Chemical 33]

R in the partial structural formula is independently hydrogen, aryl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkoxy or aryloxy, at least one of these hydrogens may be substituted by aryl, heteroaryl, alkyl or cycloalkyl.

Formula (e) - formula (q), formula (u), or formula (v) are preferred, and formula (g) - formula (j), formula (n) - formula (q), and formula (u) are more preferred or formula (v), more preferably formula (g), formula (h), formula (q) or formula (u), particularly preferably formula (g), formula (q) or formula (u).

More specifically, Z ¹ is the formula (g), the formula (q), or the formula (u), preferably the formula (g) or the formula (u), and more preferably the formula (g).

As a combination of Z ¹ and Z ² , each of formula (g), formula (g) and formula (q), formula (g) and formula (u), formula (u) and formula (g), or formula ( u) and formula (q) are preferably both formula (g), formula (g) and formula (q), formula (g) and formula (u), or formula (u) and formula (g).

Examples of the A ring, the C ring, and the D ring include the following partial structural formulae (P) to (Xb). In the following partial structural formula, the bond interrupted by the wavy line represents the bond site with the spiro ring bonding atom "B" or Z ¹ or Z ² in the general formula (1). Moreover, as for the partial structural formula in general formula (1), it is preferable that all the partial structures are the same, and the partial structure of a different kind may be sufficient. In the following partial structural formulas, illustration of substituents is also omitted.

[Chemical 34]

R in the partial structural formula is independently hydrogen, aryl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkoxy or aryloxy, at least one of these hydrogens may be substituted by aryl, heteroaryl, alkyl or cycloalkyl.

Preferably formula (P), formula (F), formula (Na), formula (Nb), formula (Ra), formula (BR), formula (Ya), formula (Yb), formula (Z), formula ( BZ), formula (S), formula (BS), formula (T), formula (BT), formula (E), formula (BE), formula (L), formula (BL), formula (G) and formula ( BG), more preferably formula (P), formula (Na), formula (Ra), formula (Ya), formula (Yb), formula (Z), formula (S), formula (T), formula (E) and formula (G), more preferably formula (P), formula (Na) and formula (S), and most preferably formula (P) and formula (Na).

Examples of the B ring include a pyridine ring, a pyridazine ring, a pyrimidine ring, or a triazine ring, and in these rings, one nitrogen is coordinated to the spiro ring atom "B". As a structural formula containing such a B ring, the following general formula (10) - a formula (145) are mentioned as an example which modified the said formula (1-C), for example. The same applies when the above-mentioned formula (1-N) or X ¹ to X ⁴ are in other combinations.

[Chemical 35]

As a structural formula, Formula (10), Formula (15), or Formula (135) is preferable, and Formula (10) is more preferable.

In the above formulas (10) to (145), when the A ring, the C ring and the D ring are, for example, partial structural formula (P), they are represented by the following general formulas.

[Chemical 36]

For example, when the same structure is selected from any of the partial structural formulae (P) to (Xb) as the A ring, the C ring and the D ring, the structure of the general formula (10) is represented by the following chemical Structural representation.

[Chemical 37]

[Chemical 38]

[Chemical 39]

[Chemical 40]

[Chemical 41]

[Chemical 42]

[Chemical 43]

[Chemical 44]

The A ring, the C ring and the D ring may have the same structure or may be different. In the above formula (10), when the A ring, the C ring and the D ring have different structures, it is represented by the following general formula.

[Chemical 45]

[Chemical 46]

[Chemical 47]

[Chemical 48]

Z ¹ and Z ² may have the same structure or may be different. An example in which Z ¹ and Z ² independently select partial structural formula (a) to partial structural formula (v) will be listed below.

[Chemical 49]

[Chemical 50]

[Chemical 51]

Among these, general formula (10P-ge-1), formula (10P-gf-1), formula (10P-g-1), formula (10P-gh-1), formula (10P-gi- 1), formula (10P-gj-1), formula (10P-gk-1), formula (10P-gm-1), formula (10P-gn-1), formula (10P-gp-1), formula ( 10P-gq-1), formula (10P-gu-1), formula (10P-qe-1), formula (10P-qf-1), formula (10P-qg-1), formula (10P-qh-1) ), formula (10P-qi-1), formula (10P-qj-1), formula (10P-qk-1), formula (10P-qm-1), formula (10P-qn-1), formula (10P -qp-1), formula (10P-q-1), formula (10P-qu-1), formula (10P-ue-1), formula (10P-uf-1), formula (10P-ug-1) , formula (10P-uh-1), formula (10P-ui-1), formula (10P-uj-1), formula (10P-uk-1), formula (10P-um-1), formula (10P- un-1), formula (10P-up-1) and formula (10P-uq-1), more preferably general formula (10P-g-1), formula (10P-gh-1), formula (10P-gi) -1), formula (10P-gj-1), formula (10P-gn-1), formula (10P-gp-1), formula (10P-gq-1), formula (10P-gu-1), formula (10P-qg-1), formula (10P-qh-1), formula (10P-qi-1), formula (10P-qj-1), formula (10P-qn-1), formula (10P-qp- 1), formula (10P-q-1), formula (10P-qu-1), formula (10P-ug-1), formula (10P-uh-1), formula (10P-ui-1), formula ( 10P-uj-1), formula (10P-un-1), formula (10P-up-1) and formula (10P-uq-1), more preferably general formula (10P-g-1), formula (10P -gh-1), formula (10P-gq-1), formula (10P-gu-1), formula (10P-qg-1), formula (10P-qh-1), formula (10P-q-1) , formula (10P-qu-1), formula (10P-ug-1), formula (10P-uh-1) and formula (10P-uq-1), especially the general formula (10P-g-1), formula (10P-gq-1), formula (10P-gu-1), formula (10P-qg-1), formula (10P-q-1), formula (10P-qu-1), formula (10P-ug -1) and formula (10P-uq-1).

In addition, general formula (10P-Z-1), formula (12P-Z-1), formula (13P-Z-1), formula (14P-Z-1), and formula (15P-Z-1) are shown below ), formula (123P-Z-1), formula (124P-Z-1), formula (125P-Z-1), formula (134P-Z-1), formula (135P-Z-1) or formula (145P In -Z-1), Z ¹ and Z ² select the case where the ether bond of the partial structural formula (g) is selected.

[Chemical 52]

Z ¹ and Z ² may have different structures, and general formula (10P-Z-1), formula (12P-Z-1), formula (13P-Z-1), and formula (14P-Z-1) are shown below ), formula (15P-Z-1), formula (123P-Z-1), formula (124P-Z-1), formula (125P-Z-1), formula (134P-Z-1), formula (135P In -Z-1) or formula (145P-Z-1), Z ¹ and Z ² are selected from the ether bond of the partial structural formula (g) and the amine bond of the formula (q), respectively.

[Chemical 53]

Z ¹ and Z ² may have different structures, and general formula (10P-Z-1), formula (12P-Z-1), formula (13P-Z-1), and formula (14P-Z-1) are shown below ), formula (15P-Z-1), formula (123P-Z-1), formula (124P-Z-1), formula (125P-Z-1), formula (134P-Z-1), formula (135P In -Z-1) or formula (145P-Z-1), the case where Z ¹ and Z ² are selected from the ether bond of the partial structural formula (g) and the single bond of the formula (u), respectively.

[Chemical 54]

Z ¹ and Z ² may have different structures, and general formula (10P-Z-1), formula (12P-Z-1), formula (13P-Z-1), and formula (14P-Z-1) are shown below ), formula (15P-Z-1), formula (123P-Z-1), formula (124P-Z-1), formula (125P-Z-1), formula (134P-Z-1), formula (135P -Z-1) or formula (145P-Z-1), when Z ¹ and Z ² are selected from the single bond of the partial structural formula (u) and the ether bond of the formula (g), respectively.

[Chemical 55]

Z ¹ and Z ² may have different structures, and general formula (10P-Z-1), formula (12P-Z-1), formula (13P-Z-1), and formula (14P-Z-1) are shown below ), formula (15P-Z-1), formula (123P-Z-1), formula (124P-Z-1), formula (125P-Z-1), formula (134P-Z-1), formula (135P In -Z-1) or formula (145P-Z-1), Z ¹ and Z ² are selected from the single bond of the partial structural formula (u) and the amine bond of the formula (q), respectively.

[Chemical 56]

"-CR ₂ -", "-C(=CR ₂ )-", "-CR=CR-", "-C(=O)NR-", "-P(=R-" in Z ¹ and Z ² )-", "-P(=O)(-R)-", "-SiR ₂ -" or "-NR-", R in the following partial structural formulae (J1) to (J74) . In addition, "Me" in each formula is a methyl group, and "tBu" is a tertiary butyl group.

[Chemical 57]

Among them, partial structural formulae (J1) to formula (J3), formula (J11), formula (J12), formula (J38) or formula (J41) to formula (J44) are preferred, and formula (J1) is more preferred ), formula (J3), formula (J11), formula (J12), formula (J41) or formula (J44), more preferably formula (J11).

For example, in the general formula (10P-j-1), formula (10P-k-1), formula (10P-p-1) or formula (10P-q-1) Z ¹ and Z ² select partial structural formula (j), formula (k), formula (p) or formula (q) and R in the partial structural formula is hydrogen, partial structural formula (J1), formula (J3), formula (J6), formula (J9) , in the case of formula (J11) or formula (J21), it is represented by the following structural formula. In addition, "Me" in each structural formula is a methyl group, "tBu" is a tertiary butyl group, and it is the same in all the following structural formulas.

[Chemical 58]

For example, in general formula (10P-gq-1), formula (10P-qg-1), formula (10P-qu-1), formula (10P-uq-1) or formula (10P-q-1) Z ¹ and Z ² select partial structural formula (q) and R in the partial structural formula is hydrogen, partial structural formula (J1), formula (J3), formula (J6), formula (J9), formula (J11) or In the case of formula (J21), it is represented by the following structural formula.

[Chemical 59]

[Chemical 60]

In addition, for example, Z in general formula (10P-gq-1), formula (10P-q-1) or formula (10P-uq- ¹ ) selects partial structural formula (q) and in the partial structural formula When R is a partial structural formula (J11), and adjacent R and B ring (b ring) are bonded to form a ring structure, it is represented by the following structural formula.

[Chemical 61]

In addition, for example, Z in general formula (10P-gq-1), formula (10P-q-1) or formula (10P-uq- ¹ ) selects partial structural formula (q) and in the partial structural formula When R is a partial structural formula (J11), and adjacent R and C ring (c ring) are bonded to form a ring structure, it is represented by the following structural formula.

[Chemical 62]

In addition, for example, Z in general formula (10P-gq-1), formula (10P-q-1) or formula (10P-uq- ¹ ) selects partial structural formula (q) and in the partial structural formula When R is a partial structural formula (J11), and adjacent R is bonded to the B ring (b ring) and the C ring (c ring) to form a ring structure, it is represented by the following structural formula.

[Chemical 63]

In addition, for example, Z ¹ in general formula (10P-q-1) or formula (10P-qg-1) selects partial structural formula (q) and R in the partial structural formula is partial structural formula (J11), In addition, when adjacent R and A ring (a ring) or D ring (d ring) are bonded to form a ring structure, it is represented by the following structural formula.

[Chemical 64]

In addition, for example, Z ¹ in general formula (10P-q-1) or formula (10P-qg-1) selects partial structural formula (q) and R in the partial structural formula is partial structural formula (J11), In addition, when adjacent R and A ring (a ring) and D ring (d ring) are bonded to form a ring structure, it is represented by the following structural formula.

[Chemical 65]

Z ¹ or Z ² in the general formula (10P-Z-1) selects partial structural formula (q) and R in partial structural formula (q) selects partial structural formula (J11), and adjacent R and A ring ( When a ring), B ring (b ring), C ring (c ring) and/or D ring (d ring) are bonded to form a ring structure, from the viewpoint of ease of synthesis, the general formula (10P-gq-21-J11), formula (10P-gq-22-J11), formula (10P-gq-23-J11), formula (10P-gq-24-J11), formula (10P-gq- 25-J11), formula (10P-q-21-J11), formula (10P-q-22-J11), formula (10P-q-23-J11), formula (10P-q-24-J11), formula (10P-q-25-J11), formula (10P-uq-21-J11), formula (10P-uq-22-J11), formula (10P-uq-23-J11), formula (10P-uq-24) -J11) and formula (10P-uq-25-J11).

1-2. Regarding the substituents for the basic skeleton of the compound Next, substituents to the basic skeleton as the specific example will be described.

Substituents for at least one hydrogen in the ring structure formed by the "aryl ring" or "heteroaryl ring" being the A ring to the D ring, and the A ring and the B ring and/or the C ring and the D ring are bonded Specifically, it is the following partial structural formula (J1) - formula (J74) and formula (J81) - formula (J91). In addition, "Me" in each formula is a methyl group, and "tBu" is a tertiary butyl group.

[Chemical 66]

[Chemical 67]

Among these, the partial structural formulae (J1) to (J3), the formula (J11), the formula (J12), the formula (J38) or the formula (J41) to the formula (J44) are preferred, and the formula (J1) is more preferred ), formula (J3), formula (J11), formula (J12), formula (J41) or formula (J44), more preferably formula (J11).

In addition, when Z ¹ or Z ² in the general formula (10P-Z-1) selects the partial structural formula (g), partial structural formula (q) or partial structural formula (u), if the partial structural formula ( J81) to formula (J91) are used as substituents for a ring and d ring, so that HOMO and LUMO can be separated between a ring and d ring and the substituents for a ring and d ring. On the other hand, when the partial structural formulae (J32) to (J46) are used as substituents for the b ring and the c ring, the HOMO can be separated between the b ring and the c ring and the substituents for the b ring and the c ring. and LUMO.

For example, in the general formula (10P-g-1), a part of the hydrogen atoms in the a ring and the d ring are substituted, or the adjacent substituents are bonded to each other to form an aryl ring or a heterocyclic ring together with the a ring or the d ring. In the case of an aryl ring, it is represented by the following structural formula. The unsubstituted compounds of formula (10P-g-100) are listed together. In addition, "Me" in each structural formula is a methyl group, "tBu" is a tertiary butyl group, and it is the same in all the following structural formulas.

[Chemical 68]

[Chemical 69]

[Chemical 70]

[Chemical 71]

In addition, for example, in the general formula (10P-g-1), a part of the hydrogen atoms in the c ring is substituted, or the adjacent substituents are bonded to each other to form an aryl ring or a heteroaryl ring together with the c ring. In this case, it is represented by the following structural formula.

[Chemical 72]

[Chemical 73]

[Chemical 74]

[Chemical 75]

In addition, for example, in the general formula (10P-g-1), a part of the hydrogen atoms in the b ring is substituted, or the adjacent substituents are bonded to each other to form an aryl ring or a heteroaryl ring together with the b ring. In this case, it is represented by the following structural formula.

[Chemical 76]

[Chemical 77]

[Chemical 78]

The hydrogen atoms in the a-rings to the d-rings in the general formula (10P-g-1) may be independently substituted with the same structure or different structures. For example, it is represented by the following structural formula.

[Chemical 79]

In addition, for example, in the general formula (10P-gq-1), a part of the hydrogen atoms in the a ring and the d ring are substituted, or the adjacent substituents are bonded to each other to form an aryl ring together with the a ring or the d ring Or in the case of a heteroaryl ring, it is represented by the following structural formula. The unsubstituted compounds of the formula (10P-gq-100) are listed together.

[Chemical 80]

[Chemical 81]

[Chemical 82]

[Chemical 83]

In addition, for example, in the general formula (10P-gq-1), a part of the hydrogen atoms in the c ring is substituted, or the adjacent substituents are bonded to each other to form an aryl ring or a heteroaryl ring together with the c ring. In this case, it is represented by the following structural formula.

[Chemical 84]

[Chemical 85]

[Chemical 86]

[Chemical 87]

In addition, for example, in the general formula (10P-gq-1), a part of the hydrogen atoms in the b ring is substituted, or the adjacent substituents are bonded to each other to form an aryl ring or a heteroaryl ring together with the b ring. In this case, it is represented by the following structural formula.

[Chemical 88]

[Chemical 89]

[Chemical 90]

The hydrogen atoms in the a-rings to the d-rings in the general formula (10P-gq-1) may be independently substituted with the same structure or different structures. For example, it is represented by the following structural formula.

[Chemical 91]

In addition, for example, when R in general formula (10P-gq-1) is formula (J11), it is represented by the following structural formula.

[Chemical 92]

[Chemical 93]

[Chemical 94]

[Chemical 95]

[Chemical 96]

[Chemical 97]

[Chemical 98]

The hydrogen atoms in the rings a to d in the general formula (10P-gq-21-J11) and the hydrogen atoms in the phenyl group serving as R of NR may be independently substituted with the same structure or different structures. From the viewpoint of ease of synthesis, it is preferable that the substituents for the b ring, the c ring, and the phenyl group as R of NR are substituted symmetrically with respect to the b ring—Z ² bond. For example, it is represented by the following structural formula.

[Chemical 99]

[Chemical 100]

[Chemical 101]

[Chemical 102]

[Chemical 103]

The hydrogen atoms in the rings a to d in the general formula (10P-gq-23-J11) and the hydrogen atoms in the phenyl group serving as R of NR may be independently substituted with the same structure or different structures. From the viewpoint of ease of synthesis, it is preferable that the substituents for the b ring, the c ring, and the phenyl group as R of NR are substituted symmetrically with respect to the b ring—Z ² bond. For example, it is represented by the following structural formula.

[Chemical 104]

[Chemical 105]

[Chemical 106]

[Chemical 107]

[Chemical 108]

The hydrogen atoms in the rings a to d in the general formula (10P-gq-25-J11) and the hydrogen atoms in the phenyl group serving as R of NR may be independently substituted with the same structure or different structures. From the viewpoint of ease of synthesis, it is preferable that the substituents for the b ring, the c ring, and the phenyl group as R of NR are substituted symmetrically with respect to the b ring—Z ² bond. For example, it is represented by the following structural formula.

[Chemical 109]

[Chemical 110]

[Chemical 111]

[Chemical 112]

[Chemical 113]

For example, in the general formula (10P-gu-1), a part of the hydrogen atoms in the a ring and the d ring are substituted, or the adjacent substituents are bonded to each other to form an aryl ring or a heterocyclic ring together with the a ring or the d ring. In the case of an aryl ring, it is represented by the following structural formula. The unsubstituted compounds of the formula (10P-gu-100) are listed together.

[Chemical 114]

[Chemical 115]

[Chemical 116]

In addition, for example, in the general formula (10P-gu-1), a part of the hydrogen atoms in the c ring is substituted, or the adjacent substituents are bonded to each other to form an aryl ring or a heteroaryl ring together with the c ring. In this case, it is represented by the following structural formula.

[Chemical 117]

[Chemical 118]

[Chemical 119]

In addition, for example, in the general formula (10P-gu-1), a part of the hydrogen atoms in the b ring is substituted, or the adjacent substituents are bonded to each other to form an aryl ring or a heteroaryl ring together with the b ring. In this case, it is represented by the following structural formula.

[Chemical 120]

[Chemical 121]

[Chemical 122]

The hydrogen atoms in the a-rings to the d-rings in the general formula (10P-gu-1) may be independently substituted with the same structure or different structures. For example, it is represented by the following structural formula.

[Chemical 123]

For example, in the general formula (10P-ug-1), a part of the hydrogen atoms in the a ring and the d ring are substituted, or the adjacent substituents are bonded to each other to form an aryl ring or a heterocyclic ring together with the a ring or the d ring. In the case of an aryl ring, it is represented by the following structural formula. The unsubstituted compounds of formula (10P-ug-100) are listed together.

[Chemical 124]

[Chemical 125]

[Chemical 126]

In addition, for example, in the general formula (10P-ug-1), a part of the hydrogen atoms in the c ring is substituted, or adjacent substituents are bonded to each other to form an aryl ring or a heteroaryl ring together with the c ring. In this case, it is represented by the following structural formula.

[Chemical 127]

[Chemical 128]

[Chemical 129]

In addition, for example, in the general formula (10P-ug-1), a part of the hydrogen atoms in the b ring is substituted, or the adjacent substituents are bonded to each other to form an aryl ring or a heteroaryl ring together with the b ring. In this case, it is represented by the following structural formula.

[Chemical 130]

[Chemical 131]

[Chemical 132]

The hydrogen atoms in the a-rings to the d-rings in the general formula (10P-ug-1) may be independently substituted by the same structure or different structures. For example, it is represented by the following structural formula.

[Chemical 133]

In addition, for example, in the general formula (10P-uq-1), a part of the hydrogen atoms in the a ring and the d ring are substituted, or the adjacent substituents are bonded to each other to form an aryl ring together with the a ring or the d ring Or in the case of a heteroaryl ring, it is represented by the following structural formula. The unsubstituted compounds of formula (10P-uq-100) are listed together.

[Chemical 134]

[Chemical 135]

[Chemical 136]

In addition, for example, in the general formula (10P-uq-1), a part of the hydrogen atoms in the c ring is substituted, or the adjacent substituents are bonded to each other to form an aryl ring or a heteroaryl ring together with the c ring. In this case, it is represented by the following structural formula.

[Chemical 137]

[Chemical 138]

[Chemical 139]

In addition, for example, in the general formula (10P-uq-1), a part of the hydrogen atoms in the b ring is substituted, or the adjacent substituents are bonded to each other to form an aryl ring or a heteroaryl ring together with the b ring. In this case, it is represented by the following structural formula.

[Chemical 140]

[Chemical 141]

[Chemical 142]

The hydrogen atoms in the a-rings to the d-rings in the general formula (10P-uq-1) may be independently substituted with the same structure or different structures. For example, it is represented by the following structural formula.

[Chemical 143]

The A ring, the C ring and the D ring in the general formula (10) may each independently have the same structure or different structures, and the hydrogen atoms in the A ring, the C ring, the D ring and the b ring may each independently be Substituted by groups of the same structure or different structures. For example, it is represented by the following structural formula.

[Chemical 144]

[Chemical 145]

[Chemical 146]

1-3. About the excitation energy of the compound The difference between the singlet excitation energy (E _S ) and the triplet excitation energy (E _T ) of the compound of the present invention, DE _ST (=E _S -E _T ), is preferably 0.20 eV or less, More preferably, it is 0.02 eV or less. This energy difference is a value sufficiently small to obtain thermally activated delayed fluorescence.

The singlet excitation energy (E _S ) was calculated from the maximum emission wavelength B (nm) of the fluorescence spectrum and using E _S =1240/B. In addition, triplet excitation energy (E _T ) was calculated from the maximum emission wavelength C (nm) of the phosphorescence spectrum and using E _T =1240/C. In addition, DE _ST , for example, can also use "Purely organic electroluminescent material realizing 100% conversion from electricity to light" (H. Kaji, H. Suzuki) , T. Fukushima, K. Shizu, K. Suzuki, S. Kubo, T. Komino, H. Oiwa, F. Suzuki , A. Wakamiya, Y. Murata, C. Adachi, "Nat. Commun." (2015, 6, 8476.)) The method described in the calculation.

The so-called "thermally activated delayed phosphor" refers to the inverse transition from the excited triplet state to the excited singlet state caused by the absorption of thermal energy, and the radiation inactivation from the excited singlet state to emit delayed fluorescence. compound of. Among them, the so-called "thermally activated delayed fluorescence" also includes those that pass through a higher-order triplet state in the excitation process from an excited triplet state to an excited singlet state. For example, the paper by Monkman et al. of Durham University ("NATURE COMMUNICATIONS" (7:13680, DOI: 10.1038/ncomms13680)), the (Hosokai et al., "Sci. Adv." (2017; 3: e1603282)), Kyoto University's Sato et al. ("Scientific Reports) ” (7:4820, DOI: 10.1038/s41598-017-05007-7)), and also published by Sato et al at Kyoto University (The 98th Spring Annual Meeting of the Chemical Society of Japan, publication number: 2I4-15, using Mechanism of high-efficiency light emission in organic EL with DABNA as a light-emitting molecule, Graduate School of Engineering, Kyoto University) et al.

2. The compound of the present invention and the method for producing the polymer compound thereof

Regarding the compound represented by the general formula (1) or the general formula (2), basically, first, the A ring (a ring) and the D ring (d ring) are formed by using a bonding group (a group including Z ¹ or Z ² ). and B ring (b ring) and C ring (c ring) are bonded to produce an intermediate (1st reaction), and then A ring (a ring), B ring (b ring), C ring The ring (c ring) and the D ring (d ring) are bonded, whereby the final product (second reaction) can be produced (scheme (1) and scheme (2)).

[Chemical 147]

In the first reaction, for example, in the case of an etherification reaction, a normal reaction such as a nucleophilic substitution reaction and a Ullmann reaction can be used, and in the case of an amination reaction, a Buchwald-Hart reaction can be used. Common reactions such as the Buchwald-Hartwig Reaction. In addition, in the second reaction, a metal-boron metal exchange reaction can be utilized.

The second reaction is a reaction in which A ring (a ring), B ring (b ring), C ring (c ring), and D ring (d ring) are bonded by introduction of a boron atom. Scheme (1) and Scheme ( In 2), for example, an intermediate substituted with halogen (Hal) such as chlorine, bromine, and iodine is used as the intermediate. The intermediate (1-A) or the intermediate (2-A), which is a dihalogen compound, is metallized at the ortho position of the halogen atom by using n-butyllithium, sec-butyllithium, or tertiary-butyllithium, etc. to prepare Intermediate (1-C) or intermediate (2-C) (M in the formula is a metal such as lithium). On the other hand, for the intermediate (1-B) or the intermediate (2-B), which is a halogen compound, the halogen atom is first metallized with n-butyllithium, sec-butyllithium, tert-butyllithium, or the like, Next, boron trichloride, boron tribromide, etc. are added to perform metal-boron metal exchange to prepare an intermediate (1-D) or an intermediate (2-D). To this is added the intermediate (1-C) or intermediate (2-C) just prepared to perform metal-boron metal exchange with the intermediate (1-D) or intermediate (2-D), whereby the A compound of general formula (1) or general formula (2) is obtained.

In addition, if an intermediate having a hydrogen atom that is highly active for metallization is used, the general formula (1) or the general formula (2) can be produced even if it is an intermediate in which a halogen atom is not introduced by selective metallization The represented compound (scheme (3), scheme (4)).

[Chemical 148]

In this second reaction, the intermediate (1-E) or the hydrogen atom of the intermediate (2-E) is metallized in the ortho position to obtain the intermediate (1-C) or the intermediate (2-C) (formula M in it is a metal such as lithium). On the other hand, the hydrogen atom of the intermediate (1-F) or the intermediate (2-F) is metallized, and then boron trichloride, boron tribromide, etc. are added to perform metal-boron metal exchange to prepare into intermediate (1-D) or intermediate (2-D). To this is added the intermediate (1-C) or intermediate (2-C) just prepared to perform metal-boron metal exchange with the intermediate (1-D) or intermediate (2-D), whereby the A compound of general formula (1) or general formula (2) is obtained.

In addition, examples of the ortho-metalating reagent used in the above-mentioned Schemes (1) to (4) include alkyl groups such as methyllithium, n-butyllithium, sec-butyllithium, and tert-butyllithium. Lithium, lithium diisopropylamide, lithium tetramethylpiperidine, lithium hexamethyldisilazide, potassium hexamethyldisilazide and other organic basic compounds.

When a coordinating additive is added at the time of metallization to dissociate the association, the reactivity can be improved. As the coordinating additive, N,N',N,N'-tetramethylethylenediamine (TMEDA), hexamethylphosphamide (HMPA), dimethylpropylene urea (DMPU), etc. may be mentioned. .

In addition, as the metal-boron metal exchange reagents used in the above-mentioned processes (1) to (4), in addition to the halogenation of boron such as boron trifluoride, boron trichloride, boron tribromide, and boron triiodide. In addition to the compounds, boron alkoxylates such as trimethyl borate, alkoxyborons such as 4,4,5,5-tetramethyl-1,3,2-dioxaborane can also be mentioned. Alkane compounds, aryloxylates such as triphenyl borate, etc.

In addition, as the form of the polymer compound having the structure represented by the general formula (1) as a repeating unit, the schematic diagrams (I) to (III) can be mentioned. , the schematic diagram (i) and the schematic diagram (ii) can be listed. In the following description, the same applies to the polymer compound of the general formula (2).

[Chemical 149]

The polymer compound (I) is a polymer compound formed by mutually sharing a part of the structure of the formula (1) (for example, any one of the A ring to the D ring, etc.), The polymer compound (II) is a polymer compound in which the structures of the formula (1) are linked via a cross-linking structure XL, wherein EC is a terminal structure, The polymer compound (III) is a polymer compound having the structure of the formula (1) as a side chain of a linear polymer, wherein EC is a terminal structure, MU is a monomer unit formed by polymerizing a polymerizable group, The dimer (i) is a dimer formed by mutually sharing a part of the structure of the formula (1) (for example, any one of the A ring to the D ring, etc.), The dimer (ii) is a dimer in which the structures of the formula (1) are linked via a cross-linking structure XL.

The structures of formula (1), which are partial structures of polymer compounds (I) to (III) and dimer (i) and dimer (ii), may be the same or different. structure. In addition, in the polymer compound (I) and the dimer (i), the partial structures of the formula (1) mutually utilize the A ring (a ring), the B ring (b ring), the C ring (c ring), and the D ring. (d ring) or an aryl ring which is NR (R=aryl ring) of Z ¹ (Z ² ) is bonded. The bonding form may be a form in which the rings are shared by a plurality of partial structures to be bonded, or a form in which the rings are condensed and bonded to each other may be used. In addition, in the polymer compound (II), the polymer compound (III), and the dimer (ii), the partial structure of the formula (1) is bound to the cross-linked structure XL, the terminal structure EC, and the monomer unit MU In addition to the shared or condensed bonding form of the rings, the form may be a single bond, a C 1-3 alkylene group, a phenylene group, a naphthylene group or other linking groups. form.

For example, when the a ring and the d ring in the partial structure of the formula (10P-g-100) are shared with each other to form the polymer compound (I), the polymer compound (I) is represented by the following formula (I-1). [Chemical 150]

For example, when a polymer compound (I) is formed by sharing a ring and an aryl ring (phenyl ring) of NR in the partial structure of the formula (10P-gq-100-J11), the following formula ( I-2) indicates. [Chemical 151]

For example, when the a ring and the d ring in the partial structure of the formula (10P-gq-100-J11) use the crosslinked structure XL (m-phenylene ring) as a linking group to form the polymer compound (II), It is represented by the following formula (II-1). Furthermore, the terminal structure EC is a phenyl group. [hua 152]

For example, the a-ring in the partial structure of the formula (10P-gq-100-J11) and the d-ring in the partial structure of the formula (10P-g-100) are formed using the cross-linked structure XL (single bond) as a linking group In the case of the dimer (ii), it is represented by the following formula (ii-1). [Chemical 153]

For example, the aryl ring (phenyl ring) of NR in the partial structure of formula (10P-gq-100-J11) and the aryl ring (phenyl ring) of NR in the partial structure of formula (10P-gq-100-J11) When the dimer (ii) is formed by using the crosslinked structure XL (single bond) as a linking group, it is represented by the following formula (ii-2). [Chemical 154]

The terminal structure EC in the polymer compound (II) is hydrogen or a monovalent aryl ring or heteroaryl ring having 6 to 30 carbon atoms, preferably hydrogen or a monovalent aryl ring having 6 to 18 carbon atoms.

The cross-linked structure XL in the polymer compound (II) and the dimer (ii) is a single bond or a divalent aryl ring or heteroaryl ring with 6 to 30 carbon atoms, preferably a single bond or 6 carbon atoms The divalent aryl ring of to 18 is more preferably a single bond or a divalent aryl ring of 6 to 12 carbon atoms.

Specific examples of "aryl rings" in structures EC and XL include a benzene ring as a monocyclic system, a biphenyl ring as a bicyclic system, a naphthalene ring as a condensed bicyclic system, and a tricyclic ring as a Bi-triphenyl ring (m-triphenyl, o-triphenyl, p-triphenyl), acenaphthylene ring, perylene ring, phenanthrene ring as condensed tricyclic system, triphenylene as condensed tetracyclic ring Ring, pyrene ring, condensed tetraphenyl ring, benzopyridine ring, perylene ring, condensed pentaphenyl ring, etc. as condensed pentacyclic system. In addition, the perylene ring or the benzopyridine ring also includes a structure in which the perylene ring or the benzopyridine ring is spiro-bonded.

Specific examples of "heteroaryl rings" in the structures EC and XL include pyrrole rings, oxazole rings, isoxazole rings, thiazole rings, isothiazole rings, imidazole rings (unsubstituted, methylated substituted by alkyl groups such as phenyl or by aryl groups such as phenyl), oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, Triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, cinnoline ring, quinazoline ring, quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, pteridine ring, carbazole ring, acridine ring, phenanthrene, phenoxazine, phenanthrene thiazine ring, phenazine ring, indolizine ring, furan ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, naphthobenzofuran ring, thiophene ring, benzothiophene ring, dibenzofuran thiophene ring, naphthobenzothiophene ring, benzophosphazene, dibenzophosphazene, benzophosphazene oxide ring, dibenzophosphazene oxide ring, furoxanyl ring, oxadiene azole ring, thianthrene ring, etc.

The polymer compound (I), the polymer compound (II), and the dimer (i) and the dimer (ii) can be synthesized by the following methods: such as the synthesis methods of the schemes (1) to (4) Generally, after synthesizing the A ring (a ring)-Z ¹ -D ring (d ring) link structure and the B ring (b ring)-Z ² -C ring (c ring) link structure, the method of introducing boron; or Halogenated aryl derivatives of the structure of formula (1) and arylboronic acid derivatives are used as starting materials, or halogenated arylboronic acid derivatives, halogenated aryl derivatives and arylboronic acid derivatives are used as starting materials, and suitable Combination of Suzuki-Miyaura coupling, Kumada-Tamao-Corriu coupling, Negishi coupling, halogenation or boronation. In addition, the polymer compound (III) can be synthesized by using a known method and combining (meth)acrylate derivatives of the structure of formula (1), (meth)acrylamide derivatives, Epoxy derivatives, oxetane derivatives, norbornene derivatives, dicyclopentadiene derivatives, or indene derivatives are used as starting materials, and radical polymerization, cationic polymerization, anionic polymerization, or ring opening is used Shift aggregation, etc.

Regarding the above-mentioned coupling reaction, the halide and boronic acid derivative in the Suzuki-Miyaura coupling can be appropriately substituted for their reactive functional groups, and in the Kuumada-Tamao-Kori coupling or Negishi coupling, the reactive functional groups can be substituted in the same way. functional group. In addition, when replacing with a Grignard reagent, metal magnesium and isopropyl Grignard reagent can be appropriately replaced. The boric acid ester can be used as it is, or can be hydrolyzed with an acid to be used as a boric acid. When used as a boronate ester, the alkyl group of the ester moiety may be an alkyl group other than those illustrated.

Specific examples of the palladium catalyst used in the coupling reaction include tetrakis(triphenylphosphine)palladium(0):Pd(PPh ₃ ) ₄ , bis(triphenylphosphine)palladium(II) dichloride : PdCl ₂ (PPh ₃ ) ₂ , Palladium(II) acetate: Pd(OAc) ₂ , Tris(dibenzylideneacetone)dipalladium(0):Pd ₂ (dba) ₃ , Tris(dibenzylideneacetone) Dipalladium(0) chloroform complex: Pd ₂ (dba) ₃ ·CHCl ₃ , bis(dibenzylideneacetone)palladium(0): Pd(dba) ₂ , bis(tri-tert-butylphosphino) Palladium(0): Pd(t-Bu ₃ P) ₂ , [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II): Pd(dppf)Cl ₂ , [1, 1'-Bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex (1:1): Pd(dppf)Cl ₂ ·CH ₂ Cl ₂ , PdCl ₂ {P( t-Bu) ₂ -(p-NMe ₂ -Ph)} ₂ : (A- ^ta Phos) ₂ PdCl ₂ , bis(dibenzylidene)palladium, [1,3-bis(diphenylphosphino)propane ] Nickel(II) dichloride, PdCl ₂ [P(t-Bu) ₂ -(p-NMe ₂ -Ph)] ₂ :(A- ^ta Phos) ₂ PdCl ₂ (Pd-132: Trademark; Johnson & Johnson Feng (Johnson Matthey) company) and so on.

In addition, in order to promote the coupling reaction, a phosphine compound may be optionally added to the palladium catalyst. Specific examples of the phosphine compound include tri(tert-butyl) phosphine, tricyclohexyl phosphine, 1-(N,N-dimethylaminomethyl)-2-(di-tert-butyl) phosphino)ferrocene, 1-(N,N-dibutylaminomethyl)-2-(di-tert-butylphosphino)ferrocene, 1-(methoxymethyl)-2 -(Di-tert-butylphosphino)ferrocene, 1,1'-bis(di-tert-butylphosphino)ferrocene, 2,2'-bis(di-tert-butylphosphino) )-1,1'-binaphthyl, 2-methoxy-2'-(di-tert-butylphosphino)-1,1'-binaphthyl, or 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl, etc.

Specific examples of the base used in the coupling reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium tert-butoxide, acetic acid Sodium, potassium acetate, tripotassium phosphate or potassium fluoride, etc.

The base can also be added in the form of an aqueous solution to react in a two-phase system. In the case of a two-phase system reaction, an interphase transfer catalyst such as a quaternary ammonium salt can also be added as needed.

In addition, the polymerizable group that can undergo radical polymerization, cationic polymerization, or anionic polymerization used in the synthesis of the polymer compound (III) includes a (meth)acrylic group, an allyl group, a vinyl group, an epoxide group, and oxetane etc. Regarding the polymerization initiators for radical polymerization, cationic polymerization, and anionic polymerization, in the case of radical polymerization, a radical generator can be preferably used, and in the case of cationic polymerization and anionic polymerization, an acid can be preferably used generator and alkali generator. The polymerization initiator may be one compound or a mixture of two or more compounds.

In addition, the polymerizable group used in the synthesis of the polymer compound (III) that can undergo ring-opening shift polymerization includes a cyclic olefin structure and a cyclic alkyne structure, and specifically, a norbornene structure, a Cyclopentadiene structure, indene structure and cyclopentene structure, etc. As the catalyst used for the ring-opening shift polymerization, a complex of ruthenium, molybdenum, and tungsten can be used, and examples thereof include a Grubbs catalyst and the like.

In addition, specific examples of the solvent used in the coupling reaction or the polymerization reaction include benzene, toluene, xylene, 1,2,4-trimethylbenzene, anisole, acetonitrile, and dimethylmethylene. Diethyl ether, N,N-dimethylformamide, tetrahydrofuran, diethyl ether, tert-butyl methyl ether, 1,4-dioxane, methanol, ethanol, tert-butanol, cyclopentyl methyl ether or isopropyl alcohol, etc. These vehicles may be appropriately selected, and may be used alone or as a mixture of vehicles.

When producing a polymer compound, it can be produced in one stage, or it can be produced in multiple stages. In addition, it can be carried out by a general polymerization method in which the reaction is started after all the raw materials are put into the reaction container, it can also be carried out by a dropwise polymerization method in which the raw materials are added dropwise to the reaction container, and the product can be carried out with the reaction. It is carried out by a precipitation polymerization method in which precipitation proceeds and precipitates, and these can be appropriately combined to synthesize. For example, when synthesizing in one stage, the partial structure compound of the formula (1) having a polymerizable group and the compound having an end structure (EC) can be reacted in a state of being added to a reaction vessel, thereby obtaining Target. In addition, when the synthesis is carried out in multiple stages, after polymerizing the monomer unit (MU) to the target molecular weight, a compound having an end structure (EC) is added and reacted to obtain the target product.

In addition, if the polymerizable group of the monomer unit (MU) is selected, the primary structure of the polymer can be controlled. For example, as shown in 1 to 3 of the scheme (5), a polymer having a random primary structure (1 of the scheme (5)) and a polymer having a regular primary structure (2 and 2 of the scheme (5) can be synthesized. 3), etc., and can be used in appropriate combination according to the target.

[Chemical 155]

It is particularly preferable that in the dimer (i) and the dimer (ii), the dipole moments formed by the two partial structures of the formula (1) and the linking group (XL), respectively, cancel each other out. In this case, dimer (i) and dimer (ii) have high symmetry.

3. Organic Components The compound of the present invention and its polymer compound can be used as a material for organic elements. As an organic element, an organic electroluminescence element, an organic field effect transistor, an organic thin film solar cell, etc. are mentioned, for example.

3-1. Organic Electroluminescence Elements The compound of the present invention and its polymer compound can be used, for example, as a material of an organic electroluminescence element. Hereinafter, the organic EL element of the present embodiment will be described in detail based on the drawings. FIG. 1 is a schematic cross-sectional view showing an organic EL element of the present embodiment.

<Structure of organic electroluminescence element> The organic electroluminescence element 100 shown in FIG. 1 includes: a substrate 101 , an anode 102 disposed on the substrate 101 , a hole injection layer 103 disposed on the anode 102 , and a hole transport layer disposed on the hole injection layer 103 104. The light-emitting layer 105 arranged on the hole transport layer 104, the electron transport layer 106 arranged on the light-emitting layer 105, the electron injection layer 107 arranged on the electron transport layer 106, and the cathode arranged on the electron injection layer 107 108.

Furthermore, the organic electroluminescence element 100 may have the following structure by reversing the manufacturing order, for example, the structure includes: the substrate 101 , the cathode 108 provided on the substrate 101 , the electron injection layer 107 provided on the cathode 108 , and the The electron transport layer 106 on the electron injection layer 107, the light emitting layer 105 on the electron transport layer 106, the hole transport layer 104 on the light emitting layer 105, the hole injection layer on the hole transport layer 104 103 , and the anode 102 disposed on the hole injection layer 103 .

The above-mentioned layers are not all indispensable layers, and the minimum structural unit is a structure including the anode 102, the light-emitting layer 105, and the cathode 108, the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection layer. The layer 107 is an arbitrarily settable layer. In addition, each of the layers may include a single layer or a plurality of layers.

As the aspect of the layer constituting the organic electroluminescence element, in addition to the aspect of the configuration of "substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode", It can also be "substrate/anode/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode", "substrate/anode/hole injection layer/light-emitting layer/electron transport layer/electron injection layer/cathode" , "Substrate / Anode / Hole Injection Layer / Hole Transport Layer / Light Emitting Layer / Electron Injection Layer / Cathode", "Substrate / Anode / Hole Injection Layer / Hole Transport Layer / Light Emitting Layer / Electron Transport Layer / Cathode" , "Substrate / Anode / Light Emitting Layer / Electron Transport Layer / Electron Injection Layer / Cathode", "Substrate / Anode / Hole Transport Layer / Light Emitting Layer / Electron Injection Layer / Cathode", "Substrate / Anode / Hole Transport Layer / Light-emitting layer/electron transport layer/cathode", "substrate/anode/hole injection layer/light-emitting layer/electron injection layer/cathode", "substrate/anode/hole injection layer/light-emitting layer/electron transport layer/cathode", The configuration of "substrate/anode/light-emitting layer/electron transport layer/cathode" and "substrate/anode/light-emitting layer/electron injection layer/cathode".

<Substrate in Organic Electroluminescence Element> The substrate 101 is a support of the organic electroluminescence element 100 , and quartz, glass, metal, plastic, etc. are generally used. The substrate 101 is formed in a plate shape, a film shape, or a sheet shape according to the purpose, and for example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like can be used. Among them, glass plates and plates made of transparent synthetic resins such as polyester, polymethacrylate, polycarbonate, and polysilicon are preferred. If it is a glass substrate, soda lime glass, alkali-free glass, or the like can be used, and the thickness may be sufficient to maintain mechanical strength, for example, it may be 0.2 mm or more. The upper limit of the thickness is, for example, 2 mm or less, or preferably 1 mm or less. As for the material of the glass, alkali-free glass is preferred because there are few ions eluted from the glass, and soda-lime glass with a barrier coating such as SiO ₂ is also commercially available, so this soda-lime glass can be used. Glass. In addition, in order to improve the gas barrier properties, a gas barrier film such as a fine silicon oxide film may be provided on at least one surface of the substrate 101 , especially when a plate, film or sheet made of synthetic resin with low gas barrier properties is used as the substrate 101 . In the case of , it is preferable to install a gas barrier film.

<Anode in organic electroluminescence element> The anode 102 functions to inject holes into the light-emitting layer 105 . Furthermore, when the hole injection layer 103 and/or the hole transport layer 104 are provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these layers.

As a material for forming the anode 102, inorganic compounds and organic compounds can be mentioned. Examples of inorganic compounds include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, and indium tin oxide (ITO)) , indium-zinc oxide (Indium Zinc Oxide, IZO, etc.), metal halide (copper iodide, etc.), copper sulfide, carbon black, ITO glass or NESA glass, etc. As an organic compound, conductive polymers, such as polythiophene, such as poly(3-methylthiophene), polypyrrole, and polyaniline, etc. are mentioned, for example. Moreover, it can select and use suitably from the substance used as an anode of an organic electroluminescent element.

The resistance of the transparent electrode is not limited as long as a sufficient current can be supplied to the light-emitting element to emit light, but from the viewpoint of the power consumption of the light-emitting element, it is preferably low. For example, if it is an ITO substrate of 300 Ω/□ or less, it functions as an element electrode, but a substrate of about 10 Ω/□ can also be supplied at present. Preferably, it is a low-resistance product of 50 Ω/□ to 5 Ω/□. The thickness of ITO can be arbitrarily selected according to the resistance value, but it is usually used between 50 nm and 300 nm in many cases.

<Hole injection layer and hole transport layer in organic electroluminescence element> The hole injection layer 103 functions to efficiently inject holes moved from the anode 102 into the light emitting layer 105 or the hole transport layer 104 . The hole transport layer 104 functions to efficiently transport holes injected from the anode 102 or holes injected from the anode 102 via the hole injection layer 103 to the light emitting layer 105 . The hole injection layer 103 and the hole transport layer 104 are formed by laminating and mixing one or two or more kinds of hole injection and transport materials, respectively, or a mixture of a hole injection and transport material and a polymer binder. Alternatively, an inorganic salt such as iron (III) chloride may be added to the hole injection/transport material to form a layer.

As the hole injecting and transporting material, it is necessary to efficiently inject and transport holes from the positive electrode between electrodes to which an electric field has been supplied. Therefore, it is preferable that the free potential is small, the hole mobility is large, and furthermore, it is excellent in stability, and does not easily generate impurities that become traps during production and use.

As a material for forming the hole injection layer 103 and the hole transport layer 104, the compound of the present invention and its polymer compound can be used. In addition, it can be selected from compounds conventionally used as charge transport materials for holes in photoconductive materials, well-known compounds used for p-type semiconductors, hole injection layers and hole transport layers of organic electroluminescence elements Use any compound. Specific examples of these are carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis(N-arylcarbazole) or bis(N-alkylcarbazole) compounds, triarylamine derivatives (polymers with aromatic tertiary amine groups on the main chain or side chains, 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane, N,N '-Diphenyl-N,N'-bis(3-methylphenyl)-4,4'-diaminobiphenyl, N,N'-diphenyl-N,N'-dinaphthyl- 4,4'-Diaminobiphenyl, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-4,4'-diphenyl-1,1'-diphenyl Amine, N,N'-dinaphthyl-N,N'-diphenyl-4,4'-diphenyl-1,1'-diamine, ^N4 , ^N4' -diphenyl- ^N4 ,N ^4' -bis(9-phenyl-9H-carbazol-3-yl)-[1,1'-biphenyl]-4,4'-diamine, N ⁴ ,N ⁴ ,N ^4' ,N 4'-tetra[1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine, 4,4', ⁴ ''-triamine (3-methylphenyl(phenyl)amino)triphenylamine and other triphenylamine derivatives, starburst amine derivatives, etc.), stilbene derivatives, phthalocyanine derivatives (metal-free, copper-free, etc.) Phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives or thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (for example, 1,4,5,8,9,12 - Hexazatriphenylene-2,3,6,7,10,11-hexacarbonitrile, etc.), heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. Among the polymer systems, polycarbonates, styrene derivatives, polyvinyl carbazoles, and polysilanes having the above-mentioned monomers in the side chains are preferred, but as long as they are thin films necessary for the production of light-emitting elements, they may be used. The compound that injects holes from the anode and can transport holes is not particularly limited.

In addition, it is also known that the conductivity of organic semiconductors is strongly influenced by their doping. Such an organic semiconductor host substance contains a compound having a good electron donating property or a compound having a good electron accepting property. For doping electron donating substances, strong electron acceptors such as tetracyanoquinodimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinodimethane (F4TCNQ) are known (See, for example, "M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, "Appl. Phys. Lett.", 73 (22), 3202-3204 (1998)" and Document "J. Blochwitz, M. Pheiffer, T. Fritz, K. Leo, "Appl. Phys. Lett.", 73 (6), 729-731 (1998)"). These generate so-called holes by a process of electron movement in an electron-donating-type basic substance (hole-transporting substance). The conductivity of the base material varies considerably depending on the number and mobility of holes. As a host substance having hole transport properties, for example, benzidine derivatives (TPD, etc.), starburst amine derivatives (TDATA, etc.), or specific metal phthalocyanines (especially zinc phthalocyanine (ZnPc), etc., are known. ) (Japanese Patent Laid-Open No. 2005-167175).

<Light-emitting layer in organic electroluminescence element> The light-emitting layer 105 is a layer that emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field has been supplied. The material for forming the light-emitting layer 105 may be a compound (light-emitting compound) that emits light by being excited by the recombination of holes and electrons, and it is preferably one that can form a stable thin film shape and exhibit strong properties in a solid state. Compounds with luminescent (fluorescence) efficiency. In the present invention, as the material for the light-emitting layer, the compound of the present invention and its polymer compound can be used.

The light-emitting layer may be a single layer or may include a plurality of layers, and each is formed of a light-emitting layer material (host material, dopant material). Each of the host material and the dopant material may be one type, or a combination of two types, or any of them may be used. The dopant material may be included in the entire host material, or may be included in a portion of the host material, either. As a doping method, it can be formed by a co-evaporation method with a host material, or it can be mixed with a host material in advance and then vapor-deposited at the same time.

The amount of the main body material to be used differs depending on the type of the main body material, and may be determined according to the characteristics of the main body material. The basis of the amount of the host material used is preferably 50 to 99.999% by weight, more preferably 80 to 99.95% by weight, and still more preferably 90 to 99.9% by weight of the entire material for the light-emitting layer. The compound of the present invention and its polymer compound can also be used as a host material.

The amount of the dopant material used varies depending on the type of the dopant material, and may be determined according to the properties of the dopant material. The reference amount of the dopant is preferably 0.001% by weight to 50% by weight, more preferably 0.05% by weight to 20% by weight, and still more preferably 0.1% by weight to 10% by weight of the entire material for the light-emitting layer. Within this range, for example, it is preferable in that the concentration quenching phenomenon can be prevented. The compound of the present invention and its polymer compound can also be used as a dopant material.

On the other hand, in an organic electroluminescence device using a thermally activated delayed fluorescence dopant material, in terms of preventing the concentration quenching phenomenon, it is preferable that the use amount of the dopant material is low in concentration. From the viewpoint of the efficiency of the thermally activated delayed fluorescence mechanism, it is preferable that the dopant material is used in a high concentration. Furthermore, in the organic electroluminescence device using the thermally activated delayed fluorescence auxiliary dopant material, in terms of the efficiency of the thermally activated delayed fluorescence mechanism of the auxiliary dopant material, it is preferable to use the auxiliary dopant material with the auxiliary dopant material. The amount of material used is comparatively low and the amount of dopant material used is low.

When the auxiliary dopant material is used, the basis of the usage amount of the host material, the auxiliary dopant material and the dopant material is 40% by weight to 99.999% by weight and 59% by weight to 1% by weight of the entire material for the light-emitting layer, respectively and 20wt% to 0.001wt%, preferably 60wt% to 99.99wt%, 39wt% to 5wt% and 10wt% to 0.01wt%, more preferably 70wt% to 99.95wt%, 29 % by weight to 10% by weight and 5% by weight to 0.05% by weight. The compounds of the present invention and their polymer compounds can also be used as auxiliary dopant materials.

Examples of the host material that can be used in combination with the compound of the present invention and its polymer compound include condensed ring derivatives such as anthracene and pyrene, bisstyryl anthracene derivatives, and stilbene groups which have been known as light-emitting bodies in the past. Bistyryl derivatives such as benzene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, styryl derivatives, benzophene derivatives, and the like.

Moreover, it does not specifically limit as a dopant material which can be used together with the compound of this invention and its polymer compound, A known compound can be used, and it can select from various materials according to a desired emission color. Specifically, for example, condensed ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, condensed pentacene, perylene, naphthopyrene, dibenzopyrene, rubrene, and pyrene, benzoxene, etc. may be mentioned. azole derivatives, benzothiazole derivatives, benzimidazole derivatives, benzotriazole derivatives, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazoles Derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyryl anthracene derivatives or stilbene benzene derivatives Derivatives such as bis-styryl derivatives (Japanese Patent Laid-Open No. 1-245087), bis-styryl aryl derivatives (Japanese Patent Laid-open No. 2-247278), diazaindacene derivatives compounds, furan derivatives, benzofuran derivatives, phenylisobenzofuran, dimesitylisobenzofuran, bis(2-methylphenyl)isobenzofuran, bis(2-trifluoromethane) phenyl) isobenzofuran, isobenzofuran derivatives such as phenylisobenzofuran, dibenzofuran derivatives, 7-dialkylamino coumarin derivatives, 7-piperidinyl coumarin Derivatives, 7-hydroxycoumarin derivatives, 7-methoxycoumarin derivatives, 7-acetyloxycoumarin derivatives, 3-benzothiazolyl coumarin derivatives, 3- Benzimidazolyl coumarin derivatives, coumarin derivatives such as 3-benzoxazolyl coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives , polymethine derivatives, cyanine derivatives, oxobenzanthracene derivatives, xanthene derivatives, rhodamine derivatives, fluorescein derivatives, pyrylium derivatives, quinolones ( carbostyril) derivatives, acridine derivatives, oxazine derivatives, phenyl ether derivatives, quinacridone derivatives, quinazoline derivatives, pyrrolopyridine derivatives, furopyridine derivatives, 1,2,5 -Thiadiazolopyrene derivatives, pyrromethylene derivatives, perinone derivatives, pyrrolopyrrole derivatives, squarylium derivatives, violanthrone derivatives , phenazine derivatives, acridone derivatives, deazaflavin derivatives, fenugreek derivatives and benzophene derivatives.

If each color-emitting light is exemplified, examples of blue-green dopant materials to blue-green dopant materials include aromatics such as naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, perylene, indene, and fen. Hydrocarbon compounds or derivatives thereof, furan, pyrrole, thiophene, silole, 9-silyl, 9,9'-spirocyclodisil, benzothiophene, benzofuran, indole, dibenzothiophene, diphenyl Aromatic heterocyclic compounds such as furan, imidazopyridine, phenanthroline, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, thioxanthene or their derivatives, distyrylbenzene derivatives, tetra Phenylbutadiene derivatives, stilbene derivatives, aldazine derivatives, coumarin derivatives, imidazole, thiazole, thiadiazole, carbazole, oxazole, oxadiazole, triazole and other azole derivatives and its metal complexes and represented by N,N'-diphenyl-N,N'-bis(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine aromatic amine derivatives, etc.

In addition, examples of green dopant materials to yellow dopant materials include coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perone derivatives, and pyrrole. Pyrrole derivatives, cyclopentadiene derivatives, acridone derivatives, quinacridone derivatives, and condensed tetraphenyl derivatives such as rubrene, and the like can also be mentioned as the blue dopant material~ Among the compounds exemplified by the blue-green dopant material, compounds in which a substituent capable of achieving a longer wavelength, such as an aryl group, a heteroaryl group, an arylvinyl group, an amine group, and a cyano group, is introduced are used as preferred examples.

Further, examples of the orange dopant material to the red dopant material include naphthalimide derivatives such as bis(diisopropylphenyl)perylenetetracarboxyimide, perylene derivatives, Rare earth complexes such as Eu complexes, 4-(dicyanomethylene)-2-methyl-6-(paradi Methylaminostyryl)-4H-pyran or its analogs, metal phthalocyanine derivatives such as magnesium phthalocyanine, aluminum chlorophthalocyanine, rhodamine compounds, deazaflavin derivatives, coumarin derivatives Compounds, Quinacridone Derivatives, Phraxazine Derivatives, Oxazine Derivatives, Quinazoline Derivatives, Pyrrolopyridine Derivatives, Squarium Derivatives, Vianthrone Derivatives, Phramenazine Derivatives , phenoxazone derivatives, thiadiazolopyrene derivatives, etc., and further, as the blue dopant material - blue-green dopant material and green dopant material - yellow dopant material Among the compounds exemplified by the agent materials, compounds in which a substituent capable of achieving a longer wavelength, such as an aryl group, a heteroaryl group, an arylvinyl group, an amino group, and a cyano group, is introduced are used as preferred examples.

In addition, the dopant can be appropriately selected and used from compounds and the like described in the chemical industry, June 2004 issue, page 13, and the references listed therein.

Among the dopant materials, amines having a stilbene structure, perylene derivatives, borane derivatives, aromatic amine derivatives, coumarin derivatives, pyran derivatives or pyrene derivatives are particularly preferred.

該式中，Ar¹ 為源自碳數6～30的芳基的m價的基，Ar² 及Ar³ 分別獨立地為碳數6～30的芳基，Ar¹ ～Ar³ 的至少一個具有二苯乙烯結構，Ar¹ ～Ar³ 可被取代，而且m為1～4的整數。The amine having a stilbene structure is represented by the following formula, for example. [Chemical 156]

In this formula, Ar ¹ is an m-valent group derived from an aryl group having 6 to 30 carbon atoms, Ar ² and Ar ³ are each independently an aryl group having 6 to 30 carbon atoms, and at least one of Ar ¹ to Ar ³ has In a stilbene structure, Ar ¹ to Ar ³ may be substituted, and m is an integer of 1 to 4.

該式中，Ar² 及Ar³ 分別獨立地為碳數6～30的芳基，Ar² 及Ar³ 可被取代。The amine having a stilbene structure is more preferably a diaminostilbene represented by the following formula. [Chemical 157]

In this formula, Ar ² and Ar ³ are each independently an aryl group having 6 to 30 carbon atoms, and Ar ² and Ar ³ may be substituted.

Specific examples of the aryl group having 6 to 30 carbon atoms include benzene, naphthalene, acenaphthene, stilbene, fentanyl, phenanthrene, anthracene, fluoranthene, triphenylene, pyrene, pyrene, condensed tetraphenyl, perylene, stilbene, diphenylene Styrylbenzene, distyryl biphenyl, distyryl fluoride, etc.

Specific examples of the amine having a stilbene structure include N,N,N',N'-tetrakis(4-biphenyl)-4,4'-diaminostilbene, N,N,N' ,N'-tetra(1-naphthyl)-4,4'-diaminostilbene, N,N,N',N'-tetra(2-naphthyl)-4,4'-diamino Stilbene, N,N'-bis(2-naphthyl)-N,N'-diphenyl-4,4'-diaminostilbene, N,N'-bis(9-phenanthrenyl) -N,N'-diphenyl-4,4'-diaminostilbene, 4,4'-bis[4''-bis(diphenylamino)styryl]-biphenyl, 1 ,4-bis[4'-bis(diphenylamino)styryl]-benzene, 2,7-bis[4'-bis(diphenylamino)styryl]-9,9-di Methyl fluoride, 4,4'-bis(9-ethyl-3-carbazolevinyl)-biphenyl, 4,4'-bis(9-phenyl-3-carbazolevinyl)-biphenyl, etc. . Moreover, the amine which has a stilbene structure as described in Unexamined-Japanese-Patent No. 2003-347056, Unexamined-Japanese-Patent No. 2001-307884, etc. can also be used.

Examples of perylene derivatives include 3,10-bis(2,6-dimethylphenyl)perylene, 3,10-bis(2,4,6-trimethylphenyl)perylene, 3,10 -Diphenylperylene, 3,4-diphenylperylene, 2,5,8,11-tetra-tert-butylperylene, 3,4,9,10-tetraphenylperylene, 3-(1'- Pyrene)-8,11-bis(tert-butyl)perylene, 3-(9'-anthryl)-8,11-bis(tert-butyl)perylene, 3,3'-bis(8,11 - bis(tert-butyl) perylene group) and the like. In addition, Japanese Patent Laid-Open No. 11-97178, Japanese Patent Laid-Open No. 2000-133457, Japanese Patent Laid-Open No. 2000-26324, Japanese Patent Laid-Open No. 2001-267079, and Japanese Patent Laid-Open No. 2001 can also be used. - those described in Japanese Patent Laid-Open No. 267078, Japanese Patent Laid-Open No. 2001-267076, Japanese Patent Laid-Open No. 2000-34234, Japanese Patent Laid-Open No. 2001-267075, and Japanese Patent Laid-Open No. 2001-217077, etc. Perylene derivatives.

As borane derivatives, for example, 1,8-diphenyl-10-(bis-mesitylboronyl)anthracene, 9-phenyl-10-(bis-mesysylboronyl)anthracene, 4 -(9'-Anthracenyl)Dimesitrylborylnaphthalene, 4-(10'-phenyl-9'-anthryl)dimesysylboronnaphthalene, 9-(Dimesitylboron base) anthracene, 9-(4'-biphenyl)-10-(dimesitylboryl)anthracene, 9-(4'-(N-carbazolyl)phenyl)-10-(dihomosyl) Trimethylboronyl) anthracene and so on. In addition, borane derivatives described in International Publication No. 2000/40586 pamphlet and the like can also be used.

該式中，Ar⁴ 為源自碳數6～30的芳基的n價的基，Ar⁵ 及Ar⁶ 分別獨立地為碳數6～30的芳基，Ar⁴ ～Ar⁶ 可被取代，而且n為1～4的整數。The aromatic amine derivative is represented by the following formula, for example. [Chemical 158]

In this formula, Ar ⁴ is an n-valent group derived from an aryl group having 6 to 30 carbon atoms, Ar ⁵ and Ar ⁶ are each independently an aryl group having 6 to 30 carbon atoms, and Ar ⁴ to Ar ⁶ may be substituted, Moreover, n is an integer of 1-4.

In particular, the following aromatic amine derivatives are more preferred: Ar ⁴ is a divalent group derived from anthracene, pycnogenol, fluoride, benzoyl, or pyrene, and Ar ⁵ and Ar ⁶ are each independently an aryl group having 6 to 30 carbon atoms. , Ar ⁴ to Ar ⁶ may be substituted, and n is 2.

Specific examples of the aryl group having 6 to 30 carbon atoms include benzene, naphthalene, acenaphthene, fentanyl, fentanyl, phenanthrene, anthracene, fluoranthene, triphenylene, pyrene, pyrene, condensed tetraphenyl, perylene, and condensed pentacene.

Examples of aromatic amine derivatives include N,N,N',N'-tetraphenylene-6,12-diamine, N,N,N',N'-tetrakis(p-tolyl) ) Qi-6,12-diamine, N,N,N',N'-tetrakis (m-tolyl) Qi-6,12-diamine, N,N,N',N'-tetrakis (4-iso Propylphenyl)-6,12-diamine, N,N,N',N'-tetra(naphthalen-2-yl)-6,12-diamine, N,N'-diphenyl- N,N'-bis(p-tolyl)di-6,12-diamine, N,N'-diphenyl-N,N'-bis(4-ethylphenyl)di-6,12-diamine Amine, N,N'-diphenyl-N,N'-bis(4-ethylphenyl)-6,12-diamine, N,N'-diphenyl-N,N'-bis( 4-Isopropylphenyl)-6,12-diamine, N,N'-diphenyl-N,N'-bis(4-tert-butylphenyl)-6,12-diamine , N,N'-bis(4-isopropylphenyl)-N,N'-bis(p-tolyl)-6,12-diamine, etc.

In addition, as a pyrene type, for example, N,N,N',N'-tetraphenylpyrene-1,6-diamine, N,N,N',N'-tetrakis(p-tolyl)pyrene-1, 6-Diamine, N,N,N',N'-tetrakis(m-tolyl)pyrene-1,6-diamine, N,N,N',N'-tetrakis(4-isopropylphenyl) Pyrene-1,6-diamine, N,N,N',N'-tetrakis(3,4-dimethylphenyl)pyrene-1,6-diamine, N,N'-diphenyl-N ,N'-bis(p-tolyl)pyrene-1,6-diamine, N,N'-diphenyl-N,N'-bis(4-ethylphenyl)pyrene-1,6-diamine , N,N'-diphenyl-N,N'-bis(4-ethylphenyl)pyrene-1,6-diamine, N,N'-diphenyl-N,N'-bis(4 -Isopropylphenyl)pyrene-1,6-diamine, N,N'-diphenyl-N,N'-bis(4-tert-butylphenyl)pyrene-1,6-diamine, N,N'-bis(4-isopropylphenyl)-N,N'-bis(p-tolyl)pyrene-1,6-diamine, N,N,N',N'-tetra(3, 4-Dimethylphenyl)-3,8-diphenylpyrene-1,6-diamine, N,N,N,N-tetraphenylpyrene-1,8-diamine, N,N'- Bis(biphenyl-4-yl)-N,N'-diphenylpyrene-1,8-diamine, N ¹ ,N ⁶ -diphenyl-N ¹ ,N ⁶ -bis-(4-triamine Methylsilyl-phenyl)-1H,8H-pyrene-1,6-diamine, etc.

Moreover, as an anthracene type|system|group, for example, N,N,N,N-tetraphenylanthracene-9,10-diamine, N,N,N',N'-tetrakis(p-tolyl)anthracene-9,10- Diamine, N,N,N',N'-tetrakis(m-tolyl)anthracene-9,10-diamine, N,N,N',N'-tetrakis(4-isopropylphenyl)anthracene- 9,10-diamine, N,N'-diphenyl-N,N'-bis(p-tolyl)anthracene-9,10-diamine, N,N'-diphenyl-N,N'- Bis(m-tolyl)anthracene-9,10-diamine, N,N'-diphenyl-N,N'-bis(4-ethylphenyl)anthracene-9,10-diamine, N,N '-Diphenyl-N,N'-bis(4-ethylphenyl)anthracene-9,10-diamine, N,N'-diphenyl-N,N'-bis(4-isopropyl) Phenyl)anthracene-9,10-diamine, N,N'-diphenyl-N,N'-bis(4-tert-butylphenyl)anthracene-9,10-diamine, N,N' -Bis(4-isopropylphenyl)-N,N'-bis(p-tolyl)anthracene-9,10-diamine, 2,6-di-tert-butyl-N,N,N', N'-tetra(p-tolyl)anthracene-9,10-diamine, 2,6-di-tert-butyl-N,N'-diphenyl-N,N'-bis(4-isopropyl) Phenyl)anthracene-9,10-diamine, 2,6-di-tert-butyl-N,N'-bis(4-isopropylphenyl)-N,N'-bis(p-tolyl) Anthracene-9,10-diamine, 2,6-dicyclohexyl-N,N'-bis(4-isopropylphenyl)-N,N'-bis(p-tolyl)anthracene-9,10- Diamine, 2,6-dicyclohexyl-N,N'-bis(4-isopropylphenyl)-N,N'-bis(4-tert-butylphenyl)anthracene-9,10-di Amine, 9,10-bis(4-diphenylamino-phenyl)anthracene, 9,10-bis(4-bis(1-naphthylamino)phenyl)anthracene, 9,10-bis(4 -Bis(2-naphthylamino)phenyl)anthracene, 10-di-p-tolylamino-9-(4-di-p-tolylamino-1-naphthyl)anthracene, 10-diphenylamino -9-(4-diphenylamino-1-naphthyl)anthracene, 10-diphenylamino-9-(6-diphenylamino-2-naphthyl)anthracene, etc.

In addition, [4-(4-diphenylamino-phenyl)naphthalene-1-yl]-diphenylamine, [6-(4-diphenylamino-phenyl)naphthalene- 2-yl]-diphenylamine, 4,4'-bis[4-diphenylaminonaphthalene-1-yl]biphenyl, 4,4'-bis[6-diphenylaminonaphthalene-2 -yl]biphenyl, 4,4''-bis[4-diphenylaminonaphthalene-1-yl]-p-terphenyl, 4,4''-bis[6-diphenylaminonaphthalene-2 -Base]-para-terphenyl and so on. In addition, aromatic amine derivatives described in Japanese Patent Laid-Open No. 2006-156888 and the like can also be used.

As a coumarin derivative, coumarin-6, coumarin-334, etc. are mentioned. In addition, coumarin derivatives described in Japanese Patent Laid-Open No. 2004-43646, Japanese Patent Laid-Open No. 2001-76876, and Japanese Patent Laid-Open No. Hei 6-298758 can also be used.

另外，亦可使用日本專利特開2005-126399號公報、日本專利特開2005-097283號公報、日本專利特開2002-234892號公報、日本專利特開2001-220577號公報、日本專利特開2001-081090號公報、及日本專利特開2001-052869號公報等中所記載的吡喃衍生物。As a pyran derivative, the following DCM, DCJTB, etc. are mentioned. [Chemical 159]

In addition, Japanese Patent Laid-Open No. 2005-126399, Japanese Patent Laid-Open No. 2005-097283, Japanese Patent Laid-Open No. 2002-234892, Japanese Patent Laid-Open No. 2001-220577, and Japanese Patent Laid-Open No. 2001 can also be used - Pyran derivatives described in Gazette No. 081090, Japanese Patent Laid-Open No. 2001-052869, and the like.

<Electron injection layer and electron transport layer in organic electroluminescence element> The electron injection layer 107 functions to efficiently inject electrons moved from the cathode 108 into the light emitting layer 105 or the electron transport layer 106 . The electron transport layer 106 functions to efficiently transport electrons injected from the cathode 108 or electrons injected from the cathode 108 via the electron injection layer 107 to the light-emitting layer 105 . The electron transport layer 106 and the electron injection layer 107 are formed by laminating and mixing one or more kinds of electron transport and injection materials, respectively, or a mixture of the electron transport and injection material and a polymer binder.

The electron injection/transport layer refers to a layer that controls the injection of electrons from the cathode and the transport of electrons, and it is desirable that the electron injection efficiency is high and the injected electrons are efficiently transported. Therefore, it is preferable to use a substance that has a high electron affinity, a high electron mobility, and is further excellent in stability, and which does not easily generate impurities that become traps during production and use. However, taking into account the transport balance between holes and electrons, when the main function is to effectively prevent holes from the anode from flowing to the cathode side without recombining, even if the electron transport ability is not so high, it is also related to A material with a high electron transport capability equally has the effect of improving the luminous efficiency. Therefore, the electron injection/transport layer in the present embodiment may also have the function of a layer that can effectively prevent the movement of holes.

As a material for forming the electron transport layer 106 or the electron injection layer 107 (electron transport material), the compound of the present invention and its polymer compound can be used. In addition, it can be arbitrarily selected and used from compounds conventionally used as electron transport compounds in photoconductive materials, and known compounds used for electron injection layers and electron transport layers of organic electroluminescence elements.

The material for the electron transport layer or the electron injection layer preferably contains at least one compound selected from the group consisting of an aromatic ring containing at least one atom selected from the group consisting of carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus. Or heteroaromatic compounds, pyrrole derivatives and their condensed ring derivatives, and metal complexes with electron-accepting nitrogen. Specifically, condensed ring-based aromatic ring derivatives such as naphthalene and anthracene, styryl-based aromatic ring derivatives represented by 4,4'-bis(diphenylvinyl)biphenyl, and violone Derivatives, coumarin derivatives, naphthalimide derivatives, quinone derivatives such as anthraquinone or diphenoquinone, phosphorus oxide derivatives, carbazole derivatives, and indole derivatives. Examples of metal complexes having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complexes, methimine complexes, cycloheptatrienol ketone metal complexes, and flavonoids. Alcohol metal complexes and benzoquinoline metal complexes, etc. These materials can be used alone or in combination with different materials.

In addition, specific examples of other electron-transporting compounds include pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perone derivatives, coumarin derivatives, and naphthalimide derivatives. compounds, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazole derivatives (1,3-bis[(4-tert-butylphenyl)1,3, 4-oxadiazolyl] phenylene, etc.), thiophene derivatives, triazole derivatives (N-naphthyl-2,5-diphenyl-1,3,4-triazole, etc.), thiadiazole derivatives compounds, metal complexes of 8-hydroxyquinoline derivatives, hydroxyquinoline-based metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzoxazole-based compounds, gallium complexes, Pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2,2'-bis(benzo[h]quinolin-2-yl) -9,9'-spirocyclic bispyridine, etc.), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (tris(N-phenylbenzimidazol-2-yl)benzene, etc.), benzos Oxazole derivatives, benzothiazole derivatives, quinoline derivatives, oligopyridine derivatives such as terpyridine, bipyridine derivatives, terpyridine derivatives (1,3-bis(4'-(2,2': 6'2''-terpyridyl))benzene, etc.), naphthyridine derivatives (bis(1-naphthyl)-4-(1,8-naphthyridin-2-yl)phenylphosphine oxide, etc.), aldehydes Azizine derivatives, carbazole derivatives, indole derivatives, phosphorus oxide derivatives, bis-styryl derivatives, and the like.

In addition, metal complexes having electron-accepting nitrogen can also be used, and examples thereof include hydroxyquinoline-based metal complexes, hydroxyazole complexes such as hydroxyphenyloxazole complexes, and methimine complexes. , cycloheptatrienol ketone metal complexes, flavonol metal complexes and benzoquinoline metal complexes, etc.

The materials can be used alone or in admixture with different materials.

Among the materials, quinoline-based metal complexes, bipyridine derivatives, phenanthroline derivatives or borane derivatives are preferred.

式中，R¹ ～R⁶ 為氫或取代基，M為Li、Al、Ga、Be或Zn，n為1～3的整數。The quinoline-based metal complex is a compound represented by the following general formula (E-1). [Chemical 160]

In the formula, R ¹ to R ⁶ are hydrogen or a substituent, M is Li, Al, Ga, Be or Zn, and n is an integer of 1 to 3.

Specific examples of quinoline-based metal complexes include lithium 8-quinolinate, tris(8-quinoline) aluminum, tris(4-methyl-8-quinoline) aluminum, tris(4-methyl-8-quinoline) aluminum, 5-Methyl-8-hydroxyquinoline)aluminum, tris(3,4-dimethyl-8-hydroxyquinoline)aluminum, tris(4,5-dimethyl-8-hydroxyquinoline)aluminum, tris(4,5-dimethyl-8-hydroxyquinoline)aluminum (4,6-Dimethyl-8-hydroxyquinoline)aluminum, bis(2-methyl-8-hydroxyquinoline)(phenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(2 -Cresol)aluminum, bis(2-methyl-8-hydroxyquinoline)(3-methylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(4-methylphenol)aluminum , bis(2-methyl-8-hydroxyquinoline)(2-phenylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(3-phenylphenol)aluminum, bis(2-methylphenol) yl-8-hydroxyquinoline)(4-phenylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(2,3-dimethylphenol)aluminum, bis(2-methyl-8 -Hydroxyquinoline)(2,6-dimethylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(3,4-dimethylphenol)aluminum, bis(2-methyl-8 -Hydroxyquinoline)(3,5-dimethylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(3,5-di-tert-butylphenol)aluminum, bis(2-methylphenol) yl-8-hydroxyquinoline)(2,6-diphenylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(2,4,6-triphenylphenol)aluminum, bis(2 -Methyl-8-hydroxyquinoline)(2,4,6-trimethylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(2,4,5,6-tetramethylphenol) ) aluminum, bis(2-methyl-8-hydroxyquinoline)(1-naphthol) aluminum, bis(2-methyl-8-hydroxyquinoline)(2-naphthol) aluminum, bis(2,4 - Dimethyl-8-hydroxyquinoline)(2-phenylphenol)aluminum, bis(2,4-dimethyl-8-hydroxyquinoline)(3-phenylphenol)aluminum, bis(2,4 - Dimethyl-8-hydroxyquinoline)(4-phenylphenol)aluminum, bis(2,4-dimethyl-8-hydroxyquinoline)(3,5-dimethylphenol)aluminum, bis(2,4-dimethyl-8-hydroxyquinoline)(3,5-dimethylphenol)aluminum 2,4-Dimethyl-8-hydroxyquinoline)(3,5-di-tert-butylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)aluminum-μ-oxo-bis (2-Methyl-8-hydroxyquinoline)aluminum, bis(2,4-dimethyl-8-hydroxyquinoline)aluminum-μ-oxo-bis(2,4-dimethyl-8-hydroxyl) quinoline)aluminum, bis(2-methyl-4-ethyl-8-hydroxyquinoline)aluminum-μ-oxo-bis(2-methyl-4-ethyl-8-hydroxyquinoline)aluminum, Bis(2-methyl-4-methoxy-8-hydroxyquinoline)aluminum-μ-oxo-bis(2-methyl-4-methoxy-8-hydroxyquinoline)aluminum, bis(2 -Methyl-5-cyano-8-hydroxyquinoline)aluminum-μ-oxo-bis(2-methyl-5-cyano-8-hydroxyquinoline)aluminum, bis(2-methyl-5 -Trifluoromethyl-8-hydroxyquinoline)aluminum-μ-oxo-bis(2-methyl-5-trifluoromethyl- 8-hydroxyquinoline) aluminum, bis(10-hydroxybenzo[h]quinoline) beryllium, etc.

式中，G表示單一的鍵結鍵或n價的連結基，n為2～8的整數。另外，未用於吡啶-吡啶或吡啶-G的鍵結的碳亦可被取代。The bipyridine derivative is a compound represented by the following general formula (E-2). [Chemical 161]

In the formula, G represents a single bond or an n-valent linking group, and n is an integer of 2 to 8. In addition, carbons not used for pyridine-pyridine or pyridine-G bonding may also be substituted.

As G of general formula (E-2), the following structural formula is mentioned, for example. Furthermore, R in the following structural formula is independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenyl or triphenyl . [hua 162]

Specific examples of pyridine derivatives include 2,5-bis(2,2'-pyridin-6-yl)-1,1-dimethyl-3,4-diphenylsilole, 2,5 -Bis(2,2'-pyridin-6-yl)-1,1-dimethyl-3,4-dimesitylsilole, 2,5-bis(2,2'-pyridine-5- base)-1,1-dimethyl-3,4-diphenylsilole, 2,5-bis(2,2'-pyridin-5-yl)-1,1-dimethyl-3,4 -Dimesitylsilole, 9,10-bis(2,2'-pyridin-6-yl)anthracene, 9,10-bis(2,2'-pyridin-5-yl)anthracene, 9,10 -Bis(2,3'-pyridin-6-yl)anthracene, 9,10-bis(2,3'-pyridin-5-yl)anthracene, 9,10-bis(2,3'-pyridin-6- base)-2-phenylanthracene, 9,10-bis(2,3'-pyridin-5-yl)-2-phenylanthracene, 9,10-bis(2,2'-pyridin-6-yl) -2-phenylanthracene, 9,10-bis(2,2'-pyridin-5-yl)-2-phenylanthracene, 9,10-bis(2,4'-pyridin-6-yl)-2 -Phenylanthracene, 9,10-bis(2,4'-pyridin-5-yl)-2-phenylanthracene, 9,10-bis(3,4'-pyridin-6-yl)-2-benzene Anthracene, 9,10-bis(3,4'-pyridin-5-yl)-2-phenylanthracene, 3,4-diphenyl-2,5-bis(2,2'-pyridine-6- base)thiophene, 3,4-diphenyl-2,5-bis(2,3'-pyridin-5-yl)thiophene, 6',6''-bis(2-pyridyl)2,2': 4',4'':2'',2'''-tetrapyridine, etc.

式中，R¹ ～R⁸ 為氫或取代基，鄰接的基可互相鍵結而形成縮合環，G表示單一的鍵結鍵或n價的連結基，n為2～8的整數。另外，作為通式（E-3-2）的G，例如可列舉與聯吡啶衍生物的欄中所說明的G相同的結構式。The phenanthroline derivative is a compound represented by the following general formula (E-3-1) or general formula (E-3-2). [Chemical 163]

In the formula, R ¹ to R ⁸ are hydrogen or a substituent, adjacent groups may be bonded to each other to form a condensed ring, G represents a single bond or an n-valent linking group, and n is an integer of 2 to 8. Moreover, as G of general formula (E-3-2), the same structural formula as G demonstrated in the column of bipyridine derivative is mentioned, for example.

Specific examples of phenanthroline derivatives include 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10-bis(1,10-phenanthroline-2-yl)anthracene, 2,6-bis(1,10-phenanthrolin-5-yl)pyridine, 1,3,5-tris(1,10- phenanthroline-5-yl)benzene, 9,9'-difluoro-bis(1,10-phenanthroline-5-yl), 2,9-dimethyl-4,7-biphenyl-1,10 -phenanthroline (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) or 1,3-bis(2-phenyl-1,10-phenanthroline-9-yl)benzene, etc.

In particular, the case where the phenanthroline derivative is used for the electron transport layer and the electron injection layer will be described. In order to obtain stable light emission for a long time, a material excellent in thermal stability and film-forming property is desired. Among the phenanthroline derivatives, it is preferable that the substituent itself has a three-dimensional structure, or has a steric repulsion with the phenanthroline skeleton or is adjacent to the phenanthroline skeleton. A derivative having a three-dimensional structure due to the steric repulsion of a substituent, or a derivative in which a plurality of phenanthroline skeletons are connected. Furthermore, when connecting a plurality of phenanthroline skeletons, it is more preferable that the connecting unit (unit) includes a conjugated bond, a substituted or unsubstituted aromatic hydrocarbon, and a substituted or unsubstituted aromatic heterocycle. compound.

式中，R¹¹ 及R¹² 分別獨立地為氫、烷基、可被取代的芳基、經取代的矽烷基、可被取代的含有氮的雜環、或氰基的至少一者，R¹³ ～R¹⁶ 分別獨立地為可被取代的烷基、或可被取代的芳基，X為可被取代的伸芳基，Y為可被取代的碳數16以下的芳基、經取代的硼基、或可被取代的咔唑基，而且n分別獨立地為0～3的整數。The borane derivative is a compound represented by the following general formula (E-4), the details of which are disclosed in Japanese Patent Laid-Open No. 2007-27587. [Chemical 164]

In the formula, R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, aryl that can be substituted, silyl that can be substituted, heterocycle that can be substituted nitrogen, or cyano, R ¹³ ~R ¹⁶ is independently a substituted alkyl group or a substituted aryl group, X is a substituted aryl group, Y is a substituted aryl group with less than 16 carbon atoms, a substituted boron group, or a carbazolyl group which may be substituted, and n is each independently an integer of 0 to 3.

式中，R¹¹ 及R¹² 分別獨立地為氫、烷基、可被取代的芳基、經取代的矽烷基、可被取代的含有氮的雜環、或氰基的至少一者，R¹³ ～R¹⁶ 分別獨立地為可被取代的烷基、或可被取代的芳基，R²¹ 及R²² 分別獨立地為氫、烷基、可被取代的芳基、經取代的矽烷基、可被取代的含有氮的雜環、或氰基的至少一者，X¹ 為可被取代的碳數20以下的伸芳基，n分別獨立地為0～3的整數，而且m分別獨立地為0～4的整數。Among the compounds represented by the general formula (E-4), the compounds represented by the following general formula (E-4-1) are preferred, and the following general formula (E-4-1-1) are more preferred. ~ A compound represented by the general formula (E-4-1-4). Specific examples include: 9-[4-(4-bis-mesysylboron-1-yl)phenyl]carbazole, 9-[4-(4-bis-mesysylboron-naphthalene] -1-yl)naphthalene-1-yl]carbazole and the like. [Chemical 165]

In the formula, R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, aryl that can be substituted, silyl that can be substituted, heterocycle that can be substituted nitrogen, or cyano, R ¹³ ~R ¹⁶ are each independently a substituted alkyl group or a substituted aryl group, and R ²¹ and R ²² are each independently hydrogen, an alkyl group, a substituted aryl group, a substituted silyl group, a substituted aryl group, and a substituted aryl group. At least one of a substituted nitrogen-containing heterocycle or a cyano group, X ¹ is a substituted aryl group having 20 or less carbon atoms, n is each independently an integer of 0 to 3, and m is each independently An integer from 0 to 4.

各式中，R³¹ ～R³⁴ 分別獨立地為甲基、異丙基或苯基的任一者，而且R³⁵ 及R³⁶ 分別獨立地為氫、甲基、異丙基或苯基的任一者。[Chemical 166]

In each formula, R ³¹ to R ³⁴ are each independently any one of methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently any of hydrogen, methyl, isopropyl or phenyl. one.

式中，R¹¹ 及R¹² 分別獨立地為氫、烷基、可被取代的芳基、經取代的矽烷基、可被取代的含有氮的雜環、或氰基的至少一者，R¹³ ～R¹⁶ 分別獨立地為可被取代的烷基、或可被取代的芳基，X¹ 為可被取代的碳數20以下的伸芳基，而且n分別獨立地為0～3的整數。Among the compounds represented by the general formula (E-4), the compounds represented by the following general formula (E-4-2) are preferred, and the following general formula (E-4-2-1) is more preferred. represented compound. [Chemical 167]

In the formula, R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, aryl that can be substituted, silyl that can be substituted, heterocycle that can be substituted nitrogen, or cyano, R ¹³ ~R ¹⁶ is each independently a substituted alkyl group or an optionally substituted aryl group, X ¹ is a substituted aryl group with 20 or less carbon atoms, and n is each independently an integer of 0-3.

式中，R³¹ ～R³⁴ 分別獨立地為甲基、異丙基或苯基的任一者，而且R³⁵ 及R³⁶ 分別獨立地為氫、甲基、異丙基或苯基的任一者。[Chemical 168]

In the formula, R ³¹ to R ³⁴ are each independently any one of methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently any one of hydrogen, methyl, isopropyl or phenyl By.

式中，R¹¹ 及R¹² 分別獨立地為氫、烷基、可被取代的芳基、經取代的矽烷基、可被取代的含有氮的雜環、或氰基的至少一者，R¹³ ～R¹⁶ 分別獨立地為可被取代的烷基、或可被取代的芳基，X¹ 為可被取代的碳數10以下的伸芳基，Y¹ 為可被取代的碳數14以下的芳基，而且n分別獨立地為0～3的整數。Among the compounds represented by the general formula (E-4), the compounds represented by the following general formula (E-4-3) are preferred, and the following general formula (E-4-3-1) are more preferred. or a compound represented by the general formula (E-4-3-2). [Chemical 169]

In the formula, R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, aryl that can be substituted, silyl that can be substituted, heterocycle that can be substituted nitrogen, or cyano, R ¹³ ~R ¹⁶ are each independently a substituted alkyl group or a substituted aryl group, X ¹ is a substituted aryl group with less than 10 carbon atoms, and Y ¹ is a substituted aryl group with less than 14 carbon atoms aryl group, and n is each independently an integer of 0 to 3.

各式中，R³¹ ～R³⁴ 分別獨立地為甲基、異丙基或苯基的任一者，而且R³⁵ 及R³⁶ 分別獨立地為氫、甲基、異丙基或苯基的任一者。[Chemical 170]

In each formula, R ³¹ to R ³⁴ are each independently any one of methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently any of hydrogen, methyl, isopropyl or phenyl. one.

式中，Ar¹ ～Ar³ 分別獨立地為氫或可被取代的碳數6～30的芳基。特佳為Ar¹ 為可被取代的蒽基的苯并咪唑衍生物。The benzimidazole derivative is a compound represented by the following general formula (E-5). [Chemical 171]

In the formula, Ar ¹ to Ar ³ are each independently hydrogen or a substituted aryl group having 6 to 30 carbon atoms. Particularly preferred are benzimidazole derivatives in which Ar ¹ is an anthracenyl group which may be substituted.

Specific examples of the aryl group having 6 to 30 carbon atoms are phenyl, 1-naphthyl, 2-naphthyl, acenaphthene-1-yl, acenaphthene-3-yl, acenaphthene-4-yl, acenaphthene-5-yl, perylene -1-yl, phenyl-2-yl, phenyl-3-yl, phenyl-4-yl, phenyl-9-yl, phenyl-1-yl, phenyl-2-yl, 1-phenanthrene, 2-phenanthyl , 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-anthracenyl, 2-anthracene, 9-anthracene, fluoranthene-1-yl, fluoranthene-2-yl, fluoranthene-3- base, fluoranthene-7-yl, fluoranthene-8-yl, triphenylene-1-yl, triphenylene-2-yl, pyrene-1-yl, pyrene-2-yl, pyrene-4-yl, En-1-yl, En-2-yl, En-3-yl, En-4-yl, En-5-yl, En-6-yl, Condensed tetraphenyl-1-yl, Condensed tetraphenyl-2- base, fused tetraphenyl-5-yl, perylene-1-yl, perylene-2-yl, perylene-3-yl, fused pentaphenyl-1-yl, fused pentaphenyl-2-yl, fused pentaphenyl-5-yl base, fused pentaphenyl-6-yl.

Specific examples of benzimidazole derivatives are 1-phenyl-2-(4-(10-phenylanthracene-9-yl)phenyl)-1H-benzo[d]imidazole, 2-(4-(10 -(Naphthalen-2-yl)anthracene-9-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 2-(3-(10-(naphthalen-2-yl)anthracene-9 -yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 5-(10-(naphthalen-2-yl)anthracene-9-yl)-1,2-diphenyl-1H- Benz[d]imidazole, 1-(4-(10-(naphthalen-2-yl)anthracene-9-yl)phenyl)-2-phenyl-1H-benzo[d]imidazole, 2-(4 -(9,10-Bis(naphthalen-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 1-(4-(9,10-bis( Naphthalene-2-yl)anthracene-2-yl)phenyl)-2-phenyl-1H-benzo[d]imidazole, 5-(9,10-bis(naphthalen-2-yl)anthracene-2-yl )-1,2-diphenyl-1H-benzo[d]imidazole.

The electron transport layer or the electron injection layer may further contain a substance that can reduce the material forming the electron transport layer or the electron injection layer. Various materials can be used as the reducing substance as long as it has a certain reducing ability, for example, a material selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, and alkaline earth metals can be preferably used. The group consisting of metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes at least one of the group.

Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (work function 2.28 eV), Rb (work function 2.16 eV) or Cs (work function 1.95 eV), or Alkaline earth metals such as Ca (work function of 2.9 eV), Sr (work function of 2.0 eV to 2.5 eV), or Ba (work function of 2.52 eV) are particularly preferred materials with a work function of 2.9 eV or less. Among these, a more preferable reducing substance is an alkali metal of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs. These alkali metals have particularly high reducing power, and by adding a relatively small amount of these alkali metals to the material forming the electron transport layer or the electron injection layer, it is possible to improve the luminous brightness or prolong the life of the organic EL element. In addition, as a reducing substance with a work function of 2.9 eV or less, a combination of two or more of the alkali metals is also preferred, and a combination including Cs is particularly preferred, such as Cs and Na, Cs and K, Cs and Rb or Cs Combination with Na and K. By including Cs, reducing ability can be effectively exhibited, and by adding it to a material for forming an electron transport layer or an electron injection layer, it is possible to improve the light-emitting luminance and prolong the life of the organic EL element.

<Cathode in organic electroluminescence element> The cathode 108 functions to inject electrons into the light emitting layer 105 via the electron injection layer 107 and the electron transport layer 106 .

The material for forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, and the same material as the material for forming the anode 102 can be used. Among them, metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium, and magnesium, or their alloys (magnesium-silver alloys) are preferred. , magnesium-indium alloys, aluminum-lithium alloys such as lithium fluoride/aluminum, etc.), etc. In order to improve the device characteristics by increasing the electron injection efficiency, lithium, sodium, potassium, cesium, calcium, magnesium or alloys containing these low work function metals are effective. However, these low work function metals are often unstable in the atmosphere. In order to improve this aspect, for example, a method of doping a trace amount of lithium, cesium or magnesium into an organic layer and using an electrode with high stability is known. As other dopants, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide can also be used. However, it is not limited to these.

Further, the following preferred examples include metals such as platinum, gold, silver, copper, iron, tin, aluminum, and indium, or alloys using these metals, and silicon dioxide, titanium dioxide, and nitride to protect electrodes. Inorganic substances such as silicon, polyvinyl alcohol, vinyl chloride, hydrocarbon-based polymer compounds, etc. are laminated. The method for producing these electrodes is not particularly limited as long as it is a method that can achieve conduction, such as resistance heating vapor deposition, electron beam vapor deposition, sputtering, ion plating, and coating.

＜Adhesives that can be used for each layer＞ The materials used for the above hole injection layer, hole transport layer, light emitting layer, electron transport layer and electron injection layer can be formed individually for each layer, or can be dispersed in polyvinyl chloride, polycarbonate, Polystyrene, poly(N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysilicon, polyphenylene ether, polybutadiene, hydrocarbon resin, ketone resin, benzene Solvent-soluble resins such as oxygenated resins, polyamides, ethyl cellulose, vinyl acetate resins, Acrylonitrile Butadiene Styrene (ABS) resins, polyurethane resins, or phenols Resins, xylene resins, petroleum resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, silicone resins and other curable resins are used.

<Method for producing organic electroluminescent element> The layers constituting the organic electroluminescent element can be formed by vapor deposition, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination, printing, spin coating, or the like. A method such as a casting method and a coating method is used to form a thin film of a material that should constitute each layer. The film thickness of each layer formed as described above is not particularly limited, and can be appropriately set according to the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured by a crystal oscillation type film thickness measuring apparatus or the like. In the case of thinning using the vapor deposition method, the vapor deposition conditions differ depending on the type of material, the intended crystal structure and association structure of the film, and the like. The evaporation conditions are usually preferably: boat heating temperature +50℃～+400℃, vacuum degree 10 ^-6 Pa～10 ^-3 Pa, evaporation rate 0.01 nm/sec～50 nm/sec, substrate temperature -150℃ To +300°C, the film thickness is appropriately set within the range of 2 nm to 5 μm.

Next, as an example of a method of fabricating an organic electroluminescence element, a method including an anode/hole injection layer/hole transport layer/light emitting layer containing a host material and a dopant material/electron transport layer/electron injection layer/cathode The manufacturing method of an organic electroluminescent element is demonstrated. On a suitable substrate, a thin film of an anode material is formed by vapor deposition or the like to form an anode, and then thin films of a hole injection layer and a hole transport layer are formed on the anode. A host material and a dopant material are co-evaporated thereon to form a thin film as a light emitting layer, an electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film containing a cathode material is formed by vapor deposition or the like as the cathode, thereby obtaining the target organic electroluminescence element. Furthermore, in the fabrication of the organic electroluminescent element, the fabrication sequence may be reversed, and the sequence of cathode, electron injection layer, electron transport layer, light-emitting layer, hole transport layer, hole injection layer, and anode may be used. make.

When applying a direct current voltage to the organic electroluminescence element obtained in the above manner, it is sufficient to apply the anode with the polarity of + and the cathode with the polarity of -, and when a voltage of about 2 V to 40 V is applied, Light emission was observed from the transparent or translucent electrode side (anode or cathode, and both). In addition, the organic electroluminescence element emits light even when a pulse current or an alternating current is applied. In addition, the waveform of the alternating current to be applied may be arbitrary.

<Application example of organic electroluminescence element> In addition, the present invention can also be applied to a display device including an organic electroluminescence element, a lighting device including an organic electroluminescence element, and the like. A display device or lighting device including an organic electroluminescence element can be produced by a known method such as connecting the organic electroluminescence element of the present embodiment to a known driving device, and DC driving, pulse driving, and AC driving can be suitably used. It is driven by a known driving method.

Examples of display devices include panel displays such as color flat panel displays, flexible displays such as flexible color organic electroluminescence (EL) displays, and the like (see, for example, Japanese Patent Laid-Open No. 10-335066, Japanese Patent Laid-Open No. 2003 -321546, Japanese Patent Laid-Open No. 2004-281086, etc.). Moreover, as a display system of a display, a matrix and/or a segment system etc. are mentioned, for example. Furthermore, matrix display and segment display can coexist on the same panel.

In a matrix, pixels for display are arranged two-dimensionally in a lattice or mosaic shape, and characters or images are displayed by a collection of pixels. The shape or size of the pixel is determined according to the usage. For example, in the display of images and characters on personal computers, monitors, and televisions, quadrilateral pixels with one side of 300 μm or less are generally used, and in the case of a large-scale display such as a display panel, a side with a side of mm is used. 's pixels. In the case of monochrome display, it is sufficient to arrange pixels of the same color, and in the case of color display, pixels of red, green, and blue are displayed in parallel. In this case, triangular and striped types are typical. Furthermore, as a driving method of the matrix, either a line-sequential driving method or an active matrix may be used. Line-sequential driving has the advantage of a simple structure, but when considering the operating characteristics, an active matrix may be better. Therefore, the driving method must also be used according to the application.

In the segment method (type), a pattern is formed so as to display information determined in advance, and the determined area is made to emit light. For example, the time or temperature display in a digital clock or a thermometer, the operation status display of an audio device or an induction cooker, etc., and the panel display of a car, etc. are mentioned.

Examples of lighting devices include lighting devices such as indoor lighting, backlights of liquid crystal display devices, and the like (for example, refer to Japanese Patent Laid-Open No. 2003-257621, Japanese Patent Laid-Open No. 2003-277741, and Japanese Patent Laid-Open Publication No. 2003-277741). Bulletin No. 2004-119211, etc.). Backlights are mainly used to improve the visibility of display devices that do not emit light, and are used in liquid crystal display devices, clocks, audio devices, automotive panels, display panels, signs, and the like. In particular, as a backlight for a personal computer where thinning of liquid crystal display devices is becoming a problem, considering that the conventional method includes a fluorescent lamp or a light guide plate, it is difficult to reduce the thickness, and the backlight using the light-emitting element of the present embodiment is Features thin and light weight.

3-2. Other organic components In addition to the organic electroluminescence element, the compounds of the present invention and their polymer compounds can also be used in the production of organic field effect transistors, organic thin film solar cells, and the like.

The organic field effect transistor is a transistor that uses an electric field generated by a voltage input to control current, and is provided with a gate electrode in addition to a source electrode and a drain electrode. When a voltage is applied to the gate electrode, an electric field is generated, and the flow of electrons (or holes) flowing between the source electrode and the drain electrode can be interrupted arbitrarily to control the current. Compared with single transistors (bipolar transistors), field effect transistors are easier to miniaturize, and are often used as components for forming integrated circuits and the like.

The structure of the organic field effect transistor is usually set by contacting the source electrode and the drain electrode with the organic semiconductor active layer formed by using the compound of the present invention and its polymer compound, and then through the insulating layer (dielectric) contacting the organic semiconductor active layer. body layer) to set the gate electrode. As an element structure, the following structures are mentioned, for example. (1) Substrate/gate electrode/insulator layer/source electrode/drain electrode/organic semiconductor active layer (2) Substrate/gate electrode/insulator layer/organic semiconductor active layer/source electrode/drain electrode (3) Substrate/organic semiconductor active layer/source electrode/drain electrode/insulator layer/gate electrode (4) Substrate/source electrode/drain electrode/organic semiconductor active layer/insulator layer/gate electrode The organic field effect transistor thus constructed can be used as a pixel drive switching element of an active matrix driving liquid crystal display or an organic electroluminescence display, and the like.

The organic thin-film solar cell has a structure in which an anode, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a cathode are laminated with ITO or the like on a transparent substrate such as glass. The photoelectric conversion layer has a p-type semiconductor layer on the anode side and an n-type semiconductor layer on the cathode side. The compound of the present invention and its polymer compound can be used as a material for a hole transport layer, a p-type semiconductor layer, an n-type semiconductor layer, and an electron transport layer, depending on its physical properties. In organic thin film solar cells, the compounds of the present invention and their polymer compounds can function as hole transport materials or electron transport materials. In addition to the above, the organic thin film solar cell may also suitably include a hole blocking layer, an electron blocking layer, an electron injection layer, a hole injection layer, a smoothing layer, and the like. In the organic thin film solar cell, known materials for organic thin film solar cells can be appropriately selected and used in combination. [Example]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by these examples at all. The following are the compounds synthesized in the examples.

Synthesis Example (1) Compound of formula (10P-g-101): 2,8'-dimethyl-5λ ⁴ ,6λ ⁴ -spiro[benzo[e]pyrido[2,1-b][1 Synthesis of ,3,4]oxazaborin-6,10'-dibenzo[b,e][1,4]oxaborole[Chem 172]

Step 1 To bis-p-tolyl ether (10.1 g) and dimethylformamide (200 ml) was added 1,3-dibromo-5,5-dimethylhydantoin (DBH: 55.9 g) , 200 mmol), heated and stirred at 70 °C for 2 hours. The reaction solution was cooled to room temperature and water (500 ml) was added, followed by extraction with toluene (200 ml×5 times). The solvent was distilled off by performing distillation under normal pressure at 140°C. The crude product was filtered through a silica gel short-path column, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, 1,1'-oxybis(2-bromo-4-methylbenzene) (10.8 g, yield 61%) was obtained as a white solid by washing with hexane. [Chemical 173]

The structure of the obtained compound was confirmed by nuclear magnetic resonance (NMR) measurement. ¹ H-NMR (CDCl ₃ , 400 MHz): 2.31 (s, 6H), 6.71 (d, 2H), 7.02 (d, 2H), 7.35 (s, 2H). ¹³ C-NMR (CDCl ₃ , 101 MHz): 20.4 (2C), 113.7 (2C), 119.1 (2C), 129.1 (2C), 134.1 (2C), 134.8 (2C), 151.2 (2C).

Step 2: To 2-iodopyridine (3.20 ml, 30 mmol), copper iodide (0.573 g, 3.0 mmol), 2-picolinic acid (0.745 g, 61 mmol), tripotassium phosphate under nitrogen at room temperature (12.9 g, 60 mmol) and dimethylsulfoxide (150 ml) were added 2-bromophenol (3.80 ml, 36 mmol), followed by heating and stirring at 100° C. for 14 hours. The reaction solution was cooled to room temperature and water (500 ml) was added, followed by extraction with ethyl acetate (250 ml×3 times). The crude product was filtered through a silica gel short-path column, and the solvent was distilled off to obtain a crude product. After that, 2-(2-bromophenoxy)pyridine (4.88 g, yield 65%) was obtained as a white solid by washing with hexane. [Chemical 174]

The structure of the obtained compound was confirmed by NMR measurement. ¹ H-NMR (CDCl ₃ , 400MHz): 6.96-7.00 (m, 2H), 7.12 (t, 1H), 7.21 (d, 1H), 7.36 (t, 1H), 7.63 (d, 1H), 7.71 ( t, 1H), 8.15 (t, 1H). ¹³ C-NMR (CDCl ₃ , 101 MHz): 111.4 (1C), 116.7 (1C), 118.7 (1C), 123.9 (1C), 126.5 (1C), 128.7 ( 1C), 133.8 (1C), 139.6 (1C), 147.7 (1C), 151.1 (1C), 163.1 (1C).

Step 3 To 2-(2-bromophenoxy)pyridine (0.971 g, 3.9 mmol) and toluene (50 ml) at -78°C under nitrogen atmosphere was added butyllithium (245 ml, 3.9 mmol), And stirred at 0°C for 1 hour. Furthermore, boron tribromide (0.380 ml, 0.50 mmol) was added at -78°C, and the mixture was stirred at 0°C for 15 minutes to prepare a boron intermediate. Separately, 1,1'-oxybis(2-bromo-4-methylbenzene) (1.36 g, 3.8 mmol) and diethyl ether (50 ml) were added simultaneously under nitrogen atmosphere at -78°C. butyllithium (4.90 ml, 7.8 mmol) and stirred at 0 °C for 1 h to prepare the lithium intermediate. This was added to the boron intermediate at -78°C and stirred at 0°C for 1 hour. The reaction solution was filtered through a silica gel short-path column, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, the compound of formula (10P-g-101) was obtained as a pale yellow solid by washing with hexane (0.224 mg, yield 16%). [Chemical 175]

The structure of the obtained compound was confirmed by NMR measurement. ¹ H-NMR (CDCl ₃ , 400MHz): 2.13 (s, 6H), 6.80 (s, 2H), 6.93 (t, 1H), 6.98-7.08 (m, 6H), 7.18 (t, 2H), 7.23 ( d, 1H), 7.70 (d, 1H), 7.79 (t, 1H). ¹³ C-NMR (CDCl ₃ , 101 MHz): 20.8 (2C), 114.2 (1C), 115.0 (1C), 115.4 (2C), 118.9 (1C), 125.5 (1C), 126.7 (1C), 128.7 (2C), 130.9 (2C), 134.8 (2C), 135.1 (1C), 141.8 (1C), 144.4 (1C), 152.5 (1C), 154.9 (2C), 157.6 (1C).

Synthesis example (2) Synthesis of Compounds of Formula (10P-g-101) (Other Methods) The second step and the third step of the synthesis example (1) were carried out by the following method, whereby the yield was improved.

Step 2: To 2-bromopyridine (2.90 ml, 30 mmol), copper iodide (0.557 g, 2.9 mmol), 2-picolinic acid (0.372 g, 3.0 mmol), tripotassium phosphate under nitrogen at room temperature (12.5 g, 59 mmol) and dimethylsulfoxide (200 ml) were added phenol (3.20 ml, 36 mmol), followed by heating and stirring at 90°C for 4 hours. The reaction solution was cooled to room temperature, and dichloromethane (200 ml) was added, followed by extraction with 1 N aqueous sodium hydroxide solution (150 ml×2 times) and water (150 ml×2 times). The obtained crude product was washed with hexane to obtain 2-phenoxypyridine (4.88 g, yield 65%) as a white solid. [Chemical 176]

The structure of the obtained compound was confirmed by NMR measurement. ¹ H-NMR (CDCl ₃ , 400MHz): 6.96-7.00 (m, 2H), 7.12 (t, 1H), 7.21 (d, 1H), 7.36 (t, 1H), 7.63 (d, 1H), 7.71 ( t, 1H), 8.15 (t, 1H). ¹³ C-NMR (CDCl ₃ , 101 MHz): 111.4 (1C), 116.7 (1C), 118.7 (1C), 123.9 (1C), 126.5 (1C), 128.7 ( 1C), 133.8 (1C), 139.6 (1C), 147.7 (1C), 151.1 (1C), 163.1 (1C).

Step 3 To 1,1'-oxybis(2-bromo-4-methylbenzene) (1.70 g, 4.8 mmol) and diethyl ether (30 ml) was added under nitrogen at -78°C butyllithium (6.00 ml, 9.6 mmol) and stirred at 0 °C for 1 h to prepare the lithium intermediate. On the other hand, boron tribromide (0.451 ml, 4.8 mmol) was added to 2-phenoxypyridine (0.812 g, 4.8 mmol) and toluene (20 ml) at room temperature under nitrogen atmosphere, and the mixture was heated at 90 °C. The boron intermediate was prepared under heating and stirring for 1 hour. This was added to the reaction solution containing the lithium intermediate at -78°C, and stirred at 0°C for 1 hour. The reaction solution was filtered through a silica gel short-path column, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, the compound of formula (10P-g-101) was obtained as a yellow solid by washing with hexane (0.710 g, yield 40%). [Chemical 177]

The structure of the obtained compound was confirmed by NMR measurement. ¹ H-NMR (CDCl ₃ , 400MHz): 2.13 (s, 6H), 6.80 (s, 2H), 6.93 (t, 1H), 6.98-7.08 (m, 6H), 7.18 (t, 2H), 7.23 ( d, 1H), 7.70 (d, 1H), 7.79 (t, 1H). ¹³ C-NMR (CDCl ₃ , 101 MHz): 20.8 (2C), 114.2 (1C), 115.0 (1C), 115.4 (2C), 118.9 (1C), 125.5 (1C), 126.7 (1C), 128.7 (2C), 130.9 (2C), 134.8 (2C), 135.1 (1C), 141.8 (1C), 144.4 (1C), 152.5 (1C), 154.9 (2C), 157.6 (1C).

Synthesis Example (3) Compound of formula (10P-gq-101-J11): 2,8'-dimethyl-11-phenyl-11H-5λ ⁴ ,6λ ⁴ -spiro[benzo[c]pyrido [2,1-f][1,5,2]diazaborin-6,10'-dibenzo[b,e][1,4]oxaborole] Synthesis [Chemical 178]

To diphenylamine (5.06 g, 30 mmol), palladium(II) acetate (65.3 mg, 0.29 mmol), 2-dicyclohexylphosphino-2',6'-dimethylacetate under nitrogen at room temperature Oxybiphenyl (SPhos: 0.128 g, 0.31 mmol), sodium tert-butoxide (3.48 g, 36 mmol) and toluene (150 ml) were added 2-bromopyridine (3.00 ml, 31 mmol), and the mixture was heated at 90 °C Heat and stir for 1 hour. The reaction solution was cooled to room temperature, filtered through a silica gel short-path column, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, by washing with hexane, N,N-diphenylpyridin-2-amine (6.52 g, yield 88%) was obtained as a white solid. [Chemical 179]

The structure of the obtained compound was confirmed by NMR measurement. ¹ H-NMR (CDCl ₃ , 400MHz): 6.74-6.79 (m, 2H), 7.12 (t, 2H), 7.18 (d, 4H), 7.32 (t, 4H), 7.44 (dd, 1H), 8.23 ( d, 1H). ¹³ C-NMR (CDCl ₃ , 101 MHz): 13.8 (1C), 116.1 (1C), 124.5 (2C), 126.3 (4C), 129.3 (4C), 137.2 (1C), 146.1 (2C) , 148.3 (1C), 159.0 (1C).

To 1,1'-oxybis(2-bromo-4-methylbenzene) (1.04 g, 2.9 mmol) and diethyl ether (20 ml) was added butyllithium under nitrogen at -78 °C (3.80 ml, 6.1 mmol) and stirred at 0 °C for 1 hour, thereby preparing the lithium intermediate. On the other hand, to N,N-diphenylpyridin-2-amine (0.724 g, 2.9 mmol) and toluene (20 ml) were added boron tribromide (0.285 ml, 3.0 mmol) at room temperature under nitrogen atmosphere ), and heated and stirred at 90° C. for 1 hour to prepare a boron intermediate, and then concentrated under reduced pressure until the volume of the reaction solution became about two-thirds of the whole. This was added to the reaction solution containing the lithium intermediate at -78°C, and stirred at 0°C for 1 hour. The reaction solution was filtered through a silica gel short-path column, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, the compound of formula (10P-gq-101-J11) was obtained as a yellow solid by washing with hexane (0.813 mg, yield 61%). [Chemical 180]

The structure of the obtained compound was confirmed by NMR measurement. ¹ H-NMR (CDCl ₃ , 400MHz): 2.20 (s, 6H), 6.27 (d, 1H), 6.38 (d, 1H), 6.57 (dd, 1H), 6.90 (dd, 1H), 6.94 (dd, 1H), 6.98-7.01 (m, 3H), 7.04-7.06 (m, 4H), 7.32 (dd, 1H), 7.51 (d, 2H), 7.64 (t, 1H), 7.70 (d, 1H), 7.75 (t, 2H). ¹³ C-NMR (CDCl ₃ , 126MHz): 21.0 (2C), 113.4 (1C), 114.3 (1C), 114.9 (1C), 115.2 (2C), 123.9 (1C), 125.5 (1C) ), 128.2 (2C), 129.5 (1C), 130.3 (2C), 130.7 (2C), 131.5 (2C), 134.8 (2C), 135.1 (1C), 138.8 (1C), 140.0 (1C), 141.3 (1C) ), 145.1 (1C), 151.2 (1C), 154.5 (2C).

Synthesis Example (4) Compound of formula (10P-gq-100-J11): 11-phenyl-11H-5λ ⁴ ,6λ ⁴ -spiro[benzo[c]pyrido[2,1-f][1 Synthesis of ,5,2]diazaborin-6,10'-dibenzo[b,e][1,4]oxaborohexene][Chem.181]

To 2,2'-oxybis(bromobenzene) (3.46 g, 10.6 mmol) and diethyl ether (30 ml) was added butyllithium (13.7 ml, 21.2 mmol) under nitrogen at -78 °C , and stirred at 0 °C for 1 hour, thereby preparing the lithium intermediate. On the other hand, to N,N-diphenylpyridin-2-amine (2.67 g, 10.8 mmol) and toluene (30 ml) were added boron tribromide (1.01 ml, 10.6 mmol) at room temperature under nitrogen atmosphere ), and heated and stirred at 90° C. for 1 hour to prepare a boron intermediate, and then concentrated under reduced pressure until the volume of the reaction solution became about two-thirds of the whole. This was added to the reaction solution containing the lithium intermediate at -78°C, and stirred at 0°C for 1 hour. The reaction solution was filtered through a silica gel short-path column, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, the compound (1.87 g, yield 42%) of Formula (10P-gq-100-J11) was obtained as a pale yellow solid by washing with hexane. [Chemical 182]

The structure of the obtained compound was confirmed by NMR measurement. ¹ H-NMR (CDCl ₃ , 500MHz): 6.26 (d, 1H), 6.37 (d, 1H), 6.57 (dd, 1H), 6.85-6.97 (m, 5H), 7.16 (d, 2H), 7.21 ( dd, 2H), 7.28 (d, 2H), 7.32 (dd, 1H), 7.49 (d, 2H), 7.64 (t, 1H), 7.70 (d, 1H), 7.74 (dd, 2H). ¹³ C- NMR (CDCl ₃ , 128 MHz): 113.4 (1C), 114.3 (1C), 114.8 (1C), 115.6 (2C), 122.3 (2C), 124.0 (1C), 125.6 (1C), 127.4 (2C), 129.5 ( 1C), 130.3 (2C), 131.5 (2C), 134.7 (2C), 135.1 (1C), 138.9 (1C), 139.9 (1C), 141.2 (1C), 145.0 (1C), 151.2 (1C), 156.3 ( 2C).

Synthesis Example (5) Compound of formula (10P-g-100): 5λ ⁴ ,6λ ⁴ -spiro[benzo[c]pyrido[2,1-f][1,5,2]diazaboron Synthesis of Heterohexene-6,10'-Dibenzo[b,e][1,4]oxaborohexene][Chem.183]

The first step was added to 2-bromophenol (6.30 ml, 59.7 mmol), potassium carbonate (10.3 g, 77.4 mmol) and 1,3-dimethyl-2-imidazolidinone (DMI: 150 ml) was added with 1-bromo-2-fluorobenzene (5.50 ml, 50.3 mmol), followed by stirring with heating at 200°C for 24 hours. The reaction solution was cooled to room temperature and toluene (200 ml) was added, followed by extraction with water (150 ml×3 times). The crude product was distilled at 70° C. at 4.6×10 ⁻² Pa, whereby 2,2′-oxybis(bromobenzene) (3.46 g, yield 23%) was obtained as a colorless liquid. [Chemical 184]

Step 2 To 2,2'-oxybis(bromobenzene) (3.52 g, 10.7 mmol) and diethyl ether (30 ml) was added butyllithium (14.0 ml) at -78°C under nitrogen at -78°C , and stirred at 0 °C for 1 hour, thereby preparing the lithium intermediate. On the other hand, boron tribromide (1.02 ml, 10.7 mmol) was added to 2-phenoxypyridine (1.75 g, 10.2 mmol) and toluene (30 ml) at room temperature under nitrogen atmosphere, and the mixture was heated at 90 °C. The boron intermediate was prepared under stirring for 1 hour under reduced pressure, and then concentrated under reduced pressure until the volume of the reaction solution became about two-thirds of the whole. This was added to the reaction solution containing the lithium intermediate at -78°C, and stirred at 0°C for 1 hour. The reaction solution was filtered through a silica gel short-path column, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, the compound of formula (10P-g-100) was obtained as a pale yellow solid by washing with hexane (1.84 g, yield 52%). [Chemical 185]

The structure of the obtained compound was confirmed by NMR measurement. ¹ H-NMR (CDCl ₃ , 500MHz): 6.89 (t, 2H), 6.92 (dd, 1H), 7.00 (d, 1H), 7.04-7.07 (m, 3H), 7.16-7.18 (m, 3H), 7.20-7.25 (m, 4H), 7.70 (d, 1H), 7.78 (t, 1H). ¹³ C-NMR (CDCl ₃ , 128MHz): 114.2 (1C), 115.1 (1C), 115.8 (2C), 118.9 (1C), 122.3 (2C), 125.6 (1C), 126.8 (1C), 127.9 (2C), 134.7 (2C), 135.0 (1C), 141.9 (1C), 144.2 (1C), 152.5 (1C), 156.7 (2C), 157.7 (1C).

Synthesis Example (6) Compound of formula (10P-gq-303-J11): 2-methyl-11-phenyl-11H-5λ ⁴ ,6λ ⁴ -spiro[benzo[c]pyrido[2,1 Synthesis of -f][1,5,2]diazaborin-6,10'-dibenzo[b,e][1,4]oxaborohexene][Chem.186] ]

To diphenylamine (9.31 g, 5 mmol), palladium(II) acetate (0.113 g, 0.51 mmol), SPhos (0.208 g, 0.51 mmol), sodium tert-butoxide (5.58 g) under nitrogen at room temperature g, 60 mmol) and toluene (150 ml) were added 2-bromo-4-methylpyridine (5.65 ml, 50 mmol), followed by stirring with heating at 90°C for 1 hour. The reaction solution was cooled to room temperature, filtered through a silica gel short-path column, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, 4-methyl-N,N-diphenylpyridin-2-amine (7.82 g, yield 61%) was obtained as a white solid by washing with hexane. [Chemical 187]

The structure of the obtained compound was confirmed by NMR measurement. ¹ H-NMR (CDCl ₃ , 400MHz): 2.19 (s, 3H), 6.58 (s, 1H), 6.63 (d, 1H), 7.11 (t, 2H), 7.16 (d, 4H), 7.31 (t, 4H), 8.10 (d, 1H). ¹³ C-NMR (CDCl ₃ , 101 MHz): 21.2 (1C), 114.4 (1C), 117.7 (1C), 124.3 (2C), 126.2 (4C), 129.3 (4C) , 146.3 (2C), 148.0 (1C), 148.4 (1C), 159.2 (1C).

To 2,2'-oxybis(bromobenzene) (3.27 g, 10.0 mmol) and diethyl ether (30 ml) was added butyllithium (12.9 ml, 20.0 mmol) under nitrogen at -78 °C , and stirred at 0 °C for 1 hour, thereby preparing the lithium intermediate. On the other hand, to 4-methyl-N,N-diphenylpyridin-2-amine (2.60 g, 10.0 mmol) and toluene (30 ml) were added boron tribromide ( 0.946 ml, 10.0 mmol), and heated and stirred at 90° C. for 1 hour to prepare a boron intermediate, and then concentrated under reduced pressure until the volume of the reaction solution became about two-thirds of the whole. This was added to the reaction solution containing the lithium intermediate at -78°C, and stirred at 0°C for 1 hour. The reaction solution was filtered through a silica gel short-path column, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, the compound of formula (10P-gq-303-J11) was obtained as a pale yellow solid by washing with hexane (0.52 g, yield 12%). [Chemical 188]

The structure of the obtained compound was confirmed by NMR measurement. ¹ H-NMR (CDCl ₃ , 400MHz): 2.17 (s, 3H), 6.13 (s, 1H), 6.21 (d, 1H), 6.39 (d, 1H), 6.85～6.95 (m, 5H), 7.15 ( d, 2H), 7.20 (t, 2H), 7.26 (d, 2H), 7.48 (d, 2H), 7.56 (d, 1H), 7.64 (t, 1H), 7.74 (t, 2H). ¹³ C- NMR (CDCl ₃ , 101 MHz): 21.5 (1C), 112.8 (1C), 114.5 (1C), 115.5 (2C), 116.7 (1C), 122.2 (2C), 123.7 (1C), 125.5 (1C), 127.3 ( 2C), 129.4 (1C), 130.4 (2C), 131.5 (2C), 134.7 (2C), 135.1 (1C), 140.0 (1C), 141.3 (1C), 144.3 (2C), 151.0 (1C), 156.3 ( 1C), 207.0 (1C).

Synthesis Example (7) Compound of formula (10P-gq-301-J11): 4-methyl-11-phenyl-11H-5λ ⁴ ,6λ ⁴ -spiro[benzo[c]pyrido[2,1 Synthesis of -f][1,5,2]diazaborin-6,10'-dibenzo[b,e][1,4]oxaborhexene][Chem.189] ]

To diphenylamine (9.38 g, 55 mmol), palladium(II) acetate (0.116 g, 0.52 mmol), SPhos (0.214 g, 0.52 mmol), sodium tert-butoxide (6.34 g) under nitrogen at room temperature g, 66 mmol) and toluene (200 ml) were added 2-bromo-6-methylpyridine (5.68 ml, 50 mmol), followed by stirring with heating at 90°C for 2 hours. The reaction solution was cooled to room temperature, filtered through a silica gel short-path column, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, 6-methyl-N,N-diphenylpyridin-2-amine (7.80 g, yield 60%) was obtained as a white solid by washing with hexane. [Chemical 190]

The structure of the obtained compound was confirmed by NMR measurement. ¹ H-NMR (CDCl ₃ , 400MHz): 2.38 (s, 3H), 6.50 (d, 1H), 6.66 (d, 1H), 7.09 (t, 2H), 7.16 (d, 4H), 7.28 (t, 4H), 7.33 (t, 1H). ¹³ C-NMR (CDCl ₃ , 101 MHz): 24.4 (1C), 111.4 (1C), 115.9 (1C), 123.9 (2C), 126.0 (4C), 129.1 (4C) , 137.5 (1C), 146.3 (2C), 157.2 (1C), 159.2 (1C).

To 2,2'-oxybis(bromobenzene) (9.97 g, 30 mmol) and diethyl ether (100 ml) was added butyllithium (38.2 ml, 60 mmol) under nitrogen at -78 °C , and stirred at 0 °C for 1 hour, thereby preparing the lithium intermediate. On the other hand, to 6-methyl-N,N-diphenylpyridin-2-amine (7.82 g, 30.0 mmol) and toluene (100 ml) were added boron tribromide ( 2.85 ml, 30.0 mmol), and heated and stirred at 90° C. for 1 hour to prepare a boron intermediate, and then concentrated under reduced pressure until the volume of the reaction solution became about two-thirds of the whole. This was added to the reaction solution containing the lithium intermediate at -78°C, and stirred at 0°C for 1 hour. The reaction solution was filtered through a silica gel short-path column, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, the compound of formula (10P-gq-301-J11) was obtained as a pale yellow solid by washing with hexane (3.08 g, yield 24%). [Chemical 191]

The structure of the obtained compound was confirmed by NMR measurement. ¹ H-NMR (CDCl ₃ , 400MHz): 2.01 (s, 3H), 5.99 (dt, 1H), 6.41 (d, 1H), 6.48 (d, 1H), 6.71～6.76 (m, 3H), 6.88 ( t, 2H), 7.09～7.10 (m, 4H), 7.14 (t, 2H), 7.31 (dd, 1H), 7.45 (d, 2H), 7.62 (t, 1H), 7.73 (t, 2H). ¹³ C-NMR (CDCl ₃ , 101MHz): 25.4 (1C), 112.4 (1C), 113.8 (1C), 115.3 (2C), 118.5 (1C), 122.4 (2C), 123.7 (1C), 124.9 (1C), 126.8 (2C), 129.2 (1C), 130.3 (2C), 131.6 (2C), 133.3 (2C), 135.1 (1C), 138.1 (1C), 139.0 (1C), 141.2 (1C), 153.4 (1C), 154.9 (2C), 156.1 (1C).

Synthesis Example (8) Compound of formula (10P-gq-342-J11): 3,11-diphenyl-11H-5λ ⁴ ,6λ ⁴ -spiro[benzo[c]pyrido[2,1-f Synthesis of ][1,5,2]diazaborin-6,10'-dibenzo[b,e][1,4]oxaborohexene][Chem.192]

To phenylboronic acid (2.93 g, 24 mmol), tetrakis(triphenylphosphine)palladium(0) (Pd( _PPh3 ) ₄ : 1.74 g, 1.5 mmol), potassium carbonate (8.30 mmol) under nitrogen at room temperature g, 60 mmol), water (80 ml) and 1,4-dioxane (80 ml) were added 5-bromo-2-chloropyridine (3.87 g, 20 mmol) and stirred at room temperature for 45 hours. After the solvent of the reaction solution was distilled off under reduced pressure, extraction was performed with toluene (100 ml×3 times), and the solvent was distilled off under reduced pressure to obtain a crude product. Then, 2-chloro-5-phenylpyridine (1.69 g, yield 44%) was obtained as a white solid by washing|cleaning with hexane, and purifying with a silica gel short-path column. [Chemical 193]

To diphenylamine (0.934 g, 5.5 mmol), palladium(II) acetate (22.4 mg, 0.10 mmol), SPhos (82.2 mg, 0.20 mmol), sodium tert-butoxide (0.579 g, 6.0 mmol) and o-xylene (20 ml) were added 2-chloro-5-phenylpyridine (0.948 g, 5.0 mmol), and the mixture was heated and stirred at 130 °C for 6 hours. The reaction solution was filtered through a magnesium silicate short-path column, and the solvent was distilled off under reduced pressure to obtain a crude product. After that, it was purified with a silica gel short-path column, whereby N,N,5-triphenylpyridin-2-amine (1.55 g, yield 96%) was obtained as a white solid. [Chemical 194]

The structure of the obtained compound was confirmed by NMR measurement. ¹ H-NMR (CDCl ₃ , 400MHz): 6.83 (d, 1H), 7.15 (t, 2H), 7.22 (d, 4H), 7.34 (m, 5H), 7.43 (t, 2H), 7.53 (d, 2H), 7.67 (dd, 1H), 8.48 (s, 1H). ¹³ C-NMR (CDCl ₃ , 101 MHz): 113.6 (1C), 124.6 (2C), 126.3 (4C), 126.4 (2C), 127.2 ( 1C), 128.9 (2C), 129.1 (1C), 129.4 (4C), 135.8 (1C), 138.0 (1C), 146.0 (2C), 146.5 (1C), 158.2 (1C).

To 2,2'-oxybis(bromobenzene) (1.70 g, 5.2 mmol) and diethyl ether (20 ml) was added butyllithium (6.50 ml, 10 mmol) under nitrogen at -78 °C , and stirred at 0 °C for 3 hours, thereby preparing the lithium intermediate. On the other hand, to N,N,5-triphenylpyridin-2-amine (1.65 g, 5.1 mmol) and toluene (30 ml) were added boron tribromide (0.480 ml, 5.1 mmol), and heated and stirred at 90°C for 4 hours to prepare a boron intermediate, and then concentrated under reduced pressure at 0°C until the volume of the reaction solution became about one-third of the whole. It was added to the reaction solution containing the lithium intermediate at -78°C, and stirred at 0°C for 1 hour and at room temperature for 19 hours. The reaction solution was filtered through a silica gel short-path column, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, the compound (0.548 g, yield 21%) of formula (10P-gq-342-J11) was obtained as a pale yellow solid by refinement|purification using a silica gel short-path column. [Chemical 195]

The structure of the obtained compound was confirmed by NMR measurement. ¹ H-NMR (CDCl ₃ , 400MHz): 6.28 (d, 1H), 6.47 (d, 1H), 6.91 (dd, 1H), 6.95 (dd, 1H), 6.97 (dd, 2H), 7.01 (dd, 1H), 7.10 (dd, 2H), 7.18 (dd, 2H), 7.22 (m, 2H), 7.26 (m, 1H), 7.29 (d, 2H), 7.33 (dd, 2H), 7.53 (dd, 2H) ), 7.55 (dd, 1H), 7.65 (t, 1H), 7.76 (t, 2H), 7.92 (s, 1H). ¹³ C-NMR (CDCl ₃ , 101MHz): 113.7 (1C), 114.4 (1C) , 115.7 (2C), 122.3 (2C), 124.0 (1C), 125.7 (1C), 126.0 (2C), 127.5 (2C), 128.0 (1C), 128.1 (1C), 129.1 (2C), 129.5 (1C) , 130.2 (2C), 131.5 (2C), 134.6 (2C), 135.1 (1C), 135.3 (1C), 137.7 (1C), 140.0 (1C), 141.2 (1C), 142.5 (1C), 150.2 (1C) , 156.4 (2C).

Synthesis example (9) Compound of formula (10P-gq-23-J11): 5λ ⁴ ,10λ ⁴ -spiro[dibenzo[b,e][1,4]oxaborole-10, Synthesis of 6'-pyrido[1',2':1,6][1,5,2]diazaborino[3,4,5-kl]phenoxazine][Chem 196 ]

To phenoxazine (6.00 g, 33 mmol), palladium(II) acetate (79.6 mg, 0.35 mmol), SPhos (0.122 g, 0.30 mmol), sodium tertbutoxide (3.88 g) under nitrogen at room temperature , 40 mmol) and toluene (100 ml) were added 2-bromopyridine (2.90 ml, 30 mmol), and the mixture was heated and stirred at 60 °C for 2 hours. The reaction solution was cooled to room temperature, filtered through a silica gel short-path column, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, by washing with hexane, the phenoxazine derivative (6.15 g, yield 79%) was obtained as a white solid. [Chemical 197]

¹ H-NMR (CDCl ₃ , 400MHz): 6.42 (d, 2H), 6.69-6.81 (m, 6H), 7.28 (dd, 1H), 7.36 (d, 1H), 7.84 (dt, 1H), 8.68 ( dd, 1H). ¹³ C-NMR (CDCl ₃ , 101 MHz): 115.8 (2C), 116.0 (2C), 122.1 (1C), 122.3 (1C), 122.7 (1C), 123.2 (2C), 132.9 (2C) , 139.4 (1C), 145.6 (2C), 150.6 (1C), 153.9 (1C).

To 2,2'-oxybis(bromobenzene) (3.28 g, 10.0 mmol) and diethyl ether (25 ml) was added butyllithium (12.7 ml, 19.9 mmol) under nitrogen at -78 °C , and stirred at 0 °C for 2 hours, thereby preparing the lithium intermediate. On the other hand, boron tribromide (1.00 ml, 10.5 mmol) was added to the phenoxazine derivative (2.63 g, 10.1 mmol) and toluene (30 ml) at room temperature under nitrogen atmosphere, and the mixture was heated at 90°C. The boron intermediate was prepared by heating and stirring for 4 hours, and then concentrated under reduced pressure until the volume of the reaction solution became about two-thirds of the whole. This was added to the reaction solution containing the lithium intermediate at -78°C, and stirred at 0°C for 1 hour. The reaction solution was filtered through a silica gel short-path column, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, the compound of formula (10P-gq-23-J11) was obtained as a yellow solid by washing with hexane (3.30 g, yield 75%). [Chemical 198]

¹ H-NMR (CDCl ₃ , 400MHz): 6.76-6.80 (m, 3H), 6.88 (dd, 1H), 7.00-7.06 (m, 2H), 7.08-7.12 (m, 3H), 7.21-7.27 (m , 5H), 7.30 (d, 1H), 7.36 (dt, 1H), 7.60 (dt, 1H), 7.66-7.70 (m, 2H). ¹³ C-NMR (CDCl ₃ , 101MHz): 113.2 (1C), 114.0 (1C), 115.9 (1C), 116.1 (1C), 117.3 (1C), 118.4 (1C), 118.9 (1C), 122.3 (1C), 122.4 (1C), 123.6 (1C), 126.0 (1C), 126.7 (1C), 127.6 (1C), 128.3 (1C), 128.3 (1C), 128.5 (1C), 129.0 (1C), 133.3 (1C), 135.2 (1C), 139.5 (1C), 145.0 (1C), 145.1 (1C), 149.4 (1C), 149.7 (1C), 155.3 (1C), 158.7 (1C).

The compound of the present invention and its polymer compound can be synthesized by appropriately changing the compound of the raw material and by the method according to the above-mentioned synthesis example.

<Evaluation of basic physical properties> When evaluating the absorption characteristics and light emission characteristics (fluorescence and phosphorescence) of the compound to be evaluated, there are cases where the compound is dissolved in a solvent and the evaluation is performed in a solvent, and the evaluation is performed in a thin film state. Furthermore, in the case of evaluating in a thin film state, there are cases in which the compound is only thinned and evaluated according to the usage of the compound in the organic EL device (one-component vapor deposition film), and the compound is dispersed in an appropriate matrix. In the case of evaluation by adding a thin film (co-evaporated film) to the material.

Fabrication of Dispersion Films As the matrix material, commercially available PMMA (polymethyl methacrylate) or the like can be used. A thin film sample dispersed in PMMA can be prepared, for example, by dissolving PMMA and the compound to be evaluated in toluene, and then forming a thin film on a quartz transparent support substrate (10 mm×10 mm) by spin coating. .

Production of One-Component Vapor Deposition Film The method for producing a one-component vapor deposition film will be described below. A transparent support substrate made of quartz or glass was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum-made vapor deposition boat to which the compound to be evaluated was added was mounted. Next, the vacuum chamber was depressurized to 5×10 ^-4 Pa, and the vapor deposition boat containing the compound was heated and vapor-deposited so as to have an appropriate film thickness to form a one-component vapor-deposited film.

Preparation of Co-evaporated Film The method for preparing a thin film sample when the matrix material is the host material will be described below. A transparent support substrate made of quartz or glass was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum-made vapor deposition boat containing a host material was mounted, and a dopant was added. A boat for vapor deposition made of molybdenum as the agent material. Next, the vacuum chamber was depressurized to 5×10 ^-4 Pa, and the boat for vapor deposition to which the host material was added and the boat for vapor deposition to which the dopant material was added were simultaneously heated to obtain a suitable film. It vapor-deposits in a thick manner to form a mixed thin film of the host material and the dopant material. The evaporation rate is controlled according to the set weight ratio of the host material to the dopant material.

Evaluation of Absorption and Luminescence Characteristics The absorption spectrum was measured using an ultraviolet-visible-near-infrared spectrophotometer (Shimadzu Corporation, UV-2600). In addition, the measurement of the fluorescence spectrum or the phosphorescence spectrum was performed using a spectrofluorophotometer (Hitachi-hightech Co., Ltd., F-7000). For the measurement of the fluorescence spectrum, photoluminescence is measured by excitation with an appropriate excitation wavelength at room temperature. The measurement of the phosphorescence spectrum was performed in a state (temperature 77 K) in which the sample was immersed in liquid nitrogen using the attached cooling unit. In order to observe the phosphorescence spectrum, an optical chopper was used to adjust the delay time from the irradiation of the excitation light until the start of the measurement. The sample is excited at the appropriate excitation wavelength and photoluminescence is measured.

<Evaluation as an organic EL element> Hereinafter, evaluation as an organic EL device was performed using the compound of the present invention.

<Example 1> The transparent support substrate made of glass on which ITO was vapor-deposited and the molybdenum-made vapor deposition boat to which the compound (10P-gq-101-J11) was added were fixed to a commercially available vapor deposition apparatus (Showa Vacuum (Showa Vacuum (Showa Vacuum). Co., Ltd.), the vacuum chamber was depressurized to 5×10 ^-4 Pa, and the compound (10P-gq-101-J11) was heated and vapor-deposited until it became a film thickness of 50 nm to form a one-component vapor Coating. The photoelectron yield spectrum, the absorption spectrum in the visible region, the fluorescence spectrum, and the phosphorescence spectrum of the obtained single-component vapor-deposited film were measured. The ionization potential (Ip) is obtained from the photoelectron yield spectrum, and the electron affinity (Ea) is obtained from the energy gap (Eg) obtained from the end on the long wavelength side of the fluorescence peak and the ionization potential. The singlet energy (S ₁ ) was obtained from the peak top of the fluorescence spectrum, and the triplet energy (T ₁ ) was obtained from the peak top of the phosphorescence spectrum. The results are shown as differences with respect to the compound mCBP used in Comparative Example 1 (Table 1). Furthermore, unless otherwise specified, the singlet energy (S ₁ ) and the triplet energy (T ₁ ) are the first excited singlet energy and the first excited triplet energy. In addition, DE _ST is the difference between the singlet energy and the triplet energy.

<Example 2> A single-component vapor deposition film was produced by the method according to Example 1, except that the compound (10P-gq-101-J11) was replaced with the compound (10P-g-101), and each spectrum was measured. Moreover, the free potential (Ip) etc. were calculated|required from each spectrum, and it shows in Table 1 as the difference with respect to the comparative example 1.

<Comparative Example 1> The same method as in Example 1 was used except that the compound (10P-gq-101-J11) was replaced by the compound mCBP (3,3'-bis(9H-carbazolyl-9-yl)biphenyl). method to produce a single-component vapor-deposited film, and measure each spectrum. In addition, free potential (Ip) etc. were calculated|required from each spectrum, and are shown in Table 1. Comparative Example 1 is a reference with respect to Example 1, Example 2, and Comparative Example 2. [Chemical 199]

<Comparative example 2> Except having replaced the compound (10P-gq-101-J11) with compound CBP, a single-component vapor deposition film was produced by the method according to Example 1, and each spectrum was measured. Moreover, the free potential (Ip) etc. were calculated|required from each spectrum, and it shows in Table 1 as the difference with respect to the comparative example 1. [Chemical 200]

[Table 1]

As mentioned above, some of the compounds of the present invention have been evaluated for basic physical properties, and have high triplet excitation energy (T ₁ ), negative and large DE _ST , etc. However, other compounds that have not been evaluated also have the same basic skeleton and Compounds having similar structures as a whole can be similarly understood as having excellent properties for those skilled in the art.

<Production and characteristic evaluation of organic EL element> For example, the organic EL elements of Example 3, Example 4, and Comparative Example 3 can be produced with the layer configurations shown in Table 2.

[Table 2]

In Table 2, "HAT-CN" is 1,4,5,8,9,12-hexaazatriphenylhexacarbonitrile, and "TBB" is N ⁴ , N ⁴ , N ^4' , N ^4' -Tetrakis([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine, "TcTa" is tris(4-carbazolyl- 9-ylphenyl)amine, "CBP" is 4,4'-bis(9H-carbazolyl-9-yl)-1,1'-biphenyl, "Ir(PPy) ₃ " is tris(2- Phenylpyridine) iridium(III), "TPBi" is 1,3,5-tris(1-phenyl-1H-benzo[d]imidazol-2-yl)benzene. The chemical structures are shown below.

[Chemical 201]

<Example 3><Device using compound (10P-g-101) as host material for light-emitting layer> ITO film formed by sputtering was ground to a size of 26 mm×28 mm×0.7 mm to 50 nm A glass substrate (opto science (share)) was used as a transparent support substrate. The transparent support substrate was fixed on a substrate holder of a commercially available vapor deposition apparatus (Changzhou Sangyo Co., Ltd.), and HAT-CN, TBB, TcTa, compound (10P-g-101), and Ir(PPy) were added to the substrate. ) _3. TPBi and LiF tantalum vapor deposition crucibles and aluminum nitride vapor deposition crucibles added with aluminum.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 2.0×10 ^-4 Pa. First, HAT-CN was heated and vapor-deposited so as to have a film thickness of 5 nm, and then TBB was heated so that the film thickness became 5 nm. 65 nm was vapor-deposited, and TcTa was further heated and vapor-deposited so that the film thickness was 10 nm, thereby forming a hole injection layer and a hole transport layer consisting of three layers. Next, the compound (10P-g-101) was heated simultaneously with Ir(PPy) ₃ and vapor-deposited so that the film thickness might be 30 nm to form a light-emitting layer. The vapor deposition rate was adjusted so that the weight ratio of the compound (10P-g-101) and Ir(PPy) ₃ would be approximately 95 to 5. Next, TPBi was heated and vapor-deposited so as to have a film thickness of 50 nm to form an electron transport layer. The deposition rate of each layer up to this point was 0.01 nm/sec to 1 nm/sec. Then, LiF is heated and vapor-deposited at a vapor deposition rate of 0.01 nm/sec to 0.1 nm/sec so that the film thickness becomes 1 nm, and then, aluminum is heated so that the film thickness becomes 100 nm/sec. An organic EL element was obtained by vapor-depositing at a vapor-deposition rate of 0.1 nm/sec to 2 nm/sec in a nm manner to form a cathode.

When the ITO electrode is used as the anode and the LiF/aluminum electrode is used as the cathode, and a DC voltage is applied, green light emission can be obtained.

<Example 4> <Device using compound (10P-gq-101-J11) as host material for light-emitting layer> An organic EL element was obtained by the method according to Example 3, except that the compound (10P-g-101) as the host material of the light-emitting layer was replaced with the compound (10P-gq-101-J11). Also, by applying a DC voltage in the same manner, light emission can be obtained.

<Comparative Example 3> <Device using compound CBP as host material for light-emitting layer> An organic EL element was obtained by the method according to Example 3, except that the compound (10P-g-101), which is the host material of the light-emitting layer, was replaced with the compound CBP.

In addition, for example, the organic EL elements of Examples 5 and 6 can be produced with the layer configurations shown in Table 3.

[table 3]

<Example 5><Element using compound (10P-g-101) for electron transport layer> Glass of 26 mm × 28 mm × 0.7 mm with ITO formed by sputtering polished to 50 nm The substrate (opto science (share)) serves as a transparent support substrate. The transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (Changzhou Sangyo Co., Ltd.), and HAT-CN, TBB, TcTa, CBP, Ir(PPy) ₃ , compound (10P- g-101) and LiF-made tantalum vapor deposition crucible and aluminum-filled aluminum nitride vapor deposition crucible.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 2.0×10 ^-4 Pa. First, HAT-CN was heated and vapor-deposited so as to have a film thickness of 10 nm, and then TBB was heated so that the film thickness became 10 nm. A hole injection layer and a hole transport layer consisting of three layers were formed by vapor-depositing so as to be 20 nm, and further heating TcTa and vapor-depositing so that the film thickness became 10 nm. Next, CBP and Ir(PPy) ₃ were heated at the same time, and vapor-deposited so that the film thickness might be 30 nm to form a light-emitting layer. The vapor deposition rate was adjusted so that the weight ratio of CBP and Ir(PPy) ₃ would be approximately 95 to 5. Next, the compound (10P-g-101) was heated and vapor-deposited so that the film thickness might be 50 nm to form an electron transport layer. The deposition rate of each layer up to this point was 0.01 nm/sec to 1 nm/sec. Then, LiF is heated and vapor-deposited at a vapor deposition rate of 0.01 nm/sec to 0.1 nm/sec so that the film thickness becomes 1 nm, and then, aluminum is heated so that the film thickness becomes 100 nm/sec. An organic EL element was obtained by vapor-depositing at a vapor-deposition rate of 0.1 nm/sec to 2 nm/sec in a nm manner to form a cathode.

When the ITO electrode is used as the anode and the LiF/aluminum electrode is used as the cathode, and a DC voltage is applied, green light emission can be obtained.

<Example 6> <Element using compound (10P-gq-101-J11) for electron transport layer> An organic EL element was obtained by the method according to Example 5, except that the compound (10P-g-101) of the electron transport layer was replaced with the compound (10P-gq-101-J11). Also, by applying a DC voltage in the same manner, light emission can be obtained.

In addition, for example, the organic EL elements of Example 7, Example 8, and Comparative Example 4 can be produced with the layer configurations shown in Table 4.

[Table 4]

In Table 4, "Firpic" is bis[2-(4,6-difluorophenyl)pyridine-N,C2](picolino)iridium(III). The chemical structures are shown below. [Chemical 202]

<Example 7> <Device using compound (10P-g-101) as host material for light-emitting layer> A glass substrate of 26 mm × 28 mm × 0.7 mm (opto science (stock)) was used as a transparent support substrate by polishing the ITO formed into a film by sputtering to 50 nm. The transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (Changshu Sangyo Co., Ltd.), and HAT-CN, TBB, TcTa, compound (10P-g-101), Fripic, and TPBi were added to each. and LiF tantalum vapor deposition crucibles and aluminum nitride vapor deposition crucibles filled with aluminum.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 2.0×10 ^-4 Pa. First, HAT-CN was heated and vapor-deposited so as to have a film thickness of 5 nm, and then TBB was heated so that the film thickness became 5 nm. 65 nm was vapor-deposited, and TcTa was further heated and vapor-deposited so that the film thickness was 10 nm, thereby forming a hole injection layer and a hole transport layer consisting of three layers. Next, the compound (10P-g-101) was heated simultaneously with Firpic, and vapor-deposited so that the film thickness might be 30 nm to form a light-emitting layer. The vapor deposition rate was adjusted so that the weight ratio of the compound (10P-g-101) and Firpic would be approximately 95 to 5. Next, TPBi was heated and vapor-deposited so as to have a film thickness of 50 nm to form an electron transport layer. The vapor deposition rate of each layer is 0.01 nm/sec to 1 nm/sec. Then, LiF is heated and vapor-deposited at a vapor deposition rate of 0.01 nm/sec to 0.1 nm/sec so that the film thickness becomes 1 nm, and then, aluminum is heated so that the film thickness becomes 100 nm/sec. An organic EL element was obtained by vapor-depositing at a vapor-deposition rate of 0.1 nm/sec to 2 nm/sec in a nm manner to form a cathode.

When the ITO electrode is used as the anode and the LiF/aluminum electrode is used as the cathode, and a DC voltage is applied, blue light emission can be obtained.

<Example 8> <Device using compound (10P-gq-101-J11) as host material for light-emitting layer> An organic EL element was obtained by the method according to Example 7, except that the compound (10P-g-101) as the host material of the light-emitting layer was replaced with the compound (10P-gq-101-J11). When a DC voltage is applied to both electrodes, blue light emission can be obtained.

<Comparative Example 4> <Device using compound mCBP as host material for light-emitting layer> An organic EL element was obtained by the method according to Example 7, except that the compound (10P-g-101) as the host material of the light-emitting layer was replaced with the compound mCBP. When a DC voltage is applied to both electrodes, blue light emission can be obtained.

Next, the organic EL elements of Examples 9 to 16 and Comparative Examples 5 to 8 were produced with the layer configurations shown in Table 5.

[table 5]

In Table 5, "NPD" is N,N'-bis(naphthylene-1-yl)-N,N'-bis(phenyl)benzene, and "mCP" is 1,3-bis(carbazolyl- 9-yl)benzene, "DABNA2" is 9-[1,1'-biphenyl]-3-yl-N,N,5,11-tetraphenyl-5,9-dihydro-5,9- Diaza-13b-boraznaphtho[3,2,1-de]anthracene-3-amine, "DABNA3" is N,N,5,9-tetraphenyl-5,9-dihydro-5, 9-diaza-13b-boraznaphtho[3,2,1-de]anthracene-7-amines are dimers of a benzene ring shared with each other, "4CzIPN" is 2,4,5,6-tetra( 9H-carbazol-9-yl) isophthalonitrile, "CzBPCN" is 4,4',6,6'-tetrakis(9H-carbazol-9-yl)-[1,1'-biphenyl ]-3,3'-dicarbonitrile, "TSPO1" is diphenyl-4-triphenylsilylphenylphosphine oxide. The chemical structures are shown below.

[Chemical 203]

<Example 9> <Element using compound (10P-g-101) as host and DABNA2 as dopant> A glass substrate of 26 mm × 28 mm × 0.7 mm (opto science (stock)) was used as a transparent support substrate by polishing the ITO formed into a film by sputtering to 50 nm. The transparent support substrate was fixed on a substrate holder of a commercially available vapor deposition apparatus (Changzhou Sangyo Co., Ltd.), and NPD, TcTa, mCP, compound (10P-g-101), DABNA2, TSPO1, and LiF were added to the substrate. tantalum vapor deposition crucible and aluminum nitride vapor deposition crucible added with aluminum.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was decompressed to 2.0×10 ^-4 Pa, first, NPD was heated and vapor-deposited so that the film thickness would be 40 nm, and then TcTa was heated so that the film thickness would be 15 nm. Vapor deposition was performed in a manner of , and the mCP was further heated and vapor deposited so that the film thickness was 15 nm, thereby forming a hole injection layer and a hole transport layer including three layers. Next, the compound (10P-g-101) and DABNA2 were heated at the same time, and vapor-deposited so that the film thickness might be 20 nm to form a light-emitting layer. The vapor deposition rate was adjusted so that the weight ratio of the compound (10P-g-101) to DABNA2 was approximately 98 to 2. Next, TSPO1 was heated and vapor-deposited so that the film thickness might be 40 nm to form an electron transport layer. The vapor deposition rate of each layer is 0.01 nm/sec to 1 nm/sec. Then, LiF is heated and vapor-deposited at a vapor deposition rate of 0.01 nm/sec to 0.1 nm/sec so that the film thickness becomes 1 nm, and then, aluminum is heated so that the film thickness becomes 100 nm/sec. An organic EL element was obtained by vapor-depositing at a vapor-deposition rate of 0.1 nm/sec to 2 nm/sec in a nm manner to form a cathode.

When the ITO electrode is used as the anode and the LiF/Al electrode is used as the cathode, and a DC voltage is applied, blue emission with a peak at about 466 nm can be obtained. Under the driving voltage of 4.10 V and the current density of 0.05 mA/cm ² , the luminous brightness was 10 cd/m ² , and the external quantum efficiency at this time was 18.2%.

<Example 10><The element using the compound (10P-gq-101-J1) as the host and DABNA2 as the dopant> The compound (10P-g-101) as the host material of the light-emitting layer was replaced with Except for the compound (10P-gq-101-J11), an organic EL element was obtained by the method according to Example 9. When a DC voltage is applied to both electrodes, blue light emission can be obtained. Under the driving voltage of 3.82 V and the current density of 0.04 mA/cm ² , the luminous brightness was 10 cd/m ² , and the external quantum efficiency was 22.6%. Under the driving voltage of 4.70 V and the current density of 0.66 mA/cm ² , the luminous brightness was 100 cd/m ² , and the external quantum efficiency at this time was 15.3%. Compared with Comparative Example 5, the external quantum efficiencies at both 10 cd/m ² and 100 cd/m ² were excellent.

<Comparative Example 5><The device using the compound mCBP as the host and DABNA2 as the dopant> In addition to replacing the compound (10P-g-101) as the host material of the light-emitting layer with the compound mCBP, use According to the method of Example 5, an organic EL element was obtained. When a DC voltage was applied to both electrodes, blue light emission with a peak at about 467 nm was obtained. Under the driving voltage of 3.65 V and the current density of 0.06 mA/cm ² , the luminous brightness was 10 cd/m ² , and the external quantum efficiency at this time was 18.2%. Under the driving voltage of 5.13 V and the current density of 0.92 mA/cm ² , the luminous brightness was 100 cd/m ² , and the external quantum efficiency at this time was 11.4%.

<Example 11> <Element using compound (10P-g-101) as host and DABNA3 as dopant> An organic EL element was obtained by the method according to Example 9, except that the compound DABNA2, which is the dopant material of the light-emitting layer, was replaced with the compound DABNA3. When a DC voltage is applied to both electrodes, blue light emission can be obtained.

<Example 12> <Element using compound (10P-gq-101-J11) as host and DABNA3 as dopant> In addition to replacing the compound (10P-g-101) as the host material of the light-emitting layer with the compound (10P-gq-101-J11), and replacing the compound DABNA2 as the dopant material with the compound DABNA3, use the basis The method of Example 9 obtained an organic EL element. When a DC voltage is applied to both electrodes, blue light emission can be obtained.

<Comparative Example 6> <Element using compound mCBP as host and DABNA3 as dopant> Organic EL was obtained by the method according to Example 9, except that the compound (10P-g-101) as the host material of the light-emitting layer was replaced by the compound mCBP, and the compound DABNA2 as the dopant material was replaced by the compound DABNA3 element. When a DC voltage is applied to both electrodes, blue light emission can be obtained.

<Example 13> <Element using compound (10P-g-101) as host and 4CzIPN as dopant> An organic EL element was obtained by the method according to Example 9, except that the compound DABNA2, which is the dopant material of the light-emitting layer, was replaced with the compound 4CzIPN. When a DC voltage is applied to both electrodes, green light emission can be obtained.

<Example 14> <Element using compound (10P-gq-101-J11) as host and 4CzIPN as dopant> In addition to replacing the compound (10P-g-101) as the host material of the light-emitting layer with the compound (10P-gq-101-J11), and replacing the compound DABNA2 as the dopant material with the compound 4CzIPN, the basis The method of Example 9 obtained an organic EL element. When a DC voltage is applied to both electrodes, green light emission can be obtained.

<Comparative Example 7> <Element using compound mCBP as host and 4CzIPN as dopant> In addition to replacing the compound (10P-g-101) as the host material of the light-emitting layer with the compound mCBP, and replacing the compound DABNA2 as the dopant material with the compound 4CzIPN, organic EL was obtained by the method according to Example 9. element. When a DC voltage is applied to both electrodes, green light emission can be obtained.

<Example 15> <Element using compound (10P-g-101) as host and CzBPCN as dopant> An organic EL element was obtained by the method according to Example 9, except that the compound DABNA2, which is the dopant material of the light-emitting layer, was replaced with the compound CzBPCN. When a DC voltage is applied to both electrodes, blue light emission can be obtained.

<Example 16> <Element using compound (10P-gq-101-J11) as host and CzBPCN as dopant> In addition to replacing the compound (10P-g-101) as the host material of the light-emitting layer with the compound (10P-gq-101-J11), and replacing the compound DABNA2 as the dopant material with the compound CzBPCN, the basis The method of Example 9 obtained an organic EL element. When a DC voltage is applied to both electrodes, blue light emission can be obtained.

<Comparative Example 8> <A device using the compound mCBP as a host and CzBPCN as a dopant> Organic EL was obtained by the method according to Example 9, except that the compound (10P-g-101) as the host material of the light-emitting layer was replaced with the compound mCBP, and the compound DABNA2 as the dopant material was replaced with the compound CzBPCN. element. When a DC voltage is applied to both electrodes, blue light emission can be obtained.

Next, the organic EL element of Example 17 can be produced with the layer configuration shown in Table 6.

[Table 6]

<Example 17> <Element using compound (10P-gq-100-J11) as host and DABNA2 as dopant> A glass substrate of 26 mm × 28 mm × 0.7 mm (opto science (stock)) was used as a transparent support substrate by polishing the ITO formed into a film by sputtering to 50 nm. The transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (Changzhou Sangyo Co., Ltd.), and each of NPD, TcTa, mCP, compound (10P-gq-100-J11), DABNA2, and TSPO1 was installed. and LiF tantalum vapor deposition crucibles and aluminum nitride vapor deposition crucibles filled with aluminum.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was decompressed to 2.0×10 ^-4 Pa, first, NPD was heated and vapor-deposited so that the film thickness would be 40 nm, and then TcTa was heated so that the film thickness would be 15 nm. Vapor deposition was performed in a manner of , and the mCP was further heated and vapor deposited so that the film thickness was 15 nm, thereby forming a hole injection layer and a hole transport layer including three layers. Next, the compound (10P-gq-100-J11) was heated simultaneously with DABNA2, and vapor-deposited so that the film thickness might be 20 nm to form a light-emitting layer. The vapor deposition rate was adjusted so that the weight ratio of the compound (10P-gq-100-J11) to DABNA2 was approximately 98 to 2. Next, TSPO1 was heated and vapor-deposited so that the film thickness might be 40 nm to form an electron transport layer. The vapor deposition rate of each layer is 0.01 nm/sec to 1 nm/sec. Then, LiF is heated and vapor-deposited at a vapor deposition rate of 0.01 nm/sec to 0.1 nm/sec so that the film thickness becomes 1 nm, and then, aluminum is heated so that the film thickness becomes 100 nm/sec. An organic EL element was obtained by vapor-depositing at a vapor-deposition rate of 0.1 nm/sec to 2 nm/sec in a nm manner to form a cathode.

When the ITO electrode was used as the anode and the LiF/aluminum electrode was used as the cathode, and a DC voltage was applied, blue emission with a peak at about 469 nm was obtained. Under the driving voltage of 4.00 V and the current density of 0.04 mA/cm ² , the luminous brightness was 10 cd/m ² , and the external quantum efficiency at this time was 25.0%. Under the driving voltage of 4.84 V and the current density of 0.48 mA/cm ² , the luminous brightness was 100 cd/m ² , and the external quantum efficiency at this time was 21.0%.

Next, the organic EL elements of Example 18, Example 19, Comparative Example 9, and Comparative Example 10 were fabricated with the layer configurations shown in Table 7.

[Table 7]

<Example 18> <Element using compound (10P-gq-100-J11) as host and DABNA2 as dopant> A glass substrate of 26 mm × 28 mm × 0.7 mm (opto science (stock)) was used as a transparent support substrate by polishing the ITO formed into a film by sputtering to 50 nm. The transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (Changzhou Sangyo Co., Ltd.), and each of NPD, TcTa, mCP, compound (10P-gq-100-J11), DABNA2, and TSPO1 was installed. and LiF tantalum vapor deposition crucibles and aluminum nitride vapor deposition crucibles filled with aluminum.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was decompressed to 2.0×10 ^-4 Pa, first, NPD was heated and vapor-deposited so that the film thickness would be 40 nm, and then TcTa was heated so that the film thickness would be 15 nm. Vapor deposition was performed in a manner of , and the mCP was further heated and vapor deposited so that the film thickness was 15 nm, thereby forming a hole injection layer and a hole transport layer including three layers. Next, the compound (10P-gq-100-J11) was heated simultaneously with DABNA2, and vapor-deposited so that the film thickness might be 20 nm to form a light-emitting layer. The vapor deposition rate was adjusted so that the weight ratio of the compound (10P-gq-100-J11) to DABNA2 was approximately 98 to 2. Next, TSPO1 was heated, and vapor-deposited so that a film thickness might become 30 nm, and the electron transport layer was formed. The vapor deposition rate of each layer is 0.01 nm/sec to 1 nm/sec. Then, LiF is heated and vapor-deposited at a vapor deposition rate of 0.01 nm/sec to 0.1 nm/sec so that the film thickness becomes 1 nm, and then, aluminum is heated so that the film thickness becomes 100 nm/sec. An organic EL element was obtained by vapor-depositing at a vapor-deposition rate of 0.1 nm/sec to 2 nm/sec in a nm manner to form a cathode.

When the ITO electrode is used as the anode and the LiF/Al electrode is used as the cathode, and a DC voltage is applied, blue emission with a peak at about 469 nm can be obtained. Under the driving voltage of 3.98 V and the current density of 0.04 mA/cm ² , the luminous brightness was 10 cd/m ² , and the external quantum efficiency was 25.0%. Under the driving voltage of 4.66 V and the current density of 0.48 mA/cm ² , the luminance was 100 cd/m ² , and the external quantum efficiency was 19.8%. Compared with Comparative Example 9 described below, the external quantum efficiencies at both 10 cd/m ² and 100 cd/m ² were excellent.

<Comparative Example 9><Element using compound mCBP as host and DABNA2 as dopant> Except that the compound (10P-gq-100-J11) as the host material of the light-emitting layer was replaced with the compound mCBP , using the method according to Example 18 to obtain an organic EL element. When a DC voltage was applied to both electrodes, blue light emission with a peak at about 467 nm was obtained. Under the driving voltage of 4.50 V and the current density of 0.06 mA/cm ² , the luminous brightness was 10 cd/m ² , and the external quantum efficiency at this time was 17.6%. Under the driving voltage of 5.38 V and the current density of 0.83 mA/cm ² , the luminance was 100 cd/m ² , and the external quantum efficiency was 12.4%.

<Example 19><The element using the compound (10P-gq-100-J11) as the host and DABNA3 as the dopant> In addition to replacing DABNA3 as the dopant material of the light-emitting layer, the According to the method of Example 18, an organic EL element was obtained. When a DC voltage was applied to both electrodes, blue light emission with a peak at about 472 nm was obtained. Under the driving voltage of 4.00 V and the current density of 0.03 mA/cm ² , the luminous brightness was 10 cd/m ² , and the external quantum efficiency at this time was 34.5%. Under the driving voltage of 5.38 V and the current density of 0.34 mA/cm ² , the luminous brightness was 100 cd/m ² , and the external quantum efficiency was 32.7%. Compared with Comparative Example 10 described below, the external quantum efficiencies at both 10 cd/m ² and 100 cd/m ² were excellent.

<Comparative Example 10><The element using the compound mCBP as the host and DABNA3 as the dopant> The compound (10P-gq-100-J11) as the host material of the light-emitting layer was replaced with the compound mCBP, and replaced with An organic EL element was obtained by the method according to Example 18 except for DABNA3, which is a dopant material of the light-emitting layer. When a DC voltage was applied to both electrodes, blue light emission with a peak at about 471 nm was obtained. Under the driving voltage of 4.43 V and the current density of 0.05 mA/cm ² , the luminous brightness was 10 cd/m ² , and the external quantum efficiency was 22.5%. Under the driving voltage of 5.20 V and the current density of 0.63 mA/cm ² , the luminous brightness was 100 cd/m ² , and the external quantum efficiency at this time was 18.7%.

<Evaluation as a TADF compound> Next, the structure of the light-emitting material having TADF activity was designed using DFT (Density Functional Theory, density functional theory) calculation. After optimizing the structure of the base state using the PBE0/6-31G(d) method, use the Time-dependent DFT (time-dependent density functional theory) method to calculate the vertical excitation energy from the base state, and estimate the DE _ST and oscillator strength. All calculations were performed using the quantum chemical calculation program Firefly (AA Granovsky, Firefly version 8).

<Calculation Comparative Example 1> The S ₁ excitation energy, oscillator strength, and DE _ST of the following comparative compound (TADF-EM1) were estimated to be 2.37 eV (522 nm in terms of wavelength), 0.0003, and 0.008 eV, respectively. [Chemical 204]

According to the publication of Professor Yasuda of Kyushu University et al. ("Chem. Commun." (2017, 53, 8723-8726)), calculated using PBE0/6-31G(d) as the calculation method in the paper , S ₁ excitation energy, oscillator strength, and DE _ST were estimated to be 2.34 eV (530 nm when converted to wavelength), 0.0057, and 0.008 eV, respectively. In addition, the measured values of emission wavelength, photoluminescence quantum yield (PLQY) and DE _ST were 504 nm, 97% and 0.06 eV, respectively.

In this comparative example of calculation, the S ₁ excitation energy calculated by the PBE0/6-31G(d) method is 18 nm longer than the emission wavelength obtained by the actual measurement, and the DE _ST is about 10 times smaller. In addition, the value of the oscillator strength calculated by the calculation is very small, and the measured PLQY is very high.

In the case of a molecule having a boron-containing spiro structure of the present invention, it is determined whether the compound is a TADF active fluorescent material based on the assumption that the calculated comparative example 1 has the same tendency as the measured value. Specifically, assuming that there is a possibility that the actual emission wavelength is shorter than the calculated result of the S ₁ excitation energy, and that there is a possibility that the measured DE _ST is larger than the calculated result, there is also a possibility that the PLQY is related to the oscillator strength. The calculated result is more likely than the . Therefore, those with a calculated DE _ST less than 0.20 eV can be used as TADF fluorescent materials, and those with a DE ST less than 0.02 eV can be used more effectively as TADF fluorescent materials. In addition, when the oscillator strength is 0.0002 or more, a high PLQY is obtained, and when it is less than 0.0002, a low PLQY is obtained. In addition, there is a possibility that the actual emission wavelength is close to the calculation result of the S ₁ excitation energy, but is shifted to some extent.

<Calculation Example 1> The S ₁ excitation energy, oscillator strength, and DE _ST of the compound (10P-g-295) were estimated to be 3.08 eV (403 nm in terms of wavelength), 0.0138, and 0.135 eV, respectively. According to the calculation results, it is predicted that the compound (10P-g-295) can obtain very deep blue emission, can be used as a TADF fluorescent material, and has a high PLQY. [Chemical 205]

<Calculation Example 2> The S ₁ excitation energy, oscillator strength, and DE _ST of the compound (10P-g-2011) were estimated to be 2.76 eV (449 nm in terms of wavelength), 0.0000, and 0.003 eV, respectively. According to the calculation results, it is predicted that the compound (10P-g-2011) can obtain blue emission, can be used more effectively as a TADF fluorescent material, and has a low PLQY. [Chemical 206]

<Calculation Example 3> The S ₁ excitation energy, oscillator strength, and DE _ST of the compound (10P-g-2021) were estimated to be 2.40 eV (517 nm in terms of wavelength), 0.0000, and 0.003 eV, respectively. According to the calculation results, it is predicted that the compound (10P-g-2021) can obtain green luminescence, can be used more effectively as a TADF fluorescent material, and has a low PLQY. [Chemical 207]

<Calculation Example 4> The S ₁ excitation energy, oscillator strength, and DE _ST of the compound (10P-g-2031) were estimated to be 2.90 eV (427 nm in terms of wavelength), 0.0000, and 0.004 eV, respectively. According to the calculation results, it is predicted that the compound (10P-g-2031) can obtain blue emission, can be used more effectively as a TADF fluorescent material, and has a low PLQY. [Chemical 208]

<Calculation Example 5> The S ₁ excitation energy, oscillator strength, and DE _ST of the compound (10P-g-2041) were estimated to be 2.77 eV (447 nm in terms of wavelength), 0.0000, and 0.003 eV, respectively. According to the calculation results, it is predicted that the compound (10P-g-2041) can obtain blue emission, can be used more effectively as a TADF fluorescent material, and has a low PLQY. [Chemical 209]

<Calculation Example 6> The S ₁ excitation energy, oscillator intensity, and DE _ST of the compound (10P-gq-2011-J11) were estimated to be 2.88 eV (430 nm in terms of wavelength), 0.0020, and 0.038 eV, respectively. According to the calculation results, it is predicted that the compound (10P-gq-2011-J11) can obtain deep blue emission, can be used as a TADF fluorescent material, and has a high PLQY. [hua 210]

<Calculation Example 7> The S ₁ excitation energy, oscillator strength, and DE _ST of the compound (10P-gq-2021-J11) were estimated to be 2.54 eV (488 nm in terms of wavelength), 0.0042, and 0.014 eV, respectively. According to the calculation results, it is predicted that the compound (10P-gq-2021-J11) can obtain blue to green light emission, can be used more effectively as a TADF fluorescent material, and has a high PLQY. [hua 211]

<Calculation Example 8> The S ₁ excitation energy, oscillator strength, and DE _ST of the compound (10P-gq-2031-J11) were estimated to be 3.05 eV (406 nm in terms of wavelength), 0.0016, and 0.147 eV, respectively. According to the calculation results, it is predicted that the compound (10P-gq-2031-J11) can obtain deep blue emission, can be used as a TADF fluorescent material, and has a high PLQY. [hua 212]

<Calculation Example 9> The S ₁ excitation energy, oscillator strength, and DE _ST of the compound (10P-gq-2041-J11) were estimated to be 4.62 eV (474 nm in terms of wavelength), 0.0006, and 0.006 eV, respectively. According to the calculation results, it is predicted that the compound (10P-gq-2041-J11) can obtain blue to green luminescence, can be used more effectively as a TADF fluorescent material, and has a high PLQY. [hua 213]

As mentioned above, some of the compounds of the present invention were evaluated as materials for organic EL elements and were shown to be excellent materials for organic elements, but other compounds that were not evaluated also have the same basic skeleton and are similar as a whole. The compound of the structure can be similarly understood as an excellent material for organic elements for those skilled in the art. [Industrial Availability]

In the present invention, by providing a novel compound having boron as a spiro ring atom, options for materials for organic devices such as organic EL devices can be increased. In addition, by using a novel compound having boron as a spiro ring atom as a material for an organic EL element, an excellent organic EL element, a display device including the same, a lighting device including the same, and the like can be provided.

100‧‧‧Organic Electroluminescent Devices 101‧‧‧Substrate 102‧‧‧Anode 103‧‧‧Hole injection layer 104‧‧‧Hole Transport Layer 105‧‧‧Light Emitting Layer 106‧‧‧Electron transport layer 107‧‧‧Electron injection layer 108‧‧‧Cathode

FIG. 1 is a schematic cross-sectional view showing an organic EL element of the present embodiment.

Claims (32)

A compound having boron as a spiro ring attachment atom, represented by the following general formula (1);

(In the formula (1), A ring, C ring and D ring are respectively independently an aryl ring with a carbon number of 6 to 30 or a heteroaryl ring with a carbon number of 2 to 30, and the B ring is a carbon number of 2 to 30. The heteroaryl ring, the A ring and the B ring and/or the C ring and the D ring can be bonded to form a ring structure, and at least one hydrogen in these rings can be substituted, wherein, as for the A ring alone and the D ring alone The acridine-based substituent is removed, X ¹ ~X ⁴ are independently C or N, Z ¹ and Z ² are independently a single bond, an alkylene group, an alkenylene group, an alkynylene group or an extension group. Aryl, any of these -CH ₂ - may be -C(=CR ₂ )-, -C(=C(=O))-, -C(=O)-, -C(=S)- , -C(=O)O-, -C(=S)O-, -C(=O)S-, -C(=S)S-, -C(=O)NR-, -O-, -S-, -Se-, -Po-, -P(=O)-, -P(=S)-, -S(=O)-, -S(=O) ₂ -, -SiR ₂ -, -NR-, or -N=N-substituted, where R is independently hydrogen, aryl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, Alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, at least one hydrogen in R can be substituted by aryl, heteroaryl, alkyl or cycloalkyl, adjacent R, and A ring , B ring, C ring and/or D ring can be bonded to form a ring structure, wherein Z ¹ and Z ² cannot be single bonds at the same time, and at least one hydrogen in the compound represented by formula (1) can be cyano, halogen or deuterium substitution). The compound with boron as spiro ring attachment atom according to the first item of the claimed scope, wherein X ¹ to X ⁴ are independently C or N, Z ¹ and Z ² are independently a single bond, -(CR ₂ ) _n -(n is 1~12), -CR=CR-, -C≡C-, -(CR=CR-CR ₂ ) _n -(n is 1~4), -C(=CR ₂ )- , -C(=C(=O))-, -C(=O)-, -C(=S)-, -C(=O)O-, -C(=S)O-, -C( =O)S-, -C(=S)S-, -C(=O)NR-, -C(=O)C(=O)-, -C(=O)OC(=O)-, -(CR ₂ -O) _n -(n is 1~12), -(CR ₂ ) _n -O-(n is 1~12), -(CR ₂ -CR ₂ -O) _n -(n is 1 ~6), -O-, -S-, -SS-, -Se-, -Po-, -P(=O)-, -P(=S)-, -S(=O)-, -S (=O) ₂ -, -SiR ₂ -, -NR-, -N=N-, or phenylene, where R is independently hydrogen, aryl, heteroaryl, diarylamine, Diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, at least one hydrogen in R can be aryl, heteroaryl, Alkyl or cycloalkyl substitution, adjacent R, and A ring, B ring, C ring and/or D ring can be bonded to form a ring structure, wherein, Z ¹ and Z ² will not be a single bond at the same time, formula ( 1) At least one hydrogen in the compound represented by cyano, halogen or deuterium may be substituted. The compound with boron as spiro ring attachment atom according to the first item of the scope of application, wherein A ring, C ring and D ring are respectively independently benzene ring, naphthalene ring, indane ring, node ring, furan ring, thiophene Ring, benzofuran ring or benzothiophene ring, B ring is pyrrole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, quinoline ring or isoquinoline ring, A ring and B ring and/or C The ring and the D ring can be bonded to form a ring structure, and at least one hydrogen in these rings can be substituted, wherein, as the independent substituent for the A ring and the D ring, the acridine-based substituent is removed, and X ¹ ~ X ⁴ is C, Z ¹ and Z ² are each independently a single bond, -CR ₂ -, -CR=CR-, -C(=O)-, -C(=S)-, -O-, -S -, -Se-, -P(=O)-, -P(=S)-, -S(=O)-, -SiR ₂ -, -NR-, or phenylene, where R is each independently is hydrogen, aryl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, or aryl Oxygen, at least one hydrogen in R can be substituted by aryl, heteroaryl, alkyl or cycloalkyl, the adjacent R, and ring A, ring B, ring C and/or ring D can be bonded to form a ring structure , wherein Z ¹ and Z ² cannot be single bonds at the same time, and at least one hydrogen in the compound represented by formula (1) can be substituted by cyano, halogen or deuterium. The compound having boron as a spiro ring attachment atom as described in item 1 of the claimed scope is represented by the following general formula (2);

(In the formula (2), Z ¹ and Z ² are each independently a single bond, -O-, -S-, -Se-, -NR-, or 1,2-phenylene, where R is hydrogen, aryl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, or aryloxy base, at least one hydrogen in R can be substituted by aryl, heteroaryl, alkyl or cycloalkyl, wherein Z ¹ and Z ² will not be single bonds at the same time, R ¹ ~R ¹⁶ are independently hydrogen, aryl alkynyl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, these At least one hydrogen can be substituted by an aryl group, a heteroaryl group, an alkyl group or a cycloalkyl group, wherein, as R ¹ ～R ⁴ and R ¹³ ～R ¹⁶ , the acridine-based substituent is removed, and in addition, R ¹ ～R The adjacent groups in ⁴ and R ⁹ to R ¹⁶ can be bonded to each other to form an aryl ring with 9 to 30 carbon atoms or a heteroaryl ring with 6 to 30 carbon atoms together with a ring, c ring or d ring, R The adjacent groups in ⁵ to R ⁸ can be bonded to each other to form a heteroaryl ring with a carbon number of 6 to 30 together with the b ring, and at least one hydrogen in the formed ring can be an aryl group, a heteroaryl group, a diaryl group amine, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkoxy or aryloxy substituted at least one of these hydrogens can be aryl, heteroaryl, alkane group or cycloalkyl group, wherein the acridine-based substituent is removed as a substituent for the ring formed by the a ring or the d ring, and at least one hydrogen in the compound represented by the formula (2) can be cyano, halogen or deuterium substitution). The compound having boron as a spiro ring attachment atom according to the claim 4, wherein in the formula (2), Z ¹ and Z ² are independently a single bond, -O-, -S-, - Se-, -NR-, or 1,2-phenylene, where R is hydrogen, aryl, heteroaryl, alkyl or cycloalkyl, wherein Z ¹ and Z ² cannot be single bonds at the same time , R ¹ to R ¹⁶ are independently hydrogen, aryl, heteroaryl, diarylamine, alkyl, cycloalkyl, alkoxy or aryloxy, and at least one of these hydrogens can be aryl , heteroaryl, alkyl or cycloalkyl substitution, wherein, as R ¹ to R ⁴ and R ¹³ to R ¹⁶ , the acridine-based substituent is removed, and in addition, R ¹ to R ⁴ and R ⁹ to R ¹⁶ The adjacent groups can be bonded to each other to form an aryl ring with a carbon number of ⁹ to ¹⁶ or a heteroaryl ring with a carbon number of 6 to 15 together with the a ring, the c ring or the d ring. The groups can be bonded to each other to form a heteroaryl ring with a carbon number of 6 to 15 together with the b ring, and at least one hydrogen in the formed ring can be an aryl group, a heteroaryl group, a diarylamine group, an alkyl group, a cycloalkane substituted with aryl, alkoxy or aryloxy, at least one of these hydrogens may be substituted with aryl, heteroaryl, alkyl or cycloalkyl, wherein as a substitution for a ring formed comprising a ring or d ring group, the acridine-based substituent is removed, and at least one hydrogen in the compound represented by the formula (2) may be substituted with a cyano group, a halogen group or a deuterium group. The compound having boron as a spiro ring attachment atom according to the claim 4, wherein in the formula (2), Z ¹ and Z ² are independently a single bond, -O-, -S-, - Se-, -NR-, or 1,2-phenylene, where R is hydrogen, an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. Or a cycloalkyl group with a carbon number of 3 to 12, wherein Z ¹ and Z ² will not be a single bond at the same time, and R ¹ to R ¹⁶ are independently hydrogen, an aryl group with a carbon number of 6 to 16, and a carbon number of 2 to 15. Heteroaryl, diarylamine (wherein, aryl is aryl with carbon number 6~12), alkyl group with carbon number 1~6, cycloalkyl group with carbon number 3~12, carbon number 1~6 alkoxy group or aryloxy group with carbon number 6~16, at least one hydrogen in these can be aryl group with carbon number 6~16, heteroaryl group with carbon number 2~15, alkyl group with carbon number 1~6 Or substituted with a cycloalkyl group having 3 to 12 carbon atoms, wherein, as R ¹ to R ⁴ and R ¹³ to R ¹⁶ , the acridine-based substituent is removed, and in addition, among R ¹ to R ⁴ and R ⁹ to R ¹⁶ Adjacent groups can be bonded to each other to form an aryl ring with a carbon number of 9 to 12 or a heteroaryl ring with a carbon number of 6 to 10 together with the a ring, the c ring or the d ring, and the adjacent groups in R ⁵ ～R ⁸ They can be bonded to each other to form a heteroaryl ring with a carbon number of 6 to 10 together with the b ring, and at least one hydrogen in the formed ring can be an aryl group with a carbon number of 6 to 16, a heteroaryl group with a carbon number of 2 to 15, Diarylamine group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms), an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or The aryloxy group of carbon number 6~16 is substituted, and at least one hydrogen in these can be aryl group with carbon number 6~16, heteroaryl group with carbon number 2~15, alkyl group with carbon number 1~6 or carbon number 3 Cycloalkyl substitution of ~12, wherein the acridine-based substituent is removed as a substituent for the ring formed including the a ring or the d ring, and at least one hydrogen in the compound represented by the formula (2) may be a cyano group , halogen or deuterium substitution. The compound having boron as a spiro ring attachment atom according to the claim 4, wherein in the formula (2), Z ¹ and Z ² are independently a single bond, -O-, -S-, - Se-, -NR-, or 1,2-phenylene, where R is hydrogen, an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. Or a cycloalkyl group with 3 to 12 carbon atoms, wherein Z ¹ and Z ² are not single bonds at the same time, R ¹ to R ⁴ and R ⁹ to R ¹⁶ are hydrogen, and R ⁵ to R ⁸ are independently hydrogen, Aryl with 6 to 16 carbon atoms, heteroaryl with 2 to 15 carbon atoms, diarylamine group (wherein, the aryl group is an aryl group with 6 to 12 carbon atoms), alkyl with 1 to 6 carbon atoms, carbon Cycloalkyl with 3 to 12 carbons, alkoxy with 1 to 6 carbons or aryloxy with 6 to 16 carbons, at least one hydrogen in these The heteroaryl group of 15, the alkyl group of carbon number 1 to 6 or the cycloalkyl group of carbon number 3 to 12 is substituted, and the adjacent groups in R ⁵ to R ⁸ can be bonded to each other to form a carbon number together with the b ring. Heteroaryl ring of 6～10, at least one hydrogen in the formed ring can be aryl with carbon number 6～16, heteroaryl with carbon number 2～15, diarylamine group (wherein, aryl is carbon 6-12 aryl), alkyl with 1-6 carbons, cycloalkyl with 3-12 carbons, alkoxy with 1-6 carbons or aryloxy with 6-16 carbons, the At least one hydrogen in these can be substituted by an aryl group with a carbon number of 6 to 16, a heteroaryl group with a carbon number of 2 to 15, an alkyl group with a carbon number of 1 to 6 or a cycloalkyl group with a carbon number of 3 to 12, formula (2) At least one hydrogen in the represented compounds may be replaced by cyano, halogen or deuterium. The compound with boron as spiro ring attachment atom as described in item 1 of the claimed scope is represented by the following chemical structural formula;

The compound having boron as a spiro ring attachment atom according to the claim 4, wherein in the formula (2), Z ¹ and Z ² are independently a single bond, -O-, -S-, - Se-, -NR-, or 1,2-phenylene, where R is aryl, heteroaryl or cycloalkyl, and at least one hydrogen in R can be aryl, heteroaryl, alkyl or cycloalkyl Alkyl-substituted, wherein one or more of Z ¹ or Z ² is -NR-, and the R and R ¹ , R ⁸ , R ⁹ and/or R ¹⁶ are connected by a single bond, -CR ₂ -, -CR =CR-, -C(=O)-, -C(=S)-, -O-, -S-, -Se-, -P(=O)-, -P(=S)-, -S (=O)-, -SiR ₂ -, -NR-, or phenylene groups are bonded to form a ring structure, where R is independently hydrogen, aryl, heteroaryl, diarylamine, Diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, at least one hydrogen in R can be aryl, heteroaryl, Alkyl or cycloalkyl substitution, R ¹ to R ¹⁶ are independently hydrogen, aryl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, alkyl, Cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, at least one of these hydrogens can be substituted by aryl, heteroaryl, alkyl or cycloalkyl, wherein, as R ¹ ~R ⁴ and R ¹³ to R ¹⁶ , the acridine-based substituent is removed, and the adjacent groups among R ¹ to R ⁴ and R ⁹ to R ¹⁶ may be bonded to each other to form a carbon number together with a ring, c ring or d ring 9~30 aryl ring or carbon number 6~30 heteroaryl ring, the adjacent groups in R ⁵ ~R ⁸ can be bonded to each other to form a carbon number 6~30 heteroaryl ring together with b ring, At least one hydrogen in the formed ring can be aryl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, alkyl, cycloalkyl, alkoxy, or aryl Oxygen substitution, at least one hydrogen in these may be substituted by aryl, heteroaryl, alkyl or cycloalkyl, wherein, as a substituent for the ring formed by including a ring or d ring, an acridine is substituted group is removed, and at least one hydrogen in the compound represented by the formula (2) may be replaced by a cyano group, a halogen group or a deuterium group. The compound having boron as a spiro ring attachment atom according to the claim 4, wherein in the formula (2), Z ¹ and Z ² are independently a single bond, -O-, -S-, - Se- or -NR-, where R is an aryl group, and at least one hydrogen in R can be substituted by an aryl group, a heteroaryl group, an alkyl group or a cycloalkyl group, wherein any one or more of Z ¹ or Z ² is -NR-, the R and R ¹ , R ⁸ , R ⁹ and/or R ¹⁶ are bonded by a single bond, -CR ₂ -, -O-, -S- or -NR- to form a ring structure, Here, R is independently hydrogen, aryl, alkyl or cycloalkyl, at least one hydrogen in R can be substituted by aryl, alkyl or cycloalkyl, and R ¹ to R ¹⁶ are independently hydrogen, aryl aryl, heteroaryl, diarylamine, alkyl, cycloalkyl, alkoxy or aryloxy, at least one hydrogen of which may be substituted by aryl, heteroaryl, alkyl or cycloalkyl, Among them, as R ¹ to R ⁴ and R ¹³ to R ¹⁶ , the acridine-based substituent is removed, and the adjacent groups among R ¹ to R ⁴ and R ⁹ to R ¹⁶ may be bonded to each other to form a ring, The c ring or the d ring together forms an aryl ring with a carbon number of 9 to 16 or a heteroaryl ring with a carbon number of 6 to 15, and the adjacent groups in R ⁵ to R ⁸ can be bonded to each other to form a carbon number together with the b ring. The heteroaryl ring of 6 to 15, at least one hydrogen in the formed ring can be substituted by aryl, heteroaryl, diarylamine, alkyl, cycloalkyl, alkoxy or aryloxy, these At least one hydrogen can be substituted by an aryl group, a heteroaryl group, an alkyl group or a cycloalkyl group, wherein, as the substituent for the ring formed by the a ring or the d ring, the acridine-based substituent is removed, and the formula (2 ) in the compound represented by at least one hydrogen may be substituted with cyano, halogen or deuterium. The compound having boron as a spiro ring attachment atom according to the claim 4, wherein in the formula (2), Z ¹ and Z ² are independently a single bond, -O-, -S-, - Se- or -NR-, where R is an aryl group with a carbon number of 6-16, and at least one hydrogen in R can be an aryl group with a carbon number of 6-16, a heteroaryl group with a carbon number of 2-15, a carbon number of 1 Substituted with an alkyl group of ~6 or a cycloalkyl group having 3 to 12 carbon atoms, wherein, any one or more of Z ¹ or Z ² is -NR-, and the R and R ¹ , R ⁸ , R ⁹ and/or R ¹⁶ is bonded by a single bond, -CR ₂ -, -O-, -S- or -NR- to form a ring structure, where R is independently hydrogen, an aryl group having 6 to 16 carbon atoms, a carbon Alkyl group with 1~6 carbon number or cycloalkyl group with carbon number 3~12, at least one hydrogen in R can be aryl group with carbon number 6~16, alkyl group with carbon number 1~6 or ring with carbon number 3~12 Alkyl substitution, R ¹ ~R ¹⁶ are independently hydrogen, aryl group with carbon number 6~16, heteroaryl group with carbon number 2~15, diarylamine group (wherein, aryl group is carbon number 6~12 aryl), alkyl with 1 to 6 carbons, cycloalkyl with 3 to 12 carbons, alkoxy with 1 to 6 carbons or aryloxy with 6 to 16 carbons, at least one of these Hydrogen can be substituted by an aryl group with a carbon number of 6-16, a heteroaryl group with a carbon number of 2-15, an alkyl group with a carbon number of 1-6 or a cycloalkyl group with a carbon number of 3-12, wherein, as R ¹ to R ⁴ and R ¹³ to R ¹⁶ , the acridine-based substituent is removed, and the adjacent groups among R ¹ to R ⁴ and R ⁹ to R ¹⁶ may be bonded to each other to form a carbon number together with a ring, c ring or d ring The aryl ring of 9～12 or the heteroaryl ring of carbon number 6～10, the adjacent groups in R ⁵ ～R ⁸ can be bonded to each other and form the heteroaryl ring of carbon number 6～10 together with b ring, At least one hydrogen in the formed ring can be an aryl group with a carbon number of 6 to 16, a heteroaryl group with a carbon number of 2 to 15, a diarylamine group (wherein, the aryl group is an aryl group with a carbon number of 6 to 12), Alkyl with 1 to 6 carbons, cycloalkyl with 3 to 12 carbons, alkoxy with 1 to 6 carbons, or aryloxy with 6 to 16 carbons, and at least one of these hydrogens can be substituted with carbon atoms Aryl of 6 to 16, heteroaryl of carbon number 2 to 15, alkyl of carbon number of 1 to 6 or cycloalkyl of carbon number of 3 to 12 is substituted, wherein, as a ring formed for a ring containing a or ring d As the substituent of the ring, the acridine-based substituent is removed, and at least one hydrogen in the compound represented by the formula (2) may be substituted with a cyano group, a halogen or a deuterium group. The compound having boron as a spiro ring attachment atom according to any one of items 9 to 11 of the claimed scope, wherein in the formula (2), Z ¹ is a single bond, -O-, -S- , -Se- or -NR-, Z ² is -NR-, here, R is an aryl group with a carbon number of 6~16, and at least one hydrogen in R can be an aryl group with a carbon number of 6~16, an aryl group with a carbon number of 2~ The heteroaryl group of 15, the alkyl group of carbon number 1~6 or the cycloalkyl group of carbon number 3~12 is substituted, and R and R ⁸ or R ⁹ in the -NR- of Z ² are substituted by a single bond, -CR ₂ - , -O-, -S- or -NR- are bonded to form a ring structure, where R is independently hydrogen, an aryl group having 6 to 16 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having a carbon number of 1 to 6. 3 to 12 cycloalkyl groups. The compound with boron as spiro ring attachment atom as described in item 1 of the claimed scope is represented by the following chemical structural formula;

The compound having boron as spiro ring attachment atom as described in item 1 or item 4 of the claimed scope, wherein the substituent for C ring or at least one of R ⁹ to R ¹² is represented by the following partial structural formula (TSG1) the base represented;

At least one hydrogen in the group represented by the formula (TSG1) can be substituted by an aryl group, a heteroaryl group, a diarylamine group, an alkyl group, a cycloalkyl group, an alkoxy group or an aryloxy group, and Y is a single bond, -O-, -S-, -Se-, -NR-, >CR ₂ , or >SiR ₂ , where R is each independently hydrogen, aryl, heteroaryl, diarylamine, alkyl , cycloalkyl, alkoxy or aryloxy, and adjacent groups in R may be bonded to each other to form an aryl ring having 6 to 15 carbon atoms. For the compound having boron as a spiro ring attachment atom according to the claim 14, the group represented by the partial structural formula (TSG1) is the following partial structural formula (TSG100), formula (TSG110), formula (TSG111) ), formula (TSG112), formula (TSG113), formula (TSG120) or formula (TSG121);

At least one hydrogen in the structural formula can be substituted by an aryl, heteroaryl, diarylamine, alkyl, cycloalkyl, alkoxy, or aryloxy group. The compound having boron as spiro ring attachment atom as described in item 14 of the scope of the application is represented by the following chemical structural formula;

The compound having boron as a spiro ring attachment atom as described in item 14 of the patent application scope satisfies the following formula: ΔE _ST ≦0.20eV. A polymer compound, which uses the structure represented by the general formula (1) as a repeating unit;

In the formula (1), A ring, C ring and D ring are respectively independently an aryl ring having 6 to 30 carbon atoms or a heteroaryl ring having 2 to 30 carbon atoms, and ring B is a carbon number 2 to 30 ring. Heteroaryl ring, A ring and B ring and/or C ring and D ring may be bonded to form a ring structure, and at least one hydrogen in these rings may be substituted, wherein, as a single ring for A and D ring alone Substituent, remove the acridine-based substituent, X ¹ ~X ⁴ are independently C or N, Z ¹ and Z ² are independently a single bond, alkylene, alkenylene, alkynylene or arylene base, any of these -CH ₂ - can be selected from -C(=CR ₂ )-, -C(=C(=O))-, -C(=O)-, -C(=S)-, -C(=O)O-, -C(=S)O-, -C(=O)S-, -C(=S)S-, -C(=O)NR-, -O-, - S-, -Se-, -Po-, -P(=O)-, -P(=S)-, -S(=O)-, -S(=O) ₂ -, -SiR ₂ -, - NR-, or -N=N-substituted, where R is independently hydrogen, aryl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, alkane group, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, at least one hydrogen in R can be substituted by aryl, heteroaryl, alkyl or cycloalkyl, adjacent R, and A ring, Ring B, ring C and/or ring D may be bonded to form a ring structure, wherein Z ¹ and Z ² are not simultaneously single bonds, and at least one hydrogen in the structure represented by formula (1) may be cyano, halogen or deuterium substitution. The polymer compound according to claim 18, wherein Z ¹ and Z ² are each independently a single bond, -(CR ₂ ) _n -(n is 1 to 12), -CR=CR-, -C ≡C-, -(CR=CR-CR ₂ ) _n -(n is 1~4), -C(=CR ₂ )-, -C(=C(=O))-, -C(=O) -, -C(=S)-, -C(=O)O-, -C(=S)O-, -C(=O)S-, -C(=S)S-, -C(= O)NR-, -C(=O)C(=O)-, -C(=O)OC(=O)-, -(CR ₂ -O) _n -(n is 1~12), -( CR ₂ ) _n -O-(n is 1~12), -(CR ₂ -CR ₂ -O) _n -(n is 1~6), -O-, -S-, -SS-, -Se- , -Po-, -P(=O)-, -P(=S)-, -S(=O)-, -S(=O) ₂ -, -SiR ₂ -, -NR-, -N= N-, or phenylene extension, where R is independently hydrogen, aryl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, alkyl, ring Alkyl, alkenyl, alkynyl, alkoxy or aryloxy, at least one hydrogen in R can be substituted by aryl, heteroaryl, alkyl or cycloalkyl, adjacent R, and A ring, B ring, Ring C and/or ring D may be bonded to form a ring structure, wherein Z ¹ and Z ² are not simultaneously single bonds, and at least one hydrogen in the structure represented by formula (1) may be cyano, halogen or deuterium replace. The polymer compound according to item 18 of the scope of the application, wherein the substituent for the C ring or at least one of R ⁹ to R ¹² is a group represented by the following partial structural formula (TSG1);

At least one hydrogen in the group represented by the formula (TSG1) can be substituted by an aryl group, a heteroaryl group, a diarylamine group, an alkyl group, a cycloalkyl group, an alkoxy group or an aryloxy group, and Y is a single bond, -O-, -S-, -Se-, -NR-, >CR ₂ , or >SiR ₂ , where R is each independently hydrogen, aryl, heteroaryl, diarylamine, alkyl , cycloalkyl, alkoxy or aryloxy, and adjacent groups in R may be bonded to each other to form an aryl ring having 6 to 15 carbon atoms. The polymer compound described in claim 20, wherein the group represented by the partial structural formula (TSG1) is the following partial structural formula (TSG100), formula (TSG110), formula (TSG111), formula (TSG112) , a base represented by formula (TSG113), formula (TSG120) or formula (TSG121);

At least one hydrogen in the structural formula can be substituted by an aryl, heteroaryl, diarylamine, alkyl, cycloalkyl, alkoxy, or aryloxy group. The polymer compound according to claim 20, which satisfies the following formula: ΔE _ST ≦0.20eV. A material for an organic element, which contains the compound or polymer compound described in any one of items 1 to 22 of the scope of the application. The material for an organic element according to claim 23, wherein the material for an organic element is a material for an organic electroluminescence element, a material for an organic field effect transistor, or a material for an organic thin film solar cell. An organic electroluminescence element including a pair of electrodes including an anode and a cathode, and an organic layer disposed between the pair of electrodes and containing the material for an organic electroluminescence element as described in claim 24. The organic electroluminescence device according to claim 25, further comprising an electron transport layer and/or an electron injection layer, and at least one of the electron transport layer and the electron injection layer contains a metal selected from the group consisting of quinoline At least one of the group consisting of complexes, pyridine derivatives, phenanthroline derivatives, borane derivatives and benzimidazole derivatives. The organic electroluminescent element according to claim 26, wherein the electron transport layer and/or the electron injection layer further contains a compound selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, and Halides, oxides of alkaline earth metals, halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals at least one of the groups. An organic electroluminescence element having a light-emitting layer comprising at least one host compound as a first component and at least one thermally activated delayed phosphor as a second component , and has a compound represented by the following general formula (1), or a polymer compound having a structure represented by the general formula (1) as a repeating unit as the first component or the second component,

(In the formula (1), A ring, C ring and D ring are respectively independently an aryl ring with a carbon number of 6 to 30 or a heteroaryl ring with a carbon number of 2 to 30, and the B ring is a carbon number of 2 to 30. The heteroaryl ring, the A ring and the B ring and/or the C ring and the D ring can be bonded to form a ring structure, and at least one hydrogen in these rings can be substituted, wherein, as for the A ring alone and the D ring alone The acridine-based substituent is removed, X ¹ ~X ⁴ are independently C or N, Z ¹ and Z ² are independently a single bond, an alkylene group, an alkenylene group, an alkynylene group or an extension group. Aryl, any of these -CH ₂ - may be -C(=CR ₂ )-, -C(=C(=O))-, -C(=O)-, -C(=S)- , -C(=O)O-, -C(=S)O-, -C(=O)S-, -C(=S)S-, -C(=O)NR-, -O-, -S-, -Se-, -Po-, -P(=O)-, -P(=S)-, -S(=O)-, -S(=O) ₂ -, -SiR ₂ -, -NR-, or -N=N-substituted, where R is independently hydrogen, aryl, heteroaryl, diarylamine, diheteroarylamine, arylheteroarylamine, Alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, at least one hydrogen in R can be substituted by aryl, heteroaryl, alkyl or cycloalkyl, adjacent R, and A ring , B ring, C ring and/or D ring can be bonded to form a ring structure, wherein Z ¹ and Z ² cannot be single bonds at the same time, and at least one hydrogen in the compound or structure represented by formula (1) can be cyanogen group, halogen or deuterium substitution). The organic electroluminescence device according to claim 28, comprising a compound represented by general formula (1) or a polymer compound having a structure represented by general formula (1) as a repeating unit as a first component . The organic electroluminescence element according to claim 28, comprising a compound represented by general formula (1) or a polymer compound having a structure represented by general formula (1) as a repeating unit as a second component . A display device comprising the organic electroluminescence element according to any one of items 25 to 30 of the application scope. A lighting device comprising the organic electroluminescence element as described in any one of items 25 to 30 of the patent application scope.

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