Patent Application
20230111104
The present specification relates to a compound, a composition for forming an optical film and an optical film including the same, and a display device including the optical film.
Existing light emitting diodes (LED) are obtained by mixing a green phosphorescent substance and a red phosphorescent substance to a blue light emitting diode, or mixing a yellow phosphorescent substance and a blue-green phosphorescent substance to a UV light emitting diode. However, with such a method, it is difficult to control colors, and therefore, color rendering is not favorable. Accordingly, color gamut declines.
In order to overcome such color gamut decline and to reduce production costs, methods of obtaining green and red in a manner of filming quantum dots and binding the dots to a blue LED have been recently tried. However, cadmium series quantum dots have safety problems, and other quantum dots have significantly reduced efficiency compared to cadmium series quantum dots. In addition, quantum dots have reduced stability for oxygen and water, and have a disadvantage in that the performance is significantly degraded when aggregated. Furthermore, unit costs of production are high since, when producing quantum dots, maintaining the sizes to be constant is difficult.
Existing compounds having a BF2 or B(CN)2-based BODIPY structure provide, as a fluorescent dye having high light efficiency and a narrow full width at half maximum, excellent optical properties when used in an optical film, but have insufficient light resistance and heat resistance to be commercialized, and development of compounds having high durability has been required.
The present specification is directed to providing a compound, a composition for forming an optical film including the compound, an optical film formed using the composition, and a display device including the optical film.
One embodiment of the present specification provides a compound represented by the following Chemical Formula 1.
In Chemical Formula 1,
X is Zn; Co; Ni or Pd,
R1 to R14 are the same as or different from each other, and each independently hydrogen; deuterium; a halogen group; a nitrile group; a nitro group; —C(═O)OR; —(C═O)NR′R″; —CHO; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted heteroaryloxy group; a substituted or unsubstituted arylthio group; a substituted or unsubstituted heteroarylthio group; a substituted or unsubstituted alkylthio group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group,
at least one of R3, R4, R10 and R11 is a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted heteroaryloxy group; a substituted or unsubstituted arylthio group; a substituted or unsubstituted heteroarylthio group; or a substituted or unsubstituted alkylthio group,
at least one of R2, R5, R9 and R12 is a halogen group; a nitrile group; a nitro group; —C(═O)OR; —(C═O)NR′R″; —CHO; a substituted or unsubstituted aryl group; an alkyl group substituted with fluorine; or a substituted or unsubstituted heteroaryl group, and
R, R′ and R″ are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group.
In addition, one embodiment of the present specification provides a composition for forming an optical film, the composition including a binder resin; and the compound.
In addition, one embodiment of the present specification provides an optical film including a resin matrix into which the compound is dispersed.
In addition, one embodiment of the present specification provides a display device including the optical film.
A compound according to one embodiment of the present specification has excellent light resistance and heat resistance compared to an existing compound having a BODIPY structure. Accordingly, by using the compound described in the present specification as a light absorbing material of an optical film, an optical film having excellent luminance (brightness) and color gamut, and having excellent durability can be provided.
Hereinafter, the present specification will be described in more detail.
In the present specification, one member being placed “on” another member includes not only a case of the one member being in contact with the another member but a case of still another member being present between the two members.
In the present specification, a certain part “including” certain constituents means capable of further including other constituents, and does not exclude other constituents unless particularly stated on the contrary.
One embodiment of the present specification provides a compound represented by the following Chemical Formula 1.
In Chemical Formula 1,
X is Zn; Co; Ni or Pd,
R1 to R14 are the same as or different from each other, and each independently hydrogen; deuterium; a halogen group; a nitrile group; a nitro group; —C(═O)OR; —(C═O)NR′R″; —CHO; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted heteroaryloxy group; a substituted or unsubstituted arylthio group; a substituted or unsubstituted heteroarylthio group; a substituted or unsubstituted alkylthio group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group,
at least one of R3, R4, R10 and R11 is a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted heteroaryloxy group; a substituted or unsubstituted arylthio group; a substituted or unsubstituted heteroarylthio group; or a substituted or unsubstituted alkylthio group,
at least one of R2, R5, R9 and R12 is a halogen group; a nitrile group; a nitro group; —C(═O)OR; —(C═O)NR′R″; —CHO; a substituted or unsubstituted aryl group; an alkyl group substituted with fluorine; or a substituted or unsubstituted heteroaryl group, and
R, R′ and R″ are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group.
The compound represented by Chemical Formula 1 according to one embodiment of the present specification has a novel BODIPY metal complex structure. The compound represented by Chemical Formula 1 is an excellent light absorbing material with a high extinction coefficient, and has excellent light resistance and heat resistance compared to an existing compound having a BODIPY structure.
In addition, it is experimentally identified that, by the compound represented by Chemical Formula 1 introducing an electron withdrawing group as a substituent, light resistance and heat resistance are more enhanced. Accordingly, by using the compound described in the present specification as a light absorbing material of an optical film, an optical film having excellent luminance and color gamut, and having excellent durability may be provided.
In the present specification, the electron withdrawing group means a halogen group; a nitrile group; a nitro group; —C(═O)OR; —(C═O)NR′R″; —CHO; a substituted or unsubstituted aryl group; an alkyl group substituted with fluorine; or a substituted or unsubstituted heteroaryl group.
Examples of substituents in the present specification are described below, however, the substituents are not limited thereto.
The term “substitution” means a hydrogen atom bonding to a carbon atom of a compound being changed to another substituent, and the position of substitution is not limited as long as it is a position at which the hydrogen atom is substituted, that is, a position at which a substituent can substitute, and when two or more substituents substitute, the two or more substituents may be the same as or different from each other.
The term “substituted or unsubstituted” in the present specification means being substituted with one, two or more substituents selected from the group consisting of deuterium; a halogen group; a nitrile group; a nitro group; —C(═O)OR; —(C═O)NR′R″; a hydroxyl group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted haloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryl group; an aryloxy group; a heteroaryloxy group; an alkylthio group; an arylthio group; a heteroarylthio group; and a substituted or unsubstituted heteroaryl group, or being substituted with a substituent linking two or more substituents among the substituents illustrated above, or having no substituents. R, R′ and R″ are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group.
In the present specification, the nitrile group is represented by —CN.
In the present specification, examples of the halogen group may include fluorine, chlorine, bromine or iodine.
In the present specification, in the amide group, the nitrogen of the amide group may be substituted with hydrogen, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. The amide group of the present specification may be represented by —(C═O)NR′R″, and definitions of R′ and R″ follow the definitions provided in the present specification.
In the present specification, the alkyl group may be linear or branched, and although not particularly limited thereto, the number of carbon atoms is preferably from 1 to 30. Specific examples thereof may include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.
In the present specification, the alkyl group substituted with fluorine may mean a trifluoromethyl group.
In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and specific examples thereof may include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like, but are not limited thereto.
In the present specification, the haloalkyl group represents an alkyl group in which hydrogen atoms of the alkyl group are replaced by the same or a different halogen group. The haloalkyl group may be linear or branched, and although not particularly limited thereto, the number of carbon atoms is preferably from 1 to 10. Specific examples thereof may include —CH2Cl, —CF3, —CH2CF3, —CF2CF3 and the like, but are not limited thereto.
In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably from 1 to 20. Specific examples thereof may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like, but are not limited thereto.
In the present specification, the alkyl group in the alkylthio group is the same as the examples of the alkyl group described above. Specific examples of the alkylthio group may include a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group, an octylthio group and the like, but are not limited thereto.
In the present specification, the heteroaryl group in the heteroaryloxy group and the heteroarylthio group is the same as the examples of the heteroaryl group described above.
In the present specification, the aryl group in the aryloxy group and the arylthio group is the same as the examples of the aryl group described above. Specific examples of the aryloxy group may include phenoxy, p-tolyloxy, m-tolyloxy, 3,5-dimethyl-phenoxy, 2,4,6-trimethylphenoxy, p-tert-butylphenoxy, 3-biphenyloxy, 4-biphenyloxy, 1-naphthyloxy, 2-naphthyloxy, 4-methyl-1-naphthyloxy, 5-methyl-2-naphthyloxy, 1-anthryloxy, 2-anthryloxy, 9-anthryloxy, 1-phenanthryloxy, 3-phenanthryloxy, 9-phenanthryloxy and the like, and specific examples of the arylthio group may include a phenylthio group, a 2-methylphenylthio group, a 4-tert-butylphenylthio group and the like, however, the aryloxy group and the arylthio group are not limited thereto.
In the present specification, the aryl group is not particularly limited, but preferably has 6 to carbon atoms, and the aryl group may be monocyclic or polycyclic.
When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably from 6 to 30. Specific examples of the monocyclic aryl group may include a phenyl group, a biphenyl group, a terphenyl group and the like, but are not limited thereto.
When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably from 10 to 30. Specific examples of the polycyclic aryl group may include a naphthyl group, an anthracenyl group, a phenanthryl group, a triphenylene group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group and the like, but are not limited thereto.
In the present specification, the fluorenyl group may be substituted, and adjacent groups may bond to each other to form a ring.
When the fluorenyl group is substituted,
and the like may be included. However, the structure is not limited thereto.
In the present specification, the aryl group in the aryloxy group and the arylthio group is the same as the examples of the aryl group described above. Specific examples of the aryloxy group may include a phenoxy group, a p-tolyloxy group, an m-tolyloxy group, a 3,5-dimethyl-phenoxy group, a 2,4,6-trimethylphenoxy group, a p-tert-butylphenoxy group, a 3-biphenyloxy group, a 4-biphenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methyl-1-naphthyloxy group, a 5-methyl-2-naphthyloxy group, a 1-anthryloxy group, a 2-anthryloxy group, a 9-anthryloxy group, a 1-phenanthryloxy group, a 3-phenanthryloxy group, a 9-phenanthryloxy group and the like, and examples of the arylthio group may include a phenylthio group, a 2-methylphenylthio group, a 4-tert-butylphenylthio group and the like, however, the aryloxy group and the arylthiol group are not limited thereto.
In the present specification, the heteroaryl group is a group including one or more atoms that are not carbon, that is, heteroatoms, and specifically, the heteroatom may include one or more atoms selected from the group consisting of O, N, Se, S and the like. The number of carbon atoms is not particularly limited, but is preferably from 2 to 30, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heteroaryl group may include a thiophene group, a furanyl group, a pyrrole group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazinyl group, a triazolyl group, an acridyl group, a pyridazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidyl group, a pyridopyrazinyl group, a pyrazinopyrazinyl group, an isoquinolinyl group, an indolyl group, a carbazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a benzocarbazolyl group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthrolinyl group, an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, a dibenzofuranyl group and the like, but are not limited thereto.
In one embodiment of the present specification, X is Zn; Co; Ni or Pd.
In one embodiment of the present specification, X is Zn.
In one embodiment of the present specification, X is Co.
In one embodiment of the present specification, X is Ni.
In one embodiment of the present specification, X is Pd.
In one embodiment of the present specification, R1 to R14 are the same as or different from each other, and each independently hydrogen; deuterium; a halogen group; a nitrile group; a nitro group; —C(═O)OR; —(C═O)NR′R″; —CHO; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted heteroaryloxy group; a substituted or unsubstituted arylthio group; a substituted or unsubstituted heteroarylthio group; a substituted or unsubstituted alkylthio group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group.
In one embodiment of the present specification, R1 to R14 are the same as or different from each other, and each independently hydrogen; deuterium; a halogen group; a nitrile group; a nitro group; —C(═O)OR; —(C═O)NR′R″; —CHO; a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms; a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms; a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms; a substituted or unsubstituted heteroaryloxy group having 2 to 30 carbon atoms; a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms; a substituted or unsubstituted heteroarylthio group having 2 to 30 carbon atoms; a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.
In one embodiment of the present specification, R1 to R14 are the same as or different from each other, and each independently hydrogen; deuterium; a halogen group; a nitrile group; a nitro group; —C(═O)OR; —(C═O)NR′R″; —CHO; a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms; a substituted or unsubstituted heteroaryloxy group having 2 to 20 carbon atoms; a substituted or unsubstituted arylthio group having 6 to 20 carbon atoms; a substituted or unsubstituted heteroarylthio group having 2 to 20 carbon atoms; a substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms; a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.
In one embodiment of the present specification, R1 to R14 are the same as or different from each other, and each independently hydrogen; deuterium; a halogen group; a nitrile group; a nitro group; —C(═O)OR; —(C═O)NR′R″; —CHO; a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms; a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms; a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms; a substituted or unsubstituted heteroaryloxy group having 2 to 10 carbon atoms; a substituted or unsubstituted arylthio group having 6 to 12 carbon atoms; a substituted or unsubstituted heteroarylthio group having 3 to 10 carbon atoms; a substituted or unsubstituted alkylthio group having 1 to 10 carbon atoms; a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 10 carbon atoms.
In one embodiment of the present specification, at least one of R3, R4, R10 and R11 is a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted heteroaryloxy group; a substituted or unsubstituted arylthio group; a substituted or unsubstituted heteroarylthio group; or a substituted or unsubstituted alkylthio group.
In one embodiment of the present specification, at least one of R3, R4, R10 and R11 is a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms; a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms; a substituted or unsubstituted heteroaryloxy group having 2 to 30 carbon atoms; a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms; a substituted or unsubstituted heteroarylthio group having 2 to 30 carbon atoms; or a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms.
In one embodiment of the present specification, at least one of R3, R4, R10 and R11 is a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms; a substituted or unsubstituted heteroaryloxy group having 2 to 20 carbon atoms; a substituted or unsubstituted arylthio group having 6 to 20 carbon atoms; a substituted or unsubstituted heteroarylthio group having 2 to 20 carbon atoms; or a substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms.
In one embodiment of the present specification, at least one of R3, R4, R10 and R11 is a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms; a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms; a substituted or unsubstituted heteroaryloxy group having 2 to 10 carbon atoms; a substituted or unsubstituted arylthio group having 6 to 12 carbon atoms; a substituted or unsubstituted heteroarylthio group having 2 to 10 carbon atoms; or a substituted or unsubstituted alkylthio group having 1 to 10 carbon atoms.
In one embodiment of the present specification, at least one of R3, R4, R10 and R11 is a substituted or unsubstituted phenyloxy group; a substituted or unsubstituted isopropoxy group; a substituted or unsubstituted ethoxy group; a substituted or unsubstituted phenylthio group; a substituted or unsubstituted pyridinethio group; a substituted or unsubstituted isopropylthio group; or a substituted or unsubstituted pyridinoxy group.
In one embodiment of the present specification, at least one of R3, R4, R10 and R11 is a phenyloxy group unsubstituted or substituted with an ethyl group, a tert-butyl group, a methoxy group, fluorine, a nitrile group, a nitro group or a trifluoromethyl group; an isopropoxy group substituted with fluorine; an ethoxy group substituted with fluorine; a phenylthio group substituted with chlorine; a pyridinethiogroup; an isopropylthiogroup; or a pyridinoxy group.
In one embodiment of the present specification, R3, R4, R10 and R11 are a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted heteroaryloxy group; a substituted or unsubstituted arylthio group; a substituted or unsubstituted heteroarylthio group; or a substituted or unsubstituted alkylthio group.
In one embodiment of the present specification, R3, R4, R10 and R11 are a phenyloxy group unsubstituted or substituted with an ethyl group, a tert-butyl group, a methoxy group, fluorine, a nitrile group, a nitro group or a trifluoromethyl group; an isopropoxy group substituted with fluorine; an ethoxy group substituted with fluorine; a phenylthio group substituted with chlorine; a pyridinethio group; an isopropylthiogroup; or a pyridinoxy group.
In one embodiment of the present specification, R1, R6, R8 and R13 are the same as or different from each other, and each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted heteroaryloxy group; a substituted or unsubstituted arylthio group; a substituted or unsubstituted heteroarylthio group; or a substituted or unsubstituted alkylthio group.
In one embodiment of the present specification, R1, R6, R8 and R13 are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted methyl group; a substituted or unsubstituted cyclopentyl group; a substituted or unsubstituted cyclohexyl group; a substituted or unsubstituted isopropylthio group; a substituted or unsubstituted phenyloxy group; or a substituted or unsubstituted phenylthio group.
In one embodiment of the present specification, R1, R6, R8 and R13 are the same as or different from each other, and each independently hydrogen; a methyl group; a cyclopentyl group; a cyclohexyl group; an isopropylthio group; a phenyloxy group substituted with a nitrile group; or a phenylthio group substituted with chlorine.
In one embodiment of the present specification, R2, R5, R9 and R12 are the same as or different from each other and each independently hydrogen; deuterium; a halogen group; a nitrile group; a nitro group; —C(═O)OR; —(C═O)NR′R″; —CHO; a substituted or unsubstituted aryl group; an alkyl group substituted with fluorine; or a substituted or unsubstituted heteroaryl group, at least one of R2, R5, R9 and R12 is a halogen group; a nitrile group; a nitro group; —C(═O)OR; —(C═O)NR′R″; —CHO; a substituted or unsubstituted aryl group; an alkyl group substituted with fluorine; or a substituted or unsubstituted heteroaryl group, and R, R′ and R″ have the same definitions as in Chemical Formula 1.
In one embodiment of the present specification, R2, R5, R9 and R12 are the same as or different from each other and each independently hydrogen; a halogen group; a nitrile group; a substituted or unsubstituted phenyl group; —COOR; or —CONR′R″, and at least one of R2, R5, R9 and R12 is a halogen group; a nitrile group; a substituted or unsubstituted phenyl group; —COOR; or —CONR′R″.
In one embodiment of the present specification, R2, R5, R9 and R12 are the same as or different from each other and each independently hydrogen; chlorine; fluorine; bromine; iodine; a nitrile group; a substituted or unsubstituted phenyl group; —COOR; or —CONR′R″, and at least one of R2, R5, R9 and R12 is chlorine; fluorine; bromine; iodine; a nitrile group; a substituted or unsubstituted phenyl group; —COOR; or —CONR′R″.
In one embodiment of the present specification, R2, R5, R9 and R12 are the same as or different from each other and each independently hydrogen; chlorine; fluorine; bromine; iodine; a nitrile group; a phenyl group substituted with a trifluoromethyl group; —COOR; or —CONR′R″, and at least one of R2, R5, R9 and R12 is chlorine; fluorine; bromine; iodine; a nitrile group; a phenyl group substituted with a trifluoromethyl group; —COOR; or —CONR′R″.
In one embodiment of the present specification, R, R′ and R″ are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group.
In one embodiment of the present specification, R, R′ and R″ are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.
In one embodiment of the present specification, R, R′ and R″ are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.
In one embodiment of the present specification, R, R′ and R″ are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 10 carbon atoms.
In one embodiment of the present specification, R, R′ and R″ are the same as or different from each other, and each independently a substituted or unsubstituted methyl group; a substituted or unsubstituted ethyl group; a substituted or unsubstituted phenyl group; or a substituted or unsubstituted coumarinyl group.
In one embodiment of the present specification, R, R′ and R″ are the same as or different from each other, and each independently a methyl group; a methyl group substituted with a phenyl group substituted with a nitro group; an ethyl group; a phenyl group substituted with a trifluoromethyl group; or a coumarinyl group.
In one embodiment of the present specification, R is a methyl group substituted with a phenyl group substituted with a nitro group; an ethyl group; or a coumarinyl group.
In one embodiment of the present specification, R′ and R″ are a methyl group.
In one embodiment of the present specification, R7 and R14 are the same as or different from each other, and each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group.
In one embodiment of the present specification, R7 and R14 are the same as or different from each other, and each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.
In one embodiment of the present specification, R7 and R14 are the same as or different from each other, and each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.
In one embodiment of the present specification, R7 and R14 are the same as or different from each other, and each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 10 carbon atoms.
In one embodiment of the present specification, R7 and R14 are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted methyl group; a substituted or unsubstituted phenyl group; a substituted or unsubstituted pyridinyl group; a substituted or unsubstituted dibenzofuranyl group; a substituted or unsubstituted quinolinyl group; a substituted or unsubstituted furanyl group; a substituted or unsubstituted thiophenyl group; or a substituted or unsubstituted benzofuranyl group.
In one embodiment of the present specification, R7 and R14 are the same as or different from each other, and each independently hydrogen; a methyl group; a trifluoromethyl group; a phenyl group unsubstituted or substituted with fluorine, a methyl group, a trifluoromethyl group, a tert-butyl group or a methoxy group; a pyridinyl group; a dibenzofuranyl group; a quinolinyl group; a furanyl group; a thiophenyl group; or a benzofuranyl group.
In one embodiment of the present specification, R7 and R14 are the same as or different from each other, and each independently hydrogen; a methyl group; a trifluoromethyl group; a phenyl group; a phenyl group substituted with fluorine; a phenyl group substituted with a methyl group; a phenyl group substituted with a trifluoromethyl group; a phenyl group substituted with a tert-butyl group; a phenyl group substituted with a methyl group and a methoxy group; a phenyl group substituted with a methyl group and a tert-butyl group; a pyridinyl group; a dibenzofuranyl group; a quinolinyl group; a furanyl group; a thiophenyl group; or a benzofuranyl group.
According to another embodiment of the present specification, Chemical Formula 1 may be represented by any one of the following chemical formulae, but is not limited thereto.
In the chemical formulae,
Me means a methyl group, and Et means an ethyl group.
One embodiment of the present specification provides a composition for forming an optical film, the composition including a binder resin; and the compound described above. Specifically, the composition for forming an optical film is a composition for forming a color conversion film or a composition for forming an adhesive film.
In one embodiment of the present specification, a content of the compound represented by Chemical Formula 1 is from 0.001 wt % to 10 wt % based on 100 wt % of the binder resin. When the compound represented by Chemical Formula 1 is included in the above-mentioned range, an advantage of preparing a uniform composition is obtained.
In one embodiment of the present specification, the binder resin is a copolymer resin of a monomer providing mechanical strength; and a monomer providing alkali solubility.
The monomer providing mechanical strength of the film may be any one or more of unsaturated carboxylic acid esters; aromatic vinyls; unsaturated ethers; unsaturated imides; and acid anhydrides.
Specific examples of the unsaturated carboxylic acid ester may include benzyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, acyloctyloxy-2-hydroxypropyl (meth)acrylate, glycerol (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethoxy diethylene glycol (meth)acrylate, methoxy triethylene glycol (meth)acrylate, methoxy tripropylene glycol (meth)acrylate, poly(ethylene glycol)methyl ether (meth)acrylate, phenoxy diethylene glycol (meth)acrylate, p-nonylphenoxy polyethylene glycol (meth)acrylate, p-nonylphenoxy polypropylene glycol (meth)acrylate, glycidyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, tribromophenyl (meth)acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate and the like, but are not limited thereto.
Specific examples of the aromatic vinyl may include styrene, α-methylstyrene, (o,m,p)-vinyl toluene, (o,m,p)-methoxystyrene, (o,m,p)-chlorostyrene and the like, but are not limited thereto.
Specific examples of the unsaturated ether may include vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether and the like, but are not limited thereto.
Specific examples of the unsaturated imide may include N-phenylmaleimide, N-(4-chlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, N-cyclohexylmaleimide and the like, but are not limited thereto.
Specific examples of the acid anhydride may include maleic anhydride, methyl maleic anhydride, tetrahydrophthalic anhydride and the like, but are not limited thereto.
The monomer providing alkali solubility may be a monomer containing an acid group. Specific examples of the monomer containing an acid group may include (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprenesulfonic acid, styrenesulfonic acid, 5-norbornene-2-carboxylic acid and the like, but are not limited thereto.
In one embodiment of the present specification, the binder resin is SAN (styrene-acrylonitrile-based).
In one embodiment of the present specification, the binder resin has a weight average molecular weight of 1,000 g/mol to 200,000 g/mol.
In one embodiment of the present specification, a content of the binder resin may be from 1 wt % to 50 wt % in 100 wt % of the composition for forming an optical film.
In one embodiment of the present specification, the composition for forming an optical film may further include a functional monomer, a photoinitiator and a solvent.
In one embodiment of the present specification, the functional monomer may be a monofunctional monomer or a multifunctional monomer. The monofunctional monomer may be one or more types selected from among polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and phenoxyethyl (meth)acrylate, and the multifunctional monomer may be one or more types selected from among polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, neopentyl glycol (meth)acrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, however, the monofunctional monomer or the multifunctional monomer are not limited thereto.
In one embodiment of the present specification, a content of the functional monomer may be from 1 wt % to 30 wt % in 100 wt % of the composition for forming an optical film.
In one embodiment of the present specification, the photoinitiator is not particularly limited as long as it is an initiator generating radicals by light to trigger crosslinkage, and examples thereof may include one or more types selected from the group consisting of acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds and oxime-based compounds.
Examples of the acetophenone-based compound may include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin butyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-(4-methylthio)phenyl-2-morpholino-1-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(4-bromo-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one or the like, but are not limited thereto.
Examples of the biimidazole-based compound may include 2,2-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl biimidazole, 2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetrakis(3,4,5-trimethoxyphenyl)-1,2′-biimidazole, 2,2′-bis(2,3-dichlorophenyl)-4,4′,5,5′-tetraphenyl biimidazole, 2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole or the like, but are not limited thereto.
Examples of the triazine-based compound may include 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionic acid, 1,1,1,3,3,3-hexafluoroisopropyl-3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionate, ethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, 2-epoxyethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, cyclohexyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, benzyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, 3-{chloro-4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionic acid, 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionamide, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1,3-butadienyl-s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine or the like, but are not limited thereto.
Examples of the oxime-based compound may include 1,2-octadione-1-(4-phenylthio)phenyl-2-(o-benzoyloxime) (Ciba Specialty Chemicals, CGI124), ethanone-1-(9-ethyl)-6-(2-methylbenzoyl-3-yl)-1-(O-acetyloxime) (CGI242), N-1919 (Adeka Corporation) or the like, but are not limited thereto.
A content of the photoinitiator may be from 0.1 wt % to 10 wt % in 100 wt % of the composition for forming an optical film.
In one embodiment of the present specification, as the solvent, one or more types selected from among xylene, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, propyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methylethyl ether, propylene glycol dimethyl ether, propyl glycol diethyl ether, propylene glycol methylethyl ether, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclopentanone, cyclohexanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxy propionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate and dipropylene glycol monomethyl ether may be used, however, the solvent is not limited thereto.
In one embodiment of the present specification, the composition for forming an optical film may further include additives such as a curing agent, a surfactant, an adhesion promoter, an adhesion aid, an ultraviolet absorber, an antioxidant and an anti-aggregation agent, and a content of the additive may be from 0.1 wt % to 10 wt % in 100 wt % of the composition for forming an optical film.
In one embodiment of the present specification, the remainder other than the compound represented by Chemical Formula 1, the binder resin, the functional monomer, the photoinitiator and the additive may all be a solvent.
In one embodiment of the present specification, the optical film includes a resin matrix into which the compound is dispersed. The optical film is a color conversion film or an adhesive film.
The resin matrix means a result obtained by removing the solvent from the composition for forming an optical film described above, and thermal curing or UV curing the solvent-removed composition. Specifically, the resin matrix means a state in which the binder resin and the functional monomer are polymerized into a chain structure and solidified, and the compound represented by Chemical Formula 1, the additive and the like are uniformly distributed between the polymerized chains.
In another embodiment of the present specification, the optical film includes a cured material of the composition for forming an optical film. The cured material is obtained by drying the solvent included in the composition and then curing the solvent-dried composition, and means that each of the constituents included in the composition are crosslinked through chemical and/or physical bonding.
In one embodiment of the present specification, a content of the compound represented by Chemical Formula 1 is from 0.001 wt % to 10 wt % in 100 wt % of the optical film. The content of the compound represented by Chemical Formula 1 in the optical film may be identified through an indirect method of measuring absorption efficiency through optical properties in the film.
The optical film may include one type of the compound, or two or more types thereof.
Hereinafter, the optical film is described dividing into cases where the optical film is a color conversion film and where the optical film is an adhesive film.
In one embodiment of the present specification, when the optical film is a color conversion film, a full width at half maximum of the absorption peak is from 30 nm to 70 nm, and the maximum absorption peak is present in a range of 480 nm to 550 nm when irradiating light including a wavelength of 450 nm.
The color conversion film may further include an additional fluorescent material in addition to the compound represented by Chemical Formula 1. When using a light source emitting blue light, the color conversion film preferably includes both a green light emitting fluorescent material and a red light emitting fluorescent material. In addition, when using a light source emitting blue light and green light, the color conversion film may only include a red light emitting fluorescent material. However, the color conversion film is not limited thereto, and even when using a light source emitting blue light, the color conversion film may only include a red light emitting compound when a separate film including a green light emitting fluorescent material is laminated. On the other hand, even when using a light source emitting blue light, the color conversion film may only include a green light emitting compound when a separate film including a red light emitting fluorescent material is laminated.
The color conversion film may further include an additional layer including another resin matrix into which a compound absorbing light in a wavelength different from the wavelength of the compound represented by Chemical Formula 1 is dispersed. The compound absorbing light in a wavelength different from the wavelength of the compound represented by Chemical Formula 1 may also be the compound represented by Chemical Formula 1, or may be other known light absorbing materials.
In one embodiment of the present specification, the color conversion film further includes light diffusing particles. By dispersing light diffusing particles into the color conversion film instead of a light diffusing film used in the art for enhancing luminance, higher luminance may be obtained compared to using a separate light diffusing film, and an adhering process may be skipped as well.
As the light diffusing particles, particles having a high refractive index with the resin matrix may be used, and examples thereof may include TiO2, silica, borosilicate, alumina, sapphire, air or other air-filled hollow beads or particles (for example, air/gas-filled glass or polymer); polystyrene, polycarbonate, polymethyl methacrylate, acryl, methyl methacrylate, styrene, a melamine resin, a formaldehyde resin, or polymer particles including melamine and formaldehyde resins, or any suitable combination thereof.
In one embodiment of the present specification, the light diffusing particles may have a particle diameter in a range of 0.1 μm to 5 μm, for example, in a range of 0.3 μm to 1 μm. A content of the light diffusing particles may be determined as necessary, and for example, may be in a range of 1 parts by weight to to 30 parts by weight based on 100 parts by weight of the resin matrix.
In one embodiment of the present specification, the color conversion film may have a thickness of 2 μm to 200 μm. Specifically, the thickness may be from 2 μm to 20 am, from 2 μm to 10 μm, and from 2 μm to 5 μm. Particularly, the color conversion film may exhibit high luminance even with a small thickness of 2 μm to 20 μm. This is due to the fact that the content of the fluorescent material molecules included in the unit volume is higher compared to quantum dots.
In one embodiment of the present specification, a base may be provided on one surface of the color conversion film. This base may function as a support when preparing the color conversion film. Types of the base are not particularly limited, and the material or thickness is not limited as long as it is transparent and is capable of functioning as the support. Herein, being transparent means having visible light transmittance of 70% or higher. For example, a polyethylene terephthalate (PET) film may be used as the base.
In one embodiment of the present specification, the color conversion film may be prepared using a method of coating and drying the composition for forming a color conversion film described above on a base; or a method of extruding and filming the compound represented by Chemical Formula 1 described above with a resin.
In one embodiment of the present specification, the process of coating the composition for forming a color conversion film on a base may use a roll-to-roll process. For example, a process of unwinding a base from a base-wound roll, coating the composition for forming a color conversion film on one surface of the base, drying the result, and then winding the result again on the roll may be used. When a roll-to-roll process is used, viscosity of the composition is preferably determined in a range capable of conducting the process, and for example, may be determined in a range of 200 cps to 2,000 cps. The viscosity of the composition may be a value measured at 20° C.
As the coating method, various known methods may be used, and for example, various coating methods such as spin coating, die coating, comma coating and reverse comma coating may be used.
After the coating, a drying process is conducted. The drying process may be conducted under a condition required to remove a solvent. For example, a color conversion film including a fluorescent material including the compound represented by Chemical Formula 1 having target thickness and concentration may be obtained on a base by carrying out the drying in an oven located close to a coater under a condition to sufficiently evaporate a solvent, in a direction of the base progressing during the coating process.
In one embodiment of the present specification, when the compound represented by Chemical Formula 1 is extruded and filmed with a resin, extrusion methods known in the art may be used, and for example, the color conversion film may be prepared by extruding the compound represented by Chemical Formula 1 with a polycarbonate (PC)-based, a poly(meth)acryl-based and/or a styrene-acrylonitrile (SAN)-based resin.
In one embodiment of the present specification, the color conversion film may have a protective film or a barrier film provided on at least one surface. As the protective film or the barrier film, those known in the art may be used.
In one embodiment of the present specification, a backlight unit includes the color conversion film described above. The backlight unit may have backlight unit constitutions known in the art except for including the color conversion film.
In one embodiment of the present specification, the rate of change between initial absorption intensity measured under the backlight at the maximum absorption wavelength value of the optical film and absorption intensity measured after 1,000 hours is from 93% to 99.9%.
The maximum absorption wavelength value of the optical film is from 500 nm to 600 nm, and from 503 nm to 600 nm.
Specifically, the rate of change means (the absorption intensity measured after 1,000 hours/the initial absorption intensity)×100.
The initial absorption intensity means a value measured immediately after manufacturing the optical film.
The rate of change is specifically from 93.4% to 99.5%. The rate of change is more specifically from 93.45% to 99.41%.
When the rate of change satisfies the above-described range, the optical film has excellent light resistance and durability.
In one embodiment of the present specification, the backlight unit includes a light source and a light guide plate; the color conversion film; a prism sheet; and a double brightness enhancement film.
In examples to describe later, a structure in which a prism sheet is laminated on a color conversion film laminated on one surface of a light guide plate of a backlight unit including an LED blue back light and the light guide plate, and a double brightness enhancement film is laminated on the prism sheet. However, the structure of the backlight unit is not limited thereto, and the backlight unit structure according to
In the constitution of the backlight unit as in
One embodiment of the present specification provides a display device including the backlight unit. The display device is not particularly limited as long as it includes the backlight unit. For example, the display device includes a display module and the backlight unit.
In the present specification, when the optical film is an adhesive film, the adhesive film may function as an optical adhesive layer. The function as an optical adhesive layer means forming a black color adhesive film incorporating an organic dye capable of absorbing visible light, and an OLED panel including the same suppresses high panel reflectance. In other words, visible light transmittance of the adhesive film may be controlled in a range of approximately 30% to 90%, and transmittance in a visible region may be properly adjusted depending on the panel reflectance and the reflected color.
In one embodiment of the present application, the adhesive film may have a thickness of greater than or equal to 3 μm and less than or equal to 100 μm.
In another embodiment, the adhesive film may have a thickness of greater than or equal to 3 μm and less than or equal to 100 m, preferably greater than or equal to 5 μm and less than or equal to 80 am, and more preferably greater than or equal to 10 μm and less than or equal to 50 μm.
In one embodiment of the present specification, the adhesive film further includes a release layer provided on one surface thereof.
In the present specification, the release layer means a transparent layer formed on one surface of the adhesive film through a release treatment, and, as long as it does not adversely affect in the manufacturing process of the adhesive film, may be employed without limit in terms of materials, thicknesses, properties and the like. The release layer provided on one surface of the adhesive film may be removed after manufacturing the adhesive film.
The release layer may include one or more selected from the group consisting of acetate-based, polyester-based, polyethersulphone-based, polycarbonate-based, polyamide-based, polyimide-based, polyolefin-based, cycloolefin-based, polyurethane-based, acryl-based, fluorine-based and silicone-based resins, but is not limited thereto.
The release layer may have a thickness of greater than or equal to 10 nm and less than or equal to 1,000 nm, preferably greater than or equal to 20 nm and less than or equal to 800 nm, and more preferably greater than or equal to 40 nm and less than or equal to 100 nm, however, the thickness is not limited thereto. In the present specification, the adhesive film may be manufactured by coating the adhesive composition described above on the release layer or a base using a bar coater.
The adhesive film may be manufactured by coating the adhesive composition described above on a base using a bar coater, and then drying the result. Descriptions on the base will be provided later.
The methods of coating and drying are not particularly limited, and methods used in the art may be properly employed.
One embodiment of the present specification provides an adhesive optical filter including an adhesive film; and an anti-reflection film provided on one surface of the adhesive film.
In addition, one embodiment of the present specification provides an adhesive optical filter further including a base between the adhesive film and the anti-reflection film.
In one embodiment of the present specification, the base of the adhesive optical filter may be selected from the group consisting of PET (polyethylene terephthalate), TAC (cellulose triacetate), polyester, PC (polycarbonate), PI (polyimide), PEN (polyethylene naphthalate), PEEK (polyether ether ketone), PAR (polyarylate), PCO (polycyclic olefin), polynorbornene, PES (polyethersulphone) and COP (cycloolefin polymer).
In one embodiment of the present application, the base of the adhesive optical filter may have a thickness of greater than or equal to 10 m and less than or equal to 200 m, preferably greater than or equal to 15 μm and less than or equal to 100 μm, and more preferably greater than or equal to 20 μm and less than or equal to 75 μm.
In addition, the base is preferably transparent. The base being transparent referred herein means that light transmittance of visible light (400 nm to 700 nm) is 80% or greater. When the base has transparency in the above-mentioned range, the laminated adhesive film may be thin-filmed.
In the present specification, the anti-reflection film functions to suppress external light reflection, and those used in the art may be employed without limit. The thickness of the anti-reflection film is not particularly limited, and may be set considering the total thickness of the display device of the present specification or aiming effects. In order to suppress high panel reflectance of an OLED panel, a black color adhesive film incorporating an organic dye that absorbs visible light is formed.
Specifically, the anti-reflection film may be formed by laminating or mixing low refractive and high refractive layers in order to minimize external light reflection. This may be manufactured using a method of dry method or wet method, and the dry method is to form by laminating a plurality of thin-film layers using deposition, sputtering or the like. The wet method is normally to form a double layer using a resin with a refractive index of 1.5 or greater and a resin with a refractive index of less 1.5, and the high refractive layer with a refractive index of 1.5 or greater may be formed using a (meth)acrylate resin and the like, and as the low refractive layer with a refractive index of less 1.5, a (meth)acrylate-based resin and a fluorine-based (meth)acrylate-based resin may be used either alone or as a mixture. Herein, in order to form a layer with a lower refractive index of 1.45 or less, silica fine particles or hollow silica particles may be further included in the fluorine-based resin.
The adhesive optical filter may be manufactured by consecutively laminating an anti-reflection film provided on one surface of a base, and then laminating the adhesive film on a surface opposite to the surface in contact with the anti-reflection film of the base.
In addition, the adhesive optical filter may be manufactured by laminating an anti-reflection film provided on one surface of a base, preparing the adhesive film separately, and then attaching the adhesive film on a surface opposite to the surface in contact with the anti-reflection film laminated on the base.
The method of laminating the anti-reflection film on one surface of the base and the method of laminating the adhesive film on a surface opposite to the surface in contact with the anti-reflection film of the base are not particularly limited, and, for example, methods such as coating may be employed, and other methods used in the art may be properly employed.
One embodiment of the present specification provides a display device including the adhesive optical filter.
When the display device includes the adhesive optical filter, haze is not caused, and very superior light resistance reliability is obtained.
In one embodiment of the present specification, the display device is an OLED device including an OLED panel; and the adhesive optical filter provided on one surface of the OLED panel.
In other words, the display device may be illustrated as an OLED (organic light emitting diode) device.
In the OLED device, the descriptions provided above are applied to the adhesive optical filter.
In the present specification, the OLED panel may consecutively include a substrate, a lower electrode, an organic material layer and an upper electrode. The organic material layer may include an organic material capable of emitting light when a voltage is applied to the lower electrode and the upper electrode. Any one of the lower electrode and the upper electrode may be an anode, and the other one may be a cathode. The anode is an electrode where holes are injected, and may be made with conductive materials having high work function. The cathode is an electrode where electrons are injected, and may be made with conductive materials having low work function. As the anode, a transparent metal oxide layer such as ITO (indium tin oxide) or IZO (indium zinc oxide) having high work function may be commonly used, and as the cathode, a metal electrode having low work function may be used. An organic material layer is generally transparent, and a transparent display may be obtained when the upper electrode and the lower electrode are made to be transparent. In one example, a transparent display may be obtained when the thickness of the upper electrode or the lower electrode is employed to be very thin.
The organic material layer may include a light emitting layer, and may further include a common layer for charge injection and transport. Specifically, the common layer for charge injection and transport may include a hole transporting layer, a hole injecting layer, an electron injecting layer and an electron transporting layer for balancing electrons and holes, but is not limited thereto.
The adhesive optical filter may be disposed on a side of the OLED panel where light emits. For example, the adhesive optical filter may be disposed on an outer side of the substrate in a bottom emission structure where light emits toward the substrate side, and the adhesive optical filter may be disposed on an outer side of the encapsulation substrate in a top emission structure where light emits toward the encapsulation substrate side.
Specifically, (a) of
(b) of
Although not illustrated in the drawings, the OLED panel may have a dual emission structure, and when the OLED panel has a dual emission structure, the adhesive optical filter may be provided on both outermost side surfaces of the OLED panel, and may also be provided on one outermost side surface of the OLED panel.
The adhesive optical filter may improve visibility and display performance by minimizing external light from being reflected by a reflective layer made of a metal such as an electrode and a wire of the OLED panel and coming out of the outer side of the OLED panel. The outer side of the OLED panel means an outer side of the encapsulation substrate in the top emission, and means an outer side of the substrate in the bottom emission.
In one example, the OLED panel may further include a color filter-formed substrate as necessary. The color filter means a layer formed by coating color resists of red, green and blue in a specific pattern, and, when light passes through, displaying colors through each color filter.
(a) of
(b) of
The OLED panel may be employed without particular limit as long as it is used in the art, but may have average reflectance of approximately 30% to 50% in a wavelength range of 400 nm to 600 nm, and may also be an OLED panel with 25% or less. The average reflectance may be expressed as a sum of regular reflected light obtained by light from a light source entering the reflective surface and reflected at the same angle and diffused reflected light that is light scattered and reflected in various directions instead of being regular reflected due to irregularities or curves on the surface, and is expressed by averaging 400 nm to 600 nm reflectance values among the measured reflectance values for each wavelength.
Hereinafter, the present specification will be described in detail with reference to examples. However, the examples according to the present specification may be modified to various other forms, and the scope of the present specification is not to be construed as being limited to the examples described below. The examples of the present specification are provided in order to more fully describe the present specification to those having average knowledge in the art.
2,2′-Dipyrrolylmethane (5.0 g) was stirred well and dissolved in a tetrahydrofuran solvent. The reaction solution was cooled to −78° C. using dry ice and acetone, and N-bromosuccinimide (NBS) (2.0 equivalent) was slowly introduced thereto in a solid state while maintaining the temperature. When the reaction was completed, the reaction solution was cooled to 0° C. using ice water, and then 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (1.1 equivalent) was introduced thereto. When the reaction was completed, triethylamine (1.5 equivalent) was introduced thereto, and the result was extracted using diethyl ether and water. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 1-1 (3.4 g, yield 32.9%).
Compound 1-1 (3.4 g) was stirred well and dissolved in a chloroform solvent. The reaction solution was cooled to 0° C. using ice water, and then triethylamine (4.0 equivalent) and a boron trifluoride ethyl ether complex (BF3.OEt2) (2.0 equivalent) were slowly introduced thereto. The reaction solution was stirred at room temperature, and when the reaction was finished, the result was extracted using chloroform and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 1-2 (2.8 g, yield 71.1%).
Compound 1-2 (2.8 g) was stirred well and dissolved in an acetonitrile solvent. Sodium carbonate (8.0 equivalent) and 4-methoxyphenol (4.0 equivalent) were introduced thereto, and the reaction solution was heated to 80° C. and stirred under reflux. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 1-3 (2.1 g, yield 60.1%) was secured.
Compound 1-3 (2.1 g) was stirred well and dissolved in an N,N-dimethylacetamide solvent. Cyclohexyltrifluoroborate potassium salt (5.0 equivalent) and manganese acetate dihydrate (10.0 equivalent) were introduced thereto while stirring well, and the reaction solution was heated to between 80° C. to 100° C. When the reaction was finished, the reaction solution was cooled to room temperature, and then solids formed by introducing water thereto were filtered using a celite pad. The obtained solids and the celite pad were dissolved again in tetrahydrofuran, dried by introducing sodium sulfate thereto, and filtered. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 1-4 (2.0 g, yield 69.2%) was secured.
Compound 1-4 (2.0 g) was stirred well and dissolved in a dichloromethane solvent. After cooling the reaction solution to 0° C. using ice water, chlorosulfonyl isocyanate (2.0 equivalent) was introduced thereto, and the result was stirred at room temperature. When the reaction was completed, N,N-dimethylformamide (5.0 equivalent) was introduced thereto, and the result was stirred well again for a sufficient period of time. The result was extracted using chloroform and water, and the organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 1-5 (1.6 g, yield 76.8%) was secured.
Compound 1-5 (1.6 g) was stirred well and dissolved in an N,N-dimethylformamide solvent. The reaction solution was cooled to 0° C. using ice water, and N-fluorosuccinimide (NFS) (2.0 equivalent) was slowly introduced thereto. The reaction solution was stirred well after raising the temperature to room temperature. After the reaction was completed, the result was extracted using an aqueous sodium thiosulfate solution and dichloromethane. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 1-6 (1.3 g, yield 79.0%) was secured.
Compound 1-6 (1.3 g) was stirred well and dissolved in a dichloromethane solvent. A boron trichloride 1.0 M heptane solution (1.0 equivalent) was slowly added dropwise thereto. When the reaction was completed, the solvent was vacuum distilled at a low temperature of 30° C. or lower, then acetone and water in a ratio of 10/1 were introduced to the reaction solution remaining in the container, and the result was stirred well again. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 1-7 (0.9 g, yield 70.5%) was secured.
Compound 1-7 (0.9 g) was stirred well and dissolved in a dichloromethane solvent. Cobalt acetate tetrahydrate (0.50 equivalent) was introduced to the reaction solution in a solid state, and triethylamine (2.5 equivalent) was further introduced thereto. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 1 (0.8 g, yield 90.0%) was secured. HR LC/MS/MS m/z calculated for C72H74CoF2N6O8 (M+): 1247.4868. found: 1247.4872.
Mesityl aldehyde (80.0 g) was introduced to a pyrrole solvent and stirred well. Trifluoroacetic acid (0.10 equivalent) was slowly introduced thereto. After identifying the completion of the reaction, the result was extracted using dichloromethane and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 2-1 (45.5 g, yield 31.9%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-1 except that Compound 2-1 (45.5 g) was used instead of 2,2′-dipyrrolylmethane. When the reaction was completed, triethylamine (1.5 equivalent) was introduced thereto, and the result was extracted using diethyl ether and water. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 2-2 (34.5 g, yield 47.7%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-2 except that Compound 2-2 (4.0 g) was used instead of Compound 1-1. When the reaction was finished, the result was extracted using chloroform and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 2-3 (3.8 g, yield 85.3%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-3 except that Compound 2-3 (3.8 g) was used instead of Compound 1-2, and 4-hydroxybenzonitrile was used instead of 4-methoxyphenol. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 2-4 (3.8 g, yield 86.0%) was secured.
Under the nitrogen atmosphere at 0° C., phosphorous oxychloride (POCl3) (2.0 equivalent) and N,N-dimethylformamide (3.0 equivalent) were introduced to a chloroform solvent, and the mixture was stirred well for 1 hour. After 1 hour, Compound 2-4 (3.8 g) was introduced to the mixture solution, and the result was stirred under reflux at 60° C. After the reaction was completed, the reaction solution was cooled to 0° C. again, and the pH was adjusted to neutral using an aqueous sodium bicarbonate solution. The result was extracted using chloroform and water, and the extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 2-5 (3.6 g, yield 90.1%) was secured.
Compound 2-5 (3.6 g) was stirred well and dissolved in a chloroform solvent. N-iodosuccinimide (NIS) (3.0 equivalent) was slowly introduced thereto at room temperature. The result was heated to 50° C. and stirred to proceed a reaction, and after the reaction was finished, the result was extracted using chloroform and an aqueous sodium thiosulfate solution. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 2-6 (3.6 g, yield 82.0%) was secured.
Under the nitrogen atmosphere at 0° C., silver fluoride (AgF) (2.0 equivalent) was introduced to an N,N-dimethylformamide solvent, and stirred well. Trimethyltrifluoromethylsilane (TMSCF3) (2.0 equivalent) was slowly added dropwise to the reaction solution while maintaining the temperature. The result was stirred well for 30 minutes while slowly raising the temperature to room temperature. When the reaction solution became uniform, Cu powder (2.0 equivalent) was introduced thereto, and the result was stirred well for 2 hours. After 2 hours, Compound 2-6 (3.6 g) was introduced to the mixture solution, and the result was heated to 60° C. and stirred. After the reaction was completed, water was introduced to the reaction solution, and the result was stirred well and filtered to obtain a material in a solid state. This was extracted again using ethyl acetate and hexane. The extracted organic layer was dried with sodium sulfate, and after removing the solvent by vacuum distillation, Compound 2-7 (3.3 g, yield 99.9%) was secured without further purification.
Compound 2-7 (3.3 g) was stirred well and dissolved in a tetrahydrofuran solvent. Amidosulfonic acid (1.5 equivalent) dissolved in water was introduced thereto, and the result was stirred at room temperature. The reaction solution was cooled to 0° C., and the result was stirred well while slowly introducing sodium chlorite (1 equivalent) dissolved in water thereto. After the reaction was completed, the result was extracted with chloroform, sodium thiosulfate and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, slurried with hexane to secure Compound 2-8 (2.9 g, yield 85.7%).
Compound 2-8 (2.9 g) was introduced to a chloroform solvent, stirred well and dissolved therein. 7-Hydroxycoumarin (2.1 equivalent), 4-dimethylaminopyridine (DMAP) (2.2 equivalent) and N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDC-HCl) (2.2 equivalent) were introduced thereto, and the result was heated and stirred. After the reaction was completed, the reaction solution was cooled to room temperature, and extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using ethanol. Through the recrystallization, purified and separated Compound 2-9 (2.6 g, yield 73.5%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-7 except that Compound 2-9 (2.6 g) was used instead of Compound 1-6. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 2-10 (2.1 g, yield 81.9%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1 except that Compound 2-10 (2.1 g) was used instead of Compound 1-7, and zinc acetate dihydrate was used instead of cobalt acetate tetrahydrate. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 2 (1.8 g, yield 86.2%) was secured. HR LC/MS/MS m/z calculated for C86H52F6N8O12Zn (M+): 1566.2900. found: 1566.2951.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-3 except that Compound 2-3 (3.0 g) was used instead of Compound 1-2, and 4-fluorophenol was used instead of 4-methoxyphenol. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 3-1 (3.2 g, yield 94.1%) was secured
Synthesis was progressed in the same manner as in Synthesis of Compound 2-6 except that Compound 3-1 (3.2 g) was used instead of Compound 2-5. After the reaction was finished, the result was extracted using chloroform and an aqueous sodium thiosulfate solution. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 3-2 (3.0 g, yield 75.8%) was secured.
Compound 3-2 (3.0 g) was introduced to a solvent with a toluene/ethanol/water ratio of 2/2/1, stirred well and dissolved therein. 2,4-Ditrifluoromethylphenylboronic acid (2.1 equivalent) and tripotassium phosphate (5.0 equivalent) were introduced thereto, and the result was heated to 80° C. and stirred for 30 minutes. After 30 minutes, tetrakistriphenylphosphine palladium (0.20 equivalent) was introduced to the heated reaction solution, and the result was stirred under reflux. When the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 3-3 (3.1 g, yield 91.3%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-7 except that Compound 3-3 (3.1 g) was used instead of Compound 1-6. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 3-4 (2.6 g, yield 85.2%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1 except that Compound 3-4 (2.6 g) was used instead of Compound 1-7. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 3 (2.0 g, yield 77.8%) was secured. HR LC/MS/MS m/z calculated for C76H50CoF16N4O4 (M+): 1445.2909. found: 1445.2955.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-1 except that 4-t-butylbenzaldehyde (40.0 g) was used instead of mesityl aldehyde. After identifying the completion of the reaction, the result was extracted using dichloromethane and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 4-1 (28.5 g, yield 41.5%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-1 except that Compound 4-1 (28.5 g) was used instead of 2,2′-dipyrrolylmethane. When the reaction was completed, triethylamine (1.5 equivalent) was introduced thereto, and the result was extracted using diethyl ether and water. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 4-2 (26.5 g, yield 59.6%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-2 except that Compound 4-2 (8.0 g) was used instead of Compound 1-1. When the reaction was finished, the result was extracted using chloroform and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 4-3 (7.6 g, yield 85.6%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-3 except that Compound 4-3 (7.6 g) was used instead of Compound 1-2. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 4-4 (7.0 g, yield 78.1%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-4 except that Compound 4-4 (3.5 g) was used instead of Compound 1-3, and cyclopentylfluoroborate potassium salt was used instead of cyclohexyltrifluoroborate potassium salt. When the reaction was finished, the reaction solution was cooled to room temperature, and then solids formed by introducing water thereto were filtered using a celite pad. The obtained solids and the celite pad were dissolved again in tetrahydrofuran, dried by introducing sodium sulfate thereto, and filtered. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 4-5 (3.6 g, yield 83.0%) was secured.
Compound 4-5 (3.6 g) was stirred well and dissolved in a dichloromethane solvent. After cooling the reaction solution to 0° C. using ice water, chlorosulfonyl isocyanate (10.0 equivalent) was introduced thereto, and the result was stirred at room temperature. When the reaction was completed, N,N-dimethylformamide (20.0 equivalent) was introduced thereto, and the result was stirred well again for a sufficient period of time. The result was extracted using chloroform and water, and the organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 4-6 (2.6 g, yield 67.4%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-7 except that Compound 4-6 (2.6 g) was used instead of Compound 1-6. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 4-7 (1.9 g, yield 74.2%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 4-6 except that Compound 4-4 (3.5 g) was used instead of Compound 4-5. When the reaction was completed, N,N-dimethylformamide (20.0 equivalent) was introduced thereto, and the result was stirred well again for a sufficient period of time. The result was extracted using chloroform and water, and the organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 4-8 (1.6 g, yield 42.0%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-7 except that Compound 4-8 (1.6 g) was used instead of Compound 1-6. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 4-9 (1.4 g, yield 89.1%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1 except that Compound 4-7 (1.5 g) and Compound 4-9 (1.2 g) were used in a molar ratio of 1/1 instead of Compound 1-7, and palladium acetate was used instead of cobalt acetate tetrahydrate. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. The mixture compound purified and separated through the recrystallization was purified and separated again using a silica gel column to secure Compound 4 (0.6 g, yield 20.5%). HR LC/MS/MS m/z calculated for C80H74N8O8Pd (M+): 1380.4664. found: 1380.4659.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-8 except that Compound 2-5 (2.0 g) was used instead of Compound 2-7. After the reaction was completed, the result was extracted with chloroform, sodium thiosulfate and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, slurried with hexane to secure Compound 5-1 (1.7 g, yield 82.7%).
Synthesis was progressed in the same manner as in Synthesis of Compound 2-9 except that Compound 5-1 (1.7 g) was used instead of Compound 2-8, and 4-hydroxybenzotrifluoride was used instead of 7-hydroxycoumarin. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using ethanol. Through the recrystallization, purified and separated Compound 5-2 (1.6 g, yield 75.6%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-7 except that Compound 5-2 (1.6 g) was used instead of Compound 1-6. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 5-3 (1.4 g, yield 88.9%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1 except that Compound 5-3 (1.4 g) was used instead of Compound 1-7. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 5 (1.3 g, yield 93.9%) was secured. HR LC/MS/MS m/z calculated for C80H52CoF6N8O8 (M+): 1425.3144. found: 1425.3148.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-1 except that pentafluorobenzaldehyde (20.0 g) was used instead of mesityl aldehyde. After identifying the completion of the reaction, the result was extracted using dichloromethane and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 6-1 (11.5 g, yield 36.1%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-1 except that Compound 6-1 (11.5 g) was used instead of 2,2′-dipyrrolylmethane. When the reaction was completed, triethylamine (1.5 equivalent) was introduced thereto, and the result was extracted using diethyl ether and water. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 6-2 (9.9 g, yield 57.4%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-2 except that Compound 6-2 (3.0 g) was used instead of Compound 1-1. When the reaction was finished, the result was extracted using chloroform and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 6-3 (2.7 g, yield 81.7%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-3 except that Compound 6-3 (2.7 g) was used instead of Compound 1-2, and 4-nitrophenol was used instead of 4-methoxyphenol. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 6-4 (2.8 g, yield 84.6%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 4-6 except that Compound 6-4 (2.8 g) was used instead of Compound 4-5. When the reaction was completed, N,N-dimethylformamide (20.0 equivalent) was introduced thereto, and the result was stirred well again for a sufficient period of time. The result was extracted using chloroform and water, and the organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 6-5 (2.0 g, yield 66.2%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-7 except that Compound 6-5 (2.0 g) was used instead of Compound 1-6. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 6-6 (1.7 g, yield 86.4%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1 except that Compound 6-6 (1.7 g) was used instead of Compound 1-7, and zinc acetate dihydrate was used instead of cobalt acetate tetrahydrate. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 6 (1.4 g, yield 82.9%) was secured. HR LC/MS/MS m/z calculated for C58H20F10N12O12Zn (M+): 1330.0455. found: 1330.0460.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-1 except that 4-t-butyl-2,6-dimethylbenzaldehyde (20.0 g) was used instead of mesityl aldehyde. After identifying the completion of the reaction, the result was extracted using dichloromethane and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 7-1 (12.8 g, yield 39.7%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-1 except that Compound 7-1 (12.8 g) was used instead of 2,2′-dipyrrolylmethane. When the reaction was completed, triethylamine (1.5 equivalent) was introduced thereto, and the result was extracted using diethyl ether and water. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 7-2 (10.6 g, yield 54.9%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-2 except that Compound 7-2 (3.0 g) was used instead of Compound 1-1. When the reaction was finished, the result was extracted using chloroform and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 7-3 (2.7 g, yield 81.6%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-3 except that Compound 7-3 (2.7 g) was used instead of Compound 1-2, and 1,1,1,3,3,3-hexafluoro-2-propanol was used instead of 4-methoxyphenol. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 7-4 (2.1 g, yield 58.0%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-5 except that Compound 7-4 (2.1 g) was used instead of Compound 1-4. When the reaction was completed, N,N-dimethylformamide (5.0 equivalent) was introduced thereto, and the result was stirred well again for a sufficient period of time. The result was extracted using chloroform and water, and the organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 7-5 (1.9 g, yield 87.3%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-7 except that Compound 7-5 (1.9 g) was used instead of Compound 1-6. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 7-6 (1.6 g, yield 85.6%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1 except that Compound 7-6 (1.6 g) was used instead of Compound 1-7. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 7 (1.4 g, yield 88.5%) was secured. HR LC/MS/MS m/z calculated for C56H44CoF24N6O4 (M+): 1379.2373. found: 1379.2380.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-1 except that 3,5-dimethylbenzaldehyde (10.0 g) was used instead of mesityl aldehyde. After identifying the completion of the reaction, the result was extracted using dichloromethane and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 8-1 (5.8 g, yield 31.1%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-1 except that Compound 8-1 (5.8 g) was used instead of 2,2′-dipyrrolylmethane. When the reaction was completed, triethylamine (1.5 equivalent) was introduced thereto, and the result was extracted using diethyl ether and water. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 8-2 (4.5 g, yield 47.8%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-2 except that Compound 8-2 (3.0 g) was used instead of Compound 1-1. When the reaction was finished, the result was extracted using chloroform and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 8-3 (2.5 g, yield 74.6%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-3 except that Compound 8-3 (2.5 g) was used instead of Compound 1-2, and 2,4-difluorophenol was used instead of 4-methoxyphenol. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 8-4 (2.2 g, yield 72.3%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-5 except that Compound 8-4 (2.2 g) was used instead of Compound 2-4. After the reaction was completed, the reaction solution was cooled to 0° C. again, and the pH was adjusted to neutral using an aqueous sodium bicarbonate solution. The result was extracted using chloroform and water, and the extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 8-5 (2.0 g, yield 86.5%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-8 except that Compound 8-5 (2.0 g) was used instead of Compound 2-7. After the reaction was completed, the result was extracted with chloroform, sodium thiosulfate and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, slurried with hexane to secure Compound 8-6 (1.9 g, yield 92.5%).
Compound 8-6 (1.9 g) was introduced to an N,N-dimethylformamide solvent, stirred well and dissolved therein. After cooling the reaction solution to 0° C. using ice water, 4-nitrobenzyl bromide (1.0 equivalent) and cesium carbonate (2.1 equivalent) were introduced thereto, and the result was stirred well while raising the temperature to room temperature. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using ethanol. Through the recrystallization, purified and separated Compound 8-7 (1.5 g, yield 64.4%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-7 except that Compound 8-7 (1.5 g) was used instead of Compound 1-6. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 8-8 (1.3 g, yield 88.0%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1 except that Compound 8-8 (1.3 g) was used instead of Compound 1-7. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol.
Through the recrystallization, purified and separated Compound 8 (1.1 g, yield 85.5%) was secured.
HR LC/MS/MS m/z calculated for C74H48CoF8N6O12 (M+): 1423.2534. found: 1423.2539.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-1 except that 4-pyridinecarboxaldehyde (10.0 g) was used instead of mesityl aldehyde. After identifying the completion of the reaction, the result was extracted using dichloromethane and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 9-1 (4.5 g, yield 21.6%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-1 except that Compound 9-1 (4.5 g) was used instead of 2,2′-dipyrrolylmethane. When the reaction was completed, triethylamine (1.5 equivalent) was introduced thereto, and the result was extracted using diethyl ether and water. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 9-2 (4.0 g, yield 52.4%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-2 except that Compound 9-2 (4.0 g) was used instead of Compound 1-1. When the reaction was finished, the result was extracted using chloroform and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 9-3 (3.3 g, yield 73.3%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-3 except that Compound 9-3 (3.3 g) was used instead of Compound 1-2, and 3-methoxyphenol was used instead of 4-methoxyphenol. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 9-4 (2.9 g, yield 73.1%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-4 except that Compound 9-4 (2.9 g) was used instead of Compound 1-3. When the reaction was finished, the reaction solution was cooled to room temperature, and then solids formed by introducing water thereto were filtered using a celite pad. The obtained solids and the celite pad were dissolved again in tetrahydrofuran, dried by introducing sodium sulfate thereto, and filtered. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 9-5 (2.6 g, yield 67.9%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-5 except that Compound 9-5 (2.6 g) was used instead of Compound 1-4. When the reaction was completed, N,N-dimethylformamide (5.0 equivalent) was introduced thereto, and the result was stirred well again for a sufficient period of time. The result was extracted using chloroform and water, and the organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 9-6 (2.5 g, yield 92.7%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-7 except that Compound 9-6 (2.5 g) was used instead of Compound 1-6. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 9-7 (1.8 g, yield 73.2%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1 except that Compound 9-7 (1.8 g) was used instead of Compound 1-7, and zinc acetate dihydrate was used instead of cobalt acetate tetrahydrate. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 9 (1.5 g, yield 83.9%) was secured. HR LC/MS/MS m/z calculated for C82H82N8O8Zn (M+): 1370.5547. found: 1370.5543.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-1 except that 8-quinolinecarboxaldehyde (10.0 g) was used instead of mesityl aldehyde. After identifying the completion of the reaction, the result was extracted using dichloromethane and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 10-1 (3.8 g, yield 21.9%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-1 except that Compound 10-1 (3.8 g) was used instead of 2,2′-dipyrrolylmethane. When the reaction was completed, triethylamine (1.5 equivalent) was introduced thereto, and the result was extracted using diethyl ether and water. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 10-2 (3.1 g, yield 52.0%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-2 except that Compound 10-2 (3.1 g) was used instead of Compound 1-1. When the reaction was finished, the result was extracted using chloroform and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 10-3 (2.4 g, yield 69.7%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-3 except that Compound 10-3 (2.4 g) was used instead of Compound 1-2, and 4-nitrophenol was used instead of 4-methoxyphenol. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 10-4 (2.1 g, yield 70.3%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-5 except that Compound 10-4 (2.1 g) was used instead of Compound 2-4. After the reaction was completed, the reaction solution was cooled to 0° C. again, and the pH was adjusted to neutral using an aqueous sodium bicarbonate solution. The result was extracted using chloroform and water, and the extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 10-5 (1.8 g, yield 81.9%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-8 except that Compound 10-5 (1.8 g) was used instead of Compound 2-7. After the reaction was completed, the result was extracted with chloroform, sodium thiosulfate and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, slurried with hexane to secure Compound 10-6 (1.6 g, yield 86.7%).
Synthesis was progressed in the same manner as in Synthesis of Compound 2-9 except that Compound 10-6 (1.6 g) was used instead of Compound 2-8, and dimethylamine hydrochloride salt was used instead of 7-hydroxycoumarin. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using ethanol. Through the recrystallization, purified and separated Compound 10-7 (1.5 g, yield 89.9%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-7 except that Compound 10-7 (1.5 g) was used instead of Compound 1-6. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 10-8 (1.2 g, yield 81.4%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1 except that Compound 10-8 (1.2 g) was used instead of Compound 1-7. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 10 (1.0 g, yield 84.4%) was secured. HR LC/MS/MS m/z calculated for C66H46CoN12O14 (M+): 1289.2588. found: 1289.2594.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-3 except that Compound 2-3 (4.0 g) was used instead of Compound 1-2, and 2-hydroxypyridine was used instead of 4-methoxyphenol. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 11-1 (3.7 g, yield 87.3%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-4 except that Compound 11-1 (3.7 g) was used instead of Compound 1-3, and cyclopentylfluoroborate potassium salt was used instead of cyclohexyltrifluoroborate potassium salt. When the reaction was finished, the reaction solution was cooled to room temperature, and then solids formed by introducing water thereto were filtered using a celite pad. The obtained solids and the celite pad were dissolved again in tetrahydrofuran, dried by introducing sodium sulfate thereto, and filtered. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 11-2 (3.0 g, yield 64.0%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-5 except that Compound 11-2 (3.0 g) was used instead of Compound 1-4. When the reaction was completed, N,N-dimethylformamide (5.0 equivalent) was introduced thereto, and the result was stirred well again for a sufficient period of time. The result was extracted using chloroform and water, and the organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 11-3 (2.8 g, yield 89.9%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-7 except that Compound 11-3 (2.8 g) was used instead of Compound 1-6. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 11-4 (2.5 g, yield 90.8%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1 except that Compound 11-4 (2.5 g) was used instead of Compound 1-7, and zinc acetate dihydrate was used instead of cobalt acetate tetrahydrate. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 11 (2.2 g, yield 88.6%) was secured. HR LC/MS/MS m/z calculated for C80H80N10O4Zn (M+): 1308.5655. found: 1308.5660.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-1 except that 4-methoxy-2,6-dimethylbenzaldehyde (20.0 g) was used instead of mesityl aldehyde. After identifying the completion of the reaction, the result was extracted using dichloromethane and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 12-1 (14.7 g, yield 43.0%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-1 except that Compound 12-1 (14.7 g) was used instead of 2,2′-dipyrrolylmethane. When the reaction was completed, triethylamine (1.5 equivalent) was introduced thereto, and the result was extracted using diethyl ether and water. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 12-2 (12.6 g, yield 55.1%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-2 except that Compound 12-2 (5.0 g) was used instead of Compound 1-1. When the reaction was finished, the result was extracted using chloroform and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 12-3 (4.5 g, yield 81.1%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-3 except that Compound 12-3 (4.5 g) was used instead of Compound 1-2, and 2,4-difluorophenol was used instead of 4-methoxyphenol. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 12-4 (3.9 g, yield 72.0%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-5 except that Compound 12-4 (3.9 g) was used instead of Compound 2-4. After the reaction was completed, the reaction solution was cooled to 0° C. again, and the pH was adjusted to neutral using an aqueous sodium bicarbonate solution. The result was extracted using chloroform and water, and the extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 12-5 (3.7 g, yield 90.5%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-6 except that Compound 12-5 (3.7 g) was used instead of Compound 2-5. After the reaction was finished, the result was extracted using chloroform and an aqueous sodium thiosulfate solution. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 12-6 (3.4 g, yield 76.2%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 3-3 except that Compound 12-6 (3.4 g) was used instead of Compound 3-2, and 2-trifluoromethylphenylboronic acid was used instead of 2,4-ditrifluoromethylphenylboronic acid. When the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 12-7 (3.2 g, yield 91.8%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-8 except that Compound 12-7 (3.2 g) was used instead of Compound 2-7. After the reaction was completed, the result was extracted with chloroform, sodium thiosulfate and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, slurried with hexane to secure Compound 12-8 (2.9 g, yield 88.7%).
Synthesis was progressed in the same manner as in Synthesis of Compound 8-7 except that Compound 12-8 (2.9 g) was used instead of Compound 8-6. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using ethanol. Through the recrystallization, purified and separated Compound 12-9 (3.1 g, yield 90.9%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-7 except that Compound 12-9 (3.1 g) was used instead of Compound 1-6. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 12-10 (2.7 g, yield 88.2%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1 except that Compound 12-10 (2.7 g) was used instead of Compound 1-7, and zinc acetate dihydrate was used instead of cobalt acetate tetrahydrate. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 12 (2.4 g, yield 89.4%) was secured. HR LC/MS/MS m/z calculated for C90H58F14N6O14Zn (M+): 1776.3079. found: 1776.3071.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-1 except that benzaldehyde (20.0 g) was used instead of mesityl aldehyde. After identifying the completion of the reaction, the result was extracted using dichloromethane and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 13-1 (8.5 g, yield 20.3%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-1 except that Compound 13-1 (8.5 g) was used instead of 2,2′-dipyrrolylmethane. When the reaction was completed, triethylamine (1.5 equivalent) was introduced thereto, and the result was extracted using diethyl ether and water. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 13-2 (7.7 g, yield 53.3%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-2 except that Compound 13-2 (3.0 g) was used instead of Compound 1-1. When the reaction was finished, the result was extracted using chloroform and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 13-3 (2.9 g, yield 85.8%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-3 except that Compound 13-3 (2.9 g) was used instead of Compound 1-2, and thiophenol was used instead of 4-methoxyphenol. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 13-4 (2.9 g, yield 87.9%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 4-6 except that Compound 13-4 (2.9 g) was used instead of Compound 4-5. When the reaction was completed, N,N-dimethylformamide (20.0 equivalent) was introduced thereto, and the result was stirred well again for a sufficient period of time. The result was extracted using chloroform and water, and the organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 13-5 (2.2 g, yield 68.8%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-7 except that Compound 13-5 (2.2 g) was used instead of Compound 1-6. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 13-6 (1.9 g, yield 88.2%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1 except that Compound 13-6 (1.9 g) was used instead of Compound 1-7, and nickel acetate tetrahydrate was used instead of cobalt acetate tetrahydrate. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 13 (1.5 g, yield 80.2%) was secured. HR LC/MS/MS m/z calculated for C58H34N8NiS4 (M+): 1028.1143. found: 1028.1145.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-2 except that Compound 13-2 (4.0 g) was used instead of Compound 1-1. When the reaction was finished, the result was extracted using chloroform and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 14-1/(3.6 g, yield 79.9%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-3 except that Compound 14-1 (3.6 g) was used instead of Compound 1-2, and 4-cyanophenol was used instead of 4-methoxyphenol. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 14-2 (3.1 g, yield 73.0%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-4 except that Compound 14-2 (3.1 g) was used instead of Compound 1-3. When the reaction was finished, the reaction solution was cooled to room temperature, and then solids formed by introducing water thereto were filtered using a celite pad. The obtained solids and the celite pad were dissolved again in tetrahydrofuran, dried by introducing sodium sulfate thereto, and filtered. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 14-3 (2.8 g, yield 68.1%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-5 except that Compound 14-3 (2.8 g) was used instead of Compound 2-4. After the reaction was completed, the reaction solution was cooled to 0° C. again, and the pH was adjusted to neutral using an aqueous sodium bicarbonate solution. The result was extracted using chloroform and water, and the extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 14-4 (2.6 g, yield 89.1%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-8 except that Compound 14-4 (2.6 g) was used instead of Compound 2-7. After the reaction was completed, the result was extracted with chloroform, sodium thiosulfate and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, slurried with hexane to secure Compound 14-5 (2.2 g, yield 82.7%).
Synthesis was progressed in the same manner as in Synthesis of Compound 2-9 except that Compound 14-5 (2.2 g) was used instead of Compound 2-8. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using ethanol. Through the recrystallization, purified and separated Compound 14-6 (2.1 g, yield 79.4%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-7 except that Compound 14-6 (2.1 g) was used instead of Compound 1-6. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 14-7 (1.8 g, yield 86.9%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1 except that Compound 14-7 (1.8 g) was used instead of Compound 1-7, and nickel acetate tetrahydrate was used instead of cobalt acetate tetrahydrate. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 14 (1.5 g, yield 84.1%) was secured. HR LC/MS/MS m/z calculated for C102H82N8NiO12 (M+): 1668.5406. found: 1668.5412.
2-Trifluoroacetylpyrrole (15.0 g) was stirred well and dissolved in a methanol solvent. Sodium bicarbonate (2.1 equivalent) dissolved in methanol was introduced to the reaction solution, and sodium tetrahydroborate (NaBH4) (2.0 equivalent) was slowly introduced thereto over 10 minutes while vigorously stirring. The reaction solution was stirred well at room temperature, and when the reaction was completed, the solvent was vacuum distilled, and the result was extracted using diethyl ether and water. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 15-1 (14.1 g, yield 92.9%).
Compound 15-1 (14.1 g) was stirred well and dissolved in a dichloromethane solvent together with pyrrole (2 equivalent). Under the nitrogen atmosphere, diphosphorous pentoxide (P2O5) (1.0 equivalent) was introduced to the reaction solution, and the reaction solution was stirred well at room temperature. When the reaction was completed, sodium bicarbonate (1.3 equivalent) was introduced thereto, and the result was stirred for 1 hour. Produced precipitates were removed through filtration, then the filtrate was vacuum distilled, and a silica gel column was used to secure purified and separated Compound 15-2 (8.5 g, yield 46.5%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-1 except that Compound 15-2 (8.5 g) was used instead of 2,2′-dipyrrolylmethane. When the reaction was completed, triethylamine 1.5 equivalent) was introduced thereto, and the result was extracted using diethyl ether and water. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 15-3 (7.9 g, yield 53.8%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-2 except that Compound 15-3 (7.9 g) was used instead of Compound 1-1. When the reaction was finished, the result was extracted using chloroform and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 15-4 (7.3 g, yield 81.8%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-3 except that Compound 15-4 (7.3 g) was used instead of Compound 1-2, and 4-mercaptopyridine was used instead of 4-methoxyphenol. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 15-5 (5.9 g, yield 70.6%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-4 except that Compound 15-5 (5.9 g) was used instead of Compound 1-3. When the reaction was finished, the reaction solution was cooled to room temperature, and then solids formed by introducing water thereto were filtered using a celite pad. The obtained solids and the celite pad were dissolved again in tetrahydrofuran, dried by introducing sodium sulfate thereto, and filtered. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 15-6 (5.3 g, yield 66.9%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-5 except that Compound 15-6 (5.3 g) was used instead of Compound 1-4. When the reaction was completed, N,N-dimethylformamide (5.0 equivalent) was introduced thereto, and the result was stirred well again for a sufficient period of time. The result was extracted using chloroform and water, and the organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 15-7 (4.5 g, yield 81.7%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-7 except that Compound 15-7 (4.5 g) was used instead of Compound 1-6. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 15-8 (3.8 g, yield 91.0%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1 except that Compound 15-8 (2.0 g) was used instead of Compound 1-7. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 15 (1.4 g, yield 66.9%) was secured. HR LC/MS/MS m/z calculated for C66H62CoF6N10S4 (M+): 1295.3278. found: 1295.3283.
Compound 13-1 (5.0 g) was stirred well and dissolved in a chloroform solvent. The reaction solution was cooled to 0° C. using ice water, and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (1.1 equivalent) was introduced thereto. The reaction solution was stirred well at room temperature, and when the reaction was completed, triethylamine (1.5 equivalent) was introduced thereto, and the result was extracted using diethyl ether and water. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 16-1 (4.1 g, yield 82.7%).
Compound 16-1 (4.1 g) was stirred well and dissolved in a chloroform solvent. The reaction solution was cooled to 0° C. using ice water, and then triethylamine (4.0 equivalent) and a boron trifluoride ethyl ether complex (BF3.OEt2) (2.0 equivalent) were slowly introduced thereto. The reaction solution was stirred at room temperature, and when the reaction was finished, the result was extracted using chloroform and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 16-2 (3.5 g, yield 70.1%).
Compound 16-2 (1.0 g) was stirred well and dissolved in a dichloromethane solvent. Liquid bromine (330 equivalent) mixed with dichloromethane was introduced thereto, and the reaction solution was stirred at room temperature. After the reaction was completed, the result was extracted using an aqueous sodium thiosulfate solution, an aqueous sodium hydroxide solution and chloroform. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 16-3 (1.9 g, yield 68.7%).
Compound 16-3 (1.9 g) was stirred well and dissolved in an acetonitrile solvent. Sodium carbonate (20.0 equivalent) and 4-hydroxybenzonitrile (10.0 equivalent) were introduced thereto, and the reaction solution was heated to 80° C. and stirred under reflux. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 16-4 (1.5 g, yield 65.4%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-7 except that Compound 16-4 (1.5 g) was used instead of Compound 1-6. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 16-5 (1.3 g, yield 87.8%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1 except that Compound 16-5 (1.3 g) was used instead of Compound 1-7, and nickel acetate tetrahydrate was used instead of cobalt acetate tetrahydrate. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 16 (1.0 g, yield 77.6%) was secured. HR LC/MS/MS m/z calculated for C86H42Br4N12NiO8 (M+): 1743.9336. found: 1743.9329.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-1 except that 2-thiophenecarboxaldehyde (20.0 g) was used instead of mesityl aldehyde. After identifying the completion of the reaction, the result was extracted using dichloromethane and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 17-1 (21.0 g, yield 51.6%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-1 except that Compound 17-1 (21.0 g) was used instead of 2,2′-dipyrrolylmethane. When the reaction was completed, triethylamine (1.5 equivalent) was introduced thereto, and the result was extracted using diethyl ether and water. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 17-2 (18.8 g, yield 53.2%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-2 except that Compound 17-2 (4.0 g) was used instead of Compound 1-1. When the reaction was finished, the result was extracted using chloroform and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 17-3 (3.5 g, yield 77.8%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-3 except that Compound 17-3 (3.5 g) was used instead of Compound 1-2, and benzenethiol was used instead of 4-methoxyphenol. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 17-4 (3.0 g, yield 75.5%) was secured.
Compound 17-4 (3.0 g) was stirred well and dissolved in a chloroform solvent. N-iodosuccinimide (NIS) (6.0 equivalent) was slowly introduced thereto at room temperature. The result was heated to 50° C. and stirred to proceed a reaction, and after the reaction was finished, the result was extracted using chloroform and an aqueous sodium thiosulfate solution. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 17-5 (4.0 g, yield 88.1%) was secured.
Compound 17-5 (4.0 g) was introduced to a solvent with a toluene/ethanol/water ratio of 2/2/1, stirred well and dissolved therein. 2-Trifluoromethylphenylboronic acid (4.2 equivalent) and tripotassium phosphate (10.0 equivalent) were introduced thereto, and the result was heated to 80° C. and stirred for 30 minutes. After 30 minutes, tetrakistriphenylphosphine palladium (0.20 equivalent) was introduced to the heated reaction solution, and the result was stirred under reflux. When the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 17-6 (3.3 g, yield 78.6%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-7 except that Compound 17-6 (3.0 g) was used instead of Compound 1-6. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 17-7 (2.4 g, yield 81.2%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1 except that Compound 17-7 (2.4 g) was used instead of Compound 1-7. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 17 (1.8 g, yield 75.8%) was secured. HR LC/MS/MS m/z calculated for C78H46CoF12N4S6 (M+): 1517.1187. found: 1517.1193.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-1 except that 2-benzofurancarboxaldehyde (20.0 g) was used instead of mesityl aldehyde. After identifying the completion of the reaction, the result was extracted using dichloromethane and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 18-1 (13.5 g, yield 37.6%).
Compound 18-1 (13.5 g) was stirred well and dissolved in a tetrahydrofuran solvent. The reaction solution was cooled to −78° C. using dry ice and acetone, and N-chlorosuccinimide (NCS) (4.0 equivalent) was slowly introduced thereto in a solid state while maintaining the temperature. When the reaction was completed, the reaction solution was cooled to 0° C. using ice water, and then 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (1.1 equivalent) was introduced thereto. When the reaction was completed, triethylamine (1.5 equivalent) was introduced thereto, and the result was extracted using diethyl ether and water. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 18-2 (11.8 g, yield 57.6%).
Compound 18-2 (3.0 g) was stirred well and dissolved in a methanol/chloroform (1/1) solvent. Cobalt acetate tetrahydrate (0.50 equivalent) was introduced to the reaction solution in a solid state. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 18-3 (2.6 g, yield 80.9%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 13-4 except that Compound 18-3 (2.6 g) was used instead of Compound 13-3. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 18 (2.5 g, yield 71.4%) was secured. HR LC/MS/MS m/z calculated for C58H34Cl4CoN4O2S4 (M+): 1144.9651. found: 1144.9658.
Synthesis was progressed in the same manner as in Synthesis of Compound 2-1 except that furfural (2-furaldehyde) (20.0 g) was used instead of mesityl aldehyde. After identifying the completion of the reaction, the result was extracted using dichloromethane and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 19-1 (18.9 g, yield 42.8%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-1 except that Compound 19-1 (18.9 g) was used instead of 2,2′-dipyrrolylmethane. When the reaction was completed, triethylamine (1.5 equivalent) was introduced thereto, and the result was extracted using diethyl ether and water. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 19-2 (16.5 g, yield 50.3%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-2 except that Compound 19-2 (4.0 g) was used instead of Compound 1-1. When the reaction was finished, the result was extracted using chloroform and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 19-3 (3.6 g, yield 79.6%).
Synthesis was progressed in the same manner as in Synthesis of Compound 1-3 except that Compound 19-3 (3.6 g) was used instead of Compound 1-2, and 4-chlorobenzenethiol was used instead of 4-methoxyphenol. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 19-4 (3.2 g, yield 68.0%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 17-5 except that Compound 19-4 (3.2 g) was used instead of Compound 17-4. After the reaction was finished, the result was extracted using chloroform and an aqueous sodium thiosulfate solution. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 19-5 (4.3 g, yield 91.8%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 17-6 except that Compound 19-5 (4.3 g) was used instead of Compound 17-5. When the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 19-6 (3.9 g, yield 86.7%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1-7 except that Compound 19-6 (3.0 g) was used instead of Compound 1-6. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 19-7 (2.5 g, yield 84.5%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 1 except that Compound 19-7 (2.5 g) was used instead of Compound 1-7. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 19 (1.9 g, yield 76.7%) was secured. HR LC/MS/MS m/z calculated for C78H42Cl4CoF12N4O2S4 (M+): 1621.0085. found: 1621.0092.
Synthesis was progressed in the same manner as in Synthesis of Compound 18-2 except that Compound 19-1 (6.0 g) was used instead of Compound 18-1, and N-bromosuccinimide (NBS) was used instead of N-chlorosuccinimide (NCS). When the reaction was completed, triethylamine (1.5 equivalent) was introduced thereto, and the result was extracted using diethyl ether and water. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 20-1 (6.8 g, yield 45.7%).
Synthesis was progressed in the same manner as in Synthesis of Compound 18-3 except that Compound 20-1 (3.0 g) was used instead of Compound 18-2. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 20-2 (2.5 g, yield 79.1%) was secured.
Synthesis was progressed in the same manner as in Synthesis of Compound 13-4 except that Compound 20-2 (2.5 g) was used instead of Compound 13-3. After the reaction was completed, the result was extracted using chloroform and water. The extracted organic layer was dried with sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound 20 (2.3 g, yield 83.2%) was secured. HR LC/MS/MS m/z calculated for C50H30Br4CoN4O2S4 (M+): 1220.7317. found: 1220.7322.
2,2′-Dipyrrolylmethane (5.0 g) was stirred well and dissolved in a chloroform solvent. The reaction solution was cooled to 0° C. using ice water, and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (1.1 equivalent) was introduced thereto. The result was stirred well at room temperature, and when the reaction was completed, triethylamine (1.5 equivalent) was introduced thereto, and the result was extracted using diethyl ether and water. After drying the extracted organic layer with sodium sulfate, the reaction solution remaining in the container obtained by vacuum distilling the filtrate was stirred well again in a chloroform solvent. The reaction solution was cooled to 0° C. using ice water, and then triethylamine (20.0 equivalent) and a boron trifluoride ethyl ether complex (BF3.OEt2) (10.0 equivalent) were slowly introduced thereto. The reaction solution was stirred at room temperature, and when the reaction was finished, the result was extracted using chloroform and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 21-1 (3.3 g, yield 50.3%).
Compound 21-1 (3.3 g) was stirred well and dissolved in an N,N-dimethylacetamide solvent. Methyltrifluoroborate potassium salt (5.0 equivalent) and manganese acetate dihydrate (10.0 equivalent) were introduced thereto while stirring well, and the reaction solution was heated to between 80° C. to 100° C. When the reaction was finished, the reaction solution was cooled to room temperature, and then solids formed by introducing water thereto were filtered using a celite pad.
The obtained solids and the celite pad were dissolved again in tetrahydrofuran, dried by introducing sodium sulfate thereto, and filtered. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 21-2 (2.9 g, yield 68.0%) was secured.
Compound 21-2 (2.9 g) was stirred well and dissolved in a dichloromethane solvent. A boron trichloride 1.0 M heptane solution (1.0 equivalent) was slowly added dropwise thereto. When the reaction was completed, the solvent was vacuum distilled at a low temperature of 30° C. or lower, then acetone and water in a ratio of 10/1 were introduced to the reaction solution remaining in the container, and the result was stirred well again. When the reaction was completed, the result was extracted with dichloromethane and water, and the extracted organic layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, and the result was recrystallized using methanol. Through the recrystallization, purified and separated Compound 21-3 (2.1 g, yield 75.9%) was secured.
Compound 21-3 (2.1 g) was stirred well and dissolved in a dichloromethane solvent. Zinc acetate dihydrate (0.50 equivalent) was introduced to the reaction solution in a solid state, and triethylamine (2.5 equivalent) was further introduced thereto. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound m-H Zn complex (1.6 g, yield 77.7%) was secured. HR LC/MS/MS m/z calculated for C26H30N4Zn (M+): 462.1762. found: 462.1765.
Benzaldehyde (5.0 g) was introduced to a 2,4-dimethylpyrrole solvent and stirred well. Trifluoroacetic acid (0.10 equivalent) was slowly introduced thereto. After identifying the completion of the reaction, the result was extracted using dichloromethane and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 22-1 (3.9 g, yield 29.7%).
Compound 22-1 (3.9 g) was stirred well and dissolved in a chloroform solvent. The reaction solution was cooled to 0° C. using ice water, and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (1.1 equivalent) was introduced thereto. The reaction solution was stirred well at room temperature, and when the reaction was completed, triethylamine (1.5 equivalent) was introduced thereto, and the result was extracted using diethyl ether and water. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound 22-2 (3.3 g, yield 85.2%).
Compound 22-2 (3.3 g) was stirred well and dissolved in a methanol/chloroform (1/1) solvent. Zinc acetate dihydrate (0.50 equivalent) was introduced to the reaction solution in a solid state. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound m-Ph Zn complex (2.6 g, yield 70.7%) was secured. HR LC/MS/MS m/z calculated for C38H38N4Zn (M+): 614.2388. found: 614.2391.
Compound 22-2 (3.0 g) was stirred well and dissolved in a chloroform solvent. The reaction solution was cooled to 0° C. using ice water, and then triethylamine (4.0 equivalent) and a boron trifluoride ethyl ether complex (BF3.OEt2) (2.0 equivalent) were slowly introduced thereto. The reaction solution was stirred at room temperature, and when the reaction was finished, the result was extracted using chloroform and an aqueous sodium bicarbonate solution. The extracted organic layer was dried with sodium sulfate, and then a silica gel column was used to secure purified and separated Compound m-Ph bodipy (2.8 g, yield 79.6%). HR LC/MS/MS m/z calculated for C19H19BF2N2(M+): 324.1609. found: 324.1611.
Compound 23-1 (2.0 g) was stirred well and dissolved in a dichloromethane solvent. Zinc acetate dihydrate (0.50 equivalent) was introduced to the reaction solution in a solid state, and triethylamine (2.5 equivalent) was further introduced thereto. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound tetra MeO Zn complex (1.2 g, yield 60.6%) was secured. HR LC/MS/MS m/z calculated for C62H76N6O4Zn (M+): 1032.5220 found: 1032.5225.
Compound 24-1 (2.0 g) was stirred well and dissolved in a dichloromethane solvent. Zinc acetate dihydrate (0.50 equivalent) was introduced to the reaction solution in a solid state, and triethylamine (2.5 equivalent) was further introduced thereto. After the reaction was completed, the result was extracted with dichloromethane and water. The extracted organic layer was dried using sodium sulfate and, after removing the solvent by vacuum distillation, recrystallized using methanol. Through the recrystallization, purified and separated Compound di MeO Zn complex (1.4 g, yield 71.1%) was secured. HR LC/MS/MS m/z calculated for C34H46N4O2Zn (M+): 606.2912 found: 606.2911.
A first solution was prepared by dissolving Compound 1 (maximum absorption wavelength 502 nm, full width at half maximum 36 nm in toluene solution), a dye-type organic light absorber, in a xylene solvent.
A second solution was prepared by dissolving a thermoplastic resin SAN (styrene-acrylonitrile-based) in a xylene solvent. The first solution and the second solution were homogeneously mixed so that the amount of Compound 1, the organic light absorber, was 0.5 parts by weight based on 100 parts by weight of the thermoplastic resin SAN (styrene-acrylonitrile). The solid content in the mixed solution was 20% by weight and viscosity was 200 cps at 20° C. This solution was coated on a PET (polyethylene terephthalate) base, and dried to prepare a color conversion film having a thickness of 3 μm.
A luminance spectrum of the prepared color conversion film was measured using a spectroradiometer (SR series of TOPCON Corporation). Specifically, the prepared color conversion film was laminated on one surface of a light guide plate of a backlight unit including an LED blue backlight (maximum emission wavelength 450 nm) and the light guide plate, and after laminating a prism sheet on the color conversion film and laminating a double brightness enhancement film on the prism sheet, a luminance spectrum of the film was measured. When measuring the luminance spectrum, an initial value was set so that the brightness of the blue LED light was 600 nit based on without the color conversion film.
An experiment was performed in the same manner as in Example 1 except that Compound 2 (maximum absorption wavelength 498 nm, full width at half maximum 39 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound 3 (maximum absorption wavelength 508 nm, full width at half maximum 31 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound 4 (maximum absorption wavelength 512 nm, full width at half maximum 24 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound 5 (maximum absorption wavelength 499 nm, full width at half maximum 29 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound 6 (maximum absorption wavelength 512 nm, full width at half maximum 36 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound 7 (maximum absorption wavelength 495 nm, full width at half maximum 42 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound 8 (maximum absorption wavelength 500 nm, full width at half maximum 43 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound 9 (maximum absorption wavelength 499 nm, full width at half maximum 47 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound (maximum absorption wavelength 511 nm, full width at half maximum 39 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound 11 (maximum absorption wavelength 503 nm, full width at half maximum 45 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound 12 (maximum absorption wavelength 498 nm, full width at half maximum 49 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound 13 (maximum absorption wavelength 566 nm, full width at half maximum 95 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound 14 (maximum absorption wavelength 498 nm, full width at half maximum 73 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound (maximum absorption wavelength 584 nm, full width at half maximum 50 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound 16 (maximum absorption wavelength 522 nm, full width at half maximum 64 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound 17 (maximum absorption wavelength 592 nm, full width at half maximum 35 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound 18 (maximum absorption wavelength 594 nm, full width at half maximum 34 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound 19 (maximum absorption wavelength 591 nm, full width at half maximum 36 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound (maximum absorption wavelength 593 nm, full width at half maximum 35 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound m-H Zn complex (maximum absorption wavelength 497 nm, full width at half maximum 20 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound m-Ph Zn complex (maximum absorption wavelength 498 nm, full width at half maximum 21 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound m-Ph bodipy (maximum absorption wavelength 496 nm, full width at half maximum 23 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound tetra MeO Zn complex (maximum absorption wavelength 501 nm, full width at half maximum 32 nm in toluene solution) was used instead of Compound 1.
An experiment was performed in the same manner as in Example 1 except that Compound di MeO Zn complex (maximum absorption wavelength 500 nm, full width at half maximum 28 nm in toluene solution) was used instead of Compound 1.
The maximum value of the film absorption wavelength, the full width at half maximum (FWHM) and the Abs intensity ratio (1000 hr, %) of each of the color conversion films according to Examples 1 to 20 and Comparative Examples 1 to 5 are as shown in the following Table 1.
In Table 1, λmax means a maximum value of the film absorption wavelength, and FWHM means, as a full width at half maximum in the absorption peak, a width of the absorption peak at half the maximum height in the maximum absorption peak. In addition, the Abs intensity ratio of Table 1 means the rate of change between initial absorption intensity measured under the backlight at Δmax (maximum value of film absorption wavelength) and absorption intensity measured after 1,000 hours, and the values of the examples are higher than the values of the comparative examples.
Accordingly, it was identified that Examples 1 to 20 had superior light resistance compared to Comparative Examples 1 to 5. When the bodipy metal complex structure of Chemical Formula 1 introduces a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted heteroaryloxy group; a substituted or unsubstituted arylthio group; a substituted or unsubstituted heteroarylthio group; or a substituted or unsubstituted alkylthio group to the substituents of R3, R4, R10 and R11, enhancement in the light resistance is clearly observed basically, and when the electron withdrawing substituent as described above is present in the substituents R2, R5, R9 and R12, the properties are further enhanced.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2020-0027250 | Mar 2020 | KR | national |
This application is a 35 U.S.C. 371 National Phase Entry Application from PCT/KR2021/002687 filed on Mar. 4, 2021, which claims priority to and the benefits of Korean Patent Application No. 10-2020-0027250, filed with the Korean Intellectual Property Office on Mar. 4, 2020, the entire contents of which are incorporated herein by reference.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2021/002687 | 3/4/2021 | WO |
