CN113874352A - Arylamine compound and use thereof - Google Patents

Arylamine compound and use thereof Download PDF

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CN113874352A
CN113874352A CN202080039976.3A CN202080039976A CN113874352A CN 113874352 A CN113874352 A CN 113874352A CN 202080039976 A CN202080039976 A CN 202080039976A CN 113874352 A CN113874352 A CN 113874352A
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小岛圭介
远藤岁幸
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Nissan Chemical Corp
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Abstract

For example, the arylamine compound represented by the formula (1) or (2) has good solubility in an organic solvent, and gives a varnish having good storage stability and good optical propertiesA thin film which can realize an organic EL element having excellent characteristics when applied to a hole injection layer or the like. (R)1Each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R2Each independently represents an aryl group which may be substituted and may contain a hetero atom, ArsEach independently represents an arylene group which may be substituted and may contain a hetero atom, and X represents an arylene group which may be substituted and may contain a hetero atom. )

Description

Arylamine compound and use thereof
Technical Field
The present invention relates to arylamine compounds and use thereof.
Background
Organic electroluminescence (hereinafter, referred to as organic EL) devices are expected to be put to practical use in the fields of displays and lighting, and various developments have been made regarding materials and device structures for the purposes of low-voltage driving, high luminance, long life, and the like.
In the organic EL device, a plurality of functional thin films are used, and one of the hole injection layers is responsible for transferring charges between the anode and the hole transport layer or the light emitting layer, and plays an important role in realizing low-voltage driving and high luminance of the organic EL device.
The method of forming the hole injection layer is roughly classified into a dry method typified by a vapor deposition method and a wet method typified by a spin coating method. By comparing these methods, the wet method can efficiently produce a thin film having high flatness over a large area.
Therefore, at present, a hole injection layer that can be formed by a wet process is desired for increasing the area of an organic EL display.
In view of such circumstances, the present inventors have developed a charge transporting material that can be applied to various wet methods and that forms a thin film that can realize excellent EL element characteristics when applied to a hole injection layer of an organic EL element, and a compound used for the charge transporting material that has good solubility in an organic solvent (see patent documents 1 to 3).
On the other hand, various studies have been made to improve the performance of organic EL devices, and for the purpose of improving light extraction efficiency, for example, studies have been made to adjust the refractive index of a functional thin film to be used. Specifically, it has been attempted to increase the efficiency of the element by using a hole injection layer and a hole transport layer having high or low refractive indices, taking into consideration the overall structure of the element and the refractive indices of other members adjacent to each other (see patent documents 4 and 5).
Therefore, the refractive index is an important factor in designing an organic EL element, and the refractive index is also considered as an important physical property value to be considered for a material for an organic EL element.
In addition, in recent years, a charge-transporting thin film for an organic EL device is desired to have high transmittance in a visible light region and high transparency in view of practical circumstances such as a decrease in color purity and color reproducibility of the organic EL device (see patent document 6).
Documents of the prior art
Patent document
Patent document 1: international publication No. 2008/129947
Patent document 2: international publication No. 2015/050253
Patent document 3: international publication No. 2017/217457
Patent document 4: japanese Kokai publication No. 2007-536718
Patent document 5: japanese Kohyo publication 2017-501585
Patent document 6: international publication No. 2013/042623
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of such circumstances, and an object of the present invention is to provide an arylamine compound which has good solubility in an organic solvent and which can form a thin film having good optical characteristics, and which can realize an organic EL element having good characteristics when the thin film is applied to a hole injection layer or the like.
Means for solving the problems
The present inventors have made extensive studies to achieve the above object, and as a result, have found that: a varnish obtained by dissolving a compound having an aryl diamine skeleton at the center and having at least one aryl carbazole bonded to each of the 2 amino groups via a predetermined spacer group having an arylene skeleton in an organic solvent has excellent solubility in an organic solvent, and can form a thin film having excellent optical characteristics, and when the thin film is applied to a hole injection layer or the like, an organic EL element having excellent characteristics is obtained, and the present invention has been completed.
Namely, the present invention provides:
1. an arylamine compound represented by any one of the following formulae (1) to (6) (wherein the compounds represented by the following formulae (P1) to (P4) are excluded),
[ solution 1]
Figure BDA0003380339930000031
[ wherein Ar iscEach independently represents a group represented by the formula (Q),
x independently of one another represents an arylene group which may be substituted and may contain hetero atoms,
each Y independently represents a phenylene group which may be substituted,
g independently represents an integer of 1 to 10.
[ solution 2]
Figure BDA0003380339930000032
(in the formula, R1Each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R2Each independently represents an aryl group which may be substituted and may contain a hetero atom, ArsEach independently represents an arylene group which may be substituted and may contain a hetero atom. )
[ solution 3]
Figure BDA0003380339930000041
2.1 arylamine compounds wherein Ar issRepresented by any one of the following formulae (101) to (118),
[ solution 4]
Figure BDA0003380339930000042
[ solution 5]
Figure BDA0003380339930000043
[ solution 6]
Figure BDA0003380339930000051
(in the formula, R3Each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, V1Each independently represents C (R)4)2(R4Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms), NR5(R5Hydrogen atom, alkyl group having 1 to 20 carbon atoms, or aryl group having 6 to 20 carbon atoms), S, O, or SO2，V2Represents NR5(R5The same meaning as described above), S or O. )
3.1 arylamine compounds wherein Ar issRepresented by any one of the following formulae (101A) to (118A),
[ solution 7]
Figure BDA0003380339930000052
[ solution 8]
Figure BDA0003380339930000061
[ solution 9]
Figure BDA0003380339930000062
[ solution 10]
Figure BDA0003380339930000063
[ solution 11]
Figure BDA0003380339930000071
[ solution 12]
Figure BDA0003380339930000072
[ solution 13]
Figure BDA0003380339930000073
[ solution 14]
Figure BDA0003380339930000074
(in the formula, R3、V1And V2The same meanings as described above are indicated. )
4.3 arylamine compounds wherein Ar issRepresented by any one of the following formulae (101A-1) to (118A-3),
[ solution 15]
Figure BDA0003380339930000081
[ solution 16]
Figure BDA0003380339930000082
[ solution 17]
Figure BDA0003380339930000083
[ solution 18]
Figure BDA0003380339930000084
[ solution 19]
Figure BDA0003380339930000091
[ solution 20]
Figure BDA0003380339930000092
[ solution 21]
Figure BDA0003380339930000093
[ solution 22]
Figure BDA0003380339930000094
[ solution 23]
Figure BDA0003380339930000101
[ solution 24]
Figure BDA0003380339930000102
[ solution 25]
Figure BDA0003380339930000103
[ solution 26]
Figure BDA0003380339930000111
[ solution 27]
Figure BDA0003380339930000112
[ solution 28]
Figure BDA0003380339930000113
[ solution 29]
Figure BDA0003380339930000121
[ solution 30]
Figure BDA0003380339930000122
[ solution 31]
Figure BDA0003380339930000123
[ solution 32]
Figure BDA0003380339930000131
[ solution 33]
Figure BDA0003380339930000132
[ chemical 34]
Figure BDA0003380339930000133
[ solution 35]
Figure BDA0003380339930000134
[ solution 36]
Figure BDA0003380339930000141
(in the formula, R4And R5The same meanings as described above are indicated. )
5.1 to 4, wherein X is represented by any one of the following formulas (201) to (207),
[ solution 37]
Figure BDA0003380339930000142
(in the formula, R6Each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, W1Each independently represents a single bond, C (R)7)2(R7Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms), S, O, or SO2，W2Represents C (R)7)2(R7Each independently represents the same meaning as described above), NR8(R8Hydrogen atom, alkyl group having 1 to 20 carbon atoms, or aryl group having 6 to 20 carbon atoms), S, O, or SO2，W3Represents NR8(R8The same meaning as described above), S or O. )
6.5 the arylamine compound, wherein X is represented by any one of the following formulae (201A) to (207A),
[ solution 38]
Figure BDA0003380339930000151
(in the formula, R6、W1、W2And W3The same meanings as described above are indicated. )
7.6 the arylamine compound, wherein X is represented by any one of the following formulae (201A-1) to (207A-1),
[ solution 39]
Figure BDA0003380339930000161
[ solution 40]
Figure BDA0003380339930000162
[ solution 41]
Figure BDA0003380339930000163
(in the formula, R7、R8And W3The same meanings as described above are indicated. )
8.1 to 7, wherein Ar iscAre the same group or groups, and are,
9. a charge-transporting varnish comprising an arylamine compound of any one of 1 to 8 and an organic solvent,
10.9A charge-transporting varnish comprising a dopant species,
11. a charge-transporting film produced using the charge-transporting varnish of 9 or 10,
12. an electronic component comprising the charge transporting thin film of 11.
ADVANTAGEOUS EFFECTS OF INVENTION
The arylamine compound of the present invention has good solubility in an organic solvent, and a charge-transporting thin film having high transparency and a high refractive index can be obtained by using a charge-transporting varnish containing the arylamine compound.
The charge-transporting thin film is suitable as a thin film for electronic devices such as organic EL devices, and particularly as a thin film for electronic devices in which a wet-process laminated thin film is used as an upper layer.
Drawings
FIG. 1 shows a schematic view of a compound obtained in production example 1-11H-NMR spectrum.
FIG. 2 shows production of the compound obtained in production example 1-21H-NMR spectrum.
FIG. 3 shows production of the compound obtained in production example 1-21H-NMR spectrum.
FIG. 4 shows production of the compound obtained in production example 1-21H-NMR spectrum.
FIG. 5 shows production of the compounds obtained in production examples 1 to 31H-NMR spectrum.
FIG. 6 shows production of the compounds obtained in production examples 1 to 31H-NMR spectrum.
FIG. 7 shows production of the compounds obtained in production examples 1 to 41H-NMR spectrum.
FIG. 8 shows production of the compounds obtained in production examples 1 to 41H-NMR spectrum.
FIG. 9 shows production of the compounds obtained in production examples 1 to 51H-NMR spectrum.
FIG. 10 shows production of the compounds obtained in production examples 1 to 51H-NMR spectrum.
FIG. 11 shows production of the compounds obtained in production examples 1 to 61H-NMR spectrum.
FIG. 12 shows production of the compounds obtained in production examples 1 to 61H-NMR spectrum.
FIG. 13 shows production of the compounds obtained in production examples 1 to 71H-NMR spectrum.
FIG. 14 shows production of the compounds obtained in production examples 1 to 71H-NMR spectrum.
FIG. 15 shows production of the compounds obtained in production examples 1 to 81H-NMR spectrum.
FIG. 16 shows production of the compounds obtained in production examples 1 to 81H-NMR spectrum.
FIG. 17 shows production of the compounds obtained in production examples 1 to 91H-NMR spectrum.
FIG. 18 shows production of the compounds obtained in production examples 1 to 91H-NMR spectrum.
FIG. 19 shows production of the compound obtained in production example 2-11H-NMR spectrum.
FIG. 20 shows production of the compound obtained in production example 2-21H-NMR spectrum.
FIG. 21 shows preparation of the Compound obtained in production example 2-21H-NMR spectrum.
FIG. 22 shows production of the compound obtained in production example 2-31H-NMR spectrum.
FIG. 23 shows production of the compounds obtained in production examples 2 to 41H-NMR spectrum.
FIG. 24 shows production of the compounds obtained in production examples 2 to 41H-NMR spectrum.
FIG. 25 shows production of the compounds obtained in production examples 2 to 51H-NMR spectrum.
FIG. 26 shows production of the compounds obtained in production examples 2 to 51H-NMR spectrum.
FIG. 27 is a photograph of the compound obtained in example 1-11H-NMR spectrum.
FIG. 28 is a photograph of the compound obtained in example 1-21H-NMR spectrum.
FIG. 29 shows production of the compound obtained in example 1 to 31H-NMR spectrum.
FIG. 30 shows examples of the compounds obtained in examples 1 to 41H-NMR spectrum.
FIG. 31 shows examples 1 to 5 in which1H-NMR spectrum.
FIG. 32 shows examples of the compounds obtained in examples 1 to 61H-NMR spectrum.
FIG. 33 is a photograph of the compounds obtained in examples 1 to 71H-NMR spectrum.
FIG. 34 shows examples of the compounds obtained in examples 1 to 81H-NMR spectrum.
FIG. 35 shows examples of the compounds obtained in examples 1 to 91H-NMR spectrum.
FIG. 36 shows examples 1 to 10 in which the compounds obtained in examples1H-NMR spectrum.
FIG. 37 is a drawing showing the results of examples 1 to 111H-NMR spectrum.
FIG. 38 shows the results of examples 1 to 121H-NMR spectrum.
FIG. 39 shows examples of compounds obtained in examples 1 to 121H-NMR spectrum.
FIG. 40 is a photograph of the compounds obtained in examples 1 to 131H-NMR spectrum.
FIG. 41 shows examples 1 to 13 in which the compounds obtained1H-NMR spectrum.
FIG. 42 shows examples of the compounds obtained in examples 1 to 141H-NMR spectrum.
FIG. 43 shows examples of the compounds obtained in examples 1 to 151H-NMR spectrum.
FIG. 44 shows the results of examples 1 to 161H-NMR spectrum.
FIG. 45 shows examples 1 to 17 in which1H-NMR spectrum.
FIG. 46 shows examples 1 to 17 in which1H-NMR spectrum.
FIG. 47 shows examples 1 to 18 in which the compounds obtained in example1H-NMR spectrum.
FIG. 48 shows examples of the compounds obtained in examples 1 to 191H-NMR spectrum.
FIG. 49 is a photograph of compounds obtained in examples 1 to 201H-NMR spectrum.
FIG. 50 is a photograph of the compounds obtained in examples 1 to 211H-NMR spectrum.
FIG. 51 shows examples of the compounds obtained in examples 1 to 221H-NMR spectrum.
FIG. 52 shows the results of examples 1 to 231H-NMR spectrum.
FIG. 53 is a photograph of the compound obtained in comparative example 1-11H-NMR spectrum.
FIG. 54 shows a sample of the compound obtained in comparative example 1-21H-NMR spectrum.
FIG. 55 shows examples of the compounds obtained in comparative examples 1 to 31H-NMR spectrum.
Detailed Description
The present invention will be described in more detail below.
The arylamine compound according to the present invention is characterized by being represented by any one of the following formulae (1) to (6), and as described above, does not include compounds represented by the formulae (P1) to (P4).
[ solution 42]
Figure BDA0003380339930000191
In formulae (1) to (6), ArcEach independently represents a group represented by the following formula (Q), X each independently represents an arylene group which may be substituted and may contain a hetero atom, Y each independently represents a phenylene group which may be substituted, g each independently represents an integer of 1 to 10, and preferably ArcEach independently represents a group represented by the following formula (Q ') or (Q').
[ solution 43]
Figure BDA0003380339930000201
In the formulae (Q), (Q ') and (Q'), R1Each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R2Each independently represents an aryl group which may be substituted and may contain a hetero atom, ArsEach independently represents an arylene group which may be substituted and may contain a hetero atom.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl groups; and C3-20 cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, and bicyclodecyl.
The alkoxy group having 1 to 20 carbon atoms, wherein the alkyl group may be straight, branched or cyclic, and specific examples thereof include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, n-hexoxy group, n-octoxy group, n-decoxy group, 2-methylhexoxy group, 2-ethylhexoxy group, 2-n-propylhexoxy group, 2-n-butylhexoxy group, 2-ethyldecoxy group and 3-ethylhexoxy group.
Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl.
The C1-20 haloalkyl group is a group in which at least one hydrogen atom in the C1-20 alkyl group is substituted with a halogen atom, and as a specific example, examples thereof include fluoromethyl group, difluoromethyl group, trifluoromethyl group, bromodifluoromethyl group, 2-chloroethyl group, 2-bromoethyl group, 1, 1-difluoroethyl group, 2,2, 2-trifluoroethyl group, 1,1,2, 2-tetrafluoroethyl group, 2-chloro-1, 1, 2-trifluoroethyl group, pentafluoroethyl group, 3-bromopropyl group, 2,2,3, 3-tetrafluoropropyl group, 1,1,2, 3,3, 3-hexafluoropropyl group, 1,1, 1,3, 3, 3-hexafluoropropan-2-yl group, 3-bromo-2-methylpropyl group, 4-bromobutyl group, perfluoropentyl group, and 2- (perfluorohexyl) ethyl group.
R1Preferably hydrogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, more preferably hydrogen atom, alkyl group having 1 to 10 carbon atoms, and further preferably all hydrogen atoms.
R in the above formulae (Q), (Q ') and (Q')2The aryl group which may be substituted and may contain a hetero atom in the above-mentioned order is an arylene group which may contain a hetero atom as its constituent atom, and may have a ring-fused structure or a ring-linked structure. The carbon number is not particularly limited, but is usually 6 to 60, preferably 40 or less, and more preferably 30 or less.
As R2Specific examples of the substituent of the aryl group which may be substituted and may contain a hetero atom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms, and the same groups as those described above are listed as specific examples of the halogen atom, the alkyl group having 1 to 20 carbon atoms, the halogenated alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms.
Specific examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, n-1-propenyl, n-2-propenyl, 1-methylvinyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, n-1-eicosenyl and the like.
Specific examples of the alkynyl group having 2 to 20 carbon atoms include an ethynyl group, an n-1-propynyl group, an n-2-propynyl group, an n-1-butynyl group, an n-2-butynyl group, an n-3-butynyl group, a 1-methyl-2-propynyl group, an n-1-pentynyl group, an n-2-pentynyl group, an n-3-pentynyl group, an n-4-pentynyl group, a 1-methyl-n-butynyl group, a 2-methyl-n-butynyl group, a 3-methyl-n-butynyl group, a1, 1-dimethyl-n-propynyl group, an n-1-hexynyl group, an n-1-decynyl group, an n-1-pentadecynyl group, an, N-1-eicosynyl, and the like.
As R2The aryl group having 6 to 10 carbon atoms which may be substituted and may contain a hetero atom is preferable, the phenyl group which may be substituted and the naphthyl group which may be substituted are more preferable, the phenyl group or the naphthyl group are even more preferable, and the phenyl group is even more preferable.
Are listed as followsR2Specific examples of preferred groups include, but are not limited to, these.
[ solution 44]
Figure BDA0003380339930000221
[ solution 45]
Figure BDA0003380339930000222
[ solution 46]
Figure BDA0003380339930000223
[ solution 47]
Figure BDA0003380339930000231
[ solution 48]
Figure BDA0003380339930000234
[ solution 49]
Figure BDA0003380339930000232
[ solution 50]
Figure BDA0003380339930000233
Ar in the above formulae (Q), (Q ') and (Q')sThe arylene group which may be substituted and may contain a hetero atom is an arylene group which may contain a hetero atom as its constituent atom, and may have a ring-fused structure or a ring-linked structure. The carbon number is not particularly limited, but is usually 6 to 60, preferably 40 or less, and more preferably 40 or lessIs 30 or less.
As ArsSpecific examples of the substituent of the arylene group which may be substituted and may contain a hetero atom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms, and the same groups as those described above are listed as the halogen atom, the alkyl group having 1 to 20 carbon atoms, the halogenated alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms.
In a preferred embodiment, ArsIs a group represented by any one of the following formulae (101) to (118).
[ solution 51]
Figure BDA0003380339930000241
[ solution 52]
Figure BDA0003380339930000243
[ Hua 53]
Figure BDA0003380339930000242
R3Each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, V1Each independently represents C (R)4)2(R4Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a haloalkyl group having 1 to 20 carbon atoms. ) NR, NR5(R5Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. ) S, O, or SO2，V2Represents NR5(R5The same meanings as described above are indicated. ) S or O.
As R3～R5Middle, halogen atom, carbon number 1-20Examples of the alkyl group, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms and haloalkyl group having 1 to 20 carbon atoms include the same groups as described above.
In particular, R3Each independently preferably represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and further preferably a hydrogen atom, a methyl group, or a trifluoromethyl group. Furthermore, from the viewpoint of reducing the extinction coefficient of the resulting film, at least one R is preferred3An electron-withdrawing group such as a halogen atom, a nitro group, a cyano group, or a fluoroalkyl group having 1 to 5 carbon atoms, and in this regard, a trifluoromethyl group is more preferable.
R4Each independently preferably represents an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and further preferably a methyl group.
R5Preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a naphthyl group, and further preferably a hydrogen atom, a methyl group, or a phenyl group.
In addition, in all R3In the case where the compound is not an electron-withdrawing group, V is a group which reduces the extinction coefficient of the resulting film1Preferably S, O, SO2. Furthermore, at V1Is S, O, SO2In the case of (1), can be at R3In the presence of an electron withdrawing group.
Further, in all R3In the case where the compound is not an electron-withdrawing group, V is a group which reduces the extinction coefficient of the resulting film2Preferably S, O. Furthermore, at V2In the case of S, O, R may be3In the presence of an electron withdrawing group.
As ArsA group represented by any one of the following formulae (101A) to (118A) is preferable.
[ solution 54]
Figure BDA0003380339930000261
[ solution 55]
Figure BDA0003380339930000262
[ solution 56]
Figure BDA0003380339930000263
[ solution 57]
Figure BDA0003380339930000271
[ solution 58]
Figure BDA0003380339930000272
[ chemical 59]
Figure BDA0003380339930000273
[ solution 60]
Figure BDA0003380339930000274
[ solution 61]
Figure BDA0003380339930000281
(in the formula, R3、V1And V2The same meanings as described above are indicated. )
Are listed below as ArsPreferred specific examples are, but not limited to, these.
[ solution 62]
Figure BDA0003380339930000282
[ solution 63]
Figure BDA0003380339930000283
[ solution 64]
Figure BDA0003380339930000284
[ solution 65]
Figure BDA0003380339930000291
[ solution 66]
Figure BDA0003380339930000292
(in the formula, R4And R5The same meanings as described above are indicated. )
[ solution 67]
Figure BDA0003380339930000293
(in the formula, R4And R5The same meanings as described above are indicated. )
[ solution 68]
Figure BDA0003380339930000294
(in the formula, R4And R5The same meanings as described above are indicated. )
[ solution 69]
Figure BDA0003380339930000301
(in the formula, R4And R5The same meanings as described above are indicated. )
[ solution 70]
Figure BDA0003380339930000302
(in the formula, R4And R5The same meanings as described above are indicated. )
[ solution 71]
Figure BDA0003380339930000303
(in the formula, R4And R5The same meanings as described above are indicated. )
[ chemical formula 72]
Figure BDA0003380339930000311
(in the formula, R4And R5The same meanings as described above are indicated. )
[ solution 73]
Figure BDA0003380339930000312
(in the formula, R4And R5The same meanings as described above are indicated. )
[ chemical formula 74]
Figure BDA0003380339930000313
(in the formula, R4And R5The same meanings as described above are indicated. )
[ solution 75]
Figure BDA0003380339930000321
(in the formula, wherein,R4and R5The same meanings as described above are indicated. )
[ 76]
Figure BDA0003380339930000322
(in the formula, R4And R5The same meanings as described above are indicated. )
[ solution 77]
Figure BDA0003380339930000323
(in the formula, R4And R5The same meanings as described above are indicated. )
[ solution 78]
Figure BDA0003380339930000331
(in the formula, R4And R5The same meanings as described above are indicated. )
[ solution 79]
Figure BDA0003380339930000332
(in the formula, R4And R5The same meanings as described above are indicated. )
[ solution 80]
Figure BDA0003380339930000333
(in the formula, R4And R5The same meanings as described above are indicated. )
[ solution 81]
Figure BDA0003380339930000341
(in the formula, R4And R5The same meanings as described above are indicated. )
[ solution 82]
Figure BDA0003380339930000342
[ solution 83]
Figure BDA0003380339930000343
(in the formula, R5The same meanings as described above are indicated. )
[ solution 84]
Figure BDA0003380339930000351
(in the formula, R5The same meanings as described above are indicated. )
The arylene group which may be substituted and may contain a hetero atom for X in the above formulae (1) and (2) is not particularly limited, and may have a ring-fused structure or a ring-linked structure. The carbon number is not particularly limited, but is usually 6 to 60, preferably 40 or less, and more preferably 30 or less.
Specific examples of the substituent of the arylene group which may be substituted with X and may contain a hetero atom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms, and the same groups as those described above are listed as the halogen atom, the alkyl group having 1 to 20 carbon atoms, the halogenated alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms.
In particular, the arylene group which may be substituted and may contain a hetero atom in X in the above formulae (1) and (2) is preferably a group having a valence of 2 represented by any one of the following formulae (201) to (207) if the balance of refractive index, transparency and electrical characteristics is taken into consideration.
[ solution 85]
Figure BDA0003380339930000361
In the formulae (201) to (207), R6Each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, W1Each independently represents a single bond, C (R)7)2(R7Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms), S, O, or SO2，W2Represents C (R)7)2(R7Each independently represents the same meaning as described above), NR8(R8Hydrogen atom, alkyl group having 1 to 20 carbon atoms, or aryl group having 6 to 20 carbon atoms), S, O, or SO2，W3Represents NR8(R8The same meaning as described above), S or O. As R6～R8In (3), the halogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms and halogenated alkyl group having 1 to 20 carbon atoms are the same as those mentioned above.
In particular, R6Each independently preferably represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and further preferably a hydrogen atom, a methyl group, or a trifluoromethyl group. Furthermore, at least one R is selected from the group consisting of6Preferably an electron-withdrawing group such as a halogen atom, a nitro group, a cyano group, or a fluoroalkyl group having 1 to 5 carbon atoms, and more preferably a trifluoromethyl group.
R7Each independently preferably represents an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and further preferably a methyl group.
R8Preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a naphthyl group, and further preferably a hydrogen atom, a methyl group, or a phenyl group.
In addition, in all R6In the case where the group is not an electron-withdrawing group, W is added to the resulting film in order to lower the extinction coefficient1Preferably S, O, SO2. Furthermore, in W1Is S, O, SO2In the case of R6Electron withdrawing groups may be present.
In addition, in all R6In the case where the group is not an electron-withdrawing group, W is added to the resulting film in order to lower the extinction coefficient2Preferably S, O, SO2. Furthermore, in W2Is S, O, SO2In the case of R6Electron withdrawing groups may be present.
Further, in all R6In the case where the group is not an electron-withdrawing group, W is added to the resulting film in order to lower the extinction coefficient3Preferably S, O. Furthermore, in W3Is S, O, SO2In the case of R6Electron withdrawing groups may be present.
Further, in the above formulas (201) to (207), the amino group on the aromatic ring and W as a spacer group1The bonding position (b) is not particularly limited, but is preferably a 2-valent group represented by any one of the following formulae (201A) to (207A).
[ solution 86]
Figure BDA0003380339930000381
(in the formula, R6、W1、W2And W3The same meanings as described above are indicated. )
From the viewpoint of improving the storage stability of a varnish using the arylamine compound of the present invention, the aromatic ring of the formulae (201) to (207) preferably has at least 1 substituent, and from this viewpoint, a group having a valence of 2 represented by any one of the formulae (201A ') to (207A') is preferable.
[ solution 87]
Figure BDA0003380339930000391
(in the formula, W1、W2And W3The same meanings as described above are indicated. )
In the formulae (201A ') to (207A'), R6’Each independently represents a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and specific examples of the halogen atom, the alkyl group having 1 to 20 carbon atoms, the haloalkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms include the same groups as described above.
In these, R6’Preferably C1-10 alkyl, C1-10 halogenated alkyl, more preferably C1-5 alkyl, C1-5 fluorinated alkyl, further preferably methyl, trifluoromethyl.
Preferred examples of X in the present invention include groups represented by the following formulae, but are not limited thereto.
[ solution 88]
Figure BDA0003380339930000401
[ solution 89]
Figure BDA0003380339930000402
[ solution 90]
Figure BDA0003380339930000403
(in the formula, R7、R8And W3The same meanings as described above are indicated. )
Examples of the optionally substituted phenylene group of Y in the formulae (3) to (6) include a1, 4-phenylene group, a1, 3-phenylene group, or a1, 2-phenylene group which may be substituted with a halogen atom, an alkyl group, an alkenyl group, or an alkynyl group, and in consideration of the balance among refractive index, transparency, and electrical characteristics, the optionally substituted 1, 4-phenylene group or 1, 3-phenylene group is preferable, and the unsubstituted 1, 4-phenylene group or 1, 3-phenylene group is more preferable.
In the above formulae (3) to (6), g independently represents an integer of 1 to 10, and considering the solubility of the compound in an organic solvent and the transparency of the obtained film, an integer of 1 to 7 is preferable, an integer of 1 to 5 is more preferable, an integer of 1 to 3 is further preferable, 1 or 2 is further preferable, and 1 is most preferable in view of the availability of the raw material compound.
In the present invention, ArsThe group represented by the formula (107) is preferable, the group represented by any one of the formulae (107A) to (107C) is more preferable, the group represented by any one of the formulae (107A-1) to (107C-5) is even more preferable, and the group represented by the formula (107B-1) or (107C-1) is even more preferable.
In the present invention, in each of the formulae (1) to (6), Ar is present in view of ease of synthesiscPreferably the same groups.
In particular, ArcPreferred is a group (Ar) represented by the formula (Q-1)C1) More preferably a group (Ar) represented by the formula (Q-2)C2) Or a group (Ar) represented by the formula (Q-3)C3)。
[ solution 91]
Figure BDA0003380339930000411
The arylamine compound of the present invention is represented by any of the following formulae (1-1) to (6-1) in a preferred embodiment, and is represented by any of the following formulae (1-2) to (6-2) and (1-3) to (6-3) in a more preferred embodiment.
[ solution 92]
Figure BDA0003380339930000421
(in the formula, X, Y, ArC1And g represents the same meaning as described above. )
[ solution 93]
Figure BDA0003380339930000422
(in the formula, X, Y, ArC2And g represents the same meaning as described above. )
[ solution 94]
Figure BDA0003380339930000431
(in the formula, X, Y, ArC3And g represents the same meaning as described above. )
The arylamine compound represented by the formula (1) or (2) (hereinafter also referred to as arylamine compound (1) or (2)) of the present invention can be produced by reacting an aryldiamine compound [ I ] with a halogenated aryl compound [ II ] in the presence of a catalyst, as shown in the following scheme.
[ solution 95]
Figure BDA0003380339930000432
(wherein Z represents a halogen atom or a pseudo-halogen group, X, R1、R2And ArsThe same meanings as described above are indicated. )
Examples of the halogen atom include the same halogen atoms as described above.
Examples of the pseudohalogen group include (fluoro) alkylsulfonyloxy groups such as methylsulfonyloxy, trifluoromethanesulfonyloxy and nonafluorobutanesulfonyloxy; and aromatic sulfonyloxy groups such as benzenesulfonyloxy and toluenesulfonyloxy.
The feeding ratio of the aryldiamine compound [ I ] to the halogenated aryl compound [ II ] is suitably determined in the range of usually 1.2 to 0.6 equivalent based on the amount of all NH groups in the aryldiamine compound [ I ] in consideration of reactivity, bulkiness and the like of the raw material compound, depending on which of the arylamine compounds (1) and (2) is the compound to be synthesized, and in the case of synthesizing the arylamine compound (1), the amount of the halogenated aryl compound is preferably 1.0 equivalent or more.
Examples of the catalyst used in the above reaction include copper catalysts such as copper chloride, copper bromide, and copper iodide; pd (PPh)3)4(tetrakis (triphenylphosphine) palladium), Pd (PPh)3)2Cl2(bis (triphenylphosphine) palladium dichloride), Pd (dba)2(bis (dibenzylideneacetone) palladium), Pd2(dba)3(tris (dibenzylideneacetone) dipalladium), Pd (P-t-Bu)3)2(bis (tris (t-butylphosphino)) palladium), Pd (OAc)2Palladium catalysts such as (palladium acetate) and the like. These catalysts may be used alone, or 2 or more of them may be used in combination. In addition, these catalysts may be used together with known appropriate ligands.
Examples of such ligands include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri-t-butylphosphine, di-t-butylphosphine (4-dimethylaminophenyl) phosphine, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, tertiary phosphines such as 1, 4-bis (diphenylphosphino) butane and 1,1 '-bis (diphenylphosphino) ferrocene, phosphite triesters such as trimethyl phosphite, triethyl phosphite and triphenyl phosphite, commercially available from Aldrich, phosphite, John Phos, Cyjohn Phos, DavePhos, SPhos, tBuXPhos, RuPhos, Me4tBuXPhos, MesSPhos, tBuPhos, MePhos, MeveuDaPhos, tBuPhos, 2' -dicyclohexylphosphino, 4, 6-trimethoxybiphenyl, Brettphos, tBuBrettphos, AdBrettphos, Me3And (OMe) tBuXPhos, (2-biphenyl) di-1-adamantylphosphine, RockPhos, CPhos, and the like.
The amount of the catalyst to be used may be about 0.01 to 0.5mol, preferably about 0.05 to 0.2mol, based on 1mol of the halogenated aryl compound [ II ].
When the ligand is used, the amount of the ligand used can be 0.1 to 5 equivalents, preferably 1 to 2 equivalents, based on the metal complex used.
In addition, a base may be used in the above reaction. Examples of the base include simple alkali metals such as lithium, sodium, potassium, lithium hydride, sodium hydride, lithium hydroxide, potassium hydroxide, t-butoxylithium, t-butoxysodium, t-butoxypotassium, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate, alkali metals such as alkali hydrides, alkali metals hydroxides, alkali metal alkoxides, alkali metals carbonates, and alkali metals hydrogencarbonate; alkali earth carbonate metals such as calcium carbonate; organolithium such as n-butyllithium, sec-butyllithium, tert-butyllithium, Lithium Diisopropylamide (LDA), lithium 2,2, 6, 6-tetramethylpiperidine (LiTMP), Lithium Hexamethyldisilazane (LHMDS); amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, and pyridine.
When a base is used, the amount of the base used can be 0.1 to 5 equivalents, preferably 1 to 2 equivalents, based on the amount of the haloaryl compound [ II ] used.
In the case where all of the starting compounds are solid or from the viewpoint of efficiently obtaining the target arylamine compound, the above-mentioned respective reactions are carried out in a solvent. When a solvent is used, the kind thereof is not particularly limited as long as it does not adversely affect the reaction. Specific examples thereof include aliphatic hydrocarbons (e.g., pentane, N-hexane, N-octane, N-decane, decalin), halogenated aliphatic hydrocarbons (e.g., chloroform, dichloromethane, dichloroethane, and carbon tetrachloride), aromatic hydrocarbons (e.g., benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene), halogenated aromatic hydrocarbons (e.g., chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene), ethers (e.g., diethyl ether, diisopropyl ether, tert-butyl methyl ether, tetrahydrofuran, dioxane, 1, 2-dimethoxyethane, 1, 2-diethoxyethane), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, di-N-butyl ketone, and cyclohexanone), amides (e.g., N-dimethylformamide and N, N-dimethylacetamide), lactams, and lactones (e.g., N-methylpyrrolidone), γ -butyrolactone, etc.), ureas (N, N-dimethylimidazolidinone, tetramethylurea, etc.), sulfoxides (dimethyl sulfoxide, sulfolane, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.), etc., and these solvents may be used alone or in combination of 2 or more.
The reaction temperature may be suitably set in a range from the melting point to the boiling point of the solvent used, and is preferably about 0 to 200 ℃ and more preferably 20 to 150 ℃. The reaction time is appropriately determined in consideration of the reaction temperature, the reactivity of the raw material compound, and the like, and is usually about 30 minutes to 50 hours.
After the reaction is completed, the target arylamine compound can be obtained by performing post-treatment according to a conventional method.
The arylamine compounds represented by the formulae (3) to (5) (hereinafter also referred to as arylamine compounds (3), (4) or (5)) of the present invention can be produced by reacting an aryldiamine compound [ I' ] with a halogenated aryl compound [ II ] in the presence of a catalyst, as shown in the following schemes.
[ solution 96]
Figure BDA0003380339930000461
(in the formula, Y, R1、R2、Z、ArsAnd g represents the same meaning as described above. )
The feeding ratio of the aryldiamine compound [ I '] to the haloaryl compound [ II ] is not particularly limited as long as the target compound is obtained, and the haloaryl compound is usually appropriately determined in a range of 1.2 equivalents or less based on the amount of all NH groups in the aryldiamine compound [ I' ] in consideration of reactivity, bulkiness and the like of the raw material compound, and in the case of synthesizing the arylamine compound (3), the haloaryl compound is preferably 1.0 equivalent or more based on the amount of all NH groups in the aryldiamine compound [ I '], and in the case of synthesizing the arylamine compound (4), the haloaryl compound is preferably 2.0 equivalents or more, preferably 2.0 to 2.4 equivalents based on the amount of all NH groups in the aryldiamine compound [ I' ], in the case of synthesizing the halogenated arylamine compound (5), the aryl compound can be 4.0 equivalents or more, preferably 4.0 to 4.8 equivalents, relative to the amount of the substance of the aryldiamine compound [ I' ].
Further, the respective conditions and preferable conditions of the coupling reaction with respect to the catalyst, ligand, base, solvent, temperature and time of the reaction, and the like are the same as those described with respect to the arylamine compound represented by the formula (1) or (2).
The arylamine compound represented by the formula (6) of the present invention (hereinafter also referred to as arylamine compound (6)) can be produced by the following method.
First, a dinitro compound [ I '-1 ] is reacted with a halogenated aryl compound [ II ] to obtain a dinitro compound [ I' -2 ].
[ solution 97]
Figure BDA0003380339930000472
(in the formula, R1、R2、Y、Z、ArsAnd g represents the same meaning as described above. )
The feeding ratio of the dinitro compound [ I' -1] to the halogenated aryl compound [ II ] can be 1 equivalent or more, preferably about 1 to 1.2 equivalents of the halogenated aryl compound relative to the amount of all NH groups in the dinitro compound.
In addition, the respective conditions and preferable conditions of the reaction with respect to the catalyst, the ligand, the base, the solvent, the temperature and time of the reaction, and the like are the same as those described with respect to the arylamine compound represented by the formula (1) or (2).
Then, the nitro group in the dinitro compound [ I '-2 ] is reduced by hydrogenation to obtain an amine compound [ I' -3 ]. The hydrogenation may be carried out by a known method, for example, by a hydrogenation reaction using Pd/C or the like.
[ solution 98]
Figure BDA0003380339930000471
(in the formula, Y, ArcAnd g represents the same meaning as described above. )
Then, the amine compound [ I' -3] is reacted with the halogenated aryl compound [ II ], whereby the arylamine compound (6) can be obtained.
[ solution 99]
Figure BDA0003380339930000481
(in the formula, R1、R2、Y、Z、Arc、ArsAnd g represents the same meaning as described above. )
The feeding ratio of the amine compound [ I' -3] to the haloaryl compound [ II ] can be about 2 equivalents or more, preferably about 2 to 2.4 equivalents of the haloaryl compound relative to the amine compound.
In addition, the respective conditions and preferable conditions of the reaction with respect to the catalyst, the ligand, the base, the solvent, the temperature and time of the reaction, and the like are the same as those described with respect to the arylamine compound represented by the formula (1) or (2).
The haloaryl compound [ II ] used as a raw material for producing the arylamine compound of the present invention can be produced by reacting the arylcarbazole compound [ III ] with the dihaloaryl compound [ IV ] in the presence of a catalyst.
[ solution 100]
Figure BDA0003380339930000482
(in the formula, R1、R2Z and ArsThe same meanings as described above are indicated. )
ZBEach independently represents a group represented by the following formula (E1) or (E2).
[ solution 101]
Figure BDA0003380339930000483
Z' represents a halogen atom or a pseudo-halogen group, and examples of the halogen atom and the pseudo-halogen group include the same groups as described above.
Wherein Z and Z' may be the same, to efficiently obtain the desiredHomohaloaryl compounds [ II]From the viewpoint of (1), it is preferable that the reactivity of the atom (group) of Z' is higher than the reactivity of the atom (group) of Z. By setting such a difference in reactivity, the arylcarbazole compound [ III]Z in (1)BThe group (B) reacts preferentially with the atom (group) of Z' as compared with the atom (group) of Z, and the desired halogenated aryl compound [ II ] can be efficiently obtained]。
D1And D2Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, D3The alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms are the same as those mentioned above.
Examples of the alkanediyl group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a propane-1, 2-diyl group, a propane-1, 3-diyl group, a2, 2-dimethylpropane-1, 3-diyl group, a 2-ethyl-2-methylpropane-1, 3-diyl group, a2, 2-diethylpropane-1, 3-diyl group, a 2-methyl-2-propylpropane-1, 3-diyl group, a butane-2, 3-diyl group, a butane-1, 4-diyl group, a 2-methylbutane-2, 3-diyl group, a2, 3-dimethylbutane-2, 3-diyl group, a pentane-1, 3-diyl group and a pentane-1, 5-diyl, pentane-2, 3-diyl, pentane-2, 4-diyl, 2-methylpentane-2, 3-diyl, 3-methylpentane-2, 3-diyl, 4-methylpentane-2, 3-diyl, 2, 3-dimethylpentane-2, 3-diyl, 3-methylpentane-2, 4-diyl, 3-ethylpentane-2, 4-diyl, 3-dimethylpentane-2, 4-diyl, 2, 4-dimethylpentane-2, 4-diyl, hexane-1, 6-diyl, hexane-1, 2-diyl, hexane-1, 3-diyl, hexane-2, 4-diyl, hexane-2, 5-diyl, 2-methylhexane-2, 3-diyl, 4-methylhexane-2, 3-diyl, 3-methylhexane-2, 4-diyl, 2, 3-dimethylhexane-2, 4-diyl, 2, 4-dimethylhexane-2, 4-diyl, 2, 5-dimethylhexane-2, 4-diyl, 2-methylhexane-2, 5-diyl, 3-methylhexane-2, 5-diyl, 2, 5-dimethylhexane-2, 5-diyl, and the like.
Examples of the arylene group having 6 to 20 carbon atoms include a1, 2-phenylene group, a1, 2-naphthylene group, a2, 3-naphthylene group, a1, 8-naphthylene group, a1, 2-anthrylene group, a2, 3-anthrylene group, a1, 2-phenanthrylene group, a3, 4-phenanthrylene group, a 9, 10-phenanthrylene group, and the like.
The feeding ratio of the arylcarbazole compound [ III ] to the dihaloaryl compound [ IV ] is a molar ratio, and the dihaloaryl compound [ IV ] can be 1.0 or more, preferably about 1.0 to 1.2 relative to the arylcarbazole compound [ III ] 1.
When all of the starting compounds are solid or from the viewpoint of efficiently obtaining the objective haloarylamine compound, the above-mentioned respective reactions are carried out in a solvent. When a solvent is used, the kind thereof is not particularly limited as long as it does not adversely affect the reaction. Specific examples thereof include cyclic ethers such as tetrahydrofuran and 1, 4-dioxane; amides such as N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone (NMP); ketones such as methyl isobutyl ketone and cyclohexanone; halogenated hydrocarbons such as dichloromethane, chloroform, 1, 2-dichloroethane, chlorobenzene, and the like; aromatic hydrocarbons such as benzene, toluene, xylene, etc. These solvents can be used alone in 1 or more than 2 kinds of mixed use. Of these, 1, 4-dioxane, toluene, xylene and the like are particularly preferable.
Examples of the catalyst used in the above reaction include [1,1' -bis (diphenylphosphino) ferrocene]Palladium (II) dichloride (PdCl)2(dppf)), tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) Bis (triphenylphosphine) palladium dichloride (Pd (PPh)3)2Cl2) Bis (benzylidene acetone) palladium (Pd (dba)2) Tris (benzylidene acetone) dipalladium (Pd)2(dba)3) Bis (tri-tert-butylphosphine) palladium (Pd (P-t-Bu)3)2) Palladium (II) acetate (Pd (OAc)2) And palladium catalysts, and the like.
The reaction temperature may be suitably set in a range from the melting point to the boiling point of the solvent used, and is preferably about 0 to 200 ℃ and more preferably 20 to 150 ℃. The reaction time is appropriately determined in consideration of the reaction temperature, the reactivity of the raw material compound, and the like, and is usually about 30 minutes to 50 hours.
After the reaction is completed, the objective haloarylamine compound can be obtained by post-treatment according to a conventional method.
Further, the dihaloaryl compound [ IV ] can be obtained by reacting a compound represented by the formula [ IV' ] with a halogenating agent as shown in the following scheme.
[ solution 102]
Figure BDA0003380339930000501
(wherein Ar issZ and Z' are as defined above. )
The halogenating agent may be a known halogenating agent, and specific examples thereof include, but are not limited to, N-bromosuccinimide. The amount of the halogenating agent is about 1 to 1.5 in terms of a molar ratio relative to the compound represented by the formula [ IV' ].
The solvent usable in the above reaction is not particularly limited as long as it is a solvent used in the above reaction.
The reaction temperature is suitably determined usually from the range of 0 to 140 ℃ and the time is suitably determined usually from the range of 0.1 to 100 hours.
The arylcarbazole compound [ III ] can be obtained by reacting the compound represented by the formula [ III' ] with the compound represented by the formula [ V ] as shown in the following scheme.
[ solution 103]
Figure BDA0003380339930000511
(in the formula, R1、R2Z and ZBThe same meanings as described above are indicated. )
The feed ratio of the compound represented by the formula [ III '] to the compound represented by the formula [ V ] is represented by a molar ratio, and the compound represented by the formula [ V ] is about 1 to 3 relative to the compound 1 represented by the formula [ III' ].
The solvent usable in the above reaction is not particularly limited as long as it is a solvent used in the above reaction.
The temperature of the above reaction is suitably determined usually from 0 to 140 ℃ and the time is suitably determined usually from 0.1 to 100 hours.
Further, is represented by the formula [ III']The compounds represented can be represented by the formula [ III' -2] as shown in the following scheme]A compound represented by (I) and a halogenated aryl compound (R)2Z) after the reaction, treatment with a halogenating agent, or treatment with a pair of halogenating agents of the formula [ III' -2]After treatment with the compound of formula (I), with a haloaryl compound (R)2Z), and the latter reaction is preferable from the viewpoint of avoiding halogenation of an aryl group at the N-position of the carbazole skeleton and obtaining the target product more efficiently.
[ solution 104]
Figure BDA0003380339930000521
(in the formula, R1、R2And Z represents the same meaning as described above. )
As the halogenating agent used in the above reaction, a known halogenating agent can be used, and the amount of the halogenating agent is about 1 to 1.5 in terms of a molar ratio with respect to the compound represented by the formula [ III '-1-1 ] or [ III' -2] which is 1.
The solvent usable in the above reaction is not particularly limited as long as it is a solvent used in the reaction.
The temperature is suitably determined usually from 0 to 140 ℃ and the time is suitably determined usually from 0.1 to 100 hours.
In addition, it is ArSA raw material having a spacer skeleton of (A) having 2 alkyl groups or the like at the 9-position of the fluorene ring represented by the formula [ VI ]]As shown in the following scheme, the compound represented by the formula [ VI']A compound represented by the formula [ VII]The compound shown in the specification.
[ solution 105]
Figure BDA0003380339930000522
(in the formula, R3Z and Z' are as defined above, R4’Each independently represents an alkyl group having 1 to 20 carbon atoms or a haloalkyl group having 1 to 20 carbon atoms. )
The feed ratio of the compound represented by the formula [ VI '] to the compound represented by the formula [ VII ] is, in terms of a molar ratio, about 1 to 1.5 relative to the compound represented by the formula [ VI' ] which is 1.
The base usable in the above reaction is not particularly limited as long as it is a base used in the above reaction, and specific examples thereof include t-BuOK, t-BuONa, CsCO3、K2CO3、Na2CO3n-BuLi, t-BuLi, s-BuLi, NaOH, KOH, LiOH and the like, preferably t-BuOK, t-BuONa, n-BuLi, t-BuLi, s-BuLi, NaOH, KOH.
The solvent usable in the above reaction is not particularly limited as long as it is a solvent used in the above reaction.
The temperature of the above reaction is suitably determined usually from 0 to 140 ℃ and the time is suitably determined usually from 0.1 to 100 hours.
Further, the amine compound usable as a raw material of the arylamine compound of the present invention can be obtained by (a) a coupling reaction of the amine compound [ I' ″ ] or [ I "] with the aryl compound [ VIII ] and (B) a reduction reaction using a hydrogenated nitro group as shown in the following scheme, and the chain length (the number of phenylene groups) can be increased by repeating the reaction of (a) and (B).
[ solution 106]
Figure BDA0003380339930000531
(wherein Y, Z and g represent the same meanings as described above.)
[ solution 107]
Figure BDA0003380339930000532
(wherein Y, Z and g represent the same meanings as described above.)
More specifically, the amine compound contained in the amine compound [ I' ] can be obtained by (A) a coupling reaction of m-phenylenediamine or 3-nitroaniline with 3-halonitrobenzene and (B) a reduction reaction using hydrogenated nitro groups as shown in the following scheme, and the chain length (number of m-phenylene groups) can be increased by repeating the reaction of (A) and (B).
[ solution 108]
Figure BDA0003380339930000541
(wherein Z represents the same meaning as described above.)
By selecting either of the above reaction and the following reaction in the above-mentioned scheme, the odd-numbered and even-numbered phenylene groups can be formed, respectively, and an amine compound [ I' ] having a desired phenylene group can be freely produced without using a method which is difficult in synthesis such that one amino group is protected with a protecting group.
In this case, the feed ratio between the raw material compounds in each reaction is represented by the amount ratio of the substance, and the raw material compound having a nitro group (raw material compound containing a halogen atom (pseudo-halogen group)) is appropriately determined in the range of about 1 to 2.4 with respect to the raw material compound having an amino group, depending on the number of phenylene groups added being 1 or 2.
The palladium catalyst used in the coupling reaction may be the same as described above. In this case, a ligand can also be used. As the ligand, in addition to the above-exemplified ligands, John Phos, CyjohnPhos, DavePhos, XPhos, SPhos, tBuXPhos, RuPhos, Me4tBuXPhos, sSPhos, tBuMePhos, MePhos, tBuDavePhos, PhDavePhos, 2' -dicyclohexylphosphino-2, 4, 6-trimethoxybiphenyl, BrettPhos, tBu BrettPhos, AdBrettPhos, commercially available from Aldrich Co, can be preferably used,Me3(OMe) tBuXPhos, (2-biphenyl) di-1-adamantylphosphine, RockPhos, CPhos and the like.
Examples of the base used in the coupling reaction include simple alkali metals such as lithium, sodium, potassium, lithium hydride, sodium hydride, lithium hydroxide, potassium hydroxide, t-butoxylithium, t-butoxysodium, t-butoxypotassium, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate and the like, alkali metals such as hydrogen oxide, alkali metals such as alkoxy, alkali metals such as carbonate, alkali metals such as hydrogen carbonate; alkali earth carbonate metals such as calcium carbonate; organolithium such as n-butyllithium, sec-butyllithium, tert-butyllithium, Lithium Diisopropylamide (LDA), lithium 2,2, 6, 6-tetramethylpiperidine (LiTMP), Lithium Hexamethyldisilazane (LHMDS); amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, and pyridine.
Further, the respective conditions and preferable conditions of the coupling reaction concerning the catalyst, the solvent, the temperature and time of the reaction, and the like are the same as those described with respect to the arylamine compound represented by the formula (1) or (2).
The hydrogenation reaction using Pd/C can be carried out by a known method.
When a p-phenylene group or an o-phenylene group is introduced in place of a m-phenylene group, a 4-halonitrobenzene or a 2-halonitrobenzene may be used in place of a 3-halonitrobenzene.
Specific examples of the arylamine compound of the present invention are listed below, but the present invention is not limited to these.
In the table, H represents a hydrogen atom, Ph represents a phenyl group, Me represents a methyl group, n-Hex represents a n-hexyl group, p-Toly represents a p-tolyl group, 2-Thie represents a 2-thienyl group, 1, 3-Ph represents a1, 3-phenylene group, and 1, 4-Ph represents a1, 4-phenylene group, and the arylamine compounds of, for example, Nos. 1 and 865 are the following compounds, respectively.
[ solution 109]
Figure BDA0003380339930000551
[ Table 1]
Serial number A compound of the formula Formula X ArcIs of the formula R1 R2 ArSIs of the formula R4
1 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (101A-1) -
2 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (105A-1) -
3 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (106A-1) -
4 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (107A-1) Me
5 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (107B-1) Me
6 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (107C-1) Me
7 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (101A-1) -
8 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (105A-1) -
9 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (106A-1) -
10 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (107A-1) Me
11 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (107B-1) Me
12 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (107C-1) Me
13 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (101A-1) -
14 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (105A-1) -
15 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (106A-1) -
16 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (107A-1) Me
17 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (107B-1) Me
18 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (107C-1) Me
19 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (101A-1) -
20 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (105A-1) -
21 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (106A-1) -
22 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (107A-1) Me
23 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (107B-1) Me
24 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (107C-1) Me
25 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (101A-1) -
26 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (105A-1) -
27 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (106A-1) -
28 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (107A-1) Me
29 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (107B-1) Me
30 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (107C-1) Me
31 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (101A-1) -
32 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (105A-1) -
33 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (106A-1) -
34 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (107A-1) Me
35 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (107B-1) Me
36 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (107C-1) Me
37 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (101A-1) -
38 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (105A-1) -
39 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (106A-1) -
40 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (107A-1) Me
41 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (107B-1) Me
42 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (107C-1) Me
43 Formula (1) Formula (202A-2)) Formula (Q') H Ph Formula (101A-1) -
44 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (105A-1) -
45 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (106A-1) -
46 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (107A-1) Me
47 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (107B-1) Me
48 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (107C-1) Me
49 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (101A-1) -
50 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (105A-1) -
51 Formula (1) Formula (202A-3) Formula (Q) ") H Ph Formula (106A-1) -
52 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (107A-1) Me
53 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (107B-1) Me
54 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (107C-1) Me
[ Table 2]]
Serial number A compound of the formula Formula X ArcIs of the formula R1 R2 ArSIs of the formula R4
55 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (101A-1) -
56 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (105A-1) -
57 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (106A-1) -
58 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (107A-1) Me
59 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (107B-1) Me
60 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (107C-1) Me
61 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (101A-1) -
62 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (105A-1) -
63 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (106A-1) -
64 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (107A-1) Me
65 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (107B-1) Me
66 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (107C-1) Me
67 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (101A-1) -
68 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (105A-1) -
69 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (106A-1) -
70 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (107A-1) Me
71 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (107B-1) Me
72 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (107C-1) Me
73 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (101A-1) -
74 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (105A-1) -
75 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (106A-1) -
76 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (107A-1) Me
77 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (107B-1) Me
78 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (107C-1) Me
79 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (101A-1) -
80 Formula (1) Formula (202A-2) Formula (Q') H D-Toly Formula (105A-1) -
81 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (106A-1) -
82 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (107A-1) Me
83 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (107B-1) Me
84 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (107C-1) Me
85 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (101A-1) -
86 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (105A-1) -
87 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (106A-1) -
88 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (107A-1) Me
89 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (107B-1) Me
90 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (107C-1) Me
91 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (101A-1) -
92 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (105A-1) -
93 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (106A-1) -
94 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (107A-1) Me
95 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (107B-1) Me
96 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (107C-1) Me
97 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (101A-1) -
98 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (105A-1) -
99 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (106A-1) -
100 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (107A-1) Me
101 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (107B-1) Me
102 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (107C-1) Me
103 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (101A-1) -
104 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (105A-1) -
105 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (106A-1) -
106 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (107A-1) Me
107 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (107B-1) Me
108 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (107C-1) Me
[ Table 3]
Serial number A compound of the formula Formula X ArcIs of the formula R1 R2 ArSIs of the formula R4
109 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (101A-1) -
110 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (105A-1) -
111 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (106A-1) -
112 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (107A-1) Me
113 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (107B-1) Me
114 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (107C-1) Me
115 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (101A-1) -
116 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (105A-1) -
117 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (106A-1) -
118 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (107A-1) Me
119 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (107B-1) Me
120 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (107C-1) Me
121 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (101A-1) -
122 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (105A-1) -
123 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (106A-1) -
124 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (107A-1) Me
125 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (107B-1) Me
126 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (107C-1) Me
127 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (101A-1) -
128 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (105A-1) -
129 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (106A-1) -
130 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (107A-1) Me
131 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (107B-1) Me
132 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (107C-1) Me
133 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (101A-1) -
134 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (105A-1) -
135 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (106A-1) -
136 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (107A-1) Me
137 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (107B-1) Me
138 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (107C-1) Me
139 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (101A-1) -
140 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (105A-1) -
141 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (106A-1) -
142 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (107A-1) Me
143 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (107B-1) Me
144 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (107C-1) Me
145 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (101A-1) -
146 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (105A-1) -
147 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (106A-1) -
148 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (107A-1) Me
149 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (107B-1) Me
150 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (107C-1) Me
151 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (101A-1) -
152 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (105A-1) -
153 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (106A-1) -
154 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (107A-1) Me
155 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (107B-1) Me
156 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (107C-1) Me
157 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (101A-1) -
158 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (105A-1) -
159 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (106A-1) -
160 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (107A-1) Me
161 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (107B-1) Me
162 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (107C-1) Me
[ Table 4]
Serial number A compound of the formula Formula X ArcIs of the formula R1 R2 ArSIs of the formula R4
163 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (101A-1) -
164 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (105A-1) -
165 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (106A-1) -
166 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (107A-1) Me
167 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (107B-1) Me
168 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (107C-1) Me
169 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (101A-1) -
170 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (105A-1) -
171 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (106A-1) -
172 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (107A-1) Me
173 Formula (1) Formula (202)A-5) Formula (Q') H 2-Thie Formula (107B-1) Me
174 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (107C-1) Me
175 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (101A-1) -
176 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (105A-1) -
177 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (106A-1) -
178 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (107A-1) Me
179 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (107B-1) Me
180 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (107C-1) Me
181 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (101A-1) -
182 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (105A-1) -
183 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (106A-1) -
184 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (107A-1) Me
185 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (1O7B-1) Me
186 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (107C-1) Me
187 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (101A-1) -
188 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (105A-1) -
189 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (106A-1) -
190 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (107A-1) Me
191 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (107B-1) Me
192 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (107C-1) Me
193 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (101A-1) -
194 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (105A-1) -
195 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (106A-1) -
196 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (107A-1) Me
197 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (107B-1) Me
198 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (107C-1) Me
199 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (101A-1) -
200 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (105A-1) -
201 Formula (1) Formula (202A-4) Formula (Q) ") H 2-Thie Formula (106A-1) -
202 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (107A-1) Me
203 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (107B-1) Me
204 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (107C-1) Me
205 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (101A-1) -
206 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (105A-1) -
207 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (106A-1) -
208 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (107A-1) Me
209 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (107B-1) Me
210 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (107C-1) Me
211 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (101A-1) -
212 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (105A-1) -
213 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (106A-1) -
214 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (107A-1) Me
215 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (107B-1) Me
216 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (107C-1) Me
[ Table 5]
Serial number A compound of the formula Formula X ArcIs of the formula R1 R2 ArSIs of the formula R4
217 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (101A-1) -
218 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (105A-1) -
219 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (106A-1) -
220 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (107A-1) n-Hex
221 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (107B-1) n-Hex
222 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (107C-1) n-Hex
223 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (101A-1) -
224 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (105A-1) -
225 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (106A-1) -
226 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (107A-1) n-Hex
227 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (107B-1) n-Hex
228 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (107C-1) n-Hex
229 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (101A-1) -
230 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (105A-1) -
231 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (106A-1) -
232 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (107A-1) n-Hex
233 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (107B-1) n-Hex
234 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (107C-1) n-Hex
235 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (101A-1) -
236 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (105A-1) -
237 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (106A-1) -
238 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (107A-1) n-Hex
239 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (107B-1) n-Hex
240 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (107C-1) n-Hex
241 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (101A-1) -
242 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (105A-1) -
243 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (106A-1) -
244 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (107A-1) n-Hex
245 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (107B-1) n-Hex
246 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (107C-1) n-Hex
247 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (101A-1) -
248 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (105A-1) -
249 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (106A-1) -
250 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (107A-1) n-Hex
251 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (107B-1) n-Hex
252 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (107C-1) n-Hex
253 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (101A-1) -
254 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (105A-1) -
255 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (106A-1) -
256 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (107A-1) n-Hex
257 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (107B-1) n-Hex
258 Formula (1) Formula (202A-1) Formula (Q') H Ph Formula (107C-1) n-Hex
259 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (101A-1) -
260 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (105A-1) -
261 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (106A-1) -
262 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (107A-1) n-Hex
263 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (107B-1) n-Hex
264 Formula (1) Formula (202A-2) Formula (Q') H Ph Formula (107C-1) n-Hex
265 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (101A-1) -
266 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (105A-1) -
267 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (106A-1) -
268 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (107A-1) n-Hex
269 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (107B-1) n-Hex
270 Formula (1) Formula (202A-3) Formula (Q') H Ph Formula (107C-1) n-Hex
[ Table 6]
Serial number A compound of the formula Formula X ArcIs of the formula R1 R2 ArSIs of the formula R4
271 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (101A-1) -
272 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (105A-1) -
273 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (106A-1) -
274 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (107A-1) n-Hex
275 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (107B-1) n-Hex
276 Formula (1) Formula (202A-4) Formula (Q') H Ph Formula (107C-1) n-Hex
277 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (101A-1) -
278 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (105A-1) -
279 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (106A-1) -
280 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (107A-1) n-Hex
281 Formula (A), (B) and1) formula (202A-5) Formula (Q') H Ph Formula (107B-1) n-Hex
282 Formula (1) Formula (202A-5) Formula (Q') H Ph Formula (107C-1) n-Hex
283 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (101A-1) -
284 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (105A-1) -
285 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (106A-1) -
286 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (107A-1) n-Hex
287 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (107B-1) n-Hex
288 Formula (1) Formula (203B-1) Formula (Q') H Ph Formula (107C-1) n-Hex
289 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (101A-1) -
290 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (105A-1) -
291 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (106A-1) -
292 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (107A-1) n-Hex
293 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (107B-1) n-Hex
294 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (107C-1) n-Hex
295 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (101A-1) -
296 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (105A-1) -
297 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (106A-1) -
298 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (107A-1) n-Hex
299 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (107B-1) n-Hex
300 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (107C-1) n-Hex
301 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (101A-1) -
302 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (105A-1) -
303 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (106A-1) -
304 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (107A-1) n-Hex
305 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (107B-1) n-Hex
306 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (107C-1) n-Hex
307 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (101A-1) -
308 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (105A-1) -
309 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (106A-1) -
310 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (107A-1) n-Hex
311 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (107B-1) n-Hex
312 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (107C-1) n-Hex
313 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (101A-1) -
314 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (105A-1) -
315 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (106A-1) -
316 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (107A-1) n-Hex
317 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (107B-1) n-Hex
318 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (107C-1) n-Hex
319 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (101A-1) -
320 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (105A-1) -
321 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (106A-1) -
322 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (107A-1) n-Hex
323 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (107B-1) n-Hex
324 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (107C-1) n-Hex
[ Table 7]
Serial number A compound of the formula Formula X ArcIs of the formula R1 R2 ArSIs of the formula R4
325 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (101A-1) -
326 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (105A-1) -
327 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (106A-1) -
328 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (107A-1) n-Hex
329 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (107B-1) n-Hex
330 Formula (1) Formula (202A-1) Formula (Q') H p-Toly Formula (107C-1) n-Hex
331 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (101A-1) -
332 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (105A-1) -
333 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (106A-1) -
334 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (107A-1) n-Hex
335 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (107B-1) n-Hex
336 Formula (1) Formula (202A-2) Formula (Q') H p-Toly Formula (107C-1) n-Hex
337 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (101A-1) -
338 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (105A-1) -
339 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (106A-1) -
340 Formula (1) Formula (202A-3) Formula, Q') H p-Toly Formula (107A-1) n-Hex
341 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (107B-1) n-Hex
342 Formula (1) Formula (202A-3) Formula (Q') H p-Toly Formula (107C-1) n-Hex
343 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (101A-1) -
344 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (105A-1) -
345 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (106A-1) -
346 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (107A-1) n-Hex
347 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (107B-1) n-Hex
348 Formula (1) Formula (202A-4) Formula (Q') H p-Toly Formula (107C1) n-Hex
349 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (101A-1) -
350 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (105A-1) -
351 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (106A-1) -
352 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (107A-1) n-Hex
353 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (107B-1) n-Hex
354 Formula (1) Formula (202A-5) Formula (Q') H p-Toly Formula (107C-1) n-He×
355 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (101A-1) -
356 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (105A-1) -
357 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (106A-1) -
358 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (107A-1) n-Hex
359 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (107B1) n-Hex
360 Formula (1) Formula (203B-1) Formula (Q') H p-Toly Formula (107C-1) n-Hex
361 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (101A-1) -
362 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (105A-1) -
363 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (106A-1) -
364 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
365 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
366 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
367 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (101A-1) -
368 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (105A-1) -
369 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (106A-1) -
370 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
371 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
372 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
373 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (101A-1) -
374 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (105A-1) -
375 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (106A-1) -
376 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
377 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
378 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
[ Table 8]
Serial number A compound of the formula Formula X ArcIs of the formula R1 R2 ArSIs of the formula R4
379 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (101A-1) -
380 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (105A-1) -
381 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (106A-1) -
382 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
383 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
384 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
385 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (101A-1) -
386 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (105A-1) -
387 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (106A-1) -
388 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
389 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
390 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
391 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (101A-1) -
392 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (105A-1) -
393 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (106A-1) -
394 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
395 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
396 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
397 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (101A-1) -
398 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (105A-1) -
399 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (106A-1) -
400 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
401 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
402 Formula (1) Formula (202A-1) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
403 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (101A-1) -
404 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (105A-1) -
405 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (106A-1) -
406 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
407 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
408 Formula (1) Formula (202A-2) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
409 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (101A-1) -
410 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (105A-1) -
411 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (106A-1) -
412 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
413 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
414 Formula (1) Formula (202A-3) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
415 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (101A-1) -
416 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (105A-1) -
417 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (106A-1) -
418 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
419 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
420 Formula (1) Formula (202A-4) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
421 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (101A-1) -
422 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (105A-1) -
423 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (106A-1) -
424 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
425 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
426 Formula (1) Formula (202A-5) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
427 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (101A-I) -
428 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (105A-1) -
429 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (106A-1) -
430 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
431 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
432 Formula (1) Formula (203B-1) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
[ Table 9]
Serial number A compound of the formula X is a formula ArcIs of the formula R1 R2 ArSOf the formula R4
433 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (101A-1) -
434 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (105A-1)
435 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (106A-1) -
436 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (107A-1) Me
437 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (107B-1) Me
438 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (107C-1) Me
439 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (101A-1) -
440 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (105A-1)
441 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (106A-1) -
442 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (107A-1) Me
443 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (107B-1) Me
444 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (107C-1) Me
445 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (101A-1) -
446 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (105A-1)
447 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (106A-1) -
448 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (107A-1) Me
449 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (107B-1) Me
450 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (107C-1) Me
451 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (101A-1) -
452 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (105A-1)
453 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (106A-1) -
454 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (107A-1) Me
455 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (107B-1) Me
456 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (107C-1) Me
457 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (101A-1) -
458 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (105A-1)
459 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (106A-1) -
460 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (107A-1) Me
461 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (107B-1) Me
462 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (107c-1) Me
463 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (101A-1) -
464 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (105A-1)
465 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (106A-1) -
466 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (107A-1) Me
467 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (107B-1) Me
468 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (107C-1) Me
469 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (101A-1) -
470 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (105A-1)
471 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (106A-1) -
472 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (107A-1) Me
473 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (107B-1) Me
474 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (107C-1) Me
475 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (101A-1) -
476 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (105A-1)
477 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (106A-1) -
478 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (107A-1) Me
479 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (107B-1) Me
480 Formula (2) Formula (202A-2) Formula (Q') H ph Formula (107C-1) Me
481 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (101A-1) -
482 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (105A-1)
483 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (106A-1) -
484 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (107A-1) Me
485 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (107B-1) Me
486 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (107C-1) Me
[ Table 10]
Serial number A compound of the formula Formula X ArcIs of the formula R1 R2 ArSIs of the formula R4
487 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (101A-1) -
488 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (105A-1) -
489 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (106A-1) -
490 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (107A-1) Me
491 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (107B-1) Me
492 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (107C-1) Me
493 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (101A-1) -
494 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (105A-1) -
495 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (106A-1) -
496 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (107A-1) Me
497 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (107B-1) Me
498 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (107C-1) Me
499 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (101A-1) -
500 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (105A-1) -
501 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (106A-1) -
502 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (107A-1) Me
503 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (107B-1) Me
504 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (107C-1) Me
505 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (101A-1) -
506 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (105A-1) -
507 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (106A-1) -
508 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (107A-1) Me
509 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (107B-1) Me
510 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (107C-1) Me
511 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (101A-1) -
512 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (105A-1) -
513 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (106A-1) -
514 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (107A-1) Me
515 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (107B-1) Me
516 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (107C-1) Me
517 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (101A-1) -
518 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (105A-1) -
519 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (106A-1) -
520 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (107A-1) Me
521 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (107B-1) Me
522 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (107C-1) Me
523 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (101A-1) -
524 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (105A-1) -
525 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (106A-1) -
526 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (107A-1) Me
527 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (107B-1) Me
528 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (107C-1) Me
529 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (101A-1) -
530 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (105A-1) -
531 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (106A-1) -
532 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (107A-1) Me
533 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (107B-1) Me
534 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (107C-1) Me
535 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (101A-1) -
536 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (105A-1) -
537 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (106A-1) -
538 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (107A-1) Me
539 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (107B-1) Me
540 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (107C-1) Me
[ Table 11]
Serial number A compound of the formula Formula X ArcIs of the formula R1 R2 ArSIs of the formula R4
541 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (101A-1) -
542 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (105A-1) -
543 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (106A-1) -
544 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (107A-1) Me
545 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (107B-1) Me
546 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (107C-1) Me
547 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (101A-1) -
548 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (105A-1) -
549 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (106A-1) -
550 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (107A-1) Me
551 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (107B-1) Me
552 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (107C-1) Me
553 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (101A-1) -
554 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (105A-1) -
555 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (106A-1) -
556 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (107A-1) Me
557 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (107B-1) Me
558 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (107C-1) Me
559 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (101A-1) -
560 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (105A-1) -
561 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (106A-1) -
562 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (107A-1) Me
563 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (107B-1) Me
564 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (107C-1) Me
565 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (101A-1) -
566 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (105A-1) -
567 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (106A-1) -
568 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (107A-1) Me
569 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (107B-1) Me
570 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (107C-1) Me
571 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (101A)-1) -
572 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (105A-1) -
573 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (106A-1) -
574 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (107A-1) Me
575 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (107B-1) Me
576 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (107C-1) Me
577 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (101A-1) -
578 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (105A-1) -
579 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (106A-1) -
580 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (107A-1) Me
581 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (107B-1) Me
582 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (107C-1) Me
583 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (101A-1) -
584 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (105A-1) -
585 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (106A-1) -
586 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (107A-1) Me
587 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (107B-1) Me
588 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (107C-1) Me
589 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (101A-1) -
590 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (105A-1) -
591 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (106A-1) -
592 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (107A-1) Me
593 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (107B-1) Me
594 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (107C-1) Me
[ Table 12]
Serial number A compound of the formula Formula X ArcIs of the formula R1 R2 ArSIs of the formula R4
595 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (101A-1) -
596 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (105A-1) -
597 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (106A-1) -
598 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (107A-1) Me
599 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (107B-1) Me
600 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (107C-1) Me
601 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (101A-1) -
602 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (105A-1) -
603 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (106A-1) -
604 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (107A-1) Me
605 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (107B-1) Me
606 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (107C-1) Me
607 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (101A-1) -
608 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (105A-1) -
609 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (106A-1) -
610 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (107A-1) Me
611 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (107B-1) Me
612 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (107C-1) Me
613 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (101A-1) -
614 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (105A-1) -
615 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (106A-1) -
616 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (107A-1) Me
617 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (107B-1) Me
618 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (107C-1) Me
619 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (101A-1) -
620 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (105A-1) -
621 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (106A-1) -
622 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (107A-1) Me
623 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (107B-1) Me
624 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (107C-1) Me
625 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (101A-1) -
626 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (105A-1) -
627 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (106A-1) -
628 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (107A-1) Me
629 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (107B-1) Me
630 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (107C-1) Me
631 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (101A-1) -
632 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (105A-1) -
633 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (106A-1) -
634 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (107A-1) Me
635 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (107B-1) Me
636 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (107C-1) Me
637 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (101A-1) -
638 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (105A-1) -
639 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (106A-1) -
640 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (107A-1) Me
641 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (107B-1) Me
642 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (107C-1) Me
643 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (101A-1) -
644 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (105A-1) -
645 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (106A-1) -
646 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (107A-1) Me
647 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (107B-1) Me
648 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (107C-1) Me
[ Table 13]
Serial number A compound of the formula Formula X ArcIs of the formula R1 R2 ArSIs of the formula R4
649 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (101A-1) -
650 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (105A-1) -
651 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (106A-1) -
652 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (107A-1) n-Hex
653 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (107B-1) n-He×
654 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (107C-1) n-Hex
655 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (101A-1) -
656 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (105A-1) -
657 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (106A-1) -
658 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (107A-1) n-Hex
659 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (107B-1) n-Hex
660 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (107C-1) n-Hex
661 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (101A-1) -
662 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (105A-1) -
663 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (106A-1) -
664 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (107A-1) n-Hex
665 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (107B-1) n-Hex
666 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (107C-1) n-Hex
667 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (101A-1) -
668 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (105A-1) -
669 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (106A-1) -
670 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (107A-1) n-Hex
671 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (107B-1) n-Hex
672 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (107C-1) n-Hex
673 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (101A-1) -
674 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (105A-1) -
675 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (106A-1) -
676 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (107A-1) n-Hex
677 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (107B-1) n-Hex
678 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (107C-1) n-Hex
679 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (101A-1) -
680 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (105A-1) -
681 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (106A-1) -
682 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (107A-1) n-Hex
683 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (107B-1) n-Hex
684 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (107C-1) n-Hex
685 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (101A-1) -
686 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (105A-1) -
687 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (106A-1) -
688 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (107A-1) n-Hex
689 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (107B-1) n-Hex
690 Formula (2) Formula (202A-1) Formula (Q') H Ph Formula (107C-1) n-Hex
691 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (101A-1) -
692 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (105A-1) -
693 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (106A-1) -
694 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (107A-1) n-Hex
695 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (107B-1) n-Hex
696 Formula (2) Formula (202A-2) Formula (Q') H Ph Formula (107C-1) n-Hex
697 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (101A-1) -
698 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (105A-1) -
699 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (106A-1) -
700 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (107A-1) n-Hex
701 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (107B-1) n-Hex
702 Formula (2) Formula (202A-3) Formula (Q') H Ph Formula (107C-1) n-Hex
[ Table 14]
Serial number A compound of the formula Formula X ArcIs of the formula R1 R2 ArSIs of the formula R4
703 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (101A-1) -
704 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (105A-1) -
705 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (106A-1) -
706 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (107A-1) n-Hex
707 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (107B-1) n-Hex
708 Formula (2) Formula (202A-4) Formula (Q') H Ph Formula (107C-1) n-Hex
709 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (101A-1) -
710 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (105A-1) -
711 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (106A-1) -
712 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (107A-1) n-Hex
713 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (107B-1) n-Hex
714 Formula (2) Formula (202A-5) Formula (Q') H Ph Formula (107C-1) n-Hex
715 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (101A-1) -
716 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (105A-1) -
717 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (106A-1) -
718 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (107A-1) n-Hex
719 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (107B-1) n-Hex
720 Formula (2) Formula (203B-1) Formula (Q') H Ph Formula (107C-1) n-Hex
721 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (101A-1) -
722 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (105A-1) -
723 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (106A-1) -
724 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (107A-1) n-Hex
725 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (107B-1) n-Hex
726 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (107C-1) n-Hex
727 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (101A-1) -
728 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (105A-1) -
729 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (106A-1) -
730 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (107A-1) n-Hex
731 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (107B-1) n-Hex
732 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (107C-1) n-Hex
733 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (101A-1) -
734 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (105A-1) -
735 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (106A-1) -
736 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (107A-1) n-Hex
737 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (107B-1) n-Hex
738 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (107C-1) n-Hex
739 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (101A-1) -
740 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (105A-1) -
741 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (106A-1) -
742 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (107A-1) n-Hex
743 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (107B-1) n-Hex
744 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (107C-1) n-Hex
745 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (101A-1) -
746 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (105A-1) -
747 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (106A-1) -
748 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (107A-1) n-Hex
749 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (107B-1) n-Hex
750 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (107C-1) n-Hex
751 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (101A-1) -
752 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (105A-1) -
753 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (106A-1) -
754 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (107A-1) n-Hex
755 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (107B-1) n-Hex
756 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (107C-1) n-Hex
[ Table 15]
Serial number A compound of the formula Formula X ArcIs of the formula R1 R2 ArSIs of the formula R4
757 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (101A-1) -
758 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (105A-1) -
759 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (106A-1) -
760 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (107A-1) n-Hex
761 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (107B-1) n-Hex
762 Formula (2) Formula (202A-1) Formula (Q') H p-Toly Formula (107C-1) n-Hex
763 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (101A-1) -
764 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (105A-1) -
765 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (106A-1) -
766 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (107A-1) n-Hex
767 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (107B-1) n-Hex
768 Formula (2) Formula (202A-2) Formula (Q') H p-Toly Formula (107C-1) n-Hex
769 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (101A-1) -
770 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (105A-1) -
771 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (106A-1) -
772 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (107A-1) n-Hex
773 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (107B-1) n-Hex
774 Formula (2) Formula (202A-3) Formula (Q') H p-Toly Formula (107C-1) n-Hex
775 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (101A-1) -
776 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (105A-1) -
777 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (106A-1) -
778 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (107A-1) n-Hex
779 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (107B-1) n-Hex
780 Formula (2) Formula (202A-4) Formula (Q') H p-Toly Formula (107C-1) n-Hex
781 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (101A-1) -
782 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (105A-1) -
783 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (106A-1) -
784 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (107A-1) n-Hex
785 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (107B-1) n-Hex
786 Formula (2) Formula (202A-5) Formula (Q') H p-Toly Formula (107C-1) n-Hex
787 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (101A-1) -
788 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (105A-1) -
789 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (106A-1) -
790 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (107A-1) n-Hex
791 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (107B-1) n-Hex
792 Formula (2) Formula (203B-1) Formula (Q') H p-Toly Formula (107C-1) n-Hex
793 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (101A-1) -
794 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (105A-1) -
795 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (106A-1) -
796 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
797 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
798 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
799 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (101A-1) -
800 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (105A-1) -
801 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (106A-1) -
802 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
803 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
804 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
805 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (101A-1) -
806 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (105A-1) -
807 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (106A-1) -
808 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
809 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
810 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
[ Table 16]
Serial number A compound of the formula Formula X ArcIs of the formula R1 R2 ArSIs of the formula R4
811 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (101A-1) -
812 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (105A-1) -
813 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (106A-1) -
814 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
815 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
816 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
817 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (101A-1) -
818 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (105A-1) -
819 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (106A-1) -
820 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
821 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
822 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (107C-1) n-He×
823 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (101A-1) -
824 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (105A-1) -
825 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (106A-1) -
826 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
827 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
828 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
829 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (101A-1) -
830 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (105A-1) -
831 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (106A-1) -
832 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
833 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
834 Formula (2) Formula (202A-1) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
835 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (101A-1) -
836 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (105A-1) -
837 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (106A-1) -
838 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (107A-1) n-He×
839 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
840 Formula (2) Formula (202A-2) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
841 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (101A-1) -
842 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (105A-1) -
843 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (106A-1) -
844 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
845 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
846 Formula (2) Formula (202A-3) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
847 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (101A-1) -
848 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (105A-1) -
849 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (106A-1) -
850 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
851 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (107B-1) n-He×
852 Formula (2) Formula (202A-4) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
853 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (101A-1) -
854 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (105A-1) -
855 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (106A-1) -
856 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
857 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
858 Formula (2) Formula (202A-5) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
859 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (101A-1) -
860 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (105A-1) -
861 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (106A-1) -
862 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (107A-1) n-Hex
863 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (107B-1) n-Hex
864 Formula (2) Formula (203B-1) Formula (Q') H 2-Thie Formula (107C-1) n-Hex
[ Table 17]
Serial number A compound of the formula Y g ArcIs of the formula R1 R2 ArSIs of the formula R4
865 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (101A-1) -
866 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (105A-1) -
867 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (106A-1) -
868 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (107A-1) Me
869 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (107B-1) Me
870 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (107c-1) Me
871 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (101A-1) -
872 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (105A-1) -
873 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (106A-1) -
874 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (107A-1) Me
875 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (107B-1) Me
876 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (107C-1) Me
877 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (101A-1) -
878 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (105A-1) -
879 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (106A-1) -
880 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (107A-1) Me
881 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (107B-1) Me
882 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (107C-1) Me
883 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (101A-1) -
884 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (105A-1) -
885 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (106A-1) -
886 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (107A-1) Me
887 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (107B-1) Me
888 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (107C-1) Me
889 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (101A-1) -
890 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (105A-1) -
891 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (106A-1) -
892 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (107A-1) Me
893 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (107B-1) Me
894 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (107C-1) Me
895 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (101A-1) -
896 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (105A-1) -
897 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (106A-1) -
898 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (107A-1) Me
899 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (107B-1) Me
900 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (107C-1) Me
901 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (101A-1) -
902 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (105A-1) -
903 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (106A-1) -
904 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (107A-1) Me
905 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (107B-1) Me
906 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (107C-1) Me
907 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (101A-1) -
908 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (105A-1) -
909 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (106A-1) -
910 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (107A-1) Me
911 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (107B-1) Me
912 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (107C-1) Me
[ Table 18]
Serial number A compound of the formula Y g ArcIs of the formula R1 R2 ArSIs of the formula R4
913 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (101A-1) -
914 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (105A-1) -
915 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (106A-1) -
916 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (107A-1) Me
917 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (107B-1) Me
918 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (107C-1) Me
919 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (101A-1) -
920 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (105A-1) -
921 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (106A-1) -
922 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (107A-1) Me
923 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (107B-1) Me
924 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (107C-1) Me
925 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (101A-1) -
926 Formula (3) 1，4-Ph 2 Formula (Q)’) H p-Toly Formula (105A-1) -
927 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (106A-1) -
928 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (107A-1) Me
929 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (107B-1) Me
930 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (107C-1) Me
931 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (101A-1) -
932 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (105A-1) -
933 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (106A)-1) -
934 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (107A-1) Me
935 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (107B-1) Me
936 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (107C-1) Me
937 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (101A-1) -
938 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (105A-1) -
939 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (106A-1) -
940 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (107A-1) Me
941 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (107B-1) Me
942 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (107C-1) Me
943 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (101A-1) -
944 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (105A-1) -
945 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (106A-1) -
946 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (107A-1) Me
947 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (107B-1) Me
948 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (107C-1) Me
949 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (101A-1) -
950 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (105A-1) -
951 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (106A-1) -
952 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (107A-1) Me
953 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (107B-1) Me
954 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (107C-1) Me
955 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (101A-1) -
956 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (105A-1) -
957 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (106A-1) -
958 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (107A-1) Me
959 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (107B-1) Me
960 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (107C-1) Me
[ Table 19]
Serial number A compound of the formula Y g ArcIs of the formula R1 R2 ArSIs of the formula R4
961 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (101A-1) -
962 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (105A-1) -
963 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (106A-1) -
964 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (107A-1) Me
965 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (107B-1) Me
966 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (107C-1) Me
967 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (101A-1) -
968 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (105A-1) -
969 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (106A-1) -
970 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (107A-1) Me
971 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (107B-1) Me
972 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (107C-1) Me
973 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (101A-1) -
974 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (105A-1) -
975 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (106A-1) -
976 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (107A-1) Me
977 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (107B-1) Me
978 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (107C-1) Me
979 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (101A-1) -
980 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (105A-1) -
981 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (106A-1) -
982 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (107A-1) Me
983 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (107B-1) Me
984 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (107C-1) Me
985 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (101A-1) -
986 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (105A-1) -
987 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (106A-1) -
988 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (107A-1) Me
989 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (107B-1) Me
990 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (107C-1) Me
991 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (101A-1) -
992 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (105A-1) -
993 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (106A-1) -
994 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (107A-1) Me
995 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (107B-1) Me
996 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (107C-1) Me
997 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (101A-1) -
998 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (105A-1) -
999 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (106A-1) -
1000 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (107A-1) Me
1001 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (107B-1) Me
1002 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (107C-1) Me
1003 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (101A-1) -
1004 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (105A-1) -
1005 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (106A-1) -
1006 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (107A-1) Me
1007 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (107B-1) Me
1008 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (107C-1) Me
[ Table 20]
Serial number A compound of the formula Y g ArcIs of the formula R1 R2 ArSIs of the formula R4
1009 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (101A-1) -
1010 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (105A-1) -
1011 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (106A-1) -
1012 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (107A-1) n-Hex
1013 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (107B-1) n-Hex
1014 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (107C-1) n-Hex
1015 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (101A-1) -
1016 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (105A-1) -
1017 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (106A-1) -
1018 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (107A-1) n-Hex
1019 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (107B-1) n-Hex
1020 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (107C-1) n-Hex
1021 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (101A-1) -
1022 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (105A-1) -
1023 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (106A-1) -
1024 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (107A-1) n-Hex
1025 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (107B-1) n-Hex
1026 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (107C-1) n-Hex
1027 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (101A-1) -
1028 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (105A-1) -
1029 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (106A-1) -
1030 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (107A-1) n-Hex
1031 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (107B-1) n-Hex
1032 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (107C-1) n-Hex
1033 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (101A-1) -
1034 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (105A-1) -
1035 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (106A-1) -
1036 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (107A-1) n-Hex
1037 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (107B-1) n-Hex
1038 Formula (3) 1，4-Ph 1 Formula (Q') H Ph Formula (107C-1) n-Hex
1039 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (101A-1) -
1040 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (105A-1) -
1041 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (106A-1) -
1042 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (107A-1) n-Hex
1043 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (107B-1) n-Hex
1044 Formula (3) 1，3-Ph 1 Formula (Q') H Ph Formula (107C-1) n-Hex
1045 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (101A-1) -
1046 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (105A-1) -
1047 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (106A-1) -
1048 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (107A-1) n-Hex
1049 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (107B-1) n-Hex
1050 Formula (3) 1，4-Ph 2 Formula (Q') H Ph Formula (107C-1) n-Hex
1051 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (101A-1) -
1052 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (105A-1) -
1053 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (106A-1) -
1054 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (107A-1) n-Hex
1055 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (107B-1) n-Hex
1056 Formula (3) 1，3-Ph 2 Formula (Q') H Ph Formula (107C-1) n-Hex
[ Table 21]
Serial number A compound of the formula Y g ArcIs of the formula R1 R2 ArSIs of the formula R4
1057 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (101A-1) -
1058 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (105A-1) -
1059 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (106A-1) -
1060 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (107A-1) n-Hex
1061 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (107B-1) n-Hex
1062 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (107C-1) n-Hex
1063 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (101A-1) -
1064 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (105A-1) -
1065 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (106A-1) -
1066 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (107A-1) n-Hex
1067 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (107B-1) n-Hex
1068 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (107C-1) n-Hex
1069 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (101A-1) -
1070 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (105A-1) -
1071 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (106A-1) -
1072 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (107A-1) n-Hex
1073 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (107B-1) n-Hex
1074 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (107C-1) n-Hex
1075 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (101A-1) -
1076 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (105A-1) -
1077 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (106A-1) -
1078 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (107A-1) n-Hex
1079 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (107B-1) n-Hex
1080 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (107c-1) n-Hex
1081 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (101A-1) -
1082 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (105A-1) -
1083 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (106A-1) -
1084 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (107A-1) n-Hex
1085 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (107B-1) n-Hex
1086 Formula (3) 1，4-Ph 1 Formula (Q') H p-Toly Formula (107C-1) n-Hex
1087 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (101A-1) -
1088 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (105A-1) -
1089 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (106A-1) -
1090 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (107A-1) n-Hex
1091 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (107B-1) n-Hex
1092 Formula (3) 1，3-Ph 1 Formula (Q') H p-Toly Formula (107c-1) n-Hex
1093 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (101A-1) -
1094 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (105A-1) -
1095 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (106A-1) -
1096 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (107A-1) n-Hex
1097 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (107B-1) n-Hex
1098 Formula (3) 1，4-Ph 2 Formula (Q') H p-Toly Formula (107C-1) n-Hex
1099 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (101A-1) -
1100 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (105A-1) -
1101 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (106A-1) -
1102 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (107A-1) n-Hex
1103 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (107B-1) n-Hex
1104 Formula (3) 1，3-Ph 2 Formula (Q') H p-Toly Formula (107C-1) n-Hex
[ Table 22]
Serial number A compound of the formula Y g ArcIs of the formula R1 R2 ArSIs of the formula R4
1105 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (101A-1) -
1106 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (105A-1) -
1107 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (106A-1) -
1108 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (107A-1) n-Hex
1109 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (107B-1) n-Hex
1110 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (107C-1) n-Hex
1111 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (101A-1) -
1112 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (105A-1) -
1113 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (106A-1) -
1114 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (107A-1) n-Hex
1115 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (107B-1) n-Hex
1116 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (107C-1) n-Hex
1117 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (101A-1) -
1118 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (105A-1) -
1119 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (106A-1) -
1120 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (107A-1) n-Hex
1121 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (107B-1) n-Hex
1122 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (107C-1) n-Hex
1123 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (101A-1) -
1124 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (105A-1) -
1125 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (106A-1) -
1126 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (107A-1) n-Hex
1127 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (107B-1) n-Hex
1128 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (107C-1) n-Hex
1129 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (101A-1) -
1130 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (105A-1) -
1131 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (106A-1) -
1132 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (107A-1) n-Hex
1133 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (107B-1) n-Hex
1134 Formula (3) 1，4-Ph 1 Formula (Q') H 2-Thie Formula (107C-1) n-Hex
1135 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (101A-1) -
1136 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (105A-1) -
1137 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (106A-1) -
1138 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (107A-1) n-Hex
1139 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (107B-1) n-Hex
1140 Formula (3) 1，3-Ph 1 Formula (Q') H 2-Thie Formula (107C-1) n-Hex
1141 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (101A-1) -
1142 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (105A-1) -
1143 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (106A-1) -
1144 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (107A-1) n-Hex
1145 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (107B-1) n-Hex
1146 Formula (3) 1，4-Ph 2 Formula (Q') H 2-Thie Formula (107C-1) n-Hex
1147 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (101A-1) -
1148 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (105A-1) -
1149 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (106A-1) -
1150 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (107A-1) n-Hex
1151 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (107B-1) n-Hex
1152 Formula (3) 1，3-Ph 2 Formula (Q') H 2-Thie Formula (107C-1) n-Hex
The arylamine compound of the present invention can be preferably used as a charge transporting substance. In this case, the aromatic amine compound of the present invention can be used as a charge-transporting varnish containing an organic solvent, and the charge-transporting varnish may contain a dopant substance for the purpose of, for example, improving the charge-transporting ability of the resulting thin film depending on the application. The arylamine compound of the present invention can be used in combination with other conventionally known charge-transporting substances such as aniline derivatives and thiophene derivatives, but it is preferable to use the arylamine compound of the present invention alone as the charge-transporting substance.
In the present invention, the term "charge transporting property" is synonymous with conductivity. The charge-transporting varnish may have a charge-transporting property by itself, or a solid film obtained therefrom may have a charge-transporting property.
The dopant substance is not particularly limited as long as it is dissolved in at least 1 kind of solvent used in the varnish, and both an inorganic dopant substance and an organic dopant substance can be used.
The dopant substance may be used alone in 1 kind or in combination of 2 or more kinds.
Further, the dopant substance may be a substance in which, for example, a part of the molecule is released by an external stimulus such as heating at the time of firing in the process of obtaining a charge-transporting thin film as a solid film from a varnish, and the function as the dopant substance is first developed or improved, and for example, an arylsulfonate compound protected with a group from which a sulfonic acid group is easily released may be used.
In particular, in the present invention, as the inorganic dopant substance, heteropoly acid is preferable.
The heteropoly acid is a polyacid having a structure in which a hetero atom is located at the center of a molecule, typically represented by a chemical structure of Keggin type represented by formula (H1) or Dawson type represented by formula (H2), and which is obtained by condensing an isopoly acid, which is an oxyacid such as vanadium (V), molybdenum (Mo), tungsten (W), or the like, with an oxyacid of a different element. Examples of the oxo acid of such a different element include oxo acids of silicon (Si), phosphorus (P), and arsenic (As).
[ solution 110]
Figure BDA0003380339930000781
Specific examples of the heteropoly-acid include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, phosphotungstomolybdic acid, and the like, and they may be used alone or in combination of 2 or more kinds. These heteropoly acids are commercially available, and can be synthesized by a known method.
In particular, in the case of using 1 kind of heteropoly acid, the 1 kind of heteropoly acid is preferably phosphotungstic acid or phosphomolybdic acid, and phosphotungstic acid is most preferable. In addition, in the case of using 2 or more kinds of heteropolyacids, 1 of the 2 or more kinds of heteropolyacids is preferably phosphotungstic acid or phosphomolybdic acid, and more preferably phosphotungstic acid.
In quantitative analysis such as elemental analysis, the heteropoly-acid can be used in the present invention regardless of the number of elements in the structure represented by the general formula, as long as it is a commercially available product or a product appropriately synthesized by a known synthesis method.
That is, for example, in general, phosphotungstic acid has the formula H3(PW12O40)·nH2O represents, phosphomolybdic acid has the chemical formula H3(PMo12O40)·nH2In the quantitative analysis, the O is used in the present invention, regardless of whether the number of P (phosphorus), O (oxygen), W (tungsten) or Mo (molybdenum) in the formula is large or small, as long as it is a product obtained as a commercially available product or a product appropriately synthesized according to a known synthesis method. In this case, the mass of the heteropoly-acid specified in the present invention is not the mass of pure phosphotungstic acid (phosphotungstic acid content) in a synthetic product or a commercially available product, but means the total mass in a state where water of hydration, other impurities and the like are contained in a form obtainable as a commercially available product or in a form separable by a known synthesis method.
The amount of the heteropoly acid used can be about 0.001 to 50.0, preferably about 0.01 to 20.0, and more preferably about 0.1 to 10.0, in terms of mass ratio, relative to 1 charge-transporting substance.
On the other hand, as the organic dopant substance, in particular, tetracyanoquinodimethane derivatives and benzoquinone derivatives can be used.
Specific examples of the tetracyanoquinodimethane derivative include 7,7,8, 8-Tetracyanoquinodimethane (TCNQ) and halogenated tetracyanoquinodimethane represented by the formula (H3).
Specific examples of the benzoquinone derivative include tetrafluoro-1, 4-benzoquinone (F4BQ), tetrachloro-1, 4-benzoquinone (tetrachloro-p-benzoquinone), tetrabromo-1, 4-benzoquinone, and 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ).
[ solution 111]
Figure BDA0003380339930000791
In the formula, R500～R503 each independently represents a hydrogen atom or a halogen atom, and at least 1 is a halogen atom, preferably at least 2 is a halogen atom, more preferably at least 3 is a halogen atom, and most preferably all are halogen atoms.
Examples of the halogen atom include the same halogen atoms as described above, preferably a fluorine atom or a chlorine atom, and more preferably a fluorine atom.
Specific examples of such a halogenated tetracyanoquinodimethane include 2-fluoro-7, 7,8, 8-tetracyanoquinodimethane, 2-chloro-7, 7,8, 8-tetracyanoquinodimethane, 2, 5-difluoro-7, 7,8, 8-tetracyanoquinodimethane, 2, 5-dichloro-7, 7,8, 8-tetracyanoquinodimethane, 2,3,5, 6-tetrachloro-7, 7,8, 8-tetracyanoquinodimethane, 2,3,5, 6-tetrafluoro-7, 7,8, 8-tetracyanoquinodimethane (F4TCNQ), and the like.
The amount of the tetracyanoquinodimethane derivative and the benzoquinone derivative to be used is preferably 0.0001 to 100 equivalents, more preferably 0.01 to 50 equivalents, and still more preferably 1 to 20 equivalents, based on the charge transporting substance.
Further, as the organic dopant substance, an electrically neutral onium borate comprising a 1-or 2-valent anion represented by the following formula (a1) and counter cations represented by the formulae (c1) to (c5) can be used.
[ solution 112]
Figure BDA0003380339930000801
(wherein each Ar independently represents an aryl group having 6 to 20 carbon atoms which may have a substituent or a heteroaryl group having 2 to 20 carbon atoms which may have a substituent, L represents an alkylene group having 1 to 20 carbon atoms, or a salt thereof,-NH-, oxygen, sulfur or-CN+-。)
[ solution 113]
Figure BDA0003380339930000811
In the formula (a1), the alkylene group having 1 to 20 carbon atoms may be any of a linear, branched, or cyclic alkylene group, and specific examples thereof include methylene, methylmethylene, dimethylmethylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, and hexamethylene. Examples of the aryl group and the heteroaryl group include the same ones as described above.
Preferred examples of the anion of the formula (a1) include anions represented by the formula (a2), but are not limited thereto.
[ chemical formula 114]
Figure BDA0003380339930000812
The amount of the onium borate to be used can be about 0.1 to 10 in terms of the amount (molar) ratio of the substance to the charge transporting substance.
The onium borate can be synthesized by a known method described in, for example, Japanese patent application laid-open No. 2005-314682.
Further, as the organic dopant substance, an arylsulfonic acid compound or an arylsulfonate compound can also be preferably used.
Specific examples of the arylsulfonic acid compound include benzenesulfonic acid, toluenesulfonic acid, p-styrenesulfonic acid, 2-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, p-dodecylbenzenesulfonic acid, dihexylbenzenesulfonic acid, 2, 5-dihexylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, 6, 7-dibutyl-2-naphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, 3-dodecyl-2-naphthalenesulfonic acid, hexylnaphthalenesulfonic acid, 4-hexyl-1-naphthalenesulfonic acid, 7-hexyl-1-naphthalenesulfonic acid, 6-hexyl-2-naphthalenesulfonic acid, octylnaphthalenesulfonic acid, 2-octyl-1-naphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, 2, 7-dinonyl-4-naphthalenesulfonic acid, p-toluenesulfonic acid, 2-naphthalenesulfonic acid, 4-naphthalenesulfonic acid, and 6-hexyl-2-naphthalenesulfonic acid, Dinonylnaphthalenedisulfonic acid, 2, 7-dinonyl-4, 5-naphthalenedisulfonic acid, a1, 4-benzodioxan disulfonic acid compound described in International publication No. 2005/000832, an arylsulfonic acid compound described in International publication No. 2006/025342, an arylsulfonic acid compound described in International publication No. 2009/096352, and the like.
Examples of preferred arylsulfonic acid compounds include arylsulfonic acid compounds represented by the formula (H4) or (H5).
[ solution 115]
Figure BDA0003380339930000821
A1Represents O or S, preferably O.
A2Represents a naphthalene ring or an anthracene ring, preferably a naphthalene ring.
A3Represents a 2-4 valent perfluorobiphenyl group, p represents A1And A3The number of bonds of (A) is an integer satisfying 2. ltoreq. p.ltoreq.4, preferably A3Is perfluorobiphenylene, preferably perfluorobiphenyl-4, 4' -diyl, and p is 2.
q represents the same as A2The number of the bonded sulfonic acid groups is an integer satisfying 1. ltoreq. q.ltoreq.4, and 2 is most preferable.
A4～A8Independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, or a haloalkenyl group having 2 to 20 carbon atoms, A4～A8At least 3 of which are halogen atoms.
Examples of the haloalkyl group having 1 to 20 carbon atoms include a trifluoromethyl group, a2, 2, 2-trifluoroethyl group, a1, 1,2,2, 2-pentafluoroethyl group, a3, 3, 3-trifluoropropyl group, a2, 2,3,3, 3-pentafluoropropyl group, a1, 1,2,2,3,3, 3-heptafluoropropyl group, a4, 4, 4-trifluorobutyl group, a3, 3,4,4, 4-pentafluorobutyl group, a2, 2,3,3,4, 4-heptafluorobutyl group, a1, 1,2,2,3,3,4,4, 4-nonafluorobutyl group and the like.
Examples of the haloalkenyl group having 2 to 20 carbon atoms include a perfluorovinyl group, a perfluoropropenyl group (perfluoroallyl group), a perfluorobutenyl group, and the like.
Examples of the halogen atom and the alkyl group having 1 to 20 carbon atoms include the same ones as described above, and the halogen atom is preferably a fluorine atom.
Of these, A is preferred4～A8Is a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or a haloalkenyl group having 2 to 10 carbon atoms, and A4～A8At least 3 of which are fluorine atoms, more preferably hydrogen atoms, fluorine atoms, cyano groups, alkyl groups having 1 to 5 carbon atoms, fluoroalkyl groups having 1 to 5 carbon atoms, or fluoroalkenyl groups having 2 to 5 carbon atoms, and A4～A8At least 3 of them are fluorine atoms, more preferably hydrogen atoms, fluorine atoms, cyano groups, perfluoroalkyl groups having 1 to 5 carbon atoms, or perfluoroalkenyl groups having 1 to 5 carbon atoms, and A4、A5And A8Is a fluorine atom.
The perfluoroalkyl group is a group in which all hydrogen atoms of the alkyl group have been substituted with fluorine atoms, and the perfluoroalkenyl group is a group in which all hydrogen atoms of the alkenyl group have been substituted with fluorine atoms.
r represents the number of sulfonic acid groups bonded to the naphthalene ring, and is an integer satisfying 1. ltoreq. r.ltoreq.4, preferably 2 to 4, and most preferably 2.
The molecular weight of the arylsulfonic acid compound used as a dopant substance is not particularly limited, but is preferably 2000 or less, more preferably 1500 or less, in consideration of solubility in an organic solvent when used together with the arylamine compound of the present invention.
Specific examples of preferred arylsulfonic acid compounds are shown below, but the aryl sulfonic acid compounds are not limited thereto.
[ solution 116]
Figure BDA0003380339930000831
[ solution 117]
Figure BDA0003380339930000841
[ chemical formula 118]
Figure BDA0003380339930000842
The amount of the arylsulfonic acid compound used is preferably about 0.01 to 20.0, and more preferably about 0.4 to 5.0, in terms of the amount (molar) ratio of the substance, relative to 1 of the charge transporting substance.
The arylsulfonic acid compound may be synthesized by a commercially available method or by a known method described in international publication No. 2006/025342, international publication No. 2009/096352, international publication No. 2015/111654, international publication No. 2015/053320, international publication No. 2015/115515, or the like.
On the other hand, examples of the arylsulfonate compound include an arylsulfonate compound disclosed in international publication No. 2017/217455, an arylsulfonate compound disclosed in international publication No. 2017/217457, and an arylsulfonate compound described in japanese patent application No. 2017-243631 (international publication No. 2019/124412), and specifically, a compound represented by any one of the following formulae (H6) to (H8) is preferable.
[ solution 119]
Figure BDA0003380339930000843
(wherein m is an integer satisfying 1. ltoreq. m.ltoreq.4, preferably 2. n is an integer satisfying 1. ltoreq. n.ltoreq.4, preferably 2.)
In the formula (H6), A11Is a m-valent group derived from perfluorobiphenyl.
A12is-O-or-S-, preferably-O-.
A13Is a (n +1) -valent group derived from naphthalene or anthracene, preferably a group derived from naphthalene.
Rs1～Rs4Each independently represents a hydrogen atom or a straight or branched alkyl group having 1 to 6 carbon atoms, Rs5Is a carbon atom which may be substitutedA 1-valent hydrocarbon group having a numerary of 2 to 20.
Specific examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl and the like, and an alkyl group having 1 to 3 carbon atoms is preferable.
The 1-valent hydrocarbon group having 2 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include alkyl groups such as ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group; aryl groups such as phenyl, naphthyl and phenanthryl.
In particular, in Rs1～Rs4Among them, R is preferreds1Or Rs3Is a straight-chain alkyl group having 1 to 3 carbon atoms, the remainder being hydrogen atoms, or Rs1Is a C1-3 linear alkyl group, Rs2～Rs4Is a hydrogen atom. In this case, the straight-chain alkyl group having 1 to 3 carbon atoms is preferably a methyl group.
In addition, as Rs5Preferably, the alkyl group or phenyl group has 2 to 4 carbon atoms.
In the formula (H7), A14Is a substituted, m-valent hydrocarbon group having 6 to 20 carbon atoms and containing 1 or more aromatic rings, wherein the hydrocarbon group is obtained by removing m hydrogen atoms from a hydrocarbon compound having 6 to 20 carbon atoms and containing 1 or more aromatic rings.
Examples of such hydrocarbon compounds include benzene, toluene, xylene, ethylbenzene, biphenyl, naphthalene, anthracene, phenanthrene, and the like.
Further, the above-mentioned hydrocarbon group may have a part or all of its hydrogen atoms substituted with a substituent, and examples of such a substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a silanol group, a thiol group, a carboxyl group, a sulfonate ester, a phosphoric acid, a phosphate ester, an ester, a thioester, an amide, an organoxy group, an organoamino group, an organosilyl group, an organosulfuryl group, an acyl group, a sulfo group, a 1-valent hydrocarbon group, and the like.
Among these, as A14Groups derived from benzene, biphenyl, etc. are preferred.
In addition, A15is-O-or-S-, preferably-O-.
A16The aromatic hydrocarbon compound is an (n +1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms, wherein the aromatic hydrocarbon group is obtained by removing (n +1) hydrogen atoms from an aromatic ring of an aromatic hydrocarbon compound having 6 to 20 carbon atoms.
Examples of the aromatic hydrocarbon compound include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, pyrene, and the like.
Wherein, as A16Preferably a naphthalene or anthracene derived group, more preferably a naphthalene derived group.
Rs6And Rs7Each independently represents a hydrogen atom or a linear or branched 1-valent aliphatic hydrocarbon group, Rs8Is a straight chain or branched chain 1-valent aliphatic hydrocarbon group. However, Rs6、Rs7And Rs8The total number of carbon atoms of (2) is 6 or more. To Rs6、Rs7And Rs8The upper limit of the total number of carbon atoms of (3) is not particularly limited, but is preferably 20 or less, and more preferably 10 or less.
Specific examples of the linear or branched 1-valent aliphatic hydrocarbon group include alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-hexyl group, a n-octyl group, a 2-ethylhexyl group, and a decyl group; and alkenyl groups having 2 to 20 carbon atoms such as vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, hexenyl, and the like.
In these, Rs6Preferably a hydrogen atom, Rs7And Rs8Each independently preferably an alkyl group having 1 to 6 carbon atoms.
In the formula (H8), Rs9～Rs13Each independently represents a hydrogen atom, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or a haloalkenyl group having 2 to 10 carbon atoms.
The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl and n-decyl groups.
The haloalkyl group having 1 to 10 carbon atoms is not particularly limited as long as it is a group in which a part or all of hydrogen atoms of the alkyl group having 1 to 10 carbon atoms are substituted with a halogen atom, and specific examples thereof include a trifluoromethyl group, a2, 2, 2-trifluoroethyl group, a1, 1,2, 2-pentafluoroethyl group, a3, 3, 3-trifluoropropyl group, a2, 2,3,3, 3-pentafluoropropyl group, a1, 1,2,2,3,3, 3-heptafluoropropyl group, a4, 4, 4-trifluorobutyl group, a3, 3,4,4, 4-pentafluorobutyl group, a2, 2,3,3,4, 4-heptafluorobutyl group, a1, 1,2,2,3,3,4,4, 4-nonafluorobutyl group and the like.
The halogenated alkenyl group having 2 to 10 carbon atoms is not particularly limited as long as it is a group in which a part or all of hydrogen atoms of the alkenyl group having 2 to 10 carbon atoms are substituted with halogen atoms, and specific examples thereof include perfluorovinyl group, perfluoro-1-propenyl group, perfluoro-2-propenyl group, perfluoro-1-butenyl group, perfluoro-2-butenyl group, perfluoro-3-butenyl group, and the like.
Among these, as Rs9The compound is preferably a nitro group, a cyano group, a haloalkyl group having 1 to 10 carbon atoms, or a haloalkenyl group having 2 to 10 carbon atoms, more preferably a nitro group, a cyano group, a haloalkyl group having 1 to 4 carbon atoms, or a haloalkenyl group having 2 to 4 carbon atoms, and still more preferably a nitro group, a cyano group, a trifluoromethyl group, or a perfluoropropenyl group.
As Rs10～Rs13Preferably a halogen atom, more preferably a fluorine atom.
A17is-O-, -S-or-NH-, preferably-O-.
A18The aromatic hydrocarbon compound is an (n +1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms, wherein the aromatic hydrocarbon group is obtained by removing (n +1) hydrogen atoms from an aromatic ring of an aromatic hydrocarbon compound having 6 to 20 carbon atoms.
Examples of the aromatic hydrocarbon compound include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, pyrene, and the like.
Among these, as A18Preferably a naphthalene or anthracene derived group, more preferably a naphthalene derived group.
Rs14～Rs17Each independently represents a hydrogen atom or a straight or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms and a valence of 1.
Specific examples of the 1-valent aliphatic hydrocarbon group include alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, and the like; an alkenyl group having 2 to 20 carbon atoms such as a vinyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a 1-methyl-2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, and a hexenyl group, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 1 to 8 carbon atoms.
Rs18Is a straight-chain OR branched-chain 1-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms, OR ORs19。Rs19Is a 1-valent hydrocarbon group having 2 to 20 carbon atoms which may be substituted.
As Rs18Examples of the linear or branched 1-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms include the same groups as described above.
At Rs18In the case of a 1-valent aliphatic hydrocarbon group, Rs18The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms.
As Rs19Examples of the 1-valent hydrocarbon group having 2 to 20 carbon atoms include aryl groups such as phenyl, naphthyl and phenanthryl groups, in addition to the groups other than methyl in the 1-valent aliphatic hydrocarbon group.
In these, Rs19Preferably a C2-4 linear alkyl group or a phenyl group.
Further, examples of the substituent that the 1-valent hydrocarbon group may have include a fluorine atom, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyano group and the like.
Specific examples of preferred arylsulfonate compounds include the following, but are not limited thereto.
[ chemical formula 120]
Figure BDA0003380339930000881
[ solution 121]
Figure BDA0003380339930000882
[ chemical formula 122]
Figure BDA0003380339930000891
The amount of the arylsulfonate compound used is preferably about 0.01 to 20, more preferably about 0.05 to 10, in terms of the amount (molar) ratio of the substance to the charge transporting substance 1.
The arylsulfonate compound may be synthesized by a commercially available method or by a known method described in international publication No. 2017/217455, international publication No. 2017/217457, international publication No. 2019/124412, or the like.
In the present invention, if it is considered that a charge transporting thin film having excellent transparency and a high refractive index is to be produced, it is preferable to use an arylsulfonic acid compound or an arylsulfonic acid ester compound as a dopant substance, and if it is considered that a thin film having a lower solubility in a solvent and a lower extinction coefficient is to be obtained, it is more preferable to use an arylsulfonic acid ester compound.
Further, when the obtained thin film is used as a hole injection layer of an organic EL device, the charge-transporting varnish may contain an organic silane compound for the purpose of improving the injectability into the hole transport layer, improving the life characteristics of the device, and the like. The content thereof is usually about 1 to 30% by mass relative to the total mass of the charge transporting substance and the dopant substance.
As the organic solvent used in the preparation of the charge-transporting varnish of the present invention, a highly polar solvent capable of dissolving the arylamine compound of the present invention can be used. The arylamine compound of the present invention is soluble in a solvent regardless of the polarity of the solvent. If necessary, a low-polarity solvent can be used because it is more suitable for the process than a high-polarity solvent. In the present invention, the low-polarity solvent is defined as a solvent having a relative dielectric constant of less than 7 at a frequency of 100kHz, and the high-polarity solvent is defined as a solvent having a relative dielectric constant of 7 or more at a frequency of 100 kHz.
Examples of the low-polarity solvent include
Chlorine-based solvents such as chloroform and chlorobenzene;
aromatic hydrocarbon solvents such as toluene, xylene, tetrahydronaphthalene, cyclohexylbenzene, and decylbenzene;
aliphatic alcohol solvents such as 1-octanol, 1-nonanol, and 1-decanol;
ether solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, and triethylene glycol butyl methyl ether;
ester solvents such as methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, di (2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.
Examples of the highly polar solvent include
Amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-dimethylisobutylamide, N-methylpyrrolidone, and 1, 3-dimethyl-2-imidazolidinone;
ketone solvents such as methyl ethyl ketone, isophorone, and cyclohexanone;
cyano solvents such as acetonitrile and 3-methoxypropionitrile;
polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1, 3-butanediol, and 2, 3-butanediol;
1-membered alcohol solvents other than aliphatic alcohols, such as diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol;
sulfoxide solvents such as dimethyl sulfoxide, and the like.
The viscosity of the charge-transporting varnish is determined appropriately depending on the solid content concentration such as the thickness of the film to be produced, and is usually 1 to 50 mPas at 25 ℃. The solid component in the present invention means a component other than the solvent contained in the charge transporting varnish of the present invention.
The solid content concentration of the charge-transporting varnish is appropriately set in consideration of viscosity, surface tension, etc. of the varnish, the thickness of the film to be produced, etc., and is usually about 0.1 to 20.0 mass%, and if the coatability of the varnish is improved, it is preferably about 0.5 to 10.0 mass%, and more preferably about 1.0 to 5.0 mass%.
The method for producing the charge-transporting varnish is not particularly limited, and examples thereof include a method in which all solid components such as a charge-transporting substance containing the arylamine compound of the present invention are dissolved in an organic solvent at once; a method of dissolving a part of the solid content in an organic solvent and then dissolving the remaining solid content.
In particular, in the production of the charge-transporting varnish, it is preferable to dissolve the charge-transporting substance, the dopant substance, and the like in the organic solvent and then perform filtration using a submicron filter or the like, from the viewpoint of obtaining a thin film having higher flatness with good reproducibility.
The charge-transporting varnish described above can be used to easily produce a charge-transporting thin film, and therefore can be suitably used for producing electronic devices, particularly organic EL devices.
In this case, the charge-transporting thin film can be formed by applying the above-mentioned charge-transporting varnish on a substrate and firing the applied varnish.
The method of applying the varnish is not particularly limited, and examples thereof include a dipping method, a spin coating method, a transfer printing method, a roll coating method, a brush coating method, an ink jet method, a spray coating method, and a slit coating method.
Further, the firing atmosphere of the charge-transporting varnish after coating is not particularly limited, and a thin film having a uniform film formation surface and a high charge-transporting property can be obtained not only in the atmospheric atmosphere but also in an inert gas such as nitrogen gas or in a vacuum.
The firing temperature is appropriately set in the range of about 100 to 260 ℃ in consideration of the application of the obtained film, the degree of charge transport property imparted to the obtained film, the kind of solvent, the boiling point, and the like, and for example, when the obtained film is used as a hole injection layer of an organic EL element, it is preferably about 140 to 250 ℃, and more preferably about 145 to 240 ℃, and when the arylamine compound of the present invention is used as a charge transport material, a film having a good charge transport property can be obtained even when fired at a low temperature of 200 ℃ or less.
In addition, in order to develop a more uniform film-forming property and to allow the reaction to proceed on the substrate, the heating may be performed by giving a temperature change of 2 stages or more, and for example, by using an appropriate device such as a hot plate or an oven.
The thickness of the charge-transporting thin film is not particularly limited, and is preferably 5 to 300nm when the charge-transporting thin film is used as a hole injection layer, a hole transport layer, or a hole injection transport layer of an organic EL device. As a method of changing the film thickness, there are methods of changing the concentration of solid components in the varnish, changing the amount of solution (amount of varnish) on the substrate at the time of coating, and the like.
The charge transport thin film of the present invention described above generally exhibits a refractive index (n) of 1.60 or more and an extinction coefficient (k) of 0.100 or less, as represented by an average value in a wavelength region of 400 to 800nm, and in one embodiment exhibits a refractive index of 1.65 or more, in another embodiment exhibits a refractive index of 1.70 or more, in another embodiment exhibits an extinction coefficient of 0.050 or less, and in another embodiment exhibits an extinction coefficient of 0.010 or less.
When the charge-transporting thin film is applied to an organic EL element, a configuration including the charge-transporting thin film between a pair of electrodes constituting the organic EL element can be formed.
Typical configurations of the organic EL element include the following (a) to (f), but are not limited thereto. In the following configuration, an electron blocking layer or the like may be provided between the light-emitting layer and the anode, and a hole (hole) blocking layer or the like may be provided between the light-emitting layer and the cathode, as necessary. The hole injection layer, the hole transport layer, or the hole injection transport layer may have a function as an electron blocking layer or the like, and the electron injection layer, the electron transport layer, or the electron injection transport layer may have a function as a hole (hole) blocking layer or the like. Further, an arbitrary functional layer may be provided between the layers as necessary.
(a) Anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode
(b) Anode/hole injection layer/hole transport layer/light emitting layer/electron injection transport layer/cathode
(c) Anode/hole injection transport layer/luminescent layer/electron transport layer/electron injection layer/cathode
(d) Anode/hole injection transport layer/light emitting layer/electron injection transport layer/cathode
(e) Anode/hole injection layer/hole transport layer/light emitting layer/cathode
(f) Anode/hole injection transport layer/light emitting layer/cathode
The "hole injection layer", "hole transport layer" and "hole injection transport layer" are layers formed between the light-emitting layer and the anode, and have a function of transporting holes from the anode to the light-emitting layer, and are "hole injection transport layer" when only 1 layer of a hole-transporting material is provided between the light-emitting layer and the anode, and are "hole injection layer" when 2 or more layers of a hole-transporting material are provided between the light-emitting layer and the anode, the layer close to the anode is the "hole injection layer", and the other layers are the "hole transport layers". In particular, a thin film excellent in hole accepting property from the anode and hole injecting property into the hole transporting (light emitting) layer is used as the hole injecting (transporting) layer.
The "electron injection layer", "electron transport layer" and "electron injection transport layer" are layers formed between the light-emitting layer and the cathode, and have a function of transporting electrons from the cathode to the light-emitting layer, and are the "electron injection transport layer" when only 1 layer of an electron-transporting material is provided between the light-emitting layer and the cathode, and are the "electron injection layer" when 2 or more layers of an electron-transporting material are provided between the light-emitting layer and the cathode, the layer close to the cathode is the "electron injection layer", and the other layers are the "electron transport layers".
The "light-emitting layer" is an organic layer having a light-emitting function, and in the case of using a dopant system, includes a host material and a dopant material. In this case, the host material mainly has a function of promoting recombination of electrons and holes and confining excitons in the light-emitting layer, and the dopant material has a function of efficiently emitting excitons obtained by the recombination. In the case of a phosphorescent element, the host material mainly has a function of confining excitons generated from the dopant within the light emitting layer.
The charge-transporting thin film produced from the charge-transporting varnish of the present invention can be used as a functional layer such as a hole injection layer, a hole transport layer, or a hole injection transport layer provided between an anode and a light-emitting layer of an organic EL element, and as described above, it is generally preferable to form the hole injection layer as an upper layer thereof by a coating method.
Examples of the materials and the production method used in the production of the organic EL element using the charge-transporting varnish of the present invention include the following materials and production methods, but are not limited thereto.
An example of a method for producing an OLED element having a hole injection layer formed of a thin film obtained from the charge-transporting varnish is as follows. Furthermore, it is preferable that the electrode is previously cleaned with alcohol, pure water, or the like within a range that does not adversely affect the electrode; surface treatment such as UV ozone treatment, oxygen-plasma treatment, or the like is employed.
On the anode substrate, a hole injection layer was formed using the charge-transporting varnish by the above-described method. The organic electroluminescent material is introduced into a vacuum evaporation device, and a hole transport layer, a luminescent layer, an electron transport layer/hole blocking layer, an electron injection layer and cathode metal are evaporated in sequence. Alternatively, in this method, instead of forming the hole transport layer and the light-emitting layer by vapor deposition, a composition for forming a hole transport layer containing a hole transport polymer and a composition for forming a light-emitting layer containing a light-emitting polymer are used, and these layers are formed by a wet method. Further, an electron blocking layer may be provided between the light-emitting layer and the hole transporting layer as necessary.
Examples of the anode material include a transparent electrode typified by Indium Tin Oxide (ITO) and Indium Zinc Oxide (IZO), a metal anode typified by aluminum, an alloy thereof, and the like, and a flattened anode material is preferable. Polythiophene derivatives and polyaniline derivatives having high charge transport properties can also be used.
Examples of the other metal constituting the metal anode include gold, silver, copper, indium, and alloys thereof, but are not limited thereto.
Examples of the material for forming the hole transport layer include triarylamines such as (triphenylamine) dimer derivatives, [ (triphenylamine) dimer ] spiro dimer, N '-bis (naphthalene-1-yl) -N, N' -bis (phenyl) -benzidine (. alpha. -NPD), 4 '-tris [ 3-methylphenyl (phenyl) amino ] triphenylamine (m-MTDATA), and 4, 4' -tris [ 1-naphthyl (phenyl) amino ] triphenylamine (1-TNATA), and 5, 5 '-bis- {4- [ bis (4-methylphenyl) amino ] phenyl } -2, 2': and oligophenes such as 5 ', 2' -terthiophene (BMA-3T).
Examples of the material for forming the light-emitting layer include low-molecular-weight light-emitting materials such as metal complexes of 8-hydroxyquinoline and the like, metal complexes of 10-hydroxybenzo [ h ] quinoline, bisstyrylbenzene derivatives, bisstyrylarylene derivatives, metal complexes of (2-hydroxyphenyl) benzothiazole, silole derivatives and the like; and a system in which a light-emitting material and an electron-transporting material are mixed in a polymer compound such as poly (p-phenylene vinylene), poly [ 2-methoxy-5- (2-ethylhexyloxy) -1, 4-phenylene vinylene ], poly (3-alkylthiophene) or polyvinylcarbazole, but the present invention is not limited thereto.
In addition, when the light-emitting layer is formed by vapor deposition, the light-emitting layer may be co-deposited with a light-emitting dopant, and examples of the light-emitting dopant include tris (2-phenylpyridine) iridium (III) (ir (ppy)3) And metal complexes thereof, tetracene derivatives such as rubrene, quinacridone derivatives, fused polycyclic aromatic rings such as perylene, and the like, but are not limited thereto.
Examples of the material for forming the electron transport layer/hole blocking layer include, but are not limited to, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, and pyrimidine derivatives.
As a material for forming the electron injection layer, lithium oxide (Li) can be mentioned2O), magnesium oxide (MgO), aluminum oxide (Al)2O3) And metal oxides such as lithium fluoride (LiF), and metal fluorides such as sodium fluoride (NaF), but the metal oxides are not limited to these.
Examples of the cathode material include, but are not limited to, aluminum, magnesium-silver alloy, and aluminum-lithium alloy.
Examples of the material for forming the electron blocking layer include, but are not limited to, tris (phenylpyrazole) iridium.
Examples of the hole-transporting polymer include poly [ (9, 9-dihexylfluorene-2, 7-diyl) -co- (N, N '-bis { p-butylphenyl } -1, 4-diaminophenylene) ], poly [ (9, 9-dioctylfluorene-2, 7-diyl) -co- (N, N' -bis { p-butylphenyl } -1,1 '-biphenylene-4, 4-diamine) ], poly [ (9, 9-bis { 1' -penten-5 '-yl } fluorene-2, 7-diyl) -co- (N, N' -bis { p-butylphenyl } -1, 4-diaminophenylene) ], poly [ N ] terminated with polysilsesquioxane, n ' -bis (4-butylphenyl) -N, N ' -bis (phenyl) -benzidine ], poly [ (9, 9-dioctylfluorene-2, 7-diyl) -co- (4,4 ' - (N- (p-butylphenyl)) diphenylamine) ], and the like.
Examples of the light-emitting polymer include polyfluorene derivatives such as poly (9, 9-dialkylfluorene) (PDAF), polyphenylene vinylene derivatives such as poly (2-methoxy-5- (2' -ethylhexyloxy) -1, 4-phenylene vinylene) (MEH-PPV), polythiophene derivatives such as poly (3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).
The charge-transporting thin film obtained from the charge-transporting varnish of the present invention can be used as a functional layer such as a hole injection layer, a hole transport layer, or a hole injection transport layer provided between an anode and a light-emitting layer of an organic EL element, and can also be used as a charge-transporting thin film in an electronic element such as an organic photoelectric conversion element, an organic thin film solar cell, an organic perovskite photoelectric conversion element, an organic integrated circuit, an organic electric field effect transistor, an organic thin film transistor, an organic light-emitting transistor, an organic optical detector, an organic light receiver, an organic electro-extinction element, a light-emitting electrochemical cell, a quantum dot light-emitting diode, a quantum laser, an organic laser diode, or an organic plasmon light-emitting element.
Examples
The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The apparatus and reagents used are as follows.
[ device ]
(1) MALDI-TOF-MS: autoflex III smartclaw manufactured by Bruker
(2)1H-NMR: JNM-ECP300FT NMR SYSTEM manufactured by Japan electronics Co., Ltd
(3) Cleaning a substrate: substrate cleaning device (reduced pressure plasma method) manufactured by Changzhou industry
(4) Coating of varnish: mikasa corporation spin coater MS-A100
(5) And (3) measuring the film thickness: SURFCORDER ET-4000 Fine shape measuring machine manufactured by Okawa research
(6) And (3) manufacturing an element: multifunctional evaporation device system C-E2L1G1-N manufactured by Changzhou industry
(7) Measurement of current density and luminance of element: multi-channel IVL measuring device manufactured by EHC
(8) Life measurement (luminance half-life measurement) of EL element: organic EL Brightness Life evaluation System PEL-105S manufactured by EHC
(9) Measurement of refractive index (n) and extinction coefficient (k): woollam Japan manufactures multiple incident angle spectroscopic ellipsometer VASE
[ reagent ]
Manufactured by RuPhos Aldrich Co
Manufactured by t-BuXPhos Aldrich Co
t-Bu3PHBF4Fuji film and photochemical preparation
Copper (I) iodide Fuji film and photochemical production
Ethylene diamine Fuji film and photochemical preparation
Pd(DBA)2Tokyo chemical industry (Kabushiki Kaisha)
Pd(OAc)2Tokyo chemical industry (Kabushiki Kaisha)
Pd[P(C6H5)3)]4Tokyo chemical industry (Kabushiki Kaisha)
Pd(dppf)Cl2Tokyo chemical industry (Kabushiki Kaisha)
Preparation of 3-bromo-9-phenylcarbazole from Tokyo chemical industry Co., Ltd
Preparation of 3-bromocarbazole from Tokyo chemical industry
Production of 4-iodotoluene Tokyo chemical industry
Preparation of 4-iodoanisole from Tokyo chemical industry
Preparation of 18-crown ether-6 Tokyo chemical industry
Manufactured by Tokyo chemical industry of bis (pinacolato) diboron
Manufactured by Tokyo chemical industry Co., Ltd., 3 ', 5, 5' -tetramethylbenzidine
Preparation of Lithium Hexamethyldisilazane (LHMDS)1.3mol/L tetrahydrofuran solution from Tokyo chemical industry Co., Ltd
Production of 2-bromo-7-iodofluorene by Tokyo chemical industry Co., Ltd
Tokyo chemical industry (Kabushiki Kaisha) preparation of benzyltriethylammonium chloride
Production of 3-nitroaniline from Tokyo chemical industry
Production of 1-bromo-3-nitrobenzene from Tokyo chemical industry
Preparation of hydrogen chloride (about 1mol/L ethyl acetate solution) from Tokyo chemical industry Co., Ltd
4, 4' -diaminodiphenylamine manufactured by Tokyo chemical industry Co., Ltd
Manufacture of t-Buona Tokyo chemical industry
Preparation of (9-phenyl-9H-carbazol-3-yl) boronic acid Tokyo chemical industry
Preparation of 1, 4-dioxane by Kanto chemical Co., Ltd
Preparation of 2, 2' -bis (trifluoromethyl) benzidine Kanto chemical
Preparation of bis (4-aminophenyl) sulfone Kanto chemical
Preparation of 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzoguan chemical
Preparation of silica gel N60 Kanto Chemicals
Pure chemical preparation of dimethyl sulfoxide
Manufacture of pure methyl iodide
Pure chemical preparation of potassium carbonate
Industrial production of potassium acetate from Tokyo
Pure chemical (plant) production of toluene
Pure chemical preparation of tetrahydrofuran
Pure chemical production of ethyl acetate
Methanol purity chemical Co., Ltd
Preparation of pure hexane by chemical method
M-tolidine and production of Gongshan essence
N, N' -bis (4-aminophenyl) terephthalamide and production of Gongshan
Pd/C CGS-10DR [ H2O ] ═ 54.40% n.e. manufactured by chemcat co
3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazole Beijing aglia technology reduction co., manufactured by ltd
[1] Synthesis of Compounds
Production example 1-1
[ solution 123]
Figure BDA0003380339930000981
30mmol (11.1g) of 2-bromo-7-iodofluorene and 3mmol (683.3mg) of benzyltriethylammonium chloride were weighed and placed in a100 mL reaction flask, and then 60mL of dimethyl sulfoxide was added thereto, followed by stirring for 10 minutes while performing nitrogen substitution.
After 14g of a 50 mass% aqueous solution of sodium hydroxide prepared separately was added thereto and stirred for 10 minutes, 72.5mmol (10.3g) of methyl iodide was added dropwise thereto and stirred at room temperature overnight. Further, a small amount of the solution in the flask was collected in the middle of the reaction, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target substance increases. At this time, no significant peak corresponding to the by-product was observed.
The obtained reaction mixture was added to 800mL of a mixed solvent of methanol and water (3/1(v/v)), and the precipitated solid was separated by filtration with a membrane filter.
Finally, the recovered solid was dried under reduced pressure at 60 ℃ to obtain 6.26g (78.4%) of 2-bromo-7-iodo-9, 9-dimethyl-9H-fluorene. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy DMSO) is shown in FIG. 1.
Production examples 1 and 2
[ solution 124]
Figure BDA0003380339930000982
In a 200mL two-necked flask, 20mmol (4.93g) of 3-bromocarbazole, 44mmol (9.61g) of 4-iodotoluene, 16mmol (3.05g) of copper (I) iodide, 50mmol (16.3g) of cesium carbonate and 100mL of toluene were charged, and after stirring at room temperature for 5 minutes under a nitrogen stream, 30mmol (1.82g) of ethylenediamine was added, and the mixture was stirred under reflux overnight under heating.
After the resulting reaction mixture was cooled to room temperature, insoluble materials were removed by filtration through Celite, the resulting filtrate was concentrated, and the concentrate was purified by column chromatography to obtain 2.84g (42.2%) of 3-bromo-9- (4-tolyl) carbazole. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIGS. 2 to 4.
Production examples 1 to 3
[ solution 125]
Figure BDA0003380339930000991
Reaction and purification were carried out in the same manner as in production example 1-2 except for using 88mmol (20.6g) of 4-iodoanisole instead of 44mmol of 4-iodotoluene and setting the equivalent weight of the other reagents to 2 times, to obtain 11.1g (78.7%) of 3-bromo-9- (4-methoxyphenyl) carbazole. Of the compound obtained1The H-NMR spectrum is shown in FIGS. 5 and 6.
Production examples 1 to 4
[ solution 126]
Figure BDA0003380339930000992
A200 mL two-necked flask was charged with 60mmol (14.76g) of 3-bromocarbazole, 4.5mmol (0.86g) of copper (I) iodide, 63mmol (8.71g) of potassium carbonate, and 61.5mmol (16.2g) of 18-crown-6, and after nitrogen substitution in the flask, 100mL of N, N-dimethylacetamide was added thereto and the mixture was stirred at room temperature for 10 minutes. Then, the temperature was raised to 160 ℃ and the mixture was stirred for 2 hours, then 63mmol (13.23g) of 2-iodothiophene was added thereto and the mixture was further stirred for 70 hours.
After the reaction mixture was cooled to room temperature, insoluble materials were removed by Celite filtration, the obtained filtrate was concentrated, and the concentrate was purified by column chromatography (elution solvent: n-hexane/ethyl acetate 100/0 → 95/5) to obtain 5.80g (29.5%) of 3-bromo-9- (thiophen-2-yl) carbazole. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIGS. 7 and 8.
Production examples 1 to 5
[ solution 127]
Figure BDA0003380339930001001
Reaction and purification were carried out in the same manner as in production examples 1 to 4 except that 60mmol (14.76g) of 2-bromocarbazole was used instead of 3-bromocarbazole to obtain 2-bromo7.36g (37.2%) of-9- (thien-2-yl) carbazole. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIGS. 9 and 10.
Production examples 1 to 6
[ solution 128]
Figure BDA0003380339930001002
A100 mL reaction flask was charged with 5mmol (1.68g) of 3-bromo-9- (p-tolyl) carbazole, 5.05mmol (1.28g) of bis (pinacolato) diboron, 15mmol (1.47g) of potassium acetate, Pd (dppf) Cl20.15mmol (0.125g) and 50mL of N, N-dimethylformamide were stirred at room temperature for 10 minutes while nitrogen substitution was performed, and then the mixture was heated to 90 ℃ and stirred overnight.
The reaction mixture, 75mL of water and 75mL of methylene chloride were mixed and extracted, and the organic layer was recovered. The recovered organic layer was dried over magnesium sulfate, and the magnesium sulfate was removed by filtration. The obtained filtrate was concentrated, and the concentrate was purified by column chromatography to obtain 1.42g (74.3%) of 9- (p-tolyl) carbazole-3-boronic acid pinacol ester. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIGS. 11 and 12.
Production examples 1 to 7
[ solution 129]
Figure BDA0003380339930001011
Reaction and purification were carried out in the same manner as in production examples 1 to 6 except that 10mmol (3.522g) of 3-bromo-9- (p-methoxyphenyl) carbazole was used instead of 5mmol of 3-bromo-9- (p-tolyl) carbazole and the equivalent weight of the other reagent was 2 times, thereby obtaining 1.53g (38.3%) of 9- (p-methoxyphenyl) carbazole-3-boronic acid pinacol ester. Of the compound obtained1The H-NMR spectrum (determination solvent: heavy THF) is shown in FIGS. 13 and 14.
Production examples 1 to 8
[ solution 130]
Figure BDA0003380339930001012
Reaction and purification were carried out in the same manner as in production examples 1 to 6 except that 15mmol (4.92g) of 3-bromo-9- (thiophen-2-yl) carbazole was used instead of 5mmol of 3-bromo-9- (p-tolyl) carbazole and the equivalent weight of the other reagents was 3 times, thereby obtaining 2.53g (44.9%) of 9- (thiophen-2-yl) carbazole-3-boronic acid pinacol ester. Of the compound obtained1The H-NMR spectrum (determination solvent: heavy THF) is shown in FIGS. 15 and 16.
Production examples 1 to 9
[ solution 131]
Figure BDA0003380339930001013
The reaction and purification were carried out in the same manner as in production examples 1 to 6 except for using 5mmol (1.64g) of 2-bromo-9- (thiophen-2-yl) carbazole instead of 3-bromo-9- (p-tolyl) carbazole to obtain 1.26g (67.2%) of 9- (thiophen-2-yl) carbazole-2-boronic acid pinacol ester. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIGS. 17 and 18.
Production example 2-1
[ solution 132]
Figure BDA0003380339930001021
In a100 mL reaction flask were placed 5mmol (1.44g) of (9-phenyl-9H-carbazol-3-yl) boronic acid, 5.25mmol (2.95g) of 2-bromo-7-iodo-9, 9-dimethyl-9H-fluorene, 15mmol (600mg) of sodium hydroxide, and 75mL of a mixed solvent of tetrahydrofuran and water (2/1(v/v)) and Pd [ P (C/v)) ]6H5)3)]40.15mmol (173.5mg) was stirred at room temperature for 10 minutes while exchanging nitrogen, and then stirred at 60 ℃ for 5 hours. Further, a small amount of the solution in the flask was collected in the middle of the reaction, and the reaction was followed by liquid chromatography. The area of the peak attributable to the target substance increases as the area of the peak attributable to the raw material decreases. At this time, no significant peak corresponding to the by-product was observed.
The resulting reaction mixture was added to 400mL of a mixed solvent of methanol and water (3/1(v/v)), the precipitated solid was separated by filtration using a membrane filter, and the solid separated by filtration was dried under reduced pressure at 60 ℃.
Further, the dried solid was dissolved in 20mL of tetrahydrofuran, 200mL of n-hexane was added to the resulting solution, the precipitated solid was separated by filtration with a membrane filter, and the solid separated by filtration was dried under reduced pressure at 60 ℃.
Finally, the dried solid was dissolved in 20mL of tetrahydrofuran, and 200mL of a mixed solvent of methanol and water (3/1(v/v)) was added to the resulting solution, and the precipitated solid was separated by filtration using a membrane filter. The obtained solid was dried under reduced pressure at 60 ℃ to obtain 1.28g (49.8%) of 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazole. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIG. 19.
Production example 2-2
[ solution 133]
Figure BDA0003380339930001031
In a100 mL reaction flask were placed 2.5mmol (0.958g) of 9- (P-tolyl) carbazole-3-boronic acid pinacol ester, 2.63mmol (1.05g) of 2-bromo-7-iodo-9, 9-dimethyl-9H-fluorene, 7.5mmol (300mg) of sodium hydroxide, a mixed solvent of tetrahydrofuran and water (2/1(v/v))37.5mL and Pd [ P (C.sub.p.) (C.sub.78 (v/v)) ]6H5)3)]40.075mmol (86.7mg) was stirred at room temperature for 10 minutes while exchanging nitrogen, and then stirred at 60 ℃ overnight.
After the resulting reaction mixture was cooled to room temperature, the aqueous layer was removed. The organic layer thus obtained was dropped into a mixed solvent of methanol and water (3/1(v/v)), the precipitated solid was separated by filtration with a membrane filter, and the solid separated by filtration was dried under reduced pressure at 60 ℃.
Further, the dried solid was dissolved in 20mL of tetrahydrofuran, the resulting solution was added to 200mL of n-hexane, and the precipitated solid was usedThe solid was dried under reduced pressure at 60 ℃. 1.10g (83.3%) of 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9- (p-tolyl) -9H-carbazole was obtained. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIGS. 20 and 21.
Production examples 2 to 3
[ solution 134]
Figure BDA0003380339930001032
The reaction and purification were carried out in the same manner as in production example 2-2 except for using 15mmol (5.99g) of 9- (p-methoxyphenyl) carbazole-3-boronic acid pinacol ester instead of 9- (p-tolyl) carbazole-3-boronic acid pinacol ester and setting the equivalent weight of the other reagents to 6 times, thereby obtaining 5.80g (70.4%) of 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9- (p-methoxyphenyl) -9H-carbazole. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIG. 22.
Production examples 2 to 4
[ solution 135]
Figure BDA0003380339930001041
The reaction and purification were carried out in the same manner as in production example 2-2 except for using 5mmol (1.79g) of 9- (thiophen-2-yl) carbazole-3-boronic acid pinacol ester instead of 9- (p-tolyl) carbazole-3-boronic acid pinacol ester and setting the equivalent weight of the other reagents to 2 times, thereby obtaining 1.86g (76.8%) of 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9- (thiophen-2-yl) -9H-carbazole. Of the compound obtained1The H-NMR spectrum is shown in FIGS. 23 and 24 (measurement solvent: heavy THF).
Production examples 2 to 5
[ solution 136]
Figure BDA0003380339930001042
The reaction and purification were carried out in the same manner as in production example 2-2 except for using 5mmol (1.88g) of 9- (thiophen-2-yl) carbazole-2-boronic acid pinacol ester instead of 9- (p-tolyl) carbazole-3-boronic acid pinacol ester and setting the equivalent weight of the other reagents to 2 times, thereby obtaining 2.0g (77.7%) of 2- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9- (thiophen-2-yl) -9H-carbazole. Of the compound obtained1The H-NMR spectrum is shown in FIGS. 25 and 26 (measurement solvent: heavy THF).
Production example 3
[ solution 137]
Figure BDA0003380339930001043
Into a 1000mL reaction flask equipped with a reflux column were placed Pd (DBA)25mmol (2.88g), t-BuXPhos10mmol (4.25g), potassium carbonate 300mmol (41.46g), 3-nitroaniline 100mmol (13.82g), 1-bromo-3-nitrobenzene 110mmol (22.22g), and 1000mL of toluene, and after nitrogen substitution in the flask, the mixture was stirred overnight in a bath at 80 ℃. Further, a small amount of the solution in the flask was collected in the middle of the reaction, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target substance increases. At this time, no significant peak corresponding to the by-product was observed.
The reaction solution was cooled to room temperature, filtered through a filter packed with silica gel N60200 g, the obtained filtrate was concentrated until the weight became 100g, the concentrate was dropped into 1000mL of toluene, and the resultant solid was separated by filtration. The obtained solid was dried to obtain 24.1g of bis (3-nitrophenyl) amine (yield 93.1%).
Production example 4
[ 138]
Figure BDA0003380339930001051
In a 300mL reaction flask equipped with a reflux column, 77.15mmol (20g) of bis (3-nitrophenyl) amine and Pd/C CGS-10DR [ H2O ] were weighed]54.40% 2g, the flask was charged with hydrogenAnd (4) changing. After adding 200mL of tetrahydrofuran thereto, the mixture was stirred at 50 ℃ overnight. The mixture was cooled to room temperature, filtered through a filter packed with 200g of Celite, and the solvent was distilled off from the filtrate under reduced pressure. Collecting small amount of residue, and using1After confirming the formation of 3, 3' -diaminodiphenylamine by H-NMR, 100g of tetrahydrofuran was added to the residue, and the resulting solution was cooled to 0 ℃ with an ice bath, and after confirming that the temperature was stable, 50mL of a hydrogen chloride solution (an ethyl acetate solution of about 1 mol/L) was added, and the precipitated solid was separated by filtration. The resulting solid was dried to give 19.8g (99.0%) of 3, 3' -diaminodiphenylamine dihydrochloride.
[ example 1-1]
[ solution 139]
Figure BDA0003380339930001061
Pd (DBA) was weighed into a 30mL reaction flask equipped with a reflux column20.1mmol (57.6mg), RuPhos0.15mmol (70.0mg), 3 ', 5, 5' -tetramethylbenzidine 0.5mmol (120.2mg), 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazole 2.1mmol (1080.4mg), and nitrogen substitution was performed in the system.
To this was added 10mL of dioxane, and the mixture was stirred at room temperature for 5 minutes, followed by addition of 1.69mL of LHMDS1.3mol/L tetrahydrofuran solution (equivalent to LHMDS2.2mmol), stirring at room temperature for 5 minutes, and then stirring by heating in a 110 ℃ bath for 8 hours (inner temperature: 92 ℃). Further, a small amount of the solution in the flask was collected in the middle of the reaction, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target substance increases. At this time, no significant peak corresponding to the by-product was observed.
After the reaction mixture was cooled to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 50mL of a saturated aqueous solution of ammonium chloride and 50mL of a mixed solvent of ethyl acetate and tetrahydrofuran (2/1(v/v)) to conduct extraction, and the organic layer remained in the separatory funnel, and the aqueous layer was recovered. 50mL of saturated saline was put into a separatory funnel, and the remaining organic layer was washed and the aqueous layer and the organic layer were collected separately. Then, all the recovered aqueous layers were combined, placed in a separatory funnel, and 20mL of ethyl acetate was added thereto to conduct extraction, and the organic layers were recovered, and all the recovered organic layers were combined and dried over magnesium sulfate.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the resulting filtrate using a rotary evaporator. The obtained residue was dissolved in 3mL of toluene, and the resulting solution was subjected to column chromatography (elution solvent: n-hexane/dichloromethane 60/40 → 0/100) to collect a fraction containing the target compound.
Finally, the solvent was removed from the separated fractions and dried under reduced pressure at 70 ℃ to obtain 0.56g (> 99%) of the arylamine compound C2d 0.56. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIG. 27.
[ examples 1-2]
[ solution 140]
Figure BDA0003380339930001071
The same procedures used in example 1-1 were repeated except for using 0.5mmol (123.2mg) of N, N ' -bis (4-aminophenyl) terephthalamide instead of 3,3 ', 5, 5 ' -tetramethylbenzidine to obtain 0.43g (70.9%) of an arylamine compound D2D 0.43. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIG. 28.
[ examples 1 to 3]
[ solution 141]
Figure BDA0003380339930001072
The same procedures used in example 1-1 were repeated except for using 0.5mmol (160.12mg) of 2,2 ' -bis (trifluoromethyl) benzidine instead of 3,3 ', 5, 5 ' -tetramethylbenzidine to obtain 3, 3d 0.46.46 g (44.8%) of an arylamine compound a. Of the compound obtained1H-NMR spectrum (determination of solvent: weight)THF) is shown in fig. 29.
[ examples 1 to 4]
[ solution 142]
Figure BDA0003380339930001081
The same procedures used in example 1-1 were repeated except for using 0.5mmol (124.5mg) of bis (4-aminophenyl) sulfone in place of 3,3 ', 5, 5' -tetramethylbenzidine to obtain 0.35g (35.3%) of an arylamine compound E3d 0.35. Of the compound obtained1H-NMR spectrum (determination solvent: CDCl)3) Shown in fig. 30.
[ examples 1 to 5]
[ solution 143]
Figure BDA0003380339930001082
The same procedures as in examples 1 to 4 were carried out except for using 2.1mmol (1.375mg) of 3- (7-bromo-9, 9-dihexyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazole instead of 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazole to obtain arylamine compound e, e3i0.71g (55.8%). Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIG. 31.
[ examples 1 to 6]
[ solution 144]
Figure BDA0003380339930001091
The same procedures used in example 1-1 were repeated except for using 0.5mmol (219.2mg) of 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene in place of 3,3 ', 5, 5' -tetramethylbenzidine to obtain 3d 0.35.35 g (32.4%) of an arylamine compound F3. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIG. 32.
[ examples 1 to 7]
[ solution 145]
Figure BDA0003380339930001092
The same procedures as in examples 1 to 3 were carried out except for using 2.1mmol (836.4mg) of 3- (4-bromophenyl) -9-phenyl-9H-carbazole instead of 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazole to obtain 3b 0.32.32 g (40.3%) of arylamine compound A3. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIG. 33.
[ examples 1 to 8]
[ solution 146]
Figure BDA0003380339930001101
Except that 3- (4 '-bromo- [1,1' -biphenyl) is used instead of 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazole]The same procedures used in examples 1 to 3 were repeated except for using 2.1mmol (996.2mg) of (E) -4-yl) -9-phenyl-9H-carbazole to give 3.3 c 0.57g (60.2%) of the arylamine compound A. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIG. 34.
[ examples 1 to 9]
[ solution 147]
Figure BDA0003380339930001111
The same procedures used in example 1-1 were repeated except for using 0.5mmol (106.1mg) of m-tolidine instead of 3,3 ', 5, 5' -tetramethylbenzidine to obtain 3d 0.17.17G (17.5%) of the arylamine compound G3. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIG. 35.
[ examples 1 to 10]
[ solution 148]
Figure BDA0003380339930001112
Pd (OAc) was weighed into a 200mL reaction flask equipped with a reflux column2 2mmol(0.45g)、t-Bu3PHBF44mmol (1.16g), t-BuONa40mmol (3.84g), 4' -diaminodiphenylamine 4mmol (797.0mg), and 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazole 20.6mmol (10.61g), and the flask was purged with nitrogen. 50mL of toluene was added thereto, and the mixture was stirred overnight in a bath at 110 ℃. Further, a small amount of the solution in the flask was collected in the middle of the reaction, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target substance increases. At this time, no significant peak corresponding to the by-product was observed.
The reaction mixture was cooled to room temperature and filtered through a membrane filter. The filtrate was concentrated, and a column chromatography (eluting solvent: n-hexane/dichloromethane ═ 70/30(v/v) → 55/45(v/v)) was performed using a solution obtained by diluting the obtained concentrate with 10mL of toluene to collect fractions of the target substance, and the collected fractions were concentrated, and a solution obtained by diluting the obtained concentrate with 10mL of toluene was again performed under the same conditions to collect fractions of the target substance. The collected fractions were concentrated, the concentrate was dissolved in 30mL of tetrahydrofuran, the resulting solution was added dropwise to a mixed solvent of ethyl acetate and methanol (1/1(v/v)), and the precipitated solid was collected by a membrane filter. The obtained solid was dried to obtain arylamine compound H3d 2.67.67 g (28.2%). Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIG. 36.
[ examples 1 to 11]
[ 149]
Figure BDA0003380339930001121
Pd (OAc) was weighed into a 30mL reaction flask equipped with a reflux column2 2.5mmol(0.56g)、t-Bu3PHBF45mmol (1.45g), t-BuONa25mmol (2.40g), 3' -diaminodiphenylamine dihydrochloride 2.5mmol (80 g)4mg), 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazole 12.6mmol (6.49g), and the inside of the flask was subjected to nitrogen substitution. 50mL of toluene was added thereto, and the mixture was stirred overnight in a bath at 110 ℃. Further, a small amount of the solution in the flask was collected in the middle of the reaction, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target substance increases. At this time, no significant peak corresponding to the by-product was observed.
The reaction mixture was cooled to room temperature and filtered through a membrane filter. The filtrate was concentrated, and a column chromatography (eluting solvent: n-hexane/dichloromethane ═ 70/30(v/v) → 55/45(v/v)) was performed using a solution obtained by diluting the obtained concentrate with 5mL of toluene to collect fractions of the target substance, and the collected fractions were concentrated, and a solution obtained by diluting the obtained concentrate with 5mL of toluene was again performed under the same conditions to collect fractions of the target substance. The collected fractions were concentrated, the concentrate was dissolved in 30mL of tetrahydrofuran, the resulting solution was added dropwise to a mixed solvent of ethyl acetate and methanol (1/1(v/v)), and the precipitated solid was collected by a membrane filter. The resulting solid was dried to yield arylamine compound I3d 2.34.34 g (39.5%). Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIG. 37.
[ examples 1 to 12]
[ solution 150]
Figure BDA0003380339930001131
In a 50mL flask were placed 0.4mmol (108.9mg) of 3, 3' -diaminodiphenylamine dihydrochloride, 2.02mmol (1067.5mg) of 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9- (p-tolyl) -9H-carbazole, Pd (OAc)20.4mmol(89.8mg)、t-Bu3PHBF4After nitrogen substitution was performed on 0.8mmol (232.1mg) and t-BuONa4mmol (384.4mg), 8mL of toluene was added and the mixture was stirred for 10 minutes, and then the mixture was stirred overnight under reflux with heating.
After cooling the reaction mixture to room temperature, the aqueous layer was removed from the cooled reaction mixture, andthe mixed solvent of methanol and water (methanol/water 3/1(v/v)) was added dropwise to the obtained organic layer. The precipitated solid was recovered by filtration, the obtained solid was dissolved in tetrahydrofuran, and the solution was dropped into n-hexane. The resulting solid was recovered by filtration and dried under reduced pressure to give arylamine compound I3e210mg (21.5%). Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIGS. 38 and 39.
[ examples 1 to 13]
[ solution 151]
Figure BDA0003380339930001141
The same procedures as in examples 1 to 12 were carried out except for using 2.02mmol (1051.4mg) of 2- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9- (thiophen-2-yl) -9H-carbazole instead of 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9- (p-tolyl) -9H-carbazole to obtain 3- (3H 157.0.0 mg (16.4%) of arylamine compound I. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIGS. 40 and 41.
[ examples 1 to 14]
[ solution 152]
Figure BDA0003380339930001151
The same procedures as in examples 1 to 3 were carried out except for using 2.1mmol (1109.8mg) of 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9- (p-tolyl) -9H-carbazole instead of 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazole to obtain 3e 323.8.8 mg (38.3%) of arylamine compound a. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIG. 42.
[ examples 1 to 15]
[ solution 153]
Figure BDA0003380339930001152
The same procedures as in examples 1 to 3 were carried out except for using 2.1mmol (1143.4mg) of 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9- (p-methoxyphenyl) -9H-carbazole instead of 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazole to obtain 3f 552.6mg (50.8%) of arylamine compound a. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIG. 43.
[ examples 1 to 16]
[ solution 154]
Figure BDA0003380339930001161
The same procedures as in examples 1 to 3 were carried out except for using 2.1mmol (1093.0mg) of 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9- (thiophen-2-yl) -9H-carbazole instead of 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazole to obtain 3g 499.9mg (48.1%) of arylamine compound a. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIG. 44.
[ examples 1 to 17]
[ solution 155]
Figure BDA0003380339930001171
The same procedures as in examples 1 to 3 were carried out except for using 2.1mmol (1093.0mg) of 2- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9- (thiophen-2-yl) -9H-carbazole instead of 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazole to obtain 3H 664.9mg (64.0%) of arylamine compound a. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIGS. 45 and 46.
[ examples 1 to 18]
[ solution 156]
Figure BDA0003380339930001172
A50 mL reaction flask was charged with 0.5mmol (164mg) of octafluorobiphenyl-4, 4' -diamine, 2.1mmol (836mg) of 3- (4-bromophenyl) -9-phenylcarbazole, Pd (OAc)2 0.2mmol(45mg)、t-Bu3PHBF40.4mmol (166mg) and t-BuONa4mmol (385mg) were subjected to nitrogen substitution, and then 10mL of toluene was added thereto, followed by stirring at room temperature for 5 minutes and then at 100 ℃ for 6 hours.
After the reaction mixture was cooled to room temperature, the cooled reaction mixture was filtered through a membrane filter, and activated carbon was added to the obtained filtrate and stirred for 1 hour. The activated carbon was removed by filtration, the obtained filtrate was concentrated, and the concentrate was purified by silica gel column chromatography (elution solvent: n-hexane/dichloromethane ═ 3/2(v/v)) to obtain arylamine compound B3B 311.8.8 mg (44.6%). Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIG. 47.
[ examples 1 to 19]
[ chemical formula 157]
Figure BDA0003380339930001181
Except that 3- (4 '-bromo- [1,1' -biphenyl) is used instead of 3- (4-bromophenyl) -9-phenylcarbazole]The same procedures used in examples 1 to 18 were repeated except for using 2.1mmol (996.2mg) of (E) -4-yl) -9-phenyl-9H-carbazole to give 3 35391 mg (41.1%) of an arylamine compound B. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIG. 48.
[ examples 1 to 20]
[ solution 158]
Figure BDA0003380339930001191
The procedure was carried out in the same manner as in examples 1 to 18 except for using 2.1mmol (1080.4mg) of 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazole instead of 3- (4-bromophenyl) -9-phenylcarbazole to obtain 3- (3 d 535) mg (51.9%) of arylamine compound B. Will obtainProcess for preparing compounds1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIG. 49.
[ examples 1 to 21]
[ chemical formula 159]
Figure BDA0003380339930001192
A50 mL reaction flask was charged with 0.5mmol (164mg) of octafluorobiphenyl-4, 4' -diamine, 2.1mmol (836mg) of 3- (4-bromophenyl) -9-phenylcarbazole, Pd (DBA)2 0.1mmol(57.5mg)、t-Bu3PHBF40.2mmol (84mg) and t-BuONa2mmol (193mg) were subjected to nitrogen substitution, and then 10mL of toluene was added thereto, followed by stirring at room temperature for 5 minutes and then at 100 ℃ for 6 hours.
After the reaction mixture was cooled to room temperature, the cooled reaction mixture was filtered through a membrane filter, and activated carbon was added to the obtained filtrate and stirred for 1 hour. The activated carbon was removed by filtration, the obtained filtrate was concentrated, and the concentrate was purified by silica gel column chromatography (elution solvent: n-hexane/dichloromethane ═ 3/2(v/v)) to obtain arylamine compound B2B 419.0mg (87.0%). Of the compound obtained1The H-NMR spectrum (measurement solvent: DMSO in weight) is shown in FIG. 50.
[ examples 1 to 22]
[ solution 160]
Figure BDA0003380339930001201
Except that 3- (4 '-bromo- [1,1' -biphenyl) is used instead of 3- (4-bromophenyl) -9-phenylcarbazole]The same procedures used in examples 1 to 21 were repeated except for using 2.1mmol (996.2mg) of (E) -4-yl) -9-phenyl-9H-carbazole to give 2.2 c 72.9.9 mg (13.1%) of an arylamine compound B2. Of the compound obtained1The H-NMR spectrum (measurement solvent: DMSO in weight) is shown in FIG. 51.
[ examples 1 to 23]
[ solution 161]
Figure BDA0003380339930001211
The same procedures as in examples 1 to 21 were carried out except for using 2.1mmol (1080.4mg) of 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazole instead of 3- (4-bromophenyl) -9-phenylcarbazole to obtain 114.0mg (19.1%) of arylamine compound B2d 114.0. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy DMSO) is shown in FIG. 52.
Comparative examples 1 to 1
[ chemical 162]
Figure BDA0003380339930001212
The same procedures as in examples 1 to 3 were carried out except for using 2.1mmol (676.6mg) of 3-bromo-N-phenylcarbazole instead of 3- (7-bromo-9, 9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazole to obtain 3-3 a 0.45.45 g (70.0%) of arylamine compound a. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy DMSO) is shown in FIG. 53.
Comparative examples 1 and 2
[ chemical 163]
Figure BDA0003380339930001221
The procedures were carried out in the same manner as in examples 1 to 18 except for using 2.1mmol (677mg) of 3-bromo-N-phenylcarbazole instead of 3- (4-bromophenyl) -9-phenylcarbazole to obtain 3a 236.2.2 mg (36.6%) of arylamine compound B3. Of the compound obtained1The H-NMR spectrum (measurement solvent: heavy THF) is shown in FIG. 54.
Comparative examples 1 to 3
[ 164]
Figure BDA0003380339930001222
Except that instead of 3- (4-bromophenyl) -9-phenylcarbazoleThe same procedures used in examples 1 to 21 were repeated except for using 2.1mmol (677mg) of 3-bromo-9-phenylcarbazole to give 272.3mg (67.2%) of arylamine compound B2a 272.3. Of the compound obtained1The H-NMR spectrum (measurement solvent: DMSO in weight) is shown in FIG. 55.
[2] Preparation of varnish for hole injection layer
Comparative example 2-1
Arylamine compound A3a (0.025g) and arylsulfonate A (0.025g) represented by the following formula were added to chloroform (10g), and the mixture was dissolved with stirring at room temperature, and the resulting solution was filtered through a syringe filter having a pore size of 0.2. mu.m, whereby charge-transporting varnish A3a-1 was obtained.
[ solution 165]
Figure BDA0003380339930001231
[ example 2-1]
Arylamine compound A3b (0.028g) and arylsulfonate A (0.022g) were added to chloroform (10g), and the mixture was dissolved by stirring at room temperature, and the resulting solution was filtered through a syringe filter having a pore size of 0.2. mu.m, whereby charge-transporting varnish A3b-1 was obtained.
[ examples 2-2]
Arylamine compound A3c (0.030g) and arylsulfonate A (0.020g) were added to chloroform (10g), and dissolved with stirring at room temperature, and the resulting solution was filtered through a syringe filter having a pore size of 0.2 μm to obtain charge-transporting varnish A3 c-1.
[ examples 2 to 3]
Arylamine compound A3d (0.031g) and arylsulfonate A (0.019g) were added to chloroform (10g), and the mixture was dissolved by stirring at room temperature, and the resulting solution was filtered through a syringe filter having a pore size of 0.2. mu.m, whereby charge-transporting varnish A3d-1 was obtained.
[ examples 2 to 4]
Arylamine compound A3e (0.031g) and arylsulfonate A (0.019g) were added to chloroform (10g), and the mixture was dissolved by stirring at room temperature, and the resulting solution was filtered through a syringe filter having a pore size of 0.2. mu.m, whereby charge-transporting varnish A3e-1 was obtained.
[ examples 2 to 5]
Arylamine compound A3f (0.032g) and arylsulfonate A (0.018g) were added to chloroform (10g), and the mixture was dissolved by stirring at room temperature, and the resulting solution was filtered through a syringe filter having a pore size of 0.2. mu.m, whereby charge-transporting varnish A3f-1 was obtained.
[ examples 2 to 6]
Arylamine compound A3g (0.031g) and arylsulfonate A (0.019g) were added to chloroform (10g), and the mixture was dissolved by stirring at room temperature, and the resulting solution was filtered through a syringe filter having a pore size of 0.2. mu.m, whereby charge-transporting varnish A3g-1 was obtained.
[ examples 2 to 7]
Arylamine compound A3h (0.031g) and arylsulfonate A (0.019g) were added to chloroform (10g), and the mixture was dissolved by stirring at room temperature, and the resulting solution was filtered through a syringe filter having a pore size of 0.2. mu.m, whereby charge-transporting varnish A3h-1 was obtained.
Comparative examples 2 and 2
Arylamine compound B3a (0.026g) and arylsulfonate A (0.024g) were added to chloroform (10g), and the mixture was dissolved with stirring at room temperature, and the resulting solution was filtered through a syringe filter having a pore size of 0.2. mu.m, whereby charge-transporting varnish B3a-1 was obtained.
[ examples 2 to 8]
Arylamine compound B3B (0.029g) and arylsulfonate A (0.021g) were added to chloroform (10g), and the mixture was dissolved with stirring at room temperature, and the resulting solution was filtered through a syringe filter having a pore size of 0.2. mu.m, whereby charge-transporting varnish B3B-1 was obtained.
[ examples 2 to 9]
Arylamine compound B3c (0.030g) and arylsulfonate A (0.020g) were added to chloroform (10g), and dissolved with stirring at room temperature, and the resulting solution was filtered through a syringe filter having a pore size of 0.2 μm to obtain charge-transporting varnish B3 c-1.
[ examples 2 to 10]
Arylamine compound B3d (0.031g) and arylsulfonate A (0.019g) were added to chloroform (10g), and the mixture was dissolved by stirring at room temperature, and the resulting solution was filtered through a syringe filter having a pore size of 0.2. mu.m, whereby charge-transporting varnish B3d-1 was obtained.
Comparative examples 2 to 3
Arylamine compound B2a (0.020g) and arylsulfonate A (0.030g) were added to chloroform (10g), and the mixture was dissolved with stirring at room temperature, and the resulting solution was filtered through a syringe filter having a pore size of 0.2. mu.m, whereby charge-transporting varnish B2a-1 was obtained.
[ examples 2 to 11]
Arylamine compound B2B (0.022g) and arylsulfonate A (0.028g) were added to chloroform (10g), and the mixture was dissolved with stirring at room temperature to obtain a solution, which was then filtered through a syringe filter having a pore size of 0.2. mu.m, to obtain charge-transporting varnish B2B-1.
[ examples 2 to 12]
Arylamine compound B2c (0.024g) and arylsulfonate A (0.026g) were added to chloroform (10g), and the mixture was dissolved with stirring at room temperature, and the resulting solution was filtered through a syringe filter having a pore size of 0.2. mu.m, whereby charge-transporting varnish B2c-1 was obtained.
[ examples 2 to 13]
Arylamine compound B2d (0.025g) and arylsulfonate A (0.025g) were added to chloroform (10g), and the mixture was dissolved with stirring at room temperature, and the resulting solution was filtered through a syringe filter having a pore size of 0.2. mu.m, whereby charge-transporting varnish B2d-1 was obtained.
[ examples 2 to 14]
Arylamine compound H3d (0.033g) and arylsulfonate A (0.017g) were added to chloroform (10g), and the mixture was dissolved with stirring at room temperature, and the resulting solution was filtered through a syringe filter having a pore size of 0.2. mu.m, whereby charge-transporting varnish H3d-1 was obtained.
[ examples 2 to 15]
Arylamine compound I3d (0.033g) and arylsulfonate A (0.017g) were added to chloroform (10g), and dissolved with stirring at room temperature, and the resulting solution was filtered through a syringe filter having a pore size of 0.2 μm to obtain charge-transporting varnish I3 d-1.
[3] Preparation of varnish for hole transport layer
Comparative example 3-1
Arylamine compound A3a (0.040g) was added to chloroform (10g), and the mixture was dissolved by stirring at room temperature, and the resulting solution was filtered through a syringe filter having a pore size of 0.2. mu.m, whereby charge-transporting varnish A3a-2 was obtained.
Examples 3-1 to 3-11
Charge-transporting varnishes A3B-2, A3c-2, A3d-2, A3e-2, A3f-2, A3g-2, A3H-2, B3d-2, B2d-2, H3d-2, or I3d-2 were obtained in the same manner as in comparative example 3-1, except that an arylamine compound A3B, A3c, A3d, A3e, A3f, A3g, A3H, B3d, B2d, H3d, or I3d was used in place of the arylamine compound A3a, respectively.
[4] Production of film and evaluation of film physical Properties
Comparative example 4-1 and examples 4-1 to 4-3
The charge-transporting varnishes A3a-1, A3b-1, A3c-1 and A3d-1 were applied to a quartz substrate by a spinner, respectively, and then dried at 120 ℃ for 1 minute by firing in the air. Next, the dried quartz substrate was fired at 200 ℃ for 15 minutes in an atmospheric atmosphere to form a uniform 50nm thin film on the quartz substrate.
The obtained quartz substrate with a film was used to measure the average refractive index (n) in the visible region and the average extinction coefficient (k) in the visible region at a wavelength of 400 to 800 nm. The results are shown in Table 23.
[ Table 23]
Figure BDA0003380339930001261
As shown in Table 23, it is understood that the film obtained from the charge-transporting varnish of the present invention has a refractive index equal to or higher than that of the film obtained from the charge-transporting varnish of comparative example 4-1, and has an extinction coefficient equal to or lower than that of the film.
[5] Production and characteristic evaluation of a Single hole device (HOD)
Comparative example 5-1
As the ITO substrate, a glass substrate of 25 mm. times.25 mm. times.0.7 t having Indium Tin Oxide (ITO) patterned on the surface thereof at a film thickness of 150nm was used, and O was used before use2The plasma cleaning apparatus (150W, 30 seconds) removed impurities on the surface. Next, the composition for forming a hole injection layer obtained by the method described later was applied by spin coating, heated to 80 ℃ on a hot plate in the air, dried for 1 minute, and further fired at 230 ℃ for 15 minutes to form a hole injection layer (film thickness: 30 nm).
Next, charge-transporting varnish A3a-2 was applied onto the hole-injecting layer using a spin coater, and then fired at 130 ℃ for 10 minutes in an atmospheric air atmosphere to form a hole-transporting layer (film thickness: 40 nm).
On the surface, a deposition apparatus (degree of vacuum 1.0X 10) was used-5Pa), an 80nm aluminum thin film was formed at 0.2 nm/sec to obtain a Hole Only Device (HOD).
Further, the composition for forming a hole injection layer was prepared by the following procedure. 0.137g of an aniline derivative represented by the formula (3) synthesized by the method described in International publication No. 2013/084664 and 0.271g of an arylsulfonic acid represented by the formula (4) synthesized by the method described in International publication No. 2006/025342 were dissolved in 6.7g of 1, 3-dimethyl-2-imidazolidinone in a nitrogen atmosphere. To the obtained solution were added 10g of cyclohexanol and 3.3g of propylene glycol in this order, followed by stirring to obtain a composition for forming a hole injection layer (the same applies below).
[ solution 166]
Figure BDA0003380339930001271
Examples 5-1 to 5-11
HOD was prepared in the same manner as in example 5-1, except that instead of the charge-transporting varnish A3a-2, charge-transporting varnishes A3B-2, A3c-2, A3d-2, A3e-2, A3f-2, A3g-2, A3H-2, B3d-2, B2d-2, H3d-2, or I3d-2 were used, respectively.
For each HOD produced in the above examples and comparative examples, the current density at a drive voltage of 4V was measured. The results are shown in Table 24.
[ Table 24]
Figure BDA0003380339930001281
As shown in table 24, it is understood that the film made of the charge-transporting varnish of the present invention exhibits a better charge-transporting property than the film made of the charge-transporting varnish of the comparative example. This improvement in charge transport property is considered to be accompanied by an increase in the effective conjugation length of the conductive site in the arylamine compound of the present invention.
[6] Fabrication of Single-layer device (SLD) and HOD and evaluation of relative intensity of Current Density of HOD with respect to Current Density of SLD
Comparative example 6-1
As the ITO substrate, a glass substrate of 25 mm. times.25 mm. times.0.7 t having Indium Tin Oxide (ITO) patterned on the surface thereof at a film thickness of 150nm was used, and O was used before use2The plasma cleaning apparatus (150W, 30 seconds) removed impurities on the surface.
Charge-transporting varnish A3a-1 was applied to an ITO substrate by spin coating, dried at 120 ℃ for 1 minute under the air, and then fired at 200 ℃ for 15 minutes to form a hole-injecting layer (film thickness: 50nm) on the ITO substrate.
On the surface, a deposition apparatus (degree of vacuum 1.0X 10) was used-5Pa), an 80nm aluminum thin film was formed at 0.2 nm/sec to obtain a Single Layer Device (SLD).
Examples 6-1 to 6-12 and comparative example 6-2
An SLD was prepared in the same manner as in comparative example 6-1, except that instead of the charge-transporting varnish A3a-1, charge-transporting varnishes A3B-1, A3c-1, A3d-1, A3e-1, A3f-1, A3g-1, A3H-1, B3B-1, B3d-1, B2d-1, H3d-1, I3d-1, or B3a-1 were used, respectively.
Comparative example 7-1
After applying the charge-transporting varnish A3a-1 to an ITO substrate using a spin coater, the substrate was dried at 120 ℃ for 1 minute under the air, and then baked at 200 ℃ for 15 minutes to form a 50nm thin film on the ITO substrate. The same ITO substrate as in comparative example 6-1 was used as the ITO substrate.
On the surface, a deposition apparatus (degree of vacuum 2.0X 10) was used-5Pa) and films of α -NPD and aluminum were laminated in this order to obtain HOD. The evaporation was carried out at an evaporation rate of 0.2 nm/sec. The film thicknesses of the α -NPD and aluminum thin films were set to 30nm and 80nm, respectively.
Examples 7-1 to 7-12 and comparative example 7-2
An HOD was produced in the same manner as in comparative example 7-1, except that instead of the charge-transporting varnish A3a-1, charge-transporting varnishes A3B-1, A3c-1, A3d-1, A3e-1, A3f-1, A3g-1, A3H-1, B3B-1, B3d-1, B2d-1, H3d-1, I3d-1, or B3a-1 were used, respectively.
The current densities when the SLDs produced in examples 6-1 to 6-12 and comparative examples 6-1 to 6-2 and the HODs produced in examples 7-1 to 7-12 and comparative examples 7-1 to 7-2 were driven at a voltage of 4V were measured. The results are shown in Table 25. The relative intensity of the current density of the HOD with respect to the current density of the SLD calculated using these measured values is also shown. Further, the high relative intensity indicates that the supply of holes to the hole transport layer is achieved with high efficiency.
[ Table 25]
Figure BDA0003380339930001301
As shown in table 25, it is understood that the devices using the hole injection layer produced from the charge-transporting varnish of the present invention have higher relative intensities of the HOD current density and the SLD current density than the devices produced in the comparative examples.
[7] Production of organic EL element and evaluation of characteristics
Comparative example 8-1
After applying the charge-transporting varnish A3a-1 to an ITO substrate using a spin coater, the substrate was dried at 120 ℃ for 1 minute under the air, and then baked at 200 ℃ for 15 minutes to form a 50nm thin film on the ITO substrate. The same ITO substrate as in comparative example 6-1 was used as the ITO substrate.
Next, an evaporation apparatus (degree of vacuum 1.0X 10) was used for the ITO substrate on which the thin film was formed-5Pa) the α -NPD was formed into a film of 30nm at 0.2 nm/sec. Secondly, the east of GuandongThe film of the electron-blocking material HTEB-01 (manufactured by Kagaku Co., Ltd.) was formed to have a thickness of 10 nm. Next, a light-emitting layer host material NS60 made by Nissian iron Corp chemical Co., Ltd and a light-emitting layer dopant material Ir (ppy)3And (4) co-evaporation. For co-evaporation, the evaporation rate was controlled so that Ir (ppy)3The concentration of (2) was 6%, and 40nm was stacked. Next, Alq was laminated in order3And lithium fluoride and aluminum thin film to obtain an organic EL element. At this time, the deposition rate is set to Alq3And aluminum at 0.2 nm/sec, and lithium fluoride at 0.02 nm/sec, with film thicknesses of 20nm, 0.5nm, and 80nm, respectively.
In order to prevent deterioration of characteristics due to the influence of oxygen, water, and the like in the air, the characteristics of the organic EL element were evaluated after sealing the organic EL element with a sealing substrate. The sealing was performed as follows. The organic EL element was put between the sealing substrates in a nitrogen atmosphere having an oxygen concentration of 2ppm or less and a dew point of-76 ℃ or less, and the sealing substrates were bonded with an adhesive (MORCO MOISTURE CUT WB90US (P)). At this time, the water-capturing agent (HD-071010W-40 manufactured by Dynic Co., Ltd.) was contained in the sealing substrate together with the organic EL element. The pasted sealing substrate was irradiated with UV light (wavelength: 365nm, dose: 6000 mJ/cm)2) Thereafter, the adhesive was cured by annealing at 80 ℃ for 1 hour.
Examples 8-1 to 8-12
An organic EL element was produced in the same manner as in comparative example 8-1 except that instead of the charge-transporting varnish A3a-1, charge-transporting varnishes A3B-1, A3c-1, A3d-1, A3e-1, A3f-1, A3g-1, A3H-1, B3B-1, B3d-1, B2d-1, H3d-1, or I3d-1 were used, respectively.
The luminance of the obtained organic EL element was measured to be 5000cd/m2Driving voltage, current density, current efficiency, light emission efficiency, external light emission quantum yield (EQE) and LT90 (initial luminance 5000 cd/m) at the time of light emission 210% reduction in time). The results are shown in Table 26.
[ Table 26]
Figure BDA0003380339930001321
As shown in table 26, the organic EL devices of the present invention all showed the same or less driving voltage and had the same or more half-life as the organic EL device of comparative example 8-1.

Claims (12)

1. An arylamine compound represented by any one of the following formulae (1) to (6), wherein the arylamine compound is characterized by being a compound represented by any one of the following formulae (P1) to (P4),
[ solution 1]
Figure FDA0003380339920000011
In the formula, ArcEach independently represents a group represented by the formula (Q),
x independently of one another represents an arylene group which may be substituted and may contain hetero atoms,
each Y independently represents a phenylene group which may be substituted,
g independently represents an integer of 1 to 10,
[ solution 2]
Figure FDA0003380339920000012
In the formula, R1Each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R2Each independently represents an aryl group which may be substituted and may contain a hetero atom, ArsEach independently represents an arylene group which may be substituted and may contain a hetero atom,
[ solution 3]
Figure FDA0003380339920000021
2. The arylamine compound according to claim 1, wherein Ar issRepresented by any one of the following formulae (101) to (118),
[ solution 4]
Figure FDA0003380339920000022
[ solution 5]
Figure FDA0003380339920000031
[ solution 6]
Figure FDA0003380339920000032
In the formula, R3Each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, V1Each independently represents wherein R4Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a C (R) of a haloalkyl group having 1 to 20 carbon atoms4)2Wherein R is5NR representing a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms5S, O, or SO2，V2Represents NR5S or O, R5The same meanings as described above are indicated.
3. The arylamine compound according to claim 1, wherein Ar issRepresented by any one of the following formulae (101A) to (118A),
[ solution 7]
Figure FDA0003380339920000041
[ solution 8]
Figure FDA0003380339920000042
[ solution 9]
Figure FDA0003380339920000043
[ solution 10]
Figure FDA0003380339920000051
[ solution 11]
Figure FDA0003380339920000052
[ solution 12]
Figure FDA0003380339920000053
[ solution 13]
Figure FDA0003380339920000061
[ solution 14]
Figure FDA0003380339920000062
In the formula, R3、V1And V2The same meanings as described above are indicated.
4. The arylamine compound of claim 3, wherein Ar issRepresented by any one of the following formulae (101A-1) to (118A-3),
[ solution 15]
Figure FDA0003380339920000063
[ solution 16]
Figure FDA0003380339920000064
[ solution 17]
Figure FDA0003380339920000071
[ solution 18]
Figure FDA0003380339920000072
[ solution 19]
Figure FDA0003380339920000073
[ solution 20]
Figure FDA0003380339920000074
[ solution 21]
Figure FDA0003380339920000081
[ solution 22]
Figure FDA0003380339920000082
[ solution 23]
Figure FDA0003380339920000083
[ solution 24]
Figure FDA0003380339920000084
[ solution 25]
Figure FDA0003380339920000091
[ solution 26]
Figure FDA0003380339920000092
[ solution 27]
Figure FDA0003380339920000093
[ solution 28]
Figure FDA0003380339920000101
[ solution 29]
Figure FDA0003380339920000102
[ solution 30]
Figure FDA0003380339920000103
[ solution 31]
Figure FDA0003380339920000111
[ solution 32]
Figure FDA0003380339920000112
[ solution 33]
Figure FDA0003380339920000113
[ chemical 34]
Figure FDA0003380339920000114
[ solution 35]
Figure FDA0003380339920000121
[ solution 36]
Figure FDA0003380339920000122
In the formula, R4And R5The same meanings as described above are indicated.
5. The arylamine compound according to any one of claims 1 to 4, wherein X is represented by any one of the following formulae (201) to (207),
[ solution 37]
Figure FDA0003380339920000131
In the formula, R6Each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, W1Each independently represents a single bond, wherein R7Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a C (R) of a haloalkyl group having 1 to 20 carbon atoms7)2S, O, or SO2，W2Is represented by the formula wherein R7Each independently represents C (R) having the same meaning as described above7)2Wherein R is8NR representing a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms8S, O, or SO2，W3Is represented by the formula wherein R8NR having the same meaning as described above8S or O.
6. The arylamine compound according to claim 5, wherein X is represented by any one of the following formulae (201A) to (207A),
[ solution 38]
Figure FDA0003380339920000141
In the formula, R6、W1、W2And W3The same meanings as described above are indicated.
7. The arylamine compound according to claim 6, wherein X is represented by any one of the following formulae (201A-1) to (207A-1),
[ solution 39]
Figure FDA0003380339920000151
[ solution 40]
Figure FDA0003380339920000152
[ solution 41]
Figure FDA0003380339920000153
In the formula, R7、R8And W3The same meanings as described above are indicated.
8. The arylamine compound according to any one of claims 1 to 7, wherein Ar iscAre the same group.
9. A charge-transporting varnish comprising the arylamine compound according to any one of claims 1 to 8 and an organic solvent.
10. The charge transport varnish of claim 9 comprising a dopant species.
11. A charge-transporting thin film produced using the charge-transporting varnish according to claim 9 or 10.
12. An electronic component comprising the charge transporting thin film according to claim 11.
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