Compound, colored resin composition, color filter and display device
阅读说明：本技术 化合物、着色树脂组合物、滤色器及显示装置 (Compound, colored resin composition, color filter and display device ) 是由 上田俊雄 森胁章太 于 2019-10-02 设计创作，主要内容包括：本发明的课题是提供一种可形成耐热性优异的滤色器的化合物。解决课题的方法是式(I)所表示的化合物、包含其的着色树脂组合物、滤色器及显示装置。(The present invention addresses the problem of providing a compound that can form a color filter having excellent heat resistance. The compound represented by formula (I), a colored resin composition containing the compound, a color filter and a display device.)
1. A compound represented by formula (I),
in the formula (I), the compound is shown in the specification,
R1to R8Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent,
R9and R10Each independently represents a divalent aliphatic hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, a methylene group contained in the aliphatic hydrocarbon group may be substituted by-O-,
R11and R12Each independently represents a hydrocarbon group having 6 to 20 carbon atoms and an aromatic hydrocarbon ring, the hydrocarbon group may have a substituent, and a methylene group contained in the hydrocarbon group may be substituted by-O-,
R13represents a hydrogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms.
2. A colored resin composition comprising a colorant and a resin, the colorant comprising the compound of claim 1.
3. The colored resin composition according to claim 2, further comprising a polymerizable compound and a polymerization initiator.
4. A color filter formed from the colored resin composition according to claim 2 or 3.
5. A display device comprising the color filter of claim 4.
Technical Field
The invention relates to a compound, a colored resin composition, a color filter and a display device.
Background
Color filters used in display devices such as liquid crystal display devices, electroluminescent display devices, and plasma displays, or solid-state imaging devices such as CCD and CMOS sensors are made of colored resin compositions. As a colorant used in such a colored resin composition, a compound represented by the formula (x) is known (patent document 1: Japanese patent laid-open publication No. 2015-86380).
Disclosure of Invention
Technical subject
However, a color filter formed from a conventionally known colored resin composition containing the above-mentioned compound may not sufficiently satisfy heat resistance. Accordingly, the present invention provides a compound capable of forming a color filter having excellent heat resistance.
Means for solving the problems
The present invention includes the following inventions.
[1] A compound represented by formula (I),
[ in the formula (I),
R1to R8Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent.
R9And R10Each independently represents a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a methylene group contained in the aliphatic hydrocarbon group may be substituted by-O-.
R11And R12Each independently represents a hydrocarbon group having 6 to 20 carbon atoms and an aromatic hydrocarbon ring, the hydrocarbon group may have a substituent, and a methylene group contained in the hydrocarbon group may be replaced by-O-And (4) generation.
R13Represents a hydrogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms]。
[2] A colored resin composition comprising a colorant and a resin, the colorant comprising the compound according to [1 ].
[3] The colored resin composition according to [2], further comprising a polymerizable compound and a polymerization initiator.
[4] A color filter formed from the colored resin composition according to [2] or [3 ].
[5] A display device comprising the color filter of [4 ].
Effects of the invention
According to the present invention, a novel compound capable of forming a color filter having excellent heat resistance is provided.
Detailed Description
< Compound >
The compound of the present invention is a compound represented by formula (I) (hereinafter, may be referred to as compound (I)). Hereinafter, the present invention will be described in detail using the formula (I), but the compound (I) also includes a compound having a resonance structure of the formula (I) or a structure obtained by rotating each group of the formula (I) around a bonding axis of a carbon-carbon single bond.
[ in the formula (I),
R1to R8Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent.
R9And R10Each independently represents a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a methylene group contained in the aliphatic hydrocarbon group may be substituted by-O-.
R11And R12Each independently represents a hydrocarbon group having 6 to 20 carbon atoms and an aromatic hydrocarbon ring, the hydrocarbon group may have a substituent, and the hydrocarbon groupThe methylene groups present may be substituted by-O-.
R13Represents a hydrogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms.]
As R1To R8Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
R1To R8The saturated hydrocarbon group having 1 to 20 carbon atoms may be any of linear, branched and cyclic. Specific examples of the linear or branched saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, a tert-butyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a heptadecyl group, and an undecyl group. Examples of the cyclic saturated hydrocarbon group include cyclopropyl, 1-methylcyclopropyl, cyclopentyl, cyclohexyl, 1, 2-dimethylcyclohexyl, cyclooctyl, 2,4, 6-trimethylcyclohexyl, and 4-cyclohexylcyclohexyl.
As R1To R8Examples of the substituent of the saturated hydrocarbon group having 1 to 20 carbon atoms include halogen atoms such as a fluorine atom, a chlorine atom, and an iodine atom; a hydroxyl group; -NRaRb(RaAnd RbEach independently a hydrogen atom or an alkyl group of 1 to 20 carbon atoms); a nitro group; alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy; alkoxycarbonyl groups having 1 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; and the like.
As R1To R8Examples of the alkoxy group having 1 to 20 carbon atoms include a group in which-O-is bonded to a bond of the saturated hydrocarbon group having 1 to 20 carbon atoms. Specific examples thereof include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, and 2-ethylhexyloxy group.
As R1To R8The substituent of the alkoxy group having 1 to 20 carbon atoms includes a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom and the like; a hydroxyl group; -NRcRd(RcAnd RdEach independently a hydrogen atom or an alkyl group of 1 to 20 carbon atoms); a nitro group; methoxy radicalAlkoxy groups having 1 to 10 carbon atoms such as an alkyl group and an ethoxy group; an alkoxycarbonyl group having 1 to 10 carbon atoms in an alkoxy moiety such as a methoxycarbonyl group or an ethoxycarbonyl group, and the like.
At R1To R8In the middle, R1To R4Preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. In addition, in R1To R4In the case of a hydrogen atom or a methyl group, more preferably in R1To R4In the case of a hydrogen atom, R5To R8Each independently is preferably a hydrogen atom, a hydroxyl group, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent, and more preferably a hydrogen atom or a hydroxyl group.
Preferably R1To R8(preferably R)5To R8) Two to four of which are each independently a hydroxyl group.
R9And R10The divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be either saturated or unsaturated, and is preferably saturated. The divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear, branched or cyclic, and is preferably linear or branched.
Examples of the divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms include methylene, ethylene, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl and nonane-1, 9-diyl, a divalent straight-chain aliphatic hydrocarbon group such as decane-1, 10-diyl, undecane-1, 11-diyl, dodecane-1, 12-diyl, tridecane-1, 13-diyl, tetradecane-1, 14-diyl, pentadecane-1, 15-diyl, hexadecane-1, 16-diyl, heptadecane-1, 17-diyl, and propenylene; and divalent branched aliphatic hydrocarbon groups such as ethane-1, 1-diyl, propane-1, 2-diyl, propane-2, 2-diyl, pentane-2, 4-diyl, 2-methylpropane-1, 3-diyl, 2-methylpropane-1, 2-diyl, 2-dimethylpropane-1, 3-diyl, pentane-1, 4-diyl and 2-methylbutane-1, 4-diyl.
The cyclic divalent aliphatic hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic divalent aliphatic hydrocarbon group include monocyclic divalent aliphatic hydrocarbon groups such as cyclobutane-1, 3-diyl, cyclopentane-1, 3-diyl, cyclohexane-1, 4-diyl and cyclooctane-1, 5-diyl; polycyclic divalent aliphatic hydrocarbon groups such as norbornane-1, 4-diyl, norbornane-2, 5-diyl, adamantane-1, 5-diyl and adamantane-2, 6-diyl.
The methylene group contained in the divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be substituted by-O-. Examples of the group in which the methylene group contained in the divalent aliphatic hydrocarbon group is substituted with-O-include groups represented by the following formulae. In the following formulae, the left-hand side indicates a bond to a nitrogen atom, and the right-hand side indicates a bond to an oxygen atom.
R9And R10The divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may be represented by the formula (I) may have a substituent, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, and an iodine atom; a hydroxyl group; -NReRf(ReAnd RfEach independently a hydrogen atom or an alkyl group of 1 to 20 carbon atoms); a nitro group; alkoxycarbonyl groups having 1 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; and the like.
As R11And R12Examples of the hydrocarbon group having 6 to 20 carbon atoms and having an aromatic hydrocarbon ring include a group having a bond to an aromatic hydrocarbon ring (hereinafter referred to as an aromatic hydrocarbon group), an aralkyl group having 7 to 20 carbon atoms, and the like. They may have a substituent.
Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and the like, and a benzene ring is preferable.
Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a tolyl group, a xylyl group, a trimethylphenyl group, a diisopropylphenyl group and the like. Among them, aromatic hydrocarbon groups having an alkyl group at the ortho-position are preferable, and examples thereof include a2, 6-dimethylphenyl group, a2, 4, 6-trimethylphenyl group, a2, 6-diisopropylphenyl group and the like. Further, if the volume of the alkyl group at the ortho position is large, light resistance tends to be excellent.
When the aromatic hydrocarbon group has a substituent, the aromatic hydrocarbon group may have one or more of the substituents. When the aromatic hydrocarbon group has a plurality of substituents, the substituents may be the same or different. Examples of the substituent include a hydroxyl group; a carboxyl group; halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; a sulfamoyl group; alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl group; alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; and the like.
The hydrocarbon group having 1 to 14 carbon atoms may have a substituent such as a hydroxyl group, a carboxyl group, a halogen atom, or an alkoxy group.
When the aforementioned aromatic hydrocarbon group which may have a substituent has a methylene group, the methylene group may be substituted by-O-.
Examples of the aralkyl group having 7 to 20 carbon atoms include a group in which an alkanediyl group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, and a propylene group is bonded to the aromatic hydrocarbon ring described in the above aromatic hydrocarbon group. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, and a naphthylethyl group.
The aralkyl group having 7 to 20 carbon atoms may have a substituent, and when a plurality of substituents are present, each substituent may be the same or different. The substituent may be bonded to the aromatic hydrocarbon ring or may be bonded to the alkanediyl group, and the substituent which may be bonded to the aromatic hydrocarbon ring is the same as the substituent described as the aromatic hydrocarbon group.
In the case where the aforementioned aralkyl group having 7 to 20 carbon atoms which may have a substituent has a methylene group, the methylene group may be substituted by-O-.
R13The saturated hydrocarbon group having 1 to 8 carbon atoms may be any of linear, branched and cyclic. Specific examples of the linear or branched saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, a tert-butyl group, a hexyl group, a heptyl group, and an octyl group. As cyclic saturated hydrocarbon radicalsExamples thereof include cyclopropyl, 1-methylcyclopropyl, cyclopentyl, cyclohexyl, 1, 2-dimethylcyclohexyl and cyclooctyl.
Examples of the compound (I) include compounds represented by the formulae (I-1) to (I-240) shown in tables 1 to 3.
[ Table 1]
[ Table 2]
[ Table 3]
In tables 1 to 3, A1-1 to A1-4 represent groups represented by the following formulae. In the following formulae, the left-hand side indicates a bond to a nitrogen atom, and the right-hand side indicates a bond to an oxygen atom.
In tables 1 to 3, A2-1 to A2-5 represent groups represented by the following formulae. In the following formulae, a represents a bond.
The compound (I) may be a compound represented by the following formula (II), preferably a compound represented by the formula (II), in addition to the compounds represented by the above-mentioned formulae (I-1) to (I-240). The light resistance of the compound represented by the formula (II) is good.
[ in the formula (II),
R1to R10Is represented by R in the formula (I)1To R10The same meaning;
X1and X2Each independently represents a hydrocarbon group having 1 to 14 carbon atoms having at least one group selected from the group consisting of a hydroxyl group and a carboxyl group, the hydroxyl group and the carboxyl group, and a methylene group contained in the hydrocarbon group may be substituted by-O-;
R14and R15Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 13 carbon atoms;
n1 and n2 each independently represent an integer of 1 to 5;
wherein (X)1)n1And (R)14)5-n1The total number of carbon atoms of (A), (B), (C) and (X)2)n2And (R)15)5-n2The total number of carbon atoms of (2) is 14 or less.]
As X1And X2Examples of the hydrocarbon group having 1 to 14 carbon atoms include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof.
Examples of the linear aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.
Examples of the branched aliphatic hydrocarbon group include an isopropyl group, a sec-butyl group, a tert-butyl group, a methylpentyl group, an ethylpentyl group, a methylhexyl group, an ethylhexyl group, a propylhexyl group, and a tert-octyl group, and preferred examples thereof include an isopropyl group, a sec-butyl group, a tert-butyl group, and an ethylhexyl group.
Examples of the cyclic aliphatic hydrocarbon group include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, adamantyl, and the like.
Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a biphenyl group, a2, 6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group.
Examples of the group formed by combining these groups include alkylcycloalkyl group, cycloalkylalkyl group, and aralkyl group.
The methylene group contained in the hydrocarbon group having 1 to 14 carbon atoms may be substituted by-O-.
As R14And R15The hydrocarbon group having 1 to 13 carbon atoms as represented by the above-mentioned X1And X2The same groups as those described for the hydrocarbon group having 1 to 14 carbon atoms are shown.
n1 and n2 each independently represent an integer of 1 to 5, more preferably 1 to 2.
(X1)n1And (R)14)5-n1The total number of carbon atoms of (A), (B), (C) and (X)2)n2And (R)15)5-n2The total number of carbon atoms of (2) is 14 or less. At X1、X2、R14And R15When there are plural, each X1、X2、R14And R15May be the same or different.
The compound (II) includes compounds represented by the following formula (II-a), and specifically includes compounds represented by the formulae (II-1) to (II-540) shown in tables 4 to 12, and the like.
[ Table 4]
R1～R4
R5
R6
R7
R8
R9
R10
R16
R17
R18
R19
R20
R21
R22
R23
R24
R25
(II-1)
H
OH
OH
OH
OH
A1-1
A1-1
A4-1
H
A3-1
H
A4-1
A4-1
H
A3-1
H
A4-1
(II-2)
H
H
H
H
H
A1-1
A1-1
A4-1
H
A3-1
H
A4-1
A4-1
H
A3-1
H
A4-1
(II-3)
H
OH
H
H
OH
A1-1
A1-1
A4-1
H
A3-1
H
A4-1
A4-1
H
A3-1
H
A4-1
(II-4)
H
OH
OH
OH
OH
A1-1
A1-1
A4-1
A3-1
H
A3-1
A4-1
A4-1
A3-1
H
A3-1
A4-1
(II-5)
H
H
H
H
H
A1-1
A1-1
A4-1
A3-1
H
A3-1
A4-1
A4-1
A3-1
H
A3-1
A4-1
(II-6)
H
OH
H
H
OH
A1-1
A1-1
A4-1
A3-1
H
A3-1
A4-1
A4-1
A3-1
H
A3-1
A4-1
(II-7)
H
OH
OH
OH
OH
A1-1
A1-1
A4-1
H
A3-2
H
A4-1
A4-1
H
A3-2
H
A4-1
(II-8)
H
H
H
H
H
A1-1
A1-1
A4-1
H
A3-2
H
A4-1
A4-1
H
A3-2
H
A4-1
(II-9)
H
OH
H
H
OH
A1-1
A1-1
A4-1
H
A3-2
H
A4-1
A4-1
H
A3-2
H
A4-1
(II-10)
H
OH
OH
OH
OH
A1-1
A1-1
A4-1
A3-2
H
A3-2
A4-1
A4-1
A3-2
H
A3-2
A4-1
(II-11)
H
H
H
H
H
A1-1
A1-1
A4-1
A3-2
H
A3-2
A4-1
A4-1
A3-2
H
A3-2
A4-1
(II-12)
H
OH
H
H
OH
A1-1
A1-1
A4-1
A3-2
H
A3-2
A4-1
A4-1
A3-2
H
A3-2
A4-1
(II-13)
H
OH
OH
OH
OH
A1-1
A1-1
A4-1
H
A3-3
H
A4-1
A4-1
H
A3-3
H
A4-1
(II-14)
H
H
H
H
H
A1-1
A1-1
A4-1
H
A3-3
H
A4-1
A4-1
H
A3-3
H
A4-1
(II-15)
H
OH
H
H
OH
A1-1
A1-1
A4-1
H
A3-3
H
A4-1
A4-1
H
A3-3
H
A4-1
(II-16)
H
OH
OH
OH
OH
A1-1
A1-1
A4-1
A3-3
H
A3-3
A4-1
A4-1
A3-3
H
A3-3
A4-1
(II-17)
H
H
H
H
H
A1-1
A1-1
A4-1
A3-3
H
A3-3
A4-1
A4-1
A3-3
H
A3-3
A4-1
(II-18)
H
OH
H
H
OH
A1-1
A1-1
A4-1
A3-3
H
A3-3
A4-1
A4-1
A3-3
H
A3-3
A4-1
(II-19)
H
OH
OH
OH
OH
A1-1
A1-1
A4-1
H
OH
H
A4-1
A4-1
H
OH
H
A4-1
(II-20)
H
H
H
H
H
A1-1
A1-1
A4-1
H
OH
H
A4-1
A4-1
H
OH
H
A4-1
(II-21)
H
OH
H
H
OH
A1-1
A1-1
A4-1
H
OH
H
A4-1
A4-1
H
OH
H
A4-1
(II-22)
H
OH
OH
OH
OH
A1-1
A1-1
A4-1
OH
H
OH
A4-1
A4-1
OH
H
OH
A4-1
(II-23)
H
H
H
H
H
A1-1
A1-1
A4-1
OH
H
OH
A4-1
A4-1
OH
H
OH
A4-1
(II-24)
H
OH
H
H
OH
A1-1
A1-1
A4-1
OH
H
OH
A4-1
A4-1
OH
H
OH
A4-1
(II-25)
H
OH
OH
OH
OH
A1-1
A1-1
A4-1
H
COOH
H
A4-1
A4-1
H
COOH
H
A4-1
(II-26)
H
H
H
H
H
A1-1
A1-1
A4-1
H
COOH
H
A4-1
A4-1
H
COOH
H
A4-1
(II-27)
H
OH
H
H
OH
A1-1
A1-1
A4-1
H
COOH
H
A4-1
A4-1
H
COOH
H
A4-1
(II-28)
H
OH
OH
OH
OH
A1-1
A1-1
A4-1
COOH
H
COOH
A4-1
A4-1
COOH
H
COOH
A4-1
(II-29)
H
H
H
H
H
A1-1
A1-1
A4-1
COOH
H
COOH
A4-1
A4-1
COOH
H
COOH
A4-1
(II-30)
H
OH
H
H
OH
A1-1
A1-1
A4-1
COOH
H
COOH
A4-1
A4-1
COOH
H
COOH
A4-1
(II-31)
H
OH
OH
OH
OH
A1-1
A1-1
A4-2
H
A3-1
H
A4-2
A4-2
H
A3-1
H
A4-2
(II-32)
H
H
H
H
H
A1-1
A1-1
A4-2
H
A3-1
H
A4-2
A4-2
H
A3-1
H
A4-2
(II-33)
H
OH
H
H
OH
A1-1
A1-1
A4-2
H
A3-1
H
A4-2
A4-2
H
A3-1
H
A4-2
(II-34)
H
OH
OH
OH
OH
A1-1
A1-1
A4-2
A3-1
H
A3-1
A4-2
A4-2
A3-1
H
A3-1
A4-2
(II-35)
H
H
H
H
H
A1-1
A1-1
A4-2
A3-1
H
A3-1
A4-2
A4-2
A3-1
H
A3-1
A4-2
(II-36)
H
OH
H
H
OH
A1-1
A1-1
A4-2
A3-1
H
A3-1
A4-2
A4-2
A3-1
H
A3-1
A4-2
(II-37)
H
OH
OH
OH
OH
A1-1
A1-1
A4-2
H
A3-2
H
A4-2
A4-2
H
A3-2
H
A4-2
(II-38)
H
H
H
H
H
A1-1
A1-1
A4-2
H
A3-2
H
A4-2
A4-2
H
A3-2
H
A4-2
(II-39)
H
OH
H
H
OH
A1-1
A1-1
A4-2
H
A3-2
H
A4-2
A4-2
H
A3-2
H
A4-2
(II-40)
H
OH
OH
OH
OH
A1-1
A1-1
A4-2
A3-2
H
A3-2
A4-2
A4-2
A3-2
H
A3-2
A4-2
(II-41)
H
H
H
H
H
A1-1
A1-1
A4-2
A3-2
H
A3-2
A4-2
A4-2
A3-2
H
A3-2
A4-2
(II-42)
H
OH
H
H
OH
A1-1
A1-1
A4-2
A3-2
H
A3-2
A4-2
A4-2
A3-2
H
A3-2
A4-2
(II-43)
H
OH
OH
OH
OH
A1-1
A1-1
A4-2
H
A3-3
H
A4-2
A4-2
H
A3-3
H
A4-2
(II-44)
H
H
H
H
H
A1-1
A1-1
A4-2
H
A3-3
H
A4-2
A4-2
H
A3-3
H
A4-2
(II-45)
H
OH
H
H
OH
A1-1
A1-1
A4-2
H
A3-3
H
A4-2
A4-2
H
A3-3
H
A4-2
(II-46)
H
OH
OH
OH
OH
A1-1
A1-1
A4-2
A3-3
H
A3-3
A4-2
A4-2
A3-3
H
A3-3
A4-2
(II-47)
H
H
H
H
H
A1-1
A1-1
A4-2
A3-3
H
A3-3
A4-2
A4-2
A3-3
H
A3-3
A4-2
(II-48)
H
OH
H
H
OH
A1-1
A1-1
A4-2
A3-3
H
A3-3
A4-2
A4-2
A3-3
H
A3-3
A4-2
(II-49)
H
OH
OH
OH
OH
A1-1
A1-1
A4-2
H
OH
H
A4-2
A4-2
H
OH
H
A4-2
(II-50)
H
H
H
H
H
A1-1
A1-1
A4-2
H
OH
H
A4-2
A4-2
H
OH
H
A4-2
(II-51)
H
OH
H
H
OH
A1-1
A1-1
A4-2
H
OH
H
A4-2
A4-2
H
OH
H
A4-2
(II-52)
H
OH
OH
OH
OH
A1-1
A1-1
A4-2
OH
H
OH
A4-2
A4-2
OH
H
OH
A4-2
(II-53)
H
H
H
H
H
A1-1
A1-1
A4-2
OH
H
OH
A4-2
A4-2
OH
H
OH
A4-2
(II-54)
H
OH
H
H
OH
A1-1
A1-1
A4-2
OH
H
OH
A4-2
A4-2
OH
H
OH
A4-2
(II-55)
H
OH
OH
OH
OH
A1-1
A1-1
A4-2
H
COOH
H
A4-2
A4-2
H
COOH
H
A4-2
(II-56)
H
H
H
H
H
A1-1
A1-1
A4-2
H
COOH
H
A4-2
A4-2
H
COOH
H
A4-2
(II-57)
H
OH
H
H
OH
A1-1
A1-1
A4-2
H
COOH
H
A4-2
A4-2
H
COOH
H
A4-2
(II-58)
H
OH
OH
OH
OH
A1-1
A1-1
A4-2
COOH
H
COOH
A4-2
A4-2
COOH
H
COOH
A4-2
(II-59)
H
H
H
H
H
A1-1
A1-1
A4-2
COOH
H
COOH
A4-2
A4-2
COOH
H
COOH
A4-2
(II-60)
H
OH
H
H
OH
A1-1
A1-1
A4-2
COOH
H
COOH
A4-2
A4-2
COOH
H
COOH
A4-2
[ Table 5]
R1～R4
R5
R6
R7
R8
R9
R10
R16
R17
R18
R19
R20
R21
R22
R23
R24
R25
(II-61)
H
OH
OH
OH
OH
A1-2
A1-2
A4-1
H
A3-1
H
A4-1
A4-1
H
A3-1
H
A4-1
(II-62)
H
H
H
H
H
A1-2
A1-2
A4-1
H
A3-1
H
A4-1
A4-1
H
A3-1
H
A4-1
(II-63)
H
OH
H
H
OH
A1-2
A1-2
A4-1
H
A3-1
H
A4-1
A4-1
H
A3-1
H
A4-1
(II-64)
H
OH
OH
OH
OH
A1-2
A1-2
A4-1
A3-1
H
A3-1
A4-1
A4-1
A3-1
H
A3-1
A4-1
(II-65)
H
H
H
H
H
A1-2
A1-2
A4-1
A3-1
H
A3-1
A4-1
A4-1
A3-1
H
A3-1
A4-1
(II-66)
H
OH
H
H
OH
A1-2
A1-2
A4-1
A3-1
H
A3-1
A4-1
A4-1
A3-1
H
A3-1
A4-1
(II-67)
H
OH
OH
OH
OH
A1-2
A1-2
A4-1
H
A3-2
H
A4-1
A4-1
H
A3-2
H
A4-1
(II-68)
H
H
H
H
H
A1-2
A1-2
A4-1
H
A3-2
H
A4-1
A4-1
H
A3-2
H
A4-1
(II-69)
H
OH
H
H
OH
A1-2
A1-2
A4-1
H
A3-2
H
A4-1
A4-1
H
A3-2
H
A4-1
(II-70)
H
OH
OH
OH
OH
A1-2
A1-2
A4-1
A3-2
H
A3-2
A4-1
A4-1
A3-2
H
A3-2
A4-1
(II-71)
H
H
H
H
H
A1-2
A1-2
A4-1
A3-2
H
A3-2
A4-1
A4-1
A3-2
H
A3-2
A4-1
(II-72)
H
OH
H
H
OH
A1-2
A1-2
A4-1
A3-2
H
A3-2
A4-1
A4-1
A3-2
H
A3-2
A4-1
(II-73)
H
OH
OH
OH
OH
A1-2
A1-2
A4-1
H
A3-3
H
A4-1
A4-1
H
A3-3
H
A4-1
(II-74)
H
H
H
H
H
A1-2
A1-2
A4-1
H
A3-3
H
A4-1
A4-1
H
A3-3
H
A4-1
(II-75)
H
OH
H
H
OH
A1-2
A1-2
A4-1
H
A3-3
H
A4-1
A4-1
H
A3-3
H
A4-1
(II-76)
H
OH
OH
OH
OH
A1-2
A1-2
A4-1
A3-3
H
A3-3
A4-1
A4-1
A3-3
H
A3-3
A4-1
(II-77)
H
H
H
H
H
A1-2
A1-2
A4-1
A3-3
H
A3-3
A4-1
A4-1
A3-3
H
A3-3
A4-1
(II-78)
H
OH
H
H
OH
A1-2
A1-2
A4-1
A3-3
H
A3-3
A4-1
A4-1
A3-3
H
A3-3
A4-1
(II-79)
H
OH
OH
OH
OH
A1-2
A1-2
A4-1
H
OH
H
A4-1
A4-1
H
OH
H
A4-1
(II-80)
H
H
H
H
H
A1-2
A1-2
A4-1
H
OH
H
A4-1
A4-1
H
OH
H
A4-1
(II-81)
H
OH
H
H
OH
A1-2
A1-2
A4-1
H
OH
H
A4-1
A4-1
H
OH
H
A4-1
(II-82)
H
OH
OH
OH
OH
A1-2
A1-2
A4-1
OH
H
OH
A4-1
A4-1
OH
H
OH
A4-1
(II-83)
H
H
H
H
H
A1-2
A1-2
A4-1
OH
H
OH
A4-1
A4-1
OH
H
OH
A4-1
(II-84)
H
OH
H
H
OH
A1-2
A1-2
A4-1
OH
H
OH
A4-1
A4-1
OH
H
OH
A4-1
(II-85)
H
OH
OH
OH
OH
A1-2
A1-2
A4-1
H
COOH
H
A4-1
A4-1
H
COOH
H
A4-1
(II-86)
H
H
H
H
H
A1-2
A1-2
A4-1
H
COOH
H
A4-1
A4-1
H
COOH
H
A4-1
(II-87)
H
OH
H
H
OH
A1-2
A1-2
A4-1
H
COOH
H
A4-1
A4-1
H
COOH
H
A4-1
(II-88)
H
OH
OH
OH
OH
A1-2
A1-2
A4-1
COOH
H
COOH
A4-1
A4-1
COOH
H
COOH
A4-1
(II-89)
H
H
H
H
H
A1-2
A1-2
A4-1
COOH
H
COOH
A4-1
A4-1
COOH
H
COOH
A4-1
(II-90)
H
OH
H
H
OH
A1-2
A1-2
A4-1
COOH
H
COOH
A4-1
A4-1
COOH
H
COOH
A4-1
(II-91)
H
OH
OH
OH
OH
A1-2
A1-2
A4-2
H
A3-1
H
A4-2
A4-2
H
A3-1
H
A4-2
(II-92)
H
H
H
H
H
A1-2
A1-2
A4-2
H
A3-1
H
A4-2
A4-2
H
A3-1
H
A4-2
(II-93)
H
OH
H
H
OH
A1-2
A1-2
A4-2
H
A3-1
H
A4-2
A4-2
H
A3-1
H
A4-2
(II-94)
H
OH
OH
OH
OH
A1-2
A1-2
A4-2
A3-1
H
A3-1
A4-2
A4-2
A3-1
H
A3-1
A4-2
(II-95)
H
H
H
H
H
A1-2
A1-2
A4-2
A3-1
H
A3-1
A4-2
A4-2
A3-1
H
A3-1
A4-2
(II-96)
H
OH
H
H
OH
A1-2
A1-2
A4-2
A3-1
H
A3-1
A4-2
A4-2
A3-1
H
A3-1
A4-2
(II-97)
H
OH
OH
OH
OH
A1-2
A1-2
A4-2
H
A3-2
H
A4-2
A4-2
H
A3-2
H
A4-2
(II-98)
H
H
H
H
H
A1-2
A1-2
A4-2
H
A3-2
H
A4-2
A4-2
H
A3-2
H
A4-2
(II-99)
H
OH
H
H
OH
A1-2
A1-2
A4-2
H
A3-2
H
A4-2
A4-2
H
A3-2
H
A4-2
(II-100)
H
OH
OH
OH
OH
A1-2
A1-2
A4-2
A3-2
H
A3-2
A4-2
A4-2
A3-2
H
A3-2
A4-2
(II-101)
H
H
H
H
H
A1-2
A1-2
A4-2
A3-2
H
A3-2
A4-2
A4-2
A3-2
H
A3-2
A4-2
(II-102)
H
OH
H
H
OH
A1-2
A1-2
A4-2
A3-2
H
A3-2
A4-2
A4-2
A3-2
H
A3-2
A4-2
(II-103)
H
OH
OH
OH
OH
A1-2
A1-2
A4-2
H
A3-3
H
A4-2
A4-2
H
A3-3
H
A4-2
(II-104)
H
H
H
H
H
A1-2
A1-2
A4-2
H
A3-3
H
A4-2
A4-2
H
A3-3
H
A4-2
(II-105)
H
OH
H
H
OH
A1-2
A1-2
A4-2
H
A3-3
H
A4-2
A4-2
H
A3-3
H
A4-2
(II-106)
H
OH
OH
OH
OH
A1-2
A1-2
A4-2
A3-3
H
A3-3
A4-2
A4-2
A3-3
H
A3-3
A4-2
(II-107)
H
H
H
H
H
A1-2
A1-2
A4-2
A3-3
H
A3-3
A4-2
A4-2
A3-3
H
A3-3
A4-2
(II-108)
H
OH
H
H
OH
A1-2
A1-2
A4-2
A3-3
H
A3-3
A4-2
A4-2
A3-3
H
A3-3
A4-2
(II-109)
H
OH
OH
OH
OH
A1-2
A1-2
A4-2
H
OH
H
A4-2
A4-2
H
OH
H
A4-2
(II-110)
H
H
H
H
H
A1-2
A1-2
A4-2
H
OH
H
A4-2
A4-2
H
OH
H
A4-2
(II-111)
H
OH
H
H
OH
A1-2
A1-2
A4-2
H
OH
H
A4-2
A4-2
H
OH
H
A4-2
(II-112)
H
OH
OH
OH
OH
A1-2
A1-2
A4-2
OH
H
OH
A4-2
A4-2
OH
H
OH
A4-2
(II-113)
H
H
H
H
H
A1-2
A1-2
A4-2
OH
H
OH
A4-2
A4-2
OH
H
OH
A4-2
(II-114)
H
OH
H
H
OH
A1-2
A1-2
A4-2
OH
H
OH
A4-2
A4-2
OH
H
OH
A4-2
(II-115)
H
OH
OH
OH
OH
A1-2
A1-2
A4-2
H
COOH
H
A4-2
A4-2
H
COOH
H
A4-2
(II-116)
H
H
H
H
H
A1-2
A1-2
A4-2
H
COOH
H
A4-2
A4-2
H
COOH
H
A4-2
(II-117)
H
OH
H
H
OH
A1-2
A1-2
A4-2
H
COOH
H
A4-2
A4-2
H
COOH
H
A4-2
(II-118)
H
OH
OH
OH
OH
A1-2
A1-2
A4-2
COOH
H
COOH
A4-2
A4-2
COOH
H
COOH
A4-2
(II-119)
H
H
H
H
H
A1-2
A1-2
A4-2
COOH
H
COOH
A4-2
A4-2
COOH
H
COOH
A4-2
(II-120)
H
OH
H
H
OH
A1-2
A1-2
A4-2
COOH
H
COOH
A4-2
A4-2
COOH
H
COOH
A4-2
[ Table 6]
R1～R4
R5
R6
R7
R8
R9
R10
R16
R17
R18
R19
R20
R21
R22
R23
R24
R25
(II-121)
H
OH
OH
OH
OH
A1-3
A1-3
A4-1
H
A3-1
H
A4-1
A4-1
H
A3-1
H
A4-1
(II-122)
H
H
H
H
H
A1-3
A1-3
A4-1
H
A3-1
H
A4-1
A4-1
H
A3-1
H
A4-1
(II-123)
H
OH
H
H
OH
A1-3
A1-3
A4-1
H
A3-1
H
A4-1
A4-1
H
A3-1
H
A4-1
(II-124)
H
OH
OH
OH
OH
A1-3
A1-3
A4-1
A3-1
H
A3-1
A4-1
A4-1
A3-1
H
A3-1
A4-1
(II-125)
H
H
H
H
H
A1-3
A1-3
A4-1
A3-1
H
A3-1
A4-1
A4-1
A3-1
H
A3-1
A4-1
(II-126)
H
OH
H
H
OH
A1-3
A1-3
A4-1
A3-1
H
A3-1
A4-1
A4-1
A3-1
H
A3-1
A4-1
(II-127)
H
OH
OH
OH
OH
A1-3
A1-3
A4-1
H
A3-2
H
A4-1
A4-1
H
A3-2
H
A4-1
(II-128)
H
H
H
H
H
A1-3
A1-3
A4-1
H
A3-2
H
A4-1
A4-1
H
A3-2
H
A4-1
(II-129)
H
OH
H
H
OH
A1-3
A1-3
A4-1
H
A3-2
H
A4-1
A4-1
H
A3-2
H
A4-1
(II-130)
H
OH
OH
OH
OH
A1-3
A1-3
A4-1
A3-2
H
A3-2
A4-1
A4-1
A3-2
H
A3-2
A4-1
(II-131)
H
H
H
H
H
A1-3
A1-3
A4-1
A3-2
H
A3-2
A4-1
A4-1
A3-2
H
A3-2
A4-1
(II-132)
H
OH
H
H
OH
A1-3
A1-3
A4-1
A3-2
H
A3-2
A4-1
A4-1
A3-2
H
A3-2
A4-1
(II-133)
H
OH
OH
OH
OH
A1-3
A1-3
A4-1
H
A3-3
H
A4-1
A4-1
H
A3-3
H
A4-1
(II-134)
H
H
H
H
H
A1-3
A1-3
A4-1
H
A3-3
H
A4-1
A4-1
H
A3-3
H
A4-1
(II-135)
H
OH
H
H
OH
A1-3
A1-3
A4-1
H
A3-3
H
A4-1
A4-1
H
A3-3
H
A4-1
(II-136)
H
OH
OH
OH
OH
A1-3
A1-3
A4-1
A3-3
H
A3-3
A4-1
A4-1
A3-3
H
A3-3
A4-1
(II-137)
H
H
H
H
H
A1-3
A1-3
A4-1
A3-3
H
A3-3
A4-1
A4-1
A3-3
H
A3-3
A4-1
(II-138)
H
OH
H
H
OH
A1-3
A1-3
A4-1
A3-3
H
A3-3
A4-1
A4-1
A3-3
H
A3-3
A4-1
(II-139)
H
OH
OH
OH
OH
A1-3
A1-3
A4-1
H
OH
H
A4-1
A4-1
H
OH
H
A4-1
(II-140)
H
H
H
H
H
A1-3
A1-3
A4-1
H
OH
H
A4-1
A4-1
H
OH
H
A4-1
(II-141)
H
OH
H
H
OH
A1-3
A1-3
A4-1
H
OH
H
A4-1
A4-1
H
OH
H
A4-1
(II-142)
H
OH
OH
OH
OH
A1-3
A1-3
A4-1
OH
H
OH
A4-1
A4-1
OH
H
OH
A4-1
(II-143)
H
H
H
H
H
A1-3
A1-3
A4-1
OH
H
OH
A4-1
A4-1
OH
H
OH
A4-1
(II-144)
H
OH
H
H
OH
A1-3
A1-3
A4-1
OH
H
OH
A4-1
A4-1
OH
H
OH
A4-1
(II-145)
H
OH
OH
OH
OH
A1-3
A1-3
A4-1
H
COOH
H
A4-1
A4-1
H
COOH
H
A4-1
(II-146)
H
H
H
H
H
A1-3
A1-3
A4-1
H
COOH
H
A4-1
A4-1
H
COOH
H
A4-1
(II-147)
H
OH
H
H
OH
A1-3
A1-3
A4-1
H
COOH
H
A4-1
A4-1
H
COOH
H
A4-1
(II-148)
H
OH
OH
OH
OH
A1-3
A1-3
A4-1
COOH
H
COOH
A4-1
A4-1
COOH
H
COOH
A4-1
(II-149)
H
H
H
H
H
A1-3
A1-3
A4-1
COOH
H
COOH
A4-1
A4-1
COOH
H
COOH
A4-1
(II-150)
H
OH
H
H
OH
A1-3
A1-3
A4-1
COOH
H
COOH
A4-1
A4-1
COOH
H
COOH
A4-1
(II-151)
H
OH
OH
OH
OH
A1-3
A1-3
A4-2
H
A3-1
H
A4-2
A4-2
H
A3-1
H
A4-2
(II-152)
H
H
H
H
H
A1-3
A1-3
A4-2
H
A3-1
H
A4-2
A4-2
H
A3-1
H
A4-2
(II-153)
H
OH
H
H
OH
A1-3
A1-3
A4-2
H
A3-1
H
A4-2
A4-2
H
A3-1
H
A4-2
(II-154)
H
OH
OH
OH
OH
A1-3
A1-3
A4-2
A3-1
H
A3-1
A4-2
A4-2
A3-1
H
A3-1
A4-2
(II-155)
H
H
H
H
H
A1-3
A1-3
A4-2
A3-1
H
A3-1
A4-2
A4-2
A3-1
H
A3-1
A4-2
(II-156)
H
OH
H
H
OH
A1-3
A1-3
A4-2
A3-1
H
A3-1
A4-2
A4-2
A3-1
H
A3-1
A4-2
(II-157)
H
OH
OH
OH
OH
A1-3
A1-3
A4-2
H
A3-2
H
A4-2
A4-2
H
A3-2
H
A4-2
(II-158)
H
H
H
H
H
A1-3
A1-3
A4-2
H
A3-2
H
A4-2
A4-2
H
A3-2
H
A4-2
(II-159)
H
OH
H
H
OH
A1-3
A1-3
A4-2
H
A3-2
H
A4-2
A4-2
H
A3-2
H
A4-2
(II-160)
H
OH
OH
OH
OH
A1-3
A1-3
A4-2
A3-2
H
A3-2
A4-2
A4-2
A3-2
H
A3-2
A4-2
(II-161)
H
H
H
H
H
A1-3
A1-3
A4-2
A3-2
H
A3-2
A4-2
A4-2
A3-2
H
A3-2
A4-2
(II-162)
H
OH
H
H
OH
A1-3
A1-3
A4-2
A3-2
H
A3-2
A4-2
A4-2
A3-2
H
A3-2
A4-2
(II-163)
H
OH
OH
OH
OH
A1-3
A1-3
A4-2
H
A3-3
H
A4-2
A4-2
H
A3-3
H
A4-2
(II-164)
H
H
H
H
H
A1-3
A1-3
A4-2
H
A3-3
H
A4-2
A4-2
H
A3-3
H
A4-2
(II-165)
H
OH
H
H
OH
A1-3
A1-3
A4-2
H
A3-3
H
A4-2
A4-2
H
A3-3
H
A4-2
(II-166)
H
OH
OH
OH
OH
A1-3
A1-3
A4-2
A3-3
H
A3-3
A4-2
A4-2
A3-3
H
A3-3
A4-2
(II-167)
H
H
H
H
H
A1-3
A1-3
A4-2
A3-3
H
A3-3
A4-2
A4-2
A3-3
H
A3-3
A4-2
(II-168)
H
OH
H
H
OH
A1-3
A1-3
A4-2
A3-3
H
A3-3
A4-2
A4-2
A3-3
H
A3-3
A4-2
(II-169)
H
OH
OH
OH
OH
A1-3
A1-3
A4-2
H
OH
H
A4-2
A4-2
H
OH
H
A4-2
(II-170)
H
H
H
H
H
A1-3
A1-3
A4-2
H
OH
H
A4-2
A4-2
H
OH
H
A4-2
(II-171)
H
OH
H
H
OH
A1-3
A1-3
A4-2
H
OH
H
A4-2
A4-2
H
OH
H
A4-2
(II-172)
H
OH
OH
OH
OH
A1-3
A1-3
A4-2
OH
H
OH
A4-2
A4-2
OH
H
OH
A4-2
(II-173)
H
H
H
H
H
A1-3
A1-3
A4-2
OH
H
OH
A4-2
A4-2
OH
H
OH
A4-2
(II-174)
H
OH
H
H
OH
A1-3
A1-3
A4-2
OH
H
OH
A4-2
A4-2
OH
H
OH
A4-2
(II-175)
H
OH
OH
OH
OH
A1-3
A1-3
A4-2
H
COOH
H
A4-2
A4-2
H
COOH
H
A4-2
(II-176)
H
H
H
H
H
A1-3
A1-3
A4-2
H
COOH
H
A4-2
A4-2
H
COOH
H
A4-2
(II-177)
H
OH
H
H
OH
A1-3
A1-3
A4-2
H
COOH
H
A4-2
A4-2
H
COOH
H
A4-2
(II-178)
H
OH
OH
OH
OH
A1-3
A1-3
A4-2
COOH
H
COOH
A4-2
A4-2
COOH
H
COOH
A4-2
(II-179)
H
H
H
H
H
A1-3
A1-3
A4-2
COOH
H
COOH
A4-2
A4-2
COOH
H
COOH
A4-2
(II-180)
H
OH
H
H
OH
A1-3
A1-3
A4-2
COOH
H
COOH
A4-2
A4-2
COOH
H
COOH
A4-2
[ Table 7]
R1～R4
R5
R6
R7
R8
R9
R10
R16
R17
R18
R19
R20
R21
R22
R23
R24
R25
(II-181)
H
OH
OH
OH
OH
A1-4
A1-4
A4-1
H
A3-1
H
A4-1
A4-1
H
A3-1
H
A4-1
(II-182)
H
H
H
H
H
A1-4
A1-4
A4-1
H
A3-1
H
A4-1
A4-1
H
A3-1
H
A4-1
(II-183)
H
OH
H
H
OH
A1-4
A1-4
A4-1
H
A3-1
H
A4-1
A4-1
H
A3-1
H
A4-1
(II-184)
H
OH
OH
OH
OH
A1-4
A1-4
A4-1
A3-1
H
A3-1
A4-1
A4-1
A3-1
H
A3-1
A4-1
(II-185)
H
H
H
H
H
A1-4
A1-4
A4-1
A3-1
H
A3-1
A4-1
A4-1
A3-1
H
A3-1
A4-1
(II-186)
H
OH
H
H
OH
A1-4
A1-4
A4-1
A3-1
H
A3-1
A4-1
A4-1
A3-1
H
A3-1
A4-1
(II-187)
H
OH
OH
OH
OH
A1-4
A1-4
A4-1
H
A3-2
H
A4-1
A4-1
H
A3-2
H
A4-1
(II-188)
H
H
H
H
H
A1-4
A1-4
A4-1
H
A3-2
H
A4-1
A4-1
H
A3-2
H
A4-1
(II-189)
H
OH
H
H
OH
A1-4
A1-4
A4-1
H
A3-2
H
A4-1
A4-1
H
A3-2
H
A4-1
(II-190)
H
OH
OH
OH
OH
A1-4
A1-4
A4-1
A3-2
H
A3-2
A4-1
A4-1
A3-2
H
A3-2
A4-1
(II-191)
H
H
H
H
H
A1-4
A1-4
A4-1
A3-2
H
A3-2
A4-1
A4-1
A3-2
H
A3-2
A4-1
(II-192)
H
OH
H
H
OH
A1-4
A1-4
A4-1
A3-2
H
A3-2
A4-1
A4-1
A3-2
H
A3-2
A4-1
(II-193)
H
OH
OH
OH
OH
A1-4
A1-4
A4-1
H
A3-3
H
A4-1
A4-1
H
A3-3
H
A4-1
(II-194)
H
H
H
H
H
A1-4
A1-4
A4-1
H
A3-3
H
A4-1
A4-1
H
A3-3
H
A4-1
(II-195)
H
OH
H
H
OH
A1-4
A1-4
A4-1
H
A3-3
H
A4-1
A4-1
H
A3-3
H
A4-1
(II-196)
H
OH
OH
OH
OH
A1-4
A1-4
A4-1
A3-3
H
A3-3
A4-1
A4-1
A3-3
H
A3-3
A4-1
(II-197)
H
H
H
H
H
A1-4
A1-4
A4-1
A3-3
H
A3-3
A4-1
A4-1
A3-3
H
A3-3
A4-1
(II-198)
H
OH
H
H
OH
A1-4
A1-4
A4-1
A3-3
H
A3-3
A4-1
A4-1
A3-3
H
A3-3
A4-1
(II-199)
H
OH
OH
OH
OH
A1-4
A1-4
A4-1
H
OH
H
A4-1
A4-1
H
OH
H
A4-1
(II-200)
H
H
H
H
H
A1-4
A1-4
A4-1
H
OH
H
A4-1
A4-1
H
OH
H
A4-1
(II-201)
H
OH
H
H
OH
A1-4
A1-4
A4-1
H
OH
H
A4-1
A4-1
H
OH
H
A4-1
(II-202)
H
OH
OH
OH
OH
A1-4
A1-4
A4-1
OH
H
OH
A4-1
A4-1
OH
H
OH
A4-1
(II-203)
H
H
H
H
H
A1-4
A1-4
A4-1
OH
H
OH
A4-1
A4-1
OH
H
OH
A4-1
(II-204)
H
OH
H
H
OH
A1-4
A1-4
A4-1
OH
H
OH
A4-1
A4-1
OH
H
OH
A4-1
(II-205)
H
OH
OH
OH
OH
A1-4
A1-4
A4-1
H
COOH
H
A4-1
A4-1
H
COOH
H
A4-1
(II-206)
H
H
H
H
H
A1-4
A1-4
A4-1
H
COOH
H
A4-1
A4-1
H
COOH
H
A4-1
(II-207)
H
OH
H
H
OH
A1-4
A1-4
A4-1
H
COOH
H
A4-1
A4-1
H
COOH
H
A4-1
(II-208)
H
OH
OH
OH
OH
A1-4
A1-4
A4-1
COOH
H
COOH
A4-1
A4-1
COOH
H
COOH
A4-1
(II-209)
H
H
H
H
H
A1-4
A1-4
A4-1
COOH
H
COOH
A4-1
A4-1
COOH
H
COOH
A4-1
(II-210)
H
OH
H
H
OH
A1-4
A1-4
A4-1
COOH
H
COOH
A4-1
A4-1
COOH
H
COOH
A4-1
(II-211)
H
OH
OH
OH
OH
A1-4
A1-4
A4-2
H
A3-1
H
A4-2
A4-2
H
A3-1
H
A4-2
(II-212)
H
H
H
H
H
A1-4
A1-4
A4-2
H
A3-1
H
A4-2
A4-2
H
A3-1
H
A4-2
(II-213)
H
OH
H
H
OH
A1-4
A1-4
A4-2
H
A3-1
H
A4-2
A4-2
H
A3-1
H
A4-2
(II-214)
H
OH
OH
OH
OH
A1-4
A1-4
A4-2
A3-1
H
A3-1
A4-2
A4-2
A3-1
H
A3-1
A4-2
(II-215)
H
H
H
H
H
A1-4
A1-4
A4-2
A3-1
H
A3-1
A4-2
A4-2
A3-1
H
A3-1
A4-2
(II-216)
H
OH
H
H
OH
A1-4
A1-4
A4-2
A3-1
H
A3-1
A4-2
A4-2
A3-1
H
A3-1
A4-2
(II-217)
H
OH
OH
OH
OH
A1-4
A1-4
A4-2
H
A3-2
H
A4-2
A4-2
H
A3-2
H
A4-2
(II-218)
H
H
H
H
H
A1-4
A1-4
A4-2
H
A3-2
H
A4-2
A4-2
H
A3-2
H
A4-2
(II-219)
H
OH
H
H
OH
A1-4
A1-4
A4-2
H
A3-2
H
A4-2
A4-2
H
A3-2
H
A4-2
(II-220)
H
OH
OH
OH
OH
A1-4
A1-4
A4-2
A3-2
H
A3-2
A4-2
A4-2
A3-2
H
A3-2
A4-2
(II-221)
H
H
H
H
H
A1-4
A1-4
A4-2
A3-2
H
A3-2
A4-2
A4-2
A3-2
H
A3-2
A4-2
(II-222)
H
OH
H
H
OH
A1-4
A1-4
A4-2
A3-2
H
A3-2
A4-2
A4-2
A3-2
H
A3-2
A4-2
(II-223)
H
OH
OH
OH
OH
A1-4
A1-4
A4-2
H
A3-3
H
A4-2
A4-2
H
A3-3
H
A4-2
(II-224)
H
H
H
H
H
A1-4
A1-4
A4-2
H
A3-3
H
A4-2
A4-2
H
A3-3
H
A4-2
(II-225)
H
OH
H
H
OH
A1-4
A1-4
A4-2
H
A3-3
H
A4-2
A4-2
H
A3-3
H
A4-2
(II-226)
H
OH
OH
OH
OH
A1-4
A1-4
A4-2
A3-3
H
A3-3
A4-2
A4-2
A3-3
H
A3-3
A4-2
(II-227)
H
H
H
H
H
A1-4
A1-4
A4-2
A3-3
H
A3-3
A4-2
A4-2
A3-3
H
A3-3
A4-2
(II-228)
H
OH
H
H
OH
A1-4
A1-4
A4-2
A3-3
H
A3-3
A4-2
A4-2
A3-3
H
A3-3
A4-2
(II-229)
H
OH
OH
OH
OH
A1-4
A1-4
A4-2
H
OH
H
A4-2
A4-2
H
OH
H
A4-2
(II-230)
H
H
H
H
H
A1-4
A1-4
A4-2
H
OH
H
A4-2
A4-2
H
OH
H
A4-2
(II-231)
H
OH
H
H
OH
A1-4
A1-4
A4-2
H
OH
H
A4-2
A4-2
H
OH
H
A4-2
(II-232)
H
OH
OH
OH
OH
A1-4
A1-4
A4-2
OH
H
OH
A4-2
A4-2
OH
H
OH
A4-2
(II-233)
H
H
H
H
H
A1-4
A1-4
A4-2
OH
H
OH
A4-2
A4-2
OH
H
OH
A4-2
(II-234)
H
OH
H
H
OH
A1-4
A1-4
A4-2
OH
H
OH
A4-2
A4-2
OH
H
OH
A4-2
(II-235)
H
OH
OH
OH
OH
A1-4
A1-4
A4-2
H
COOH
H
A4-2
A4-2
H
COOH
H
A4-2
(II-236)
H
H
H
H
H
A1-4
A1-4
A4-2
H
COOH
H
A4-2
A4-2
H
COOH
H
A4-2
(II-237)
H
OH
H
H
OH
A1-4
A1-4
A4-2
H
COOH
H
A4-2
A4-2
H
COOH
H
A4-2
(II-238)
H
OH
OH
OH
OH
A1-4
A1-4
A4-2
COOH
H
COOH
A4-2
A4-2
COOH
H
COOH
A4-2
(II-239)
H
H
H
H
H
A1-4
A1-4
A4-2
COOH
H
COOH
A4-2
A4-2
COOH
H
COOH
A4-2
(II-240)
H
OH
H
H
OH
A1-4
A1-4
A4-2
COOH
H
COOH
A4-2
A4-2
COOH
H
COOH
A4-2
[ Table 8]
R1～R4
R5
R6
R7
R8
R9
R10
R16
R17
R18
R19
R20
R21
R22
R23
R24
R25
(II-241)
H
OH
OH
OH
OH
A1-1
A1-1
H
A4-1
A3-1
H
H
H
H
A3-1
A4-1
H
(II-242)
H
H
H
H
H
A1-1
A1-1
H
A4-1
A3-1
H
H
H
H
A3-1
A4-1
H
(II-243)
H
OH
H
H
OH
A1-1
A1-1
H
A4-1
A3-1
H
H
H
H
A3-1
A4-1
H
(II-244)
H
OH
OH
OH
OH
A1-1
A1-1
H
A4-1
A3-2
H
H
H
H
A3-2
A4-1
H
(II-245)
H
H
H
H
H
A1-1
A1-1
H
A4-1
A3-2
H
H
H
H
A3-2
A4-1
H
(II-246)
H
OH
H
H
OH
A1-1
A1-1
H
A4-1
A3-2
H
H
H
H
A3-2
A4-1
H
(II-247)
H
OH
OH
OH
OH
A1-1
A1-1
H
A4-1
A3-3
H
H
H
H
A3-3
A4-1
H
(II-248)
H
H
H
H
H
A1-1
A1-1
H
A4-1
A3-3
H
H
H
H
A3-3
A4-1
H
(II-249)
H
OH
H
H
OH
A1-1
A1-1
H
A4-1
A3-3
H
H
H
H
A3-3
A4-1
H
(II-250)
H
OH
OH
OH
OH
A1-1
A1-1
H
A4-1
OH
H
H
H
H
OH
A4-1
H
(II-251)
H
H
H
H
H
A1-1
A1-1
H
A4-1
OH
H
H
H
H
OH
A4-1
H
(II-252)
H
OH
H
H
OH
A1-1
A1-1
H
A4-1
OH
H
H
H
H
OH
A4-1
H
(II-253)
H
OH
OH
OH
OH
A1-1
A1-1
H
A4-1
COOH
H
H
H
H
COOH
A4-1
H
(II-254)
H
H
H
H
H
A1-1
A1-1
H
A4-1
COOH
H
H
H
H
COOH
A4-1
H
(II-255)
H
OH
H
H
OH
A1-1
A1-1
H
A4-1
COOH
H
H
H
H
COOH
A4-1
H
(II-256)
H
OH
OH
OH
OH
A1-1
A1-1
H
A4-2
A3-1
H
H
H
H
A3-1
A4-2
H
(II-257)
H
H
H
H
H
A1-1
A1-1
H
A4-2
A3-1
H
H
H
H
A3-1
A4-2
H
(II-258)
H
OH
H
H
OH
A1-1
A1-1
H
A4-2
A3-1
H
H
H
H
A3-1
A4-2
H
(II-259)
H
OH
OH
OH
OH
A1-1
A1-1
H
A4-2
A3-2
H
H
H
H
A3-2
A4-2
H
(II-260)
H
H
H
H
H
A1-1
A1-1
H
A4-2
A3-2
H
H
H
H
A3-2
A4-2
H
(II-261)
H
OH
H
H
OH
A1-1
A1-1
H
A4-2
A3-2
H
H
H
H
A3-2
A4-2
H
(II-262)
H
OH
OH
OH
OH
A1-1
A1-1
H
A4-2
A3-3
H
H
H
H
A3-3
A4-2
H
(II-263)
H
H
H
H
H
A1-1
A1-1
H
A4-2
A3-3
H
H
H
H
A3-3
A4-2
H
(II-264)
H
OH
H
H
OH
A1-1
A1-1
H
A4-2
A3-3
H
H
H
H
A3-3
A4-2
H
(II-265)
H
OH
OH
OH
OH
A1-1
A1-1
H
A4-2
OH
H
H
H
H
OH
A4-2
H
(II-266)
H
H
H
H
H
A1-1
A1-1
H
A4-2
OH
H
H
H
H
OH
A4-2
H
(II-267)
H
OH
H
H
OH
A1-1
A1-1
H
A4-2
OH
H
H
H
H
OH
A4-2
H
(II-268)
H
OH
OH
OH
OH
A1-1
A1-1
H
A4-2
COOH
H
H
H
H
COOH
A4-2
H
(II-269)
H
H
H
H
H
A1-1
A1-1
H
A4-2
COOH
H
H
H
H
COOH
A4-2
H
(II-270)
H
OH
H
H
OH
A1-1
A1-1
H
A4-2
COOH
H
H
H
H
COOH
A4-2
H
(II-271)
H
OH
OH
OH
OH
A1-1
A1-1
H
A4-3
A3-1
H
H
H
H
A3-1
A4-3
H
(II-272)
H
H
H
H
H
A1-1
A1-1
H
A4-3
A3-1
H
H
H
H
A3-1
A4-3
H
(II-273)
H
OH
H
H
OH
A1-1
A1-1
H
A4-3
A3-1
H
H
H
H
A3-1
A4-3
H
(II-274)
H
OH
OH
OH
OH
A1-1
A1-1
H
A4-3
A3-2
H
H
H
H
A3-2
A4-3
H
(II-275)
H
H
H
H
H
A1-1
A1-1
H
A4-3
A3-2
H
H
H
H
A3-2
A4-3
H
(II-276)
H
OH
H
H
OH
A1-1
A1-1
H
A4-3
A3-2
H
H
H
H
A3-2
A4-3
H
(II-277)
H
OH
OH
OH
OH
A1-1
A1-1
H
A4-3
A3-3
H
H
H
H
A3-3
A4-3
H
(II-278)
H
H
H
H
H
A1-1
A1-1
H
A4-3
A3-3
H
H
H
H
A3-3
A4-3
H
(II-279)
H
OH
H
H
OH
A1-1
A1-1
H
A4-3
A3-3
H
H
H
H
A3-3
A4-3
H
(II-280)
H
OH
OH
OH
OH
A1-1
A1-1
H
A4-3
OH
H
H
H
H
OH
A4-3
H
(II-281)
H
H
H
H
H
A1-1
A1-1
H
A4-3
OH
H
H
H
H
OH
A4-3
H
(II-282)
H
OH
H
H
OH
A1-1
A1-1
H
A4-3
OH
H
H
H
H
OH
A4-3
H
(II-283)
H
OH
OH
OH
OH
A1-1
A1-1
H
A4-3
COOH
H
H
H
H
COOH
A4-3
H
(II-284)
H
H
H
H
H
A1-1
A1-1
H
A4-3
COOH
H
H
H
H
COOH
A4-3
H
(II-285)
H
OH
H
H
OH
A1-1
A1-1
H
A4-3
COOH
H
H
H
H
COOH
A4-3
H
(II-286)
H
OH
OH
OH
OH
A1-2
A1-2
H
A4-1
A3-1
H
H
H
H
A3-1
A4-1
H
(II-287)
H
H
H
H
H
A1-2
A1-2
H
A4-1
A3-1
H
H
H
H
A3-1
A4-1
H
(II-288)
H
OH
H
H
OH
A1-2
A1-2
H
A4-1
A3-1
H
H
H
H
A3-1
A4-1
H
(II-289)
H
OH
OH
OH
OH
A1-2
A1-2
H
A4-1
A3-2
H
H
H
H
A3-2
A4-1
H
(II-290)
H
H
H
H
H
A1-2
A1-2
H
A4-1
A3-2
H
H
H
H
A3-2
A4-1
H
(II-291)
H
OH
H
H
OH
A1-2
A1-2
H
A4-1
A3-2
H
H
H
H
A3-2
A4-1
H
(II-292)
H
OH
OH
OH
OH
A1-2
A1-2
H
A4-1
A3-3
H
H
H
H
A3-3
A4-1
H
(II-293)
H
H
H
H
H
A1-2
A1-2
H
A4-1
A3-3
H
H
H
H
A3-3
A4-1
H
(II-294)
H
OH
H
H
OH
A1-2
A1-2
H
A4-1
A3-3
H
H
H
H
A3-3
A4-1
H
(II-295)
H
OH
OH
OH
OH
A1-2
A1-2
H
A4-1
OH
H
H
H
H
OH
A4-1
H
(II-296)
H
H
H
H
H
A1-2
A1-2
H
A4-1
OH
H
H
H
H
OH
A4-1
H
(II-297)
H
OH
H
H
OH
A1-2
A1-2
H
A4-1
OH
H
H
H
H
OH
A4-1
H
(II-298)
H
OH
OH
OH
OH
A1-2
A1-2
H
A4-1
COOH
H
H
H
H
COOH
A4-1
H
(II-299)
H
H
H
H
H
A1-2
A1-2
H
A4-1
COOH
H
H
H
H
COOH
A4-1
H
(II-300)
H
OH
H
H
OH
A1-2
A1-2
H
A4-1
COOH
H
H
H
H
COOH
A4-1
H
[ Table 9]
R1～R4
R5
R6
R7
R8
R9
R10
R16
R17
R18
R19
R20
R21
R22
R23
R24
R25
(II-301)
H
OH
OH
OH
OH
A1-2
A1-2
H
A4-2
A3-1
H
H
H
H
A3-1
A4-2
H
(II-302)
H
H
H
H
H
A1-2
A1-2
H
A4-2
A3-1
H
H
H
H
A3-1
A4-2
H
(II-303)
H
OH
H
H
OH
A1-2
A1-2
H
A4-2
A3-1
H
H
H
H
A3-1
A4-2
H
(II-304)
H
OH
OH
OH
OH
A1-2
A1-2
H
A4-2
A3-2
H
H
H
H
A3-2
A4-2
H
(II-305)
H
H
H
H
H
A1-2
A1-2
H
A4-2
A3-2
H
H
H
H
A3-2
A4-2
H
(II-306)
H
OH
H
H
OH
A1-2
A1-2
H
A4-2
A3-2
H
H
H
H
A3-2
A4-2
H
(II-307)
H
OH
OH
OH
OH
A1-2
A1-2
H
A4-2
A3-3
H
H
H
H
A3-3
A4-2
H
(II-308)
H
H
H
H
H
A1-2
A1-2
H
A4-2
A3-3
H
H
H
H
A3-3
A4-2
H
(II-309)
H
OH
H
H
OH
A1-2
A1-2
H
A4-2
A3-3
H
H
H
H
A3-3
A4-2
H
(II-310)
H
OH
OH
OH
OH
A1-2
A1-2
H
A4-2
OH
H
H
H
H
OH
A4-2
H
(II-311)
H
H
H
H
H
A1-2
A1-2
H
A4-2
OH
H
H
H
H
OH
A4-2
H
(II-312)
H
OH
H
H
OH
A1-2
A1-2
H
A4-2
OH
H
H
H
H
OH
A4-2
H
(II-313)
H
OH
OH
OH
OH
A1-2
A1-2
H
A4-2
COOH
H
H
H
H
COOH
A4-2
H
(II-314)
H
H
H
H
H
A1-2
A1-2
H
A4-2
COOH
H
H
H
H
COOH
A4-2
H
(II-315)
H
OH
H
H
OH
A1-2
A1-2
H
A4-2
COOH
H
H
H
H
COOH
A4-2
H
(II-316)
H
OH
OH
OH
OH
A1-2
A1-2
H
A4-3
A3-1
H
H
H
H
A3-1
A4-3
H
(II-317)
H
H
H
H
H
A1-2
A1-2
H
A4-3
A3-1
H
H
H
H
A3-1
A4-3
H
(II-318)
H
OH
H
H
OH
A1-2
A1-2
H
A4-3
A3-1
H
H
H
H
A3-1
A4-3
H
(II-319)
H
OH
OH
OH
OH
A1-2
A1-2
H
A4-3
A3-2
H
H
H
H
A3-2
A4-3
H
(II-320)
H
H
H
H
H
A1-2
A1-2
H
A4-3
A3-2
H
H
H
H
A3-2
A4-3
H
(II-321)
H
OH
H
H
OH
A1-2
A1-2
H
A4-3
A3-2
H
H
H
H
A3-2
A4-3
H
(II-322)
H
OH
OH
OH
OH
A1-2
A1-2
H
A4-3
A3-3
H
H
H
H
A3-3
A4-3
H
(II-323)
H
H
H
H
H
A1-2
A1-2
H
A4-3
A3-3
H
H
H
H
A3-3
A4-3
H
(II-324)
H
OH
H
H
OH
A1-2
A1-2
H
A4-3
A3-3
H
H
H
H
A3-3
A4-3
H
(II-325)
H
OH
OH
OH
OH
A1-2
A1-2
H
A4-3
OH
H
H
H
H
OH
A4-3
H
(II-326)
H
H
H
H
H
A1-2
A1-2
H
A4-3
OH
H
H
H
H
OH
A4-3
H
(II-327)
H
OH
H
H
OH
A1-2
A1-2
H
A4-3
OH
H
H
H
H
OH
A4-3
H
(II-328)
H
OH
OH
OH
OH
A1-2
A1-2
H
A4-3
COOH
H
H
H
H
COOH
A4-3
H
(II-329)
H
H
H
H
H
A1-2
A1-2
H
A4-3
COOH
H
H
H
H
COOH
A4-3
H
(II-330)
H
OH
H
H
OH
A1-2
A1-2
H
A4-3
COOH
H
H
H
H
COOH
A4-3
H
(II-331)
H
OH
OH
OH
OH
A1-3
A1-3
H
A4-1
A3-1
H
H
H
H
A3-1
A4-1
H
(II-332)
H
H
H
H
H
A1-3
A1-3
H
A4-1
A3-1
H
H
H
H
A3-1
A4-1
H
(II-333)
H
OH
H
H
OH
A1-3
A1-3
H
A4-1
A3-1
H
H
H
H
A3-1
A4-1
H
(II-334)
H
OH
OH
OH
OH
A1-3
A1-3
H
A4-1
A3-2
H
H
H
H
A3-2
A4-1
H
(II-335)
H
H
H
H
H
A1-3
A1-3
H
A4-1
A3-2
H
H
H
H
A3-2
A4-1
H
(II-336)
H
OH
H
H
OH
A1-3
A1-3
H
A4-1
A3-2
H
H
H
H
A3-2
A4-1
H
(II-337)
H
OH
OH
OH
OH
A1-3
A1-3
H
A4-1
A3-3
H
H
H
H
A3-3
A4-1
H
(II-338)
H
H
H
H
H
A1-3
A1-3
H
A4-1
A3-3
H
H
H
H
A3-3
A4-1
H
(II-339)
H
OH
H
H
OH
A1-3
A1-3
H
A4-1
A3-3
H
H
H
H
A3-3
A4-1
H
(II-340)
H
OH
OH
OH
OH
A1-3
A1-3
H
A4-1
OH
H
H
H
H
OH
A4-1
H
(II-341)
H
H
H
H
H
A1-3
A1-3
H
A4-1
OH
H
H
H
H
OH
A4-1
H
(II-342)
H
OH
H
H
OH
A1-3
A1-3
H
A4-1
OH
H
H
H
H
OH
A4-1
H
(II-343)
H
OH
OH
OH
OH
A1-3
A1-3
H
A4-1
COOH
H
H
H
H
COOH
A4-1
H
(II-344)
H
H
H
H
H
A1-3
A1-3
H
A4-1
COOH
H
H
H
H
COOH
A4-1
H
(II-345)
H
OH
H
H
OH
A1-3
A1-3
H
A4-1
COOH
H
H
H
H
COOH
A4-1
H
(II-346)
H
OH
OH
OH
OH
A1-3
A1-3
H
A4-2
A3-1
H
H
H
H
A3-1
A4-2
H
(II-347)
H
H
H
H
H
A1-3
A1-3
H
A4-2
A3-1
H
H
H
H
A3-1
A4-2
H
(II-348)
H
OH
H
H
OH
A1-3
A1-3
H
A4-2
A3-1
H
H
H
H
A3-1
A4-2
H
(II-349)
H
OH
OH
OH
OH
A1-3
A1-3
H
A4-2
A3-2
H
H
H
H
A3-2
A4-2
H
(II-350)
H
H
H
H
H
A1-3
A1-3
H
A4-2
A3-2
H
H
H
H
A3-2
A4-2
H
(II-351)
H
OH
H
H
OH
A1-3
A1-3
H
A4-2
A3-2
H
H
H
H
A3-2
A4-2
H
(II-352)
H
OH
OH
OH
OH
A1-3
A1-3
H
A4-2
A3-3
H
H
H
H
A3-3
A4-2
H
(II-353)
H
H
H
H
H
A1-3
A1-3
H
A4-2
A3-3
H
H
H
H
A3-3
A4-2
H
(II-354)
H
OH
H
H
OH
A1-3
A1-3
H
A4-2
A3-3
H
H
H
H
A3-3
A4-2
H
(II-355)
H
OH
OH
OH
OH
A1-3
A1-3
H
A4-2
OH
H
H
H
H
OH
A4-2
H
(II-356)
H
H
H
H
H
A1-3
A1-3
H
A4-2
OH
H
H
H
H
OH
A4-2
H
(II-357)
H
OH
H
H
OH
A1-3
A1-3
H
A4-2
OH
H
H
H
H
OH
A4-2
H
(II-358)
H
OH
OH
OH
OH
A1-3
A1-3
H
A4-2
COOH
H
H
H
H
COOH
A4-2
H
(II-359)
H
H
H
H
H
A1-3
A1-3
H
A4-2
COOH
H
H
H
H
COOH
A4-2
H
(II-360)
H
OH
H
H
OH
A1-3
A1-3
H
A4-2
COOH
H
H
H
H
COOH
A4-2
H
[ Table 10]
R1～R4
R5
R6
R7
R8
R9
R10
R16
R17
R18
R19
R20
R21
R22
R23
R24
R25
(II-361)
H
OH
OH
OH
OH
A1-3
A1-3
H
A4-3
A3-1
H
H
H
H
A3-1
A4-3
H
(II-362)
H
H
H
H
H
A1-3
A1-3
H
A4-3
A3-1
H
H
H
H
A3-1
A4-3
H
(II-363)
H
OH
H
H
OH
A1-3
A1-3
H
A4-3
A3-1
H
H
H
H
A3-1
A4-3
H
(II-364)
H
OH
OH
OH
OH
A1-3
A1-3
H
A4-3
A3-2
H
H
H
H
A3-2
A4-3
H
(II-365)
H
H
H
H
H
A1-3
A1-3
H
A4-3
A3-2
H
H
H
H
A3-2
A4-3
H
(II-366)
H
OH
H
H
OH
A1-3
A1-3
H
A4-3
A3-2
H
H
H
H
A3-2
A4-3
H
(II-367)
H
OH
OH
OH
OH
A1-3
A1-3
H
A4-3
A3-3
H
H
H
H
A3-3
A4-3
H
(II-368)
H
H
H
H
H
A1-3
A1-3
H
A4-3
A3-3
H
H
H
H
A3-3
A4-3
H
(II-369)
H
OH
H
H
OH
A1-3
A1-3
H
A4-3
A3-3
H
H
H
H
A3-3
A4-3
H
(II-370)
H
OH
OH
OH
OH
A1-3
A1-3
H
A4-3
OH
H
H
H
H
OH
A4-3
H
(II-371)
H
H
H
H
H
A1-3
A1-3
H
A4-3
OH
H
H
H
H
OH
A4-3
H
(II-372)
H
OH
H
H
OH
A1-3
A1-3
H
A4-3
OH
H
H
H
H
OH
A4-3
H
(II-373)
H
OH
OH
OH
OH
A1-3
A1-3
H
A4-3
COOH
H
H
H
H
COOH
A4-3
H
(II-374)
H
H
H
H
H
A1-3
A1-3
H
A4-3
COOH
H
H
H
H
COOH
A4-3
H
(II-375)
H
OH
H
H
OH
A1-3
A1-3
H
A4-3
COOH
H
H
H
H
COOH
A4-3
H
(II-376)
H
OH
OH
OH
OH
A1-4
A1-4
H
A4-1
A3-1
H
H
H
H
A3-1
A4-1
H
(II-377)
H
H
H
H
H
A1-4
A1-4
H
A4-1
A3-1
H
H
H
H
A3-1
A4-1
H
(II-378)
H
OH
H
H
OH
A1-4
A1-4
H
A4-1
A3-1
H
H
H
H
A3-1
A4-1
H
(II-379)
H
OH
OH
OH
OH
A1-4
A1-4
H
A4-1
A3-2
H
H
H
H
A3-2
A4-1
H
(II-380)
H
H
H
H
H
A1-4
A1-4
H
A4-1
A3-2
H
H
H
H
A3-2
A4-1
H
(II-381)
H
OH
H
H
OH
A1-4
A1-4
H
A4-1
A3-2
H
H
H
H
A3-2
A4-1
H
(II-382)
H
OH
OH
OH
OH
A1-4
A1-4
H
A4-1
A3-3
H
H
H
H
A3-3
A4-1
H
(II-383)
H
H
H
H
H
A1-4
A1-4
H
A4-1
A3-3
H
H
H
H
A3-3
A4-1
H
(II-384)
H
OH
H
H
OH
A1-4
A1-4
H
A4-1
A3-3
H
H
H
H
A3-3
A4-1
H
(II-385)
H
OH
OH
OH
OH
A1-4
A1-4
H
A4-1
OH
H
H
H
H
OH
A4-1
H
(II-386)
H
H
H
H
H
A1-4
A1-4
H
A4-1
OH
H
H
H
H
OH
A4-1
H
(II-387)
H
OH
H
H
OH
A1-4
A1-4
H
A4-1
OH
H
H
H
H
OH
A4-1
H
(II-388)
H
OH
OH
OH
OH
A1-4
A1-4
H
A4-1
COOH
H
H
H
H
COOH
A4-1
H
(II-389)
H
H
H
H
H
A1-4
A1-4
H
A4-1
COOH
H
H
H
H
COOH
A4-1
H
(II-390)
H
OH
H
H
OH
A1-4
A1-4
H
A4-1
COOH
H
H
H
H
COOH
A4-1
H
(II-391)
H
OH
OH
OH
OH
A1-4
A1-4
H
A4-2
A3-1
H
H
H
H
A3-1
A4-2
H
(II-392)
H
H
H
H
H
A1-4
A1-4
H
A4-2
A3-1
H
H
H
H
A3-1
A4-2
H
(II-393)
H
OH
H
H
OH
A1-4
A1-4
H
A4-2
A3-1
H
H
H
H
A3-1
A4-2
H
(II-394)
H
OH
OH
OH
OH
A1-4
A1-4
H
A4-2
A3-2
H
H
H
H
A3-2
A4-2
H
(II-395)
H
H
H
H
H
A1-4
A1-4
H
A4-2
A3-2
H
H
H
H
A3-2
A4-2
H
(II-396)
H
OH
H
H
OH
A1-4
A1-4
H
A4-2
A3-2
H
H
H
H
A3-2
A4-2
H
(II-397)
H
OH
OH
OH
OH
A1-4
A1-4
H
A4-2
A3-3
H
H
H
H
A3-3
A4-2
H
(II-398)
H
H
H
H
H
A1-4
A1-4
H
A4-2
A3-3
H
H
H
H
A3-3
A4-2
H
(II-399)
H
OH
H
H
OH
A1-4
A1-4
H
A4-2
A3-3
H
H
H
H
A3-3
A4-2
H
(II-400)
H
OH
OH
OH
OH
A1-4
A1-4
H
A4-2
OH
H
H
H
H
OH
A4-2
H
(II-401)
H
H
H
H
H
A1-4
A1-4
H
A4-2
OH
H
H
H
H
OH
A4-2
H
(II-402)
H
OH
H
H
OH
A1-4
A1-4
H
A4-2
OH
H
H
H
H
OH
A4-2
H
(II-403)
H
OH
OH
OH
OH
A1-4
A1-4
H
A4-2
COOH
H
H
H
H
COOH
A4-2
H
(II-404)
H
H
H
H
H
A1-4
A1-4
H
A4-2
COOH
H
H
H
H
COOH
A4-2
H
(II-405)
H
OH
H
H
OH
A1-4
A1-4
H
A4-2
COOH
H
H
H
H
COOH
A4-2
H
(II-406)
H
OH
OH
OH
OH
A1-4
A1-4
H
A4-3
A3-1
H
H
H
H
A3-1
A4-3
H
(II-407)
H
H
H
H
H
A1-4
A1-4
H
A4-3
A3-1
H
H
H
H
A3-1
A4-3
H
(II-408)
H
OH
H
H
OH
A1-4
A1-4
H
A4-3
A3-1
H
H
H
H
A3-1
A4-3
H
(II-409)
H
OH
OH
OH
OH
A1-4
A1-4
H
A4-3
A3-2
H
H
H
H
A3-2
A4-3
H
(II-410)
H
H
H
H
H
A1-4
A1-4
H
A4-3
A3-2
H
H
H
H
A3-2
A4-3
H
(II-411)
H
OH
H
H
OH
A1-4
A1-4
H
A4-3
A3-2
H
H
H
H
A3-2
A4-3
H
(II-412)
H
OH
OH
OH
OH
A1-4
A1-4
H
A4-3
A3-3
H
H
H
H
A3-3
A4-3
H
(II-413)
H
H
H
H
H
A1-4
A1-4
H
A4-3
A3-3
H
H
H
H
A3-3
A4-3
H
(II-414)
H
OH
H
H
OH
A1-4
A1-4
H
A4-3
A3-3
H
H
H
H
A3-3
A4-3
H
(II-415)
H
OH
OH
OH
OH
A1-4
A1-4
H
A4-3
OH
H
H
H
H
OH
A4-3
H
(II-416)
H
H
H
H
H
A1-4
A1-4
H
A4-3
OH
H
H
H
H
OH
A4-3
H
(II-417)
H
OH
H
H
OH
A1-4
A1-4
H
A4-3
OH
H
H
H
H
OH
A4-3
H
(II-418)
H
OH
OH
OH
OH
A1-4
A1-4
H
A4-3
COOH
H
H
H
H
COOH
A4-3
H
(II-419)
H
H
H
H
H
A1-4
A1-4
H
A4-3
COOH
H
H
H
H
COOH
A4-3
H
(II-420)
H
OH
H
H
OH
A1-4
A1-4
H
A4-3
COOH
H
H
H
H
COOH
A4-3
H
[ Table 11]
R1～R4
R5
R6
R7
R8
R9
R10
R16
R17
R18
R19
R20
R21
R22
R23
R24
R25
(II-421)
H
OH
OH
OH
OH
A1-1
A1-1
H
H
A3-1
H
H
H
H
A3-1
H
H
(II-422)
H
H
H
H
H
A1-1
A1-1
H
H
A3-1
H
H
H
H
A3-1
H
H
(II-423)
H
OH
H
H
OH
A1-1
A1-1
H
H
A3-1
H
H
H
H
A3-1
H
H
(II-424)
H
OH
OH
OH
OH
A1-1
A1-1
H
A3-1
H
A3-1
H
H
A3-1
H
A3-1
H
(II-425)
H
H
H
H
H
A1-1
A1-1
H
A3-1
H
A3-1
H
H
A3-1
H
A3-1
H
(II-426)
H
OH
H
H
OH
A1-1
A1-1
H
A3-1
H
A3-1
H
H
A3-1
H
A3-1
H
(II-427)
H
OH
OH
OH
OH
A1-1
A1-1
H
H
A3-2
H
H
H
H
A3-2
H
H
(II-428)
H
H
H
H
H
A1-1
A1-1
H
H
A3-2
H
H
H
H
A3-2
H
H
(II-429)
H
OH
H
H
OH
A1-1
A1-1
H
H
A3-2
H
H
H
H
A3-2
H
H
(II-430)
H
OH
OH
OH
OH
A1-1
A1-1
H
A3-2
H
A3-2
H
H
A3-2
H
A3-2
H
(II-431)
H
H
H
H
H
A1-1
A1-1
H
A3-2
H
A3-2
H
H
A3-2
H
A3-2
H
(II-432)
H
OH
H
H
OH
A1-1
A1-1
H
A3-2
H
A3-2
H
H
A3-2
H
A3-2
H
(II-433)
H
OH
OH
OH
OH
A1-1
A1-1
H
H
A3-3
H
H
H
H
A3-3
H
H
(II-434)
H
H
H
H
H
A1-1
A1-1
H
H
A3-3
H
H
H
H
A3-3
H
H
(II-435)
H
OH
H
H
OH
A1-1
A1-1
H
H
A3-3
H
H
H
H
A3-3
H
H
(II-436)
H
OH
OH
OH
OH
A1-1
A1-1
H
A3-3
H
A3-3
H
H
A3-3
H
A3-3
H
(II-437)
H
H
H
H
H
A1-1
A1-1
H
A3-3
H
A3-3
H
H
A3-3
H
A3-3
H
(II-438)
H
OH
H
H
OH
A1-1
A1-1
H
A3-3
H
A3-3
H
H
A3-3
H
A3-3
H
(II-439)
H
OH
OH
OH
OH
A1-1
A1-1
H
H
OH
H
H
H
H
OH
H
H
(II-440)
H
H
H
H
H
A1-1
A1-1
H
H
OH
H
H
H
H
OH
H
H
(II-441)
H
OH
H
H
OH
A1-1
A1-1
H
H
OH
H
H
H
H
OH
H
H
(II-442)
H
OH
OH
OH
OH
A1-1
A1-1
H
OH
H
OH
H
H
OH
H
OH
H
(II-443)
H
H
H
H
H
A1-1
A1-1
H
OH
H
OH
H
H
OH
H
OH
H
(II-444)
H
OH
H
H
OH
A1-1
A1-1
H
OH
H
OH
H
H
OH
H
OH
H
(II-445)
H
OH
OH
OH
OH
A1-1
A1-1
H
H
COOH
H
H
H
H
COOH
H
H
(II-446)
H
H
H
H
H
A1-1
A1-1
H
H
COOH
H
H
H
H
COOH
H
H
(II-447)
H
OH
H
H
OH
A1-1
A1-1
H
H
COOH
H
H
H
H
COOH
H
H
(II-448)
H
OH
OH
OH
OH
A1-1
A1-1
H
COOH
H
COOH
H
H
COOH
H
COOH
H
(II-449)
H
H
H
H
H
A1-1
A1-1
H
COOH
H
COOH
H
H
COOH
H
COOH
H
(II-450)
H
OH
H
H
OH
A1-1
A1-1
H
COOH
H
COOH
H
H
COOH
H
COOH
H
(II-451)
H
OH
OH
OH
OH
A1-2
A1-2
H
H
A3-1
H
H
H
H
A3-1
H
H
(II-452)
H
H
H
H
H
A1-2
A1-2
H
H
A3-1
H
H
H
H
A3-1
H
H
(II-453)
H
OH
H
H
OH
A1-2
A1-2
H
H
A3-1
H
H
H
H
A3-1
H
H
(II-454)
H
OH
OH
OH
OH
A1-2
A1-2
H
A3-1
H
A3-1
H
H
A3-1
H
A3-1
H
(II-455)
H
H
H
H
H
A1-2
A1-2
H
A3-1
H
A3-1
H
H
A3-1
H
A3-1
H
(II-456)
H
OH
H
H
OH
A1-2
A1-2
H
A3-1
H
A3-1
H
H
A3-1
H
A3-1
H
(II-457)
H
OH
OH
OH
OH
A1-2
A1-2
H
H
A3-2
H
H
H
H
A3-2
H
H
(II-458)
H
H
H
H
H
A1-2
A1-2
H
H
A3-2
H
H
H
H
A3-2
H
H
(II-459)
H
OH
H
H
OH
A1-2
A1-2
H
H
A3-2
H
H
H
H
A3-2
H
H
(II-460)
H
OH
OH
OH
OH
A1-2
A1-2
H
A3-2
H
A3-2
H
H
A3-2
H
A3-2
H
(II-461)
H
H
H
H
H
A1-2
A1-2
H
A3-2
H
A3-2
H
H
A3-2
H
A3-2
H
(II-462)
H
OH
H
H
OH
A1-2
A1-2
H
A3-2
H
A3-2
H
H
A3-2
H
A3-2
H
(II-463)
H
OH
OH
OH
OH
A1-2
A1-2
H
H
A3-3
H
H
H
H
A3-3
H
H
(II-464)
H
H
H
H
H
A1-2
A1-2
H
H
A3-3
H
H
H
H
A3-3
H
H
(II-465)
H
OH
H
H
OH
A1-2
A1-2
H
H
A3-3
H
H
H
H
A3-3
H
H
(II-466)
H
OH
OH
OH
OH
A1-2
A1-2
H
A3-3
H
A3-3
H
H
A3-3
H
A3-3
H
(II-467)
H
H
H
H
H
A1-2
A1-2
H
A3-3
H
A3-3
H
H
A3-3
H
A3-3
H
(II-468)
H
OH
H
H
OH
A1-2
A1-2
H
A3-3
H
A3-3
H
H
A3-3
H
A3-3
H
(II-469)
H
OH
OH
OH
OH
A1-2
A1-2
H
H
OH
H
H
H
H
OH
H
H
(II-470)
H
H
H
H
H
A1-2
A1-2
H
H
OH
H
H
H
H
OH
H
H
(II-471)
H
OH
H
H
OH
A1-2
A1-2
H
H
OH
H
H
H
H
OH
H
H
(II-472)
H
OH
OH
OH
OH
A1-2
A1-2
H
OH
H
OH
H
H
OH
H
OH
H
(II-473)
H
H
H
H
H
A1-2
A1-2
H
OH
H
OH
H
H
OH
H
OH
H
(II-474)
H
OH
H
H
OH
A1-2
A1-2
H
OH
H
OH
H
H
OH
H
OH
H
(II-475)
H
OH
OH
OH
OH
A1-2
A1-2
H
H
COOH
H
H
H
H
COOH
H
H
(II-476)
H
H
H
H
H
A1-2
A1-2
H
H
COOH
H
H
H
H
COOH
H
H
(II-477)
H
OH
H
H
OH
A1-2
A1-2
H
H
COOH
H
H
H
H
COOH
H
H
(II-478)
H
OH
OH
OH
OH
A1-2
A1-2
H
COOH
H
COOH
H
H
COOH
H
COOH
H
(II-479)
H
H
H
H
H
A1-2
A1-2
H
COOH
H
COOH
H
H
COOH
H
COOH
H
(II-480)
H
OH
H
H
OH
A1-2
A1-2
H
COOH
H
COOH
H
H
COOH
H
COOH
H
[ Table 12]
R1～R4
R5
R6
R7
R8
R9
R10
R16
R17
R18
R19
R20
R21
R22
R23
R24
R25
(II-481)
H
OH
OH
OH
OH
A1-3
A1-3
H
H
A3-1
H
H
H
H
A3-1
H
H
(II-482)
H
H
H
H
H
A1-3
A1-3
H
H
A3-1
H
H
H
H
A3-1
H
H
(II-483)
H
OH
H
H
OH
A1-3
A1-3
H
H
A3-1
H
H
H
H
A3-1
H
H
(II-484)
H
OH
OH
OH
OH
A1-3
A1-3
H
A3-1
H
A3-1
H
H
A3-1
H
A3-1
H
(II-485)
H
H
H
H
H
A1-3
A1-3
H
A3-1
H
A3-1
H
H
A3-1
H
A3-1
H
(II-486)
H
OH
H
H
OH
A1-3
A1-3
H
A3-1
H
A3-1
H
H
A3-1
H
A3-1
H
(II-487)
H
OH
OH
OH
OH
A1-3
A1-3
H
H
A3-2
H
H
H
H
A3-2
H
H
(II-488)
H
H
H
H
H
A1-3
A1-3
H
H
A3-2
H
H
H
H
A3-2
H
H
(II-489)
H
OH
H
H
OH
A1-3
A1-3
H
H
A3-2
H
H
H
H
A3-2
H
H
(II-490)
H
OH
OH
OH
OH
A1-3
A1-3
H
A3-2
H
A3-2
H
H
A3-2
H
A3-2
H
(II-491)
H
H
H
H
H
A1-3
A1-3
H
A3-2
H
A3-2
H
H
A3-2
H
A3-2
H
(II-492)
H
OH
H
H
OH
A1-3
A1-3
H
A3-2
H
A3-2
H
H
A3-2
H
A3-2
H
(II-493)
H
OH
OH
OH
OH
A1-3
A1-3
H
H
A3-3
H
H
H
H
A3-3
H
H
(II-494)
H
H
H
H
H
A1-3
A1-3
H
H
A3-3
H
H
H
H
A3-3
H
H
(II-495)
H
OH
H
H
OH
A1-3
A1-3
H
H
A3-3
H
H
H
H
A3-3
H
H
(II-496)
H
OH
OH
OH
OH
A1-3
A1-3
H
A3-3
H
A3-3
H
H
A3-3
H
A3-3
H
(II-497)
H
H
H
H
H
A1-3
A1-3
H
A3-3
H
A3-3
H
H
A3-3
H
A3-3
H
(II-498)
H
OH
H
H
OH
A1-3
A1-3
H
A3-3
H
A3-3
H
H
A3-3
H
A3-3
H
(II-499)
H
OH
OH
OH
OH
A1-3
A1-3
H
H
OH
H
H
H
H
OH
H
H
(II-500)
H
H
H
H
H
A1-3
A1-3
H
H
OH
H
H
H
H
OH
H
H
(II-501)
H
OH
H
H
OH
A1-3
A1-3
H
H
OH
H
H
H
H
OH
H
H
(II-502)
H
OH
OH
OH
OH
A1-3
A1-3
H
OH
H
OH
H
H
OH
H
OH
H
(II-503)
H
H
H
H
H
A1-3
A1-3
H
OH
H
OH
H
H
OH
H
OH
H
(II-504)
H
OH
H
H
OH
A1-3
A1-3
H
OH
H
OH
H
H
OH
H
OH
H
(II-505)
H
OH
OH
OH
OH
A1-3
A1-3
H
H
COOH
H
H
H
H
COOH
H
H
(II-506)
H
H
H
H
H
A1-3
A1-3
H
H
COOH
H
H
H
H
COOH
H
H
(II-507)
H
OH
H
H
OH
A1-3
A1-3
H
H
COOH
H
H
H
H
COOH
H
H
(II-508)
H
OH
OH
OH
OH
A1-3
A1-3
H
COOH
H
COOH
H
H
COOH
H
COOH
H
(II-509)
H
H
H
H
H
A1-3
A1-3
H
COOH
H
COOH
H
H
COOH
H
COOH
H
(II-510)
H
OH
H
H
OH
A1-3
A1-3
H
COOH
H
COOH
H
H
COOH
H
COOH
H
(II-511)
H
OH
OH
OH
OH
A1-4
A1-4
H
H
A3-1
H
H
H
H
A3-1
H
H
(II-512)
H
H
H
H
H
A1-4
A1-4
H
H
A3-1
H
H
H
H
A3-1
H
H
(II-513)
H
OH
H
H
OH
A1-4
A1-4
H
H
A3-1
H
H
H
H
A3-1
H
H
(II-514)
H
OH
OH
OH
OH
A1-4
A1-4
H
A3-1
H
A3-1
H
H
A3-1
H
A3-1
H
(II-515)
H
H
H
H
H
A1-4
A1-4
H
A3-1
H
A3-1
H
H
A3-1
H
A3-1
H
(II-516)
H
OH
H
H
OH
A1-4
A1-4
H
A3-1
H
A3-1
H
H
A3-1
H
A3-1
H
(II-517)
H
OH
OH
OH
OH
A1-4
A1-4
H
H
A3-2
H
H
H
H
A3-2
H
H
(II-518)
H
H
H
H
H
A1-4
A1-4
H
H
A3-2
H
H
H
H
A3-2
H
H
(II-519)
H
OH
H
H
OH
A1-4
A1-4
H
H
A3-2
H
H
H
H
A3-2
H
H
(II-520)
H
OH
OH
OH
OH
A1-4
A1-4
H
A3-2
H
A3-2
H
H
A3-2
H
A3-2
H
(II-521)
H
H
H
H
H
A1-4
A1-4
H
A3-2
H
A3-2
H
H
A3-2
H
A3-2
H
(II-522)
H
OH
H
H
OH
A1-4
A1-4
H
A3-2
H
A3-2
H
H
A3-2
H
A3-2
H
(II-523)
H
OH
OH
OH
OH
A1-4
A1-4
H
H
A3-3
H
H
H
H
A3-3
H
H
(II-524)
H
H
H
H
H
A1-4
A1-4
H
H
A3-3
H
H
H
H
A3-3
H
H
(II-525)
H
OH
H
H
OH
A1-4
A1-4
H
H
A3-3
H
H
H
H
A3-3
H
H
(II-526)
H
OH
OH
OH
OH
A1-4
A1-4
H
A3-3
H
A3-3
H
H
A3-3
H
A3-3
H
(II-527)
H
H
H
H
H
A1-4
A1-4
H
A3-3
H
A3-3
H
H
A3-3
H
A3-3
H
(II-528)
H
OH
H
H
OH
A1-4
A1-4
H
A3-3
H
A3-3
H
H
A3-3
H
A3-3
H
(II-529)
H
OH
OH
OH
OH
A1-4
A1-4
H
H
OH
H
H
H
H
OH
H
H
(II-530)
H
H
H
H
H
A1-4
A1-4
H
H
OH
H
H
H
H
OH
H
H
(II-531)
H
OH
H
H
OH
A1-4
A1-4
H
H
OH
H
H
H
H
OH
H
H
(II-532)
H
OH
OH
OH
OH
A1-4
A1-4
H
OH
H
OH
H
H
OH
H
OH
H
(II-533)
H
H
H
H
H
A1-4
A1-4
H
OH
H
OH
H
H
OH
H
OH
H
(II-534)
H
OH
H
H
OH
A1-4
A1-4
H
OH
H
OH
H
H
OH
H
OH
H
(II-535)
H
OH
OH
OH
OH
A1-4
A1-4
H
H
COOH
H
H
H
H
COOH
H
H
(II-536)
H
H
H
H
H
A1-4
A1-4
H
H
COOH
H
H
H
H
COOH
H
H
(II-537)
H
OH
H
H
OH
A1-4
A1-4
H
H
COOH
H
H
H
H
COOH
H
H
(II-538)
H
OH
OH
OH
OH
A1-4
A1-4
H
COOH
H
COOH
H
H
COOH
H
COOH
H
(II-539)
H
H
H
H
H
A1-4
A1-4
H
COOH
H
COOH
H
H
COOH
H
COOH
H
(II-540)
H
OH
H
H
OH
A1-4
A1-4
H
COOH
H
COOH
H
H
COOH
H
COOH
H
In tables 4 to 12, A1-1 to A1-4 represent the same groups as described above.
In tables 4 to 12, A3-1 to A3-3 represent groups represented by the following formulae. In the following formulae, a represents a bond.
In tables 4 to 12, A4-1 to A4-3 represent groups represented by the following formulae. In the following formulae, a represents a bond.
The compound represented by formula (I) can be produced by: a compound represented by the formula (pt1), a compound represented by the formula (pt2), and a compound represented by the formula (pt3) are reacted. In the present reaction, the total amount of the compound represented by the formula (pt1) and the compound represented by the formula (pt2) used is preferably 1.5 to 2.5mol based on 1mol of the compound represented by the formula (pt 3).
< colored resin composition >
The colored resin composition of the present invention comprises a colorant (A) and a resin (B), wherein the colorant (A) comprises a compound represented by formula (I).
The colored resin composition of the present invention preferably further comprises a polymerizable compound (C) and a polymerization initiator (D).
The colored resin composition of the present invention may further contain a polymerization initiator (D1), a solvent (E), and a leveling agent (F).
In the present specification, unless otherwise specified, the compounds exemplified as the respective components may be used alone or in combination of plural kinds.
< colorant (A) >)
The colored resin composition of the present invention contains the compound (I) as the colorant (a). The content of the compound (I) is preferably 0.1 to 150 parts by mass, more preferably 0.3 to 100 parts by mass, and further preferably 0.5 to 80 parts by mass, relative to 100 parts by mass of the resin (B).
The content of the compound (I) in the total amount of the colorant (a) is preferably 20% by mass or more, more preferably 50% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more.
The colored resin composition of the present invention may contain a dye (a1) and a pigment (a2) as the colorant (a) in addition to the compound (I) as the colorant (a).
The dye (a1) is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of The dye include compounds classified as having a color other than a pigment in The color index (published by The Society of Dyers and Colourists), and known dyes described in The color handbook (color dyeing Co., Ltd.). Further, depending on the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, azomethine dyes, squarylium dyes (excluding the compound (I)), acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and the like can be cited. Among them, organic solvent-soluble dyes are preferable.
The pigment (a2) is not particularly limited, and known pigments can be used, and examples thereof include pigments classified as pigments by The color index (published by The Society of Dyers and Colourists).
Examples of the pigment include yellow pigments such as c.i. pigment yellow 1,3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, and 214;
orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
red pigments such as c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
c.i. pigment blue 15, 15:3, 15:4, 15:6, 60, etc.;
c.i. pigment violet 1, 19, 23, 29, 32, 36, 38 and the like violet pigment;
green pigments such as c.i. pigment green 7, 36, 58;
c.i. brown pigments such as pigment brown 23, 25;
and black pigments such as c.i. pigment black 1 and 7.
The content of the colorant (a) is preferably 0.1 to 70% by mass, more preferably 0.5 to 60% by mass, and still more preferably 1 to 50% by mass, relative to the total amount of solid components of the colored resin composition.
Here, the "total amount of solid components" in the present specification means an amount after removing the content of the solvent from the total amount of the colored resin composition. The total amount of the solid components and the contents of the components relative to the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.
< resin (B) >
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably a resin having a structural unit derived from at least one (a) (hereinafter, sometimes referred to as "(a)") selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. The resin (B) also preferably has at least one structural unit selected from the group consisting of the following structural units: a structural unit derived from a monomer (b) having a cyclic ether structure of 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter referred to as "(b)"), a structural unit derived from a monomer (c) copolymerizable with (a) (but different from (a) and (b) (hereinafter referred to as "(c)"), and a structural unit having an ethylenically unsaturated bond in a side chain.
Specific examples of (a) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, and mono [2- (meth) acryloyloxyethyl ] succinate, with acrylic acid, methacrylic acid, and maleic anhydride being preferred.
(b) Preferred are monomers having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and a (meth) acryloyloxy group.
In the present specification, "(meth) acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth) acryloyl group" and "(meth) acrylate" and the like also have the same meaning.
Examples of (b) include glycidyl (meth) acrylate, vinylbenzyl glycidyl ether, and 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)2,6]Decyl ester, 3-ethyl-3- (meth) acryloyloxymethyloxetane, tetrahydrofurfuryl (meth) acrylate, etc., preferably glycidyl (meth) acrylate, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)2,6]Decyl ester, 3-ethyl-3- (meth) acryloyloxymethyloxetane.
Examples of (c) include methyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 ] meth) acrylate2,6]Decane-8-yl ester, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyltoluene and the like, and preferably styrene, vinyltoluene, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and the like.
The resin having a structural unit having an ethylenically unsaturated bond in a side chain can be produced by adding (b) to the copolymer of (a) and (c) or adding (a) to the copolymer of (b) and (c). The resin may be a resin obtained by adding (a) to the copolymer of (b) and (c) and further reacting a carboxylic acid anhydride.
The polystyrene-reduced weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000.
The dispersity [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4.
The acid value of the resin (B) is preferably from 20mg-KOH/g to 170mg-KOH/g, more preferably from 30mg-KOH/g to 150mg-KOH/g, further preferably from 40mg-KOH/g to 135mg-KOH/g, in terms of solid content. The acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin (B), and can be determined, for example, by titration using an aqueous potassium hydroxide solution.
The content of the resin (B) is preferably 30 to 99.9% by mass, more preferably 50 to 99.5% by mass, and still more preferably 70 to 99% by mass, relative to the total amount of solid components of the colored resin composition.
In the case where the colored resin composition of the present invention contains the polymerizable compound (C) and the polymerization initiator (D), the content of the resin (B) is preferably 7 to 70% by mass, more preferably 13 to 65% by mass, and further preferably 17 to 60% by mass, relative to the total amount of solid components of the colored resin composition.
< polymerizable Compound (C) >)
The polymerizable compound (C) is a compound polymerizable by an active radical and/or an acid generated by the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and preferably (meth) acrylate compounds.
Among these, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
In the case where the polymerizable compound (C) is contained, the content of the polymerizable compound (C) is preferably 5 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass, relative to the total amount of the solid content.
< polymerization initiator (D) >)
The polymerization initiator (D) is not particularly limited as long as it is a compound which can generate an active radical, an acid, or the like by the action of light or heat to initiate polymerization, and a known polymerization initiator can be used. Examples of the polymerization initiator generating an active radical include N-benzoyloxy-1- (4-phenylthiophenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylthiophenyl) octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylthiophenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1- (4-phenylthiophenyl) -3-cyclohexylpropane-1-one-2-imine, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propane-1-one, N-phenylthiopropionic acid, N-1- (4-phenylthiophenyl) octane-1, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, 1-hydroxycyclohexylphenyl ketone, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenylbenzimidazole and the like.
When the polymerization initiator (D) is contained, the content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and further preferably 2 to 10 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). If the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be high and the exposure time tends to be shortened, so that the productivity of the color filter is improved.
< polymerization initiation assistant (D1) >)
The polymerization initiation aid (D1) is a compound or sensitizer used for promoting the polymerization of the polymerizable compound whose polymerization is initiated by the polymerization initiator. In the case of containing the polymerization initiation aid (D1), it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include 4,4' -bis (dimethylamino) benzophenone (known as Michler's ketone), 4' -bis (diethylamino) benzophenone, 9, 10-dimethoxyanthracene, 2, 4-diethylthioxanthone, and N-phenylglycine.
When these polymerization initiating aids (D1) are used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). If the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.
< solvent (E) >
The solvent (E) is not particularly limited, and a solvent generally used in the art may be used. Examples thereof include ester solvents (solvents containing-COO-but not-O-in the molecule), ether solvents (solvents containing-O-but not-COO-, in the molecule), ether ester solvents (solvents containing-COO-and-O-in the molecule), ketone solvents (solvents containing-CO-but not-COO-, in the molecule), alcohol solvents (solvents containing OH but not-O-, -CO-, and-COO-, in the molecule), aromatic hydrocarbon solvents, amide solvents, halogen solvents, and dimethyl sulfoxide.
Examples of the solvent include:
ester solvents (solvents containing-COO-but not-O-in the molecule) such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate, and γ -butyrolactone;
ether solvents (solvents containing-O-but not-COO-in the molecule) such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether;
ether ester solvents (solvents containing-COO-and-O-in the molecule) such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol monoethyl ether acetate;
ketone solvents (solvents containing-CO-but not-COO-in the molecule) such as 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), heptanone, 4-methyl-2-pentanone, and cyclohexanone;
alcohol solvents (solvents containing OH but not-O-, -CO-or-COO-) such as butanol, cyclohexanol and propylene glycol;
amide solvents such as N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
halogen solvents such as chloroform, chlorobenzene, dichloroethylene, and trichloroethylene; and the like.
More preferred examples of the solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), N-methylpyrrolidone, chloroform, ethyl lactate, and ethyl 3-ethoxypropionate.
In the case where the solvent (E) is contained, the content of the solvent (E) is preferably 60 to 95% by mass, more preferably 65 to 92% by mass, relative to the total amount of the colored resin composition of the present invention. In other words, the total amount of solid components of the colored resin composition is preferably 5 to 40 mass%, more preferably 8 to 35 mass%. When the content of the solvent (E) is within the above range, the flatness at the time of coating is good, and the color density is not insufficient at the time of forming a color filter, so that the display characteristics tend to be good.
< leveling agent (F) >
Examples of the leveling agent (F) include a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom. These may have a polymerizable group in a side chain.
Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specific examples thereof include TORAY SILICONE C3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, and TORAY SILICONE SH8400 (trade name: DONGLIDONGWANGNING (L.) (Dow Corning Toray Co., Ltd.)); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (products of Shin-Etsu Chemical co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan) and the like.
Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specific examples thereof include Fluorad (registered trademark) FC430 and Fluorad FC431 (Sumitomo 3M Limited product); MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (DIC (strain) products); EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (Mitsubishi Materials Electronic Chemicals co., Ltd.) products); SURLON (registered trademark) S381, SURLON S382, SURLON SC101, SURLON SC105 (Asahi Glass Co., Ltd.) product) and E5844 (Daikin fine chemistry research institute product).
Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, there may be mentioned MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477 and MEGAFAC F443(DIC (manufactured by DIC Co., Ltd.)).
In the case where the leveling agent (F) is contained, the content of the leveling agent (F) is preferably 0.001 to 0.2 mass%, more preferably 0.002 to 0.1 mass%, relative to the total amount of the colored resin composition. Furthermore, the content does not include the content of the pigment dispersant. If the content of the leveling agent (F) is within the above range, the flatness of the color filter can be made good.
< other ingredients >
The colored resin composition of the present invention may optionally contain additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents.
< method for producing colored resin composition >
The colored resin composition of the present invention can be prepared by mixing the colorant (a) and the resin (B), and optionally the polymerizable compound (C), the polymerization initiator (D), the polymerization initiation aid (D1), the solvent (E), the leveling agent (F), and other components.
< method for manufacturing color filter >
Examples of the method for producing a colored pattern from the colored resin composition of the present invention include photolithography, ink jet printing, and printing. Among them, photolithography is preferable.
The colored resin composition contains the compound represented by the formula (I), so that a color filter with particularly excellent heat resistance and light resistance can be manufactured. The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, or the like) or a solid-state imaging device.
[ examples ]
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, unless otherwise specified,% and part indicating the content and the amount used are on a mass basis.
Hereinafter, the structure of the compound was confirmed by MASS spectrometry (LC: Agilent 1200 type; MASS: Agilent LC/MSD type).
(Synthesis example 1)
50 parts of 3-bromoanisole (Tokyo Chemical Industry co., Ltd.) was dissolved in 36.1 parts of 2,4, 6-trimethylaniline (Tokyo Chemical Industry co., Ltd.) and 434 parts of toluene (Kanto Chemical co., Inc.) and mixed in the solution were 30 parts of potassium hydroxide (Tokyo Chemical Industry co., Ltd.) 25 parts of water, 2 parts of tetrabutylammonium bromide (Tokyo Chemical Industry Ltd.) and 1.4 parts of bis (tri-tert-butylphosphine) palladium (0) (Tokyo Chemical Industry Ltd.). After warming to 90 ℃ and stirring for 5 hours, an organic layer was obtained by extraction, and the solvent was distilled off to obtain 52.1 parts of a crude product (crude product). The obtained crude product was separated and purified by column chromatography to obtain 50.2 parts of a compound represented by the formula (1-1).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+242.3
Exact Mass (Exact Mass): +241.2
(Synthesis example 2)
33 parts of the compound represented by the formula (1-1), 26.8 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo Kasei Co., Ltd.) and 286 parts of toluene (manufactured by Kanto Kasei Co., Ltd.) were mixed, and the mixture was heated while stirring at 100 ℃ for 16 hours. After completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by column chromatography to obtain 30.7 parts of a compound represented by the formula (1-2).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+356.2
Exact Mass (Exact Mass): +355.2
(Synthesis example 3)
10 parts of the compound represented by the formula (1-2) was dissolved in 95 parts of methylene chloride (a product of Kanto chemical Co., Ltd.), and the mixture was cooled to 0 ℃ while stirring. 28.2 parts of boron tribromide (Fuji film and Wako Pure Chemical Corporation) was added dropwise while stirring). After the end of the dropwise addition, the temperature was slowly raised and stirred at 10 ℃ for 4 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and a water-organic solvent extraction operation was performed to distill off the solvent to obtain 9.1 parts of a crude product. The crude product contained 48% of the compound represented by the formula (1-3) and 36% of the compound represented by the formula (1-4).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+342.2
Exact Mass (Exact Mass): +341.2
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+328.1
Exact Mass (Exact Mass): +327.2
(Synthesis example 4)
A solution of 13.2 parts of thionyl chloride (manufactured by tokyo chemical industries, ltd.) dissolved in 72 parts of methanol (manufactured by kanto chemical industries, ltd.) was cooled to 0 ℃, and 9.1 parts of the crude product containing the compound represented by formula (1-3) and the compound represented by formula (1-4) obtained in synthesis example 3 was added while stirring. The temperature was raised to room temperature and the reaction was carried out for 16 hours. The solvent was distilled off under reduced pressure to obtain 8.3 parts of a crude product containing the compound represented by the formula (1-3). The obtained crude product was purified by silica gel column chromatography to obtain 7.4 parts of a compound represented by the formula (1-3).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+342.2
Exact Mass (Exact Mass): +341.2
(Synthesis example 5)
2 parts of the compound represented by the formula (1-3), 26.3 parts of a borane-1M tetrahydrofuran solution (Kanto chemical Co., Ltd.), and 18 parts of tetrahydrofuran (Kanto chemical Co., Ltd.) were mixed at 0 ℃ and stirred at 10 ℃ for 5 hours. After the reaction is finished, water is added for quenching, and organic solvent is used for extraction. The solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography to obtain 1.64 parts of a compound represented by the formula (1-5).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+300.2
Exact Mass (Exact Mass): +299.2
(example 1)
2.5 parts of the compound represented by the formula (1-5) and 0.55 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji film and Wako pure chemical industries, Ltd.) were dissolved in 50 parts of toluene (Kanto chemical industries, Ltd.) and 50 parts of n-butanol (Kanto chemical industries, Ltd.) and heated while stirring at 110 ℃ for 6 hours. After the completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 2.7 parts of a compound represented by the formula (I-147).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+677.4
Exact Mass (Exact Mass): +676.4
(Synthesis example 6)
10 parts of the compound represented by the formula (1-1), 7.4 parts of methylmalonyl chloride (Tokyo chemical industry Co., Ltd.) and 87 parts of toluene (Kanto chemical Co., Ltd.) were mixed, and the mixture was heated while stirring at 100 ℃ for 16 hours. After the completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by column chromatography to obtain 9.1 parts of a compound represented by formula (1-6).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+342.2
Exact Mass (Exact Mass): +341.2
(Synthesis example 7)
8.1 parts of the compound represented by the formula (1-6) was dissolved in 107 parts of methylene chloride (manufactured by Kanto chemical Co., Ltd.), and the mixture was cooled to 0 ℃ while stirring. 24 parts of boron tribromide (fuji film and Wako pure chemical industries, Ltd.) were added dropwise while stirring. After the end of the dropwise addition, the temperature was slowly raised and stirred at 23 ℃ for 3 hours. After the reaction was completed, the organic layer was extracted and concentrated to obtain 7.2 parts of a compound represented by the formula (1-7).
And (3) identification: (Mass Spectrum) ionization mode (ES)I+：m/z＝[M+H]+314.1
Exact Mass (Exact Mass): +313.1
(Synthesis example 8)
A solution prepared by dissolving 10.6 parts of thionyl chloride (manufactured by tokyo chemical industries, ltd.) in 55.5 parts of methanol (manufactured by kanto chemical industries, ltd.) was cooled to 0 ℃, and 5 parts of the compound represented by the formula (1-7) was added thereto while stirring. The temperature was raised to 23 ℃ and the reaction was carried out for 16 hours. The solvent was distilled off under reduced pressure to obtain 6.8 parts of a crude product containing the compound represented by the formula (1-8). The obtained crude product was purified by silica gel column chromatography to obtain 5.6 parts of a compound represented by the formula (1-8).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+328.2
Exact Mass (Exact Mass): +327.15
(Synthesis example 9)
5.5 parts of the compound represented by the formula (1-8), 92.3 parts of a borane-1M tetrahydrofuran solution (manufactured by KANTO CHEMICAL CO., LTD.), 49 parts of tetrahydrofuran (manufactured by KANTO CHEMICAL CO., LTD.) were mixed at 0 ℃ and stirred at 23 ℃ for 3 hours. After the reaction is finished, water is added for quenching, and organic solvent is used for extraction. The solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography to obtain 2.6 parts of a compound represented by the formula (1-9).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+286.2
Exact Mass (Exact Mass): +285.2
(example 2)
2 parts of the compound represented by the formula (1-9) and 0.4 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji film and Wako pure chemical industries, Ltd.) were dissolved in 69 parts of toluene (Kanto chemical industries, Ltd.) and 16 parts of n-butanol (Kanto chemical industries, Ltd.) and heated while stirring at 120 ℃ for 4 hours. After completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 1.3 parts of a compound represented by the formula (I-27).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+649.7
Exact Mass (Exact Mass): +648.3
(Synthesis example 10)
7 parts of mesitylene bromide (tokyo chemical industry product), 4.8 parts of 5-methoxy-2-methylaniline (tokyo chemical industry product), 0.39 parts of palladium acetate (tokyo chemical industry product), 0.84 parts of 4,5 '-bis (diphenylphosphino) -9,9' -dimethylxanthene (tokyo chemical industry product), and 6.8 parts of sodium tert-butoxide (tokyo chemical industry product) were dissolved in 126 parts of toluene (guanto chemical product) and heated and refluxed at 105 ℃ for 1 hour. After the reaction was completed, the organic layer was extracted with water, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 7 parts of a compound represented by formula (1-15).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+256.2
Exact Mass (Exact Mass): +255.2
(Synthesis example 11)
6 parts of the compound represented by the formula (1-15) and 33 parts of succinic acid monoethyl ester chloride (manufactured by Tokyo chemical Co., Ltd.) were dissolved in 20 parts of toluene (manufactured by Kanto chemical Co., Ltd.) and heated at 90 ℃ for 8 hours. After the reaction was completed, the organic layer was extracted with water, and washed with 300 parts of hexane (manufactured by kanto chemical corporation) to prepare 4 parts of the compound represented by formula (1-16).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+384.0
Exact Mass (Exact Mass): +383.2
(Synthesis example 12)
4.2 parts of the compound represented by the formula (1-16) was dissolved in 20 parts of methylene chloride (manufactured by Kanto chemical Co., Ltd.), and 46 parts of boron tribromide (manufactured by Fuji film and Wako pure chemical industries, Ltd.) was added and stirred. After completion of the reaction, the reaction mixture was quenched with water, extracted with an ethyl acetate solvent, and concentrated to obtain 5 parts of a compound represented by formula (1-17).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+370.3
Exact Mass (Exact Mass): +369.2
(Synthesis example 13)
4 parts of the compound represented by the formula (1-17) was dissolved in 40 parts of dehydrated tetrahydrofuran (a product of Kanto Chemicals), and 105 parts of a borane-1M tetrahydrofuran solution (a product of Kanto Chemicals) was added thereto while stirring the solution at 0 ℃. After further stirring at 23 ℃ for 20 hours, water was added to quench and extraction was carried out with an organic solvent. The solvent was distilled off to obtain 2.8 parts of a compound represented by the formula (1-18).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+314.3
Exact Mass (Exact Mass): +313.2
(example 3)
0.7 part of the compound represented by the formula (1-18) and 0.12 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji film and Wako pure chemical industries, Ltd.) were dissolved in 2 parts of toluene (Kanto chemical industries, Ltd.) and 3 parts of n-butanol (Kanto chemical industries, Ltd.) and heated while stirring at 110 ℃ for 13 hours. After completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 0.1 part of the compound represented by the formula (I-150).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+705.8
Exact Mass (Exact Mass): +704.4
(Synthesis example 14)
20 parts of 2, 6-diisopropylaniline (tokyo chemical industry co., ltd.), 22.4 parts of 3-bromoanisole (tokyo chemical industry co., ltd.), 0.6 part of palladium acetate (tokyo chemical industry co., ltd.), 0.9 part of 1mol/L tri-tert-butylphosphine-hexane solution (Fuji film and Wako pure chemical industries co., ltd.), and 21.7 parts of sodium tert-butoxide (tokyo chemical industry co., ltd.) were dissolved in 228 parts of toluene (Kanto chemical industries, ltd.) and heated and refluxed at 110 ℃ for 5 hours. After the reaction was completed, the organic layer was extracted with water, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 32 parts of a compound represented by formula (1-19).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+284.2
Exact Mass (Exact Mass): +283.2
(Synthesis example 15)
5 parts of the compound represented by the formula (1-19) was dissolved in 85 parts of dimethylformamide (Fuji film and Wako pure chemical industries, Ltd.) in an ice bath (ice bath). To this, 3.5 parts of sodium hydride (fuji film and Wako pure chemical industries, Ltd.) was slowly added. After stirring for 10 minutes, 3.8 parts of 1-bromo-4-methoxybutane (a product of Tokyo chemical industry Co., Ltd.) was slowly added thereto, and the mixture was heated to 120 ℃ and refluxed. After completion of the reaction, water was gradually added again in an ice bath to quench the reaction mixture, and then the organic layer was extracted, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 6.5 parts of a compound represented by the formula (1-20).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+370.5
Exact Mass (Exact Mass): +369.5
(Synthesis example 16)
5 parts of the compound represented by the formula (1-20) was dissolved in 100 parts of methylene chloride (manufactured by Kanto chemical Co., Ltd.), and 147 parts of boron tribromide (manufactured by Fuji film and Wako pure chemical industries, Ltd.) was added and stirred. After completion of the reaction, the reaction mixture was quenched with water, extracted with ethyl acetate, and concentrated. The obtained crude product was separated by means of a silica gel column to obtain 3.8 parts of a mixture containing 78% of the compound represented by the formula (1-21-1) and 22% of the compound represented by the formula (1-21-2) (hereinafter, referred to as a mixture (1-21) in some cases).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+342.4
Exact Mass (Exact Mass): +341.2
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+356.5
Exact Mass (Exact Mass): +355.3
(examples 4 to 5)
4.5 parts of the mixture (1-21) and 0.45 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji film and Wako pure chemical industries, Ltd.) were dissolved in 30 parts of toluene (Kanto chemical industries, Ltd.) and 30 parts of n-butanol (Kanto chemical industries, Ltd.) and heated while stirring at 120 ℃ for 3.5 hours. After completion of the reaction, the solvent was distilled off, and the reaction mixture was separated and purified by silica gel column chromatography to obtain 1 part of the compound represented by formula (I-171) and 1 part of the compound represented by formula (I-177), respectively.
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+761.4
Exact Mass (Exact Mass): +760.5
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+775.7
Exact Mass (Exact Mass): +774.5
(Synthesis example 17)
10 parts of 2,4, 6-trimethylaniline (tokyo chemical industry product), 16 parts of 1-bromo-3, 5-dimethoxybenzene (tokyo chemical industry product), 0.83 part of palladium acetate (tokyo chemical industry product), 2.1 parts of 4,5 '-bis (diphenylphosphino) -9,9' -dimethylxanthene (tokyo chemical industry product), and 14.2 parts of sodium tert-butoxide (tokyo chemical industry product) were dissolved in 180 parts of toluene (guanto chemical product) and heated and refluxed at 105 ℃ for 3 hours. After the reaction was completed, the organic layer was extracted with water, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 19 parts of the compound represented by formula (1-22).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+272.5
Exact Mass (Exact Mass): +271.2
(Synthesis example 18)
7.5 parts of the compound represented by the formula (1-22) and 13.6 parts of succinic acid monoethyl ester acid chloride (manufactured by Tokyo chemical Co., Ltd.) were dissolved in 150 parts of toluene (manufactured by Kanto chemical Co., Ltd.) and heated at 100 ℃ for 5 hours. After the completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 10 parts of a compound represented by formula (1-23).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+400.5
Exact Mass (Exact Mass): +399.2
(Synthesis example 19)
2.7 parts of the compound represented by the formula (1-23) was dissolved in 30 parts of methylene chloride (manufactured by Kanto chemical Co., Ltd.), and 7.7 parts of boron tribromide (manufactured by Fuji film and Wako pure chemical industries, Ltd.) was added and stirred. After completion of the reaction, the reaction mixture was quenched with water, extracted with an ethyl acetate solvent, and concentrated to obtain 2.2 parts of a compound represented by the formula (1-24).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+372.3
Exact Mass (Exact Mass): +371.2
(Synthesis example 20)
0.25 part of the compound represented by the formula (1-24) was dissolved in 7 parts of dehydrated tetrahydrofuran (manufactured by KANTO CHEMICAL CO., LTD.), and 0.4 part of borane-1M tetrahydrofuran solution (manufactured by KANTO CHEMICAL CO., LTD.) was added thereto while stirring and cooling to 0 ℃. After the temperature was raised to 23 ℃ and further stirred for 20 hours, the mixture was quenched with water and then concentrated in an organic solvent to obtain 0.12 part of a compound represented by the formula (1-25).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+316.3
Exact Mass (Exact Mass): +315.2
(example 6)
0.4 part of the compound represented by the formula (1-25) and 0.07 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji film and Wako pure chemical industries, Ltd.) were dissolved in 3 parts of toluene (Kanto chemical industries, Ltd.) and 4.5 parts of n-butanol (Kanto chemical industries, Ltd.) and heated while stirring at 110 ℃ for 3 hours. After the reaction was completed, the solvent was distilled off, and the obtained crude product was washed with water and acetone to obtain 0.22 part of a compound represented by the formula (I-145).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+709.7
Exact Mass (Exact Mass): +708.3
(Synthesis example 21)
62 parts of monomethyl 2, 2-dimethyl-malonate (Alfa chemistry product) was dissolved in 413 parts of dichloromethane (a kanto chemistry product), and 5 parts of dimethylformamide (a kanto chemistry product) and 81 parts of oxalyl chloride (a tokyo chemical industry product) were added dropwise while stirring and cooling to 0 ℃. Thereafter, the temperature was raised to 23 ℃ and the mixture was stirred for 1 hour. After the completion of the reaction, the reaction mixture was concentrated to obtain 54 parts of the compound represented by the formula (1-26).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+165.1
Exact Mass (Exact Mass): +164.0
(Synthesis example 22)
46 parts of 2,4, 6-trimethylaniline (Tokyo chemical industry Co., Ltd.) was dissolved in 219 parts of dimethylformamide (Kanto chemical industry Co., Ltd.). While the solution was stirred at 23 ℃, 50.4 parts of the compound represented by the above formula (1-26) was added dropwise. After the completion of the dropwise addition, the mixture was stirred for 1 hour. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain 46 parts of a crude product containing the compound represented by the following formula (1-27). This crude product was purified by silica gel column chromatography to obtain 40 parts of a compound represented by the formula (1-27).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+264.1
Exact Mass (Exact Mass): +263.2
(Synthesis example 23)
14.4 parts of lithium aluminum hydride (powder) (Tokyo chemical industry Co., Ltd.) was added to 40 parts of dimethyl ether (Kanto chemical Co., Ltd.) and stirred. The mixed solution was cooled to 0 ℃. On the other hand, 10 parts of the compound represented by the above formula (1-27) was added to 40 parts of dimethyl ether (manufactured by Kanto chemical Co., Ltd.), and the mixture was dissolved by stirring. This solution containing the compound represented by formula (1-27) was added dropwise to the solution containing the lithium aluminum hydride (powder) over 15 minutes while cooling to 0 ℃ and stirring. Thereafter, the temperature was slowly raised to 80 ℃ and reacted at 80 ℃ for 3 days. After the reaction was completed, the reaction mixture was poured into 200 parts of water, extracted with water and toluene, and concentrated to obtain 7.0 parts of a crude product. This crude product was purified by silica gel column chromatography to obtain 2.9 parts of a compound represented by the formula (1-28).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+222.1
Exact Mass (Exact Mass): +221.2
(Synthesis example 24)
7.8 parts of the compound represented by the formula (1-28) was dissolved in 108 parts of methylene chloride (a product of Kanto Chemicals Co., Ltd.), and 3.6 parts of imidazole (a product of Tokyo Kasei Kogyo Co., Ltd.) and 6.4 parts of t-butyldimethylsilyl chloride (a product of Tokyo Kasei Kogyo Co., Ltd.) were added thereto while stirring and cooling to 0 ℃. The temperature was raised to 23 ℃ and further stirred for 16 hours. After the reaction was completed, an extraction operation was performed using water and an organic solvent to obtain 7.8 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 7.2 parts of a compound represented by the formula (1-29).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+336.4
Exact Mass (Exact Mass): +335.3
(Synthesis example 25)
50 parts of m-bromophenol (tokyo chemical industry co., ltd.) and 30 parts of imidazole (tokyo chemical industry co., ltd.) were dissolved in 500 parts of methylene chloride (tokyo chemical industry co., ltd.) and cooled to 0 ℃, and 48 parts of t-butyldimethylchlorosilane (tokyo chemical industry co., ltd.) was added dropwise thereto. After the end of the dropwise addition, the temperature was raised to 23 ℃ and the mixture was stirred for 16 hours. After the reaction, the organic layer was extracted with water, the solvent was concentrated, and the extract was separated and purified by silica gel column chromatography to obtain 74 parts of a compound represented by formula (1-10).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+287.0
Exact Mass (Exact Mass): +286.0
(Synthesis example 26)
20 parts of the compound represented by the formula (1-10) was charged into 31 parts of 1, 4-bisAlkane (Kanto chemical Co., Ltd.) and dissolved therein. Further, to the solution were mixed 3.2 parts of N, N-dimethylethylenediamine (tokyo chemical industry products), 20.9 parts of sodium iodide (tokyo chemical industry products), and 2.7 parts of copper (I) iodide (fuji film and Wako pure chemical industries products). It was put into a pressurized vessel and reacted at 120 ℃ for 6 hours. After the reaction was completed, extraction was performed with water and a toluene solvent and concentrated to obtain 20 parts of a crude product. This crude product was purified by silica gel column chromatography to obtain 10.5 parts of a compound represented by the formula (1-30).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+335.1
Exact Mass (Exact Mass): +334.0
(Synthesis example 27)
9.6 parts of the compound represented by the formula (1-29) and 9.6 parts of the compound represented by the formula (1-30) were charged into 84 parts of a nailBenzene (manufactured by Kanto chemical Co., Ltd.) was dissolved in the solvent. To the solution were added 6.8 parts of sodium t-butoxide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 0.4 part of tri-t-butylphosphorTetrafluoroborate (manufactured by Tokyo chemical industry Co., Ltd.) and 0.52 part of tris (dibenzylideneacetone) dipalladium (0) (manufactured by Tokyo chemical industry Co., Ltd.) were dissolved. The mixed solution was subjected to microwave irradiation and reacted at 140 ℃ for 1 hour. Thereafter, the solvent was distilled off under reduced pressure, water was added to conduct an extraction operation using an organic solvent, and the solvent was distilled off to obtain 9.6 parts of a crude product. This crude product was separated and purified by silica gel column chromatography to obtain 1.8 parts of a crude product containing the compound represented by formula (1-31) (hereinafter, sometimes referred to as crude product (1-31)).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+542.4
Exact Mass (Exact Mass): +541.4
(Synthesis example 28)
1.8 parts of the crude product (1-31) was dissolved in 17.8 parts of tetrahydrofuran (a product of Kanto Chemicals), cooled to 0 ℃ and then 9.2 parts of a 1M tetrahydrofuran solution of tetrabutylammonium fluoride (Tokyo chemical Co., Ltd.) was added dropwise thereto, and after completion of the addition, the mixture was stirred at 23 ℃ for 16 hours. After completion of the reaction, water was added, tetrahydrofuran was distilled off, and the obtained crude product was subjected to an extraction operation with an organic solvent and concentrated to obtain 1.4 parts of a crude product of the compound represented by the formula (1-32). The crude product thus obtained was separated and purified by column chromatography to obtain 0.76 parts of a compound represented by the formula (1-32).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+314.2
Exact Mass (Exact Mass): +313.2
(example 7)
0.4 part of the compound represented by the formula (1-32) and 0.072 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji film and Wako pure chemical industries, Ltd.) were dissolved in 14 parts of toluene (Kanto chemical Co., Ltd.) and 3.24 parts of n-butanol (Kanto chemical Co., Ltd.) and heated while stirring at 140 ℃ for 3 hours. After completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 0.25 part of the compound represented by the formula (I-87).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+705.8
Exact Mass (Exact Mass): +704.4
(Synthesis example 29)
45 parts of 4-amino-3, 5-xylenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 400 parts of tetrahydrofuran (manufactured by Kanto Kasei Kogyo Co., Ltd.). To the solution, 127 parts of di-tert-butyl dicarbonate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added and dissolved. The reaction was stirred at 23 ℃ for 16 hours. After the reaction was completed, the solvent was distilled off to obtain 51 parts of a crude product. The obtained crude product was purified by stirring at 23 ℃ for 2 hours in a mixed solvent of 90 parts of ethyl acetate (manufactured by KANTO CHEMICAL CO., LTD.) and 272 parts of n-hexane (manufactured by KANTO CHEMICAL CO., LTD.), to obtain 47 parts of a compound represented by the formula (1-33).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+238.3
Exact Mass (Exact Mass): +237.1
(Synthesis example 30)
20 parts of 2-bromoethanol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 333 parts of methylene chloride (manufactured by Kanto Kasei Kogyo Co., Ltd.). To this solution, 32.4 parts of triethylamine (a product of kanto chemical corporation) and 0.156 part of 4-dimethylaminopyridine (a product of kanto chemical corporation) were added, and 28.95 parts of tert-butyldimethylsilyl chloride (a product of tokyo chemical industry) was added and dissolved while stirring. The reaction was stirred at 23 ℃ for 16 hours. The solvent was distilled off to obtain 20 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 20 parts of a compound represented by the formula (1-34).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+239.1
Exact Mass (Exact Mass): +238.0
(Synthesis example 31)
47 parts of the compound represented by the formula (1-33) was dissolved in 141.5 parts of the bromine compound represented by the formula (1-34) and 447 parts of dimethylformamide (Kanto chemical Co., Ltd.). 138.2 parts of potassium carbonate (manufactured by Kanto chemical Co., Ltd.) was added to the solution, and the reaction was stirred at 70 ℃ for 16 hours. After the reaction was completed, the solvent was distilled off, and an extraction operation was performed using an organic solvent to obtain 49 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 41 parts of a compound represented by the formula (1-35).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H-t-Bu+]+339.2
Exact Mass (Exact Mass): +395.3
(Synthesis example 32)
41 parts of a compound represented by the formula (1-35) was dissolved in 424 parts of 1, 4-bisTo an alkane (a product of Kanto Kabushiki Kaisha) was added 263 parts of hydrogen chloride (about 4 mol/L1, 4-bis)Alkane solution) (Tokyo chemical industry products), stirred at 23 ℃ for 1 hour and deprotected. After the reaction was completed, the solvent was distilled off to obtain 36 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 22 parts of a compound represented by the formula (1-36).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+182.2
Exact Mass (Exact Mass): +181.1
(Synthesis example 33)
22 parts of the compound represented by the formula (1-36) was dissolved in 293 parts of methylene chloride (manufactured by Kanto chemical Co., Ltd.). To this solution, 10.8 parts of imidazole (manufactured by Kanto chemical Co., Ltd.) and 22 parts of t-butyldimethylsilyl chloride (manufactured by Tokyo chemical Co., Ltd.) were added and dissolved. The reaction was stirred at 23 ℃ for 16 hours. The solvent was distilled off to obtain 23 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 20 parts of a compound represented by formula (1-37).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+296.3
Exact Mass (Exact Mass): +295.2
(Synthesis example 34)
15 parts of the compound represented by the formula (1-10) was dissolved in 14.5 parts of the compound represented by the formula (1-37) and 130 parts of toluene (a product of kanto chemical corporation), and 5.7 parts of potassium hydroxide (a product of kanto chemical corporation), 15 parts of water, 2 parts of tetrabutylammonium bromide (a product of tokyo chemical industry), and 0.26 part of bis (tri-tert-butylphosphino) palladium (0) (a product of tokyo chemical industry) were mixed in the solution. After heating to 90 ℃ and stirring for 20 minutes, an organic layer was obtained by extraction, and the solvent was distilled off to obtain 15 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 12 parts of a compound represented by the formula (1-38).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+502.4
Exact Mass (Exact Mass): +501.3
(Synthesis example 35)
12 parts of the compound represented by the formula (1-38), 11.9 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo Kasei Co., Ltd.) and 41.6 parts of toluene (manufactured by Kanto Kasei Co., Ltd.) were mixed, and the mixture was heated while stirring at 90 ℃ for 1 hour. After the completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by column chromatography to obtain 5.9 parts of a compound represented by formula (1-39).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+616.3
Exact Mass (Exact Mass): +615.3
(Synthesis example 36)
5.9 parts of the compound represented by the formula (1-39) was dissolved in 52.4 parts of tetrahydrofuran (a product of Kanto chemical Co., Ltd.), the solution was cooled to 0 ℃ and 11 parts of a 1M tetrahydrofuran solution of tetrabutylammonium fluoride (Tokyo chemical Co., Ltd.) was added dropwise thereto, and after completion of the addition, the mixture was stirred at 23 ℃ for 2 hours. After the reaction was completed, water was added, the tetrahydrofuran solvent was distilled off, and the obtained crude product was subjected to an extraction operation with an organic solvent, followed by concentration to obtain 4.3 parts of a compound represented by formula (1-40).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+388.2
Exact Mass (Exact Mass): +387.2
(Synthesis example 37)
4.3 parts of the compound represented by the formula (1-40), 56.4 parts of a borane-1M tetrahydrofuran solution (manufactured by KANTO CHEMICAL CO., LTD.), and 38.2 parts of tetrahydrofuran (manufactured by KANTO CHEMICAL CO., LTD.) were mixed at 0 ℃ and heated to 23 ℃ and stirred for 16 hours. After the reaction is finished, water is added for quenching, and organic solvent is used for extraction. The solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography to obtain 2.3 parts of a compound represented by the formula (1-41).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+346.3
Exact Mass (Exact Mass): +345.2
(example 8)
2.3 parts of the compound represented by the formula (1-41) and 0.38 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji film and Wako pure chemical industries, Ltd.) were dissolved in 80 parts of toluene (Kanto chemical industries, Ltd.) and 19 parts of n-butanol (Kanto chemical industries, Ltd.) and heated while stirring at 120 ℃ for 4 hours. After completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 1.3 parts of a compound represented by the formula (II-135).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+769.8
Exact Mass (Exact Mass): +768.4
(Synthesis example 38)
100 parts of 3-iodoanisole (a product of Tokyo chemical industry Co., Ltd.) and 85.5 parts of 4-bromo-2, 6-dimethylaniline (a product of Tokyo chemical industry Co., Ltd.) were dissolved in a mixed solvent of 72 parts of water and 867 parts of toluene (a product of Kanto chemical industry Co., Ltd.). While stirring the solution at 23 ℃, 48 parts of potassium hydroxide (a product of Kanto chemical Co., Ltd.), 5 parts of tetrabutylammonium bromide (a product of Tokyo chemical industry Co., Ltd.), and 2.2 parts of bis (tri-tert-butylphosphine) palladium (0) (a product of Tokyo chemical industry Co., Ltd.) were charged. The mixed solution was warmed to 90 ℃ and reacted for 16 hours. After the reaction was completed, extraction was performed with water and a toluene solvent and concentrated to obtain 96.8 parts of a crude product. This crude product was purified by silica gel column chromatography to obtain 60.2 parts of a compound represented by the formula (1-42).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+306.0
Exact Mass (Exact Mass): +305.0
(Synthesis example 39)
60 parts of the compound represented by the formula (1-42) and 29.5 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo Kasei Co., Ltd.) were dissolved in 520 parts of toluene (manufactured by Kanto Kasei Co., Ltd.) at 23 ℃ and reacted at 100 ℃ for 16 hours. After the reaction, an extraction operation was performed using a water-toluene solvent, and after concentration, 64.2 parts of a crude product was obtained. This crude product was purified by silica gel column chromatography to obtain 55.1 parts of a compound represented by the formula (1-43).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+419.9
Exact Mass (Exact Mass): +419.1
(Synthesis example 40)
55 parts of the compound represented by the formula (1-43) was dissolved in 732 parts of methylene chloride (a product of Kanto chemical Co., Ltd.), and the mixture was cooled to 0 ℃ while stirring. 197 parts of boron tribromide (fuji film and Wako pure chemical industries, Ltd.) was added dropwise while stirring. Stirred at 23 ℃ for 3 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and a water-organic solvent extraction operation was performed to obtain 47.3 parts of a mixture containing 66% of the compound represented by the following formula (1-44) and 23% of the compound represented by the following formula (1-45).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+392.1
Exact Mass (Exact Mass): +391.0
(Synthesis example 41)
A solution prepared by dissolving 37.9 parts of thionyl chloride (manufactured by tokyo chemical industries, ltd.) in 377 parts of methanol (manufactured by kanto chemical industries, ltd.) was cooled to 0 ℃. The temperature was raised to 23 ℃ and the reaction was carried out for 16 hours. The solvent was distilled off under reduced pressure to obtain 45.4 parts of a crude product containing the compound represented by the formula (1-45). The obtained crude product was purified by silica gel column chromatography to obtain 40.2 parts of a compound represented by the formula (1-45).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+406.1
Exact Mass (Exact Mass): +405.1
(Synthesis example 42)
40 parts of the compound represented by the formula (1-45) was dissolved in 355 parts of tetrahydrofuran (a product of Kanto chemical Co., Ltd.) and stirred. It is cooled to 0 ℃ and 442 parts of borane-1M tetrahydrofuran solution (manufactured by Kanto Chemicals) are added dropwise. After the completion of the dropwise addition, the temperature was raised to 10 ℃ and the mixture was stirred for 3 hours, then water was added to extract the mixture to obtain an organic layer, and the solvent was distilled off to obtain 37.3 parts of a compound represented by the formula (1-46).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+364.1
Exact Mass (Exact Mass): +363.08
(Synthesis example 43)
32 parts of the compound represented by the formula (1-46) was dissolved in 638 parts of methylene chloride (a product of Kanto Chemicals Co., Ltd.), and 17.9 parts of imidazole (a product of Tokyo chemical industry Co., Ltd.) and 29.1 parts of t-butyldimethylchlorosilane (a product of Tokyo chemical industry Co., Ltd.) were added thereto while stirring them while cooling to 0 ℃. The temperature was raised to 23 ℃ and the mixture was further stirred for 16 hours to effect silylation. After the reaction was completed, an extraction operation was performed using water and an organic solvent to obtain 45.8 parts of a crude product. The crude product thus obtained was separated and purified by column chromatography to obtain 40.9 parts of a compound represented by the formula (1-47).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+592.3
Exact Mass (Exact Mass): +591.3
(Synthesis example 44)
20 parts of the compound represented by the formula (1-47) and 29 parts of methyl acrylate (manufactured by Tokyo chemical industry Co., Ltd.) were dissolved in 475 parts of dimethylformamide (manufactured by Kanto chemical Co., Ltd.). To the solution, 26.2 parts of diisopropylethylamine (tokyo chemical industry co., ltd.), 2.05 parts of tri (o-tolyl) phosphine (tokyo chemical industry co., ltd.), and 0.758 parts of palladium (II) acetate (tokyo chemical industry co., ltd.) were added, and the mixture was stirred at 23 ℃ for 30 minutes. The temperature was raised to 140 ℃ and the reaction was carried out by stirring for 32 hours. Here, 14.5 parts of methyl acrylate (tokyo chemical industry co., ltd.) and 26.2 parts of diisopropylethylamine (tokyo chemical industry co., ltd.) were additionally charged. Further, the reaction was carried out at 140 ℃ for 2 days. Thereafter, the solvent was distilled off under reduced pressure, water was added to the reaction solution, an extraction operation was performed using an organic solvent, and the solvent was distilled off to obtain 17.2 parts of a crude product (hereinafter, sometimes referred to as a crude product (1 to 48)). The crude product contained 40% of the compound represented by the formula (1-48-1) and 40% of the compound represented by the formula (1-48-2).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+484.5
Exact Mass (Exact Mass): +483.3
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+598.3
Exact Mass (Exact Mass): +597.4
(Synthesis example 45)
17.2 parts of the crude product (1-48) was dissolved in 155.4 parts of tetrahydrofuran (a product of Kanto Chemicals), cooled to 0 ℃ and then 62.6 parts of a 1M tetrahydrofuran solution of tetrabutylammonium fluoride (Tokyo chemical Co., Ltd.) was added dropwise thereto, and after completion of the addition, the mixture was stirred at 23 ℃ for 16 hours. After the reaction was completed, water was added, the tetrahydrofuran solvent was distilled off, and the obtained crude product was subjected to an extraction operation with an organic solvent, followed by concentration to obtain 13.72 parts of a crude product of the compound represented by formula (1-49). The crude product thus obtained was separated and purified by column chromatography to obtain 8.1 parts of a compound represented by the formula (1-49).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+370.2
Exact Mass (Exact Mass): +369.2
(Synthesis example 46)
6.87 parts of the compound represented by the formula (1-49) was dissolved in 59.5 parts of methanol (manufactured by Kanto chemical Co., Ltd.), and 0.69 part of palladium/carbon (Pd 10%) (Fuji film and Wako pure chemical industries, Ltd.) was fed under a normal pressure hydrogen flow and stirred at 23 ℃ for 16 hours. After completion of the reaction, the reaction mixture was filtered, and the solvent was distilled off to obtain 5.49 parts of a crude product. The crude product thus obtained was separated and purified by column chromatography to obtain 4.26 parts of a compound represented by the formula (1-50).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+372.1
Exact Mass (Exact Mass): +371.2
(Synthesis example 47)
4.2 parts of the compound represented by the formula (1-50), 2.85 parts of lithium hydroxide monohydrate (Fuji film and Wako pure chemical industries, Ltd.), 33.3 parts of methanol (Kanto chemical industries, Ltd.) and 37.3 parts of tetrahydrofuran (Kanto chemical industries, Ltd.), and 21 parts of water were mixed and stirred at 23 ℃ for 16 hours. After completion of the reaction, the solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography to obtain 3.11 parts of a compound represented by the formula (1-51).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+358.0
Exact Mass (Exact Mass): +357.2
(example 9)
3 parts of the compound represented by the formula (1-51) and 0.48 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji film and Wako pure chemical industries, Ltd.) were dissolved in 104 parts of toluene (Kanto chemical industries, Ltd.) and 24.3 parts of n-butanol (Kanto chemical industries, Ltd.) and heated while stirring at 120 ℃ for 4 hours. After the completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 0.70 part of the compound represented by the formula (II-129).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+793.7
Exact Mass (Exact Mass): +792.4
(Synthesis example 48)
100 parts of 1, 3-dimethoxybenzene (Tokyo chemical industry Co., Ltd.) was dissolved in 1330 parts of dichloromethane (Kanto chemical industry Co., Ltd.), and cooled to 0 ℃. While the solution was stirred, 463 parts of bromine (a product of tokyo chemical industry Co., Ltd.) was added dropwise. After the end of the dropwise addition, the temperature was raised to 23 ℃ and the mixture was stirred for 3 hours. After the reaction was completed, the reaction mixture was extracted with water and a methylene chloride solvent and concentrated to obtain 110 parts of a compound represented by the formula (1-52).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+295.0
Exact Mass (Exact Mass): +293.9
(Synthesis example 49)
25 parts of the compound represented by the formula (1-52) was dissolved in 111 parts of tetrahydrofuran (a product of Kanto Chemicals Co., Ltd.), and 234.2 parts of a 2.5M hexane solution of n-butyllithium (Aldrich, Co., Ltd.) was added dropwise while cooling to-78 ℃ and stirring. After the charging, the mixture was stirred for 45 minutes while maintaining the temperature at-78 ℃ and 156 parts of methyl iodide (a product of Tokyo chemical industry Co., Ltd.) was added dropwise while maintaining the temperature and cooling the mixture to-78 ℃. After the addition, the temperature was raised to 23 ℃ and the mixture was stirred for 5 hours. After the reaction, the reaction mixture was gradually poured into 500 parts of ice water. Thereafter, an extraction operation was performed using a water-toluene solvent, and after concentration, 21 parts of a crude product was obtained. This crude product was purified by silica gel column chromatography to obtain 17 parts of a compound represented by the formula (1-53).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+167.1
Exact Mass (Exact Mass): +166.1
(Synthesis example 50)
13.5 parts of the compound represented by the formula (1-53) was dissolved in 200 parts of methylene chloride (manufactured by Kanto chemical Co., Ltd.), and the mixture was cooled to 0 ℃ while stirring. While stirring, 65 parts of bromine (a product of Tokyo chemical industry Co., Ltd.) was added dropwise. Thereafter, the temperature was raised to 23 ℃ and the mixture was stirred for 16 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and a water-dichloromethane solvent extraction operation was performed to obtain 21 parts of a crude product containing the compound represented by formula (1-54). The obtained crude product was purified by silica gel column chromatography to obtain 15 parts of a compound represented by the formula (1-54).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+323.0
Exact Mass (Exact Mass): +321.9
(Synthesis example 51)
14 parts of the compound represented by the formula (1-54) was dissolved in 124 parts of tetrahydrofuran (a product of Kanto chemical Co., Ltd.), and 22 parts of a 1.6M hexane solution of butyllithium (a product of Aldrich Co., Ltd.) was added dropwise while cooling to-78 ℃ and stirring. After the addition, the mixture was stirred for 1 hour while maintaining-78 ℃. Thereafter, 50 parts of water was added dropwise while stirring while maintaining the temperature at-78 ℃. Thereafter, an extraction operation was performed using a water-toluene solvent, and after concentration, 12.5 parts of a crude product containing the compound represented by the formula (1-55) was obtained. This crude product was purified by silica gel column chromatography to obtain 10.4 parts of a compound represented by the formula (1-55).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+245.1
Exact Mass (Exact Mass): +244.0
(Synthesis example 52)
10.4 parts of the compound represented by the formula (1-55) was dissolved in 200 parts of methylene chloride (manufactured by Kanto chemical Co., Ltd.), and the mixture was cooled to 0 ℃ while stirring. While stirring, 64 parts of boron tribromide (fuji film and Wako pure chemical industries, Ltd.) was added dropwise. Stirred at 23 ℃ for 3 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and a water-organic solvent extraction operation was performed to obtain 11 parts of a crude product containing the compound represented by formula (1-56). The obtained crude product was purified by silica gel column chromatography to obtain 8.9 parts of a compound represented by the formula (1-56).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+217.0
Exact Mass (Exact Mass): +216.0
(Synthesis example 53)
8.9 parts of the compound represented by the formula (1-56) was dissolved in 50 parts of dimethylformamide (a product of Kanto Chemicals), and 28.3 parts of potassium carbonate (a product of Kanto Chemicals) was added thereto while stirring the solution. Further, 29.4 parts of (2-bromoethoxy) -tert-butyldimethylsilane (product of Aldrich Co., Ltd.) was charged. The solution was warmed to 70 ℃ and stirred for 16 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and a water-organic solvent extraction operation was performed to obtain 20.6 parts of a crude product containing the compound represented by the formula (1-57). The obtained crude product was purified by silica gel column chromatography to obtain 15.7 parts of a compound represented by the formula (1-57).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+533.2
Exact Mass (Exact Mass): +532.2
(Synthesis example 54)
25 parts of 3-aminophenol (a product of Tokyo chemical industry Co., Ltd.) was dissolved in 333 parts of methylene chloride (a product of Kanto chemical Co., Ltd.), and the mixture was cooled to 0 ℃ while stirring. While the solution was stirred at 0 ℃, 20.3 parts of imidazole (tokyo chemical industry products) and 41.4 parts of tert-butyldimethylsilyl chloride (tokyo chemical industry products) were added. Thereafter, the temperature was raised to 23 ℃ and the mixture was stirred for 16 hours. After the reaction was completed, a water-organic solvent extraction operation was performed to obtain 48 parts of a crude product containing the compound represented by the formula (1-58). The obtained crude product was purified by silica gel column chromatography to obtain 42 parts of a compound represented by the formula (1-58).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+224.1
Exact Mass (Exact Mass): +223.1
(Synthesis example 55)
12.9 parts of the compound represented by the formula (1-57) and 4.5 parts of the compound represented by the formula (1-58) were dissolved in 312 parts of toluene (manufactured by Kanto Chemicals Co., Ltd.). To this solution, 18 parts of water were added, and while stirring, 3.4 parts of potassium hydroxide (a product of kanto chemical corporation), 0.5 part of tetrabutylammonium bromide (a product of tokyo chemical corporation), and 0.51 part of bis (tri-tert-butylphosphine) palladium (0) (a product of tokyo chemical corporation) were added, and the mixture was stirred at 23 ℃ for 30 minutes. Thereafter, the temperature was raised to 105 ℃ and the reaction was carried out for 3 hours. Thereafter, water was added, an extraction operation was performed using an organic solvent, and the solvent was distilled off to obtain 12.8 parts of a crude product. The obtained crude product was purified by silica gel column chromatography to obtain 10.2 parts of a compound represented by the formula (1-59).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+676.4
Exact Mass (Exact Mass): +675.4
(Synthesis example 56)
10 parts of the compound represented by the formula (1-59) and 2.7 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo Kasei Co., Ltd.) were dissolved in 87 parts of toluene (manufactured by Kanto Kasei Co., Ltd.) at 23 ℃ and reacted at 105 ℃ for 16 hours. After the reaction was completed, an extraction operation was performed using a water-toluene solvent, and after concentration, 10.3 parts of a crude product containing the compound represented by the formula (1-60) was obtained.
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+790.4
Exact Mass (Exact Mass): +789.5
(Synthesis example 57)
10 parts of the crude product containing the compound represented by the formula (1-60) was dissolved in 26.6 parts of tetrahydrofuran (a product of Kanto chemical Co., Ltd.), cooled to 0 ℃ and then 47.4 parts of a 1M tetrahydrofuran solution of tetrabutylammonium fluoride (Tokyo chemical Co., Ltd.) was added dropwise thereto, and after completion of the addition, the mixture was stirred at 23 ℃ for 16 hours. After the reaction was completed, water was added, the tetrahydrofuran solvent was distilled off, and the obtained crude product was subjected to an extraction operation with an organic solvent, followed by concentration to obtain 7.87 parts of a crude product of the compound represented by formula (1-61). The crude product thus obtained was separated and purified by column chromatography to obtain 4.1 parts of a compound represented by the formula (1-61).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+448.3
Exact Mass (Exact Mass): +447.2
(Synthesis example 58)
4 parts of the compound represented by the formula (1-61) was dissolved in 36 parts of tetrahydrofuran (a product of Kanto chemical Co., Ltd.) and stirred. It is cooled to 0 ℃ and 39.2 parts of borane-1M tetrahydrofuran solution (manufactured by Kanto Chemicals) are added dropwise. After the completion of the dropwise addition, the temperature was raised to 23 ℃ and the mixture was stirred for 5 hours, water was added to obtain an organic layer by extraction, and the solvent was distilled off to obtain 3.54 parts of a crude product containing the compound represented by the formula (1-62). The crude product thus obtained was separated and purified by column chromatography to obtain 2.5 parts of a compound represented by the formula (1-62).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+406.2
Exact Mass (Exact Mass): +405.2
(example 10)
2.5 parts of the compound represented by the formula (1-62) and 0.70 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji film and Wako pure chemical industries, Ltd.) were dissolved in 108.4 parts of toluene (manufactured by Kanto chemical Co., Ltd.) and 40.5 parts of n-butanol (manufactured by Kanto chemical Co., Ltd.) and heated while stirring at 120 ℃ for 16 hours. After the completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 1.81 parts of a compound represented by formula (II-138).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+889.8
Exact Mass (Exact Mass): +888.4
(Synthesis example 59)
10 parts of 2- (1-adamantyl) -4-bromoanisole (tokyo chemical industry product), 4 parts of 3-aminobenzyl ether (tokyo chemical industry product), 0.35 part of palladium acetate (tokyo chemical industry product), 0.90 part of 4,5 '-bis (diphenylphosphino) -9,9' -dimethylxanthene (tokyo chemical industry product), and 6 parts of sodium tert-butoxide (tokyo chemical industry product) were dissolved in 180 parts of toluene (guanto chemical product) and heated and refluxed at 105 ℃ for 2 hours. After the reaction was completed, water was added, the organic layer was extracted, and concentration was performed to obtain 25 parts of the compound represented by formula (1-63).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+364.5
Exact Mass (Exact Mass): +363.2
(Synthesis example 60)
8 parts of the compound represented by the formula (1-63) and 11 parts of succinic acid monoethyl ester chloride (manufactured by Tokyo chemical industry Co., Ltd.) were dissolved in 160 parts of toluene (manufactured by Kanto chemical Co., Ltd.), and heated to 90 ℃. After the completion of the reaction, the solvent was concentrated, and the mixture was separated and purified by column chromatography to obtain 8 parts of a compound represented by formula (1-64).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+492.3
Exact Mass (Exact Mass): +491.3
(Synthesis example 61)
8 parts of the compound represented by the formula (1-64) was dissolved in 150 parts of methylene chloride (manufactured by Kanto chemical Co., Ltd.), and added to 195 parts of boron tribromide (Fuji film and Wako pure chemical industries, Ltd.) and stirred. After the reaction was completed, the reaction mixture was poured into 200 parts of water, extracted with an ethyl acetate solvent, and concentrated to obtain 12 parts of a compound represented by formula (1-65).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+464.0
Exact Mass (Exact Mass): +463.2
(Synthesis example 62)
12 parts of the compound represented by the formula (1-65) was dissolved in 70 parts of dehydrated tetrahydrofuran (manufactured by KANTO CHEMICAL CO., LTD.), and 117 parts of borane-1M tetrahydrofuran solution (manufactured by KANTO CHEMICAL CO., LTD.) was added thereto while stirring and cooling to 0 ℃. After the temperature was raised to 23 ℃ and further stirred for 16 hours, water was added thereto for quenching, the organic solvent was concentrated, and the obtained crude product was separated and purified by column chromatography to obtain 2.5 parts of a compound represented by the formula (1-66).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+408.0
Exact Mass (Exact Mass): +407.3
(example 11)
2.5 parts of the compound represented by the formula (1-66) and 0.32 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji film and Wako pure chemical industries, Ltd.) were dissolved in 8 parts of toluene (Kanto chemical industries, Ltd.) and 10 parts of n-butanol (Kanto chemical industries, Ltd.) and heated while stirring at 110 ℃ for 2 hours. After the completion of the reaction, the solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography to obtain 0.5 part of the compound represented by formula (II-372).
And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]+893.0
Exact Mass (Exact Mass): +892.5
(resin Synthesis example 1)
An appropriate amount of nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was replaced with nitrogen gas, and 280 parts of propylene glycol monomethyl ether acetate was added thereto and heated to 80 ℃ while stirring. Then, 38 parts of acrylic acid and 289 parts of acrylic acid-3, 4-epoxytricyclo [5.2.1.0 ] are added dropwise over a period of 5 hours2,6]Decan-8-yl ester and 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid2,6]A mixture of decane-9-yl ester (mixing ratio 1:1), 125 parts of propylene glycol monomethyl ether acetate. On the other hand, a mixed solution of 33 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the flask was kept at 80 ℃ for 4 hours, and then cooled at room temperature to obtain a B-type copolymer (resin (B-1)) solution having a viscosity (23 ℃) of 125 mPas and a solid content of 35.1%. The weight-average molecular weight Mw of the resulting copolymer was 9200, the dispersity was 2.08, and the acid value of the solid portion was 77 mg-KOH/g. The resin (B-1) has the following structural unit.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin in terms of polystyrene were measured by GPC under the following conditions.
The device comprises the following steps: HLC-8120GPC (TOSOH CORPORATION product)
Column: TSK-GELG2000HXL
Column temperature: 40 deg.C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0mL/min
Concentration of solid component in liquid to be tested: 0.001 to 0.01% by mass
Injection amount: 50 μ L
A detector: RI (Ri)
Calibration standard substance: TSK STANDARD POLYSTYRENE (STANDARD POLYSTYRENE) F-40, F-4, F-288, A-2500, A-500 (Tosoh products)
The ratio (Mw/Mn) of the weight average molecular weight to the number average molecular weight in terms of polystyrene obtained above was defined as the degree of dispersion.
Examples 12 to 22 and comparative example 1
[ preparation of colored resin composition ]
The respective components were mixed so as to have the compositions shown in table 13, thereby obtaining colored resin compositions.
[ Table 13]
In table 13, each component represents the following compound.
Colorant (A-1): a compound represented by the formula (I-147)
Colorant (a-2): a compound represented by the formula (I-27)
Colorant (a-3): a compound represented by the formula (I-150)
Colorant (a-4): a compound represented by the formula (I-171)
Colorant (a-5): a compound represented by the formula (I-177)
Colorant (a-6): a compound represented by the formula (I-145)
Colorant (a-7): a compound represented by the formula (I-87)
Colorant (a-8): a compound represented by the formula (II-135)
Colorant (a-9): a compound represented by the formula (II-129)
Colorant (a-10): a compound represented by the formula (II-138)
Colorant (a-11): a compound represented by the formula (II-372)
Colorant (a-x): a compound represented by the formula (x)
Resin (B-1): resin (B-1) (conversion of solid content)
Solvent (E-1): propylene glycol monomethyl ether acetate
Solvent (E-2): diacetone alcohol
Solvent (E-3): n-methylpyrrolidinone
Solvent (E-4): chloroform
Leveling agent (F-1): polyether modified SILICONE oil (Donglidao kangning product "TORAY SILICONE SH 8400")
< production of color Filter (colored coating film) 1 >
A colored resin composition was applied to a 5cm square glass substrate (Eagle 2000; product of Corning corporation) by spin coating, and then baked (pre-cake) at 100 ℃ for 3 minutes to obtain a colored coating film.
< determination of color >
The chromaticity of the colored coating film was determined as xy chromaticity coordinates (x, Y) and stimulus value Y in the CIE XYZ color system based on the spectral distribution measured by a colorimeter (OSP-SP-200; product of Olympus, Inc.) and the characteristic function of a C light source.
< evaluation of Heat resistance >
The resulting colored coating film was heated in an oven at 230 ℃ for 2 hours.
The measurement of the color before and after heating was carried out, and the color was measured according to the measurement value as described in JIS Z8730: 2009(7. method for calculating color difference) the color difference Δ Eab was calculated by the method described above, and the results are shown in table 14. A smaller Δ Eab means a smaller color change. Further, if the heat resistance of the colored coating film is good, the heat resistance of a colored pattern made of the same colored resin composition can also be said to be good.
< evaluation of light resistance >
An ultraviolet cut filter (color OPTICAL GLASS (L38; product of HOYA CORPORATION; cut off at a wavelength of 380nm or less) was placed on the obtained COLORED coating film, and a xenon lamp was irradiated from the upper surface thereof for 48 hours using a light resistance tester (SUNTEST CPS +: product of Toyo Seiki Seisaku-sho, Ltd.).
The chromaticity was measured before and after irradiation, and the measured value was measured according to JIS Z8730: 2009(7. method for calculating color difference) the color difference Δ Eab was calculated by the method described above, and the results are shown in table 14. A smaller Δ Eab means a smaller color change. As shown in table 14, examples 12 to 22 were excellent not only in heat resistance but also in light resistance.
[ Table 14]
[ examples 23 to 33]
[ preparation of colored resin composition ]
The respective components were mixed so as to have the compositions shown in table 15, to obtain colored resin compositions.
[ Table 15]
In table 15, each component represents the following compound.
Polymerizable compound (C-1): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Nippon Kayaku Co., Ltd.; product of Japan chemical Co., Ltd.)
Polymerization initiator (D-1): n-acetyloxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine (PBG-327; oxime compound; product of Changzhou Strong New Electron Materials Co., Ltd.)
The other symbols represent the same meanings as described above.
< production of color Filter (colored coating film) 2 and evaluation of Heat resistance >
A colored resin composition was applied to a 5cm square glass substrate (Eagle 2000; product of Corning corporation) by spin coating, and then prebaked at 100 ℃ for 3 minutes to form a colored composition layer. After standing and cooling, an exposure machine (TME-150 RSK; Topcon CORPORATION, manufactured by Topcon CORPORATION) was used at 100mJ/cm in the atmospheric environment2The exposure amount (365nm basis) of (b) is used for irradiating the colored composition layer formed on the substrate with light. After the light irradiation, post baking (post bake) was performed at 230 ℃ for 30 minutes in an oven to obtain a colored coating film.
The measurement of the chromaticity was carried out before and after the postbaking, and based on the measurement value, the following measurement was carried out in accordance with JIS Z8730: 2009(7. method for calculating color difference) the color difference Δ Eab was calculated by the method described above, and the results are shown in table 16.
[ Table 16]
Industrial applicability
According to the compound of the present invention, a color filter having excellent heat resistance can be formed.
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