Ester compound

Abstract

To provide an internal donor component suitable for a solid titanium catalyst component capable of producing a propylene polymer having extremely high stereoregularity at a high productivity (high activity), when used mainly for solid titanium catalyst component.SOLUTION: The present invention provides an ester compound having a specific cyclic structure, specifically exemplified by the ester compound of the following formula (Compound 4).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to novel ester compounds. [Background technology]

[0002] As prior art related to ester compounds, there are many disclosures related to their use as additives such as resin additives, cosmetics and topical skin preparations, bactericidal compositions, antioxidants, chelating agents, etc. One of the known uses is that of Mg compound-supported titanium catalysts for olefin polymerization.

[0003] Olefin polymerization catalysts are one of the technologies that have made great advances since the discovery of the so-called Ziegler-Natta catalyst in 1953, when Ziegler reported that ethylene could be polymerized at low pressure by combining titanium tetrachloride with an organoaluminum compound, followed by Natta's report of the first propylene polymerization by combining titanium trichloride with a halogen-containing organoaluminum compound. Among them, it was discovered that a catalyst containing titanium tetrachloride, a magnesium compound, and a Lewis base, called the third generation catalyst, can achieve both high polymerization activity (high productivity) and high stereoregularity in propylene polymerization. This became one of the opportunities for propylene polymers (polypropylene) to spread around the world.

[0004] In addition, it has been found that Lewis bases (hereinafter also referred to as "internal donors"), which are one of the main components of the above-mentioned third-generation catalyst components (hereinafter also referred to as "solid titanium catalyst components"), have a significant effect on the catalytic performance, and various Lewis bases have been developed to date.

[0005] Examples of Lewis bases used in Ziegler-Natta catalysts include ethyl benzoate, phthalate esters, 1,3-diketones (Patent Document 1), malonate esters (Patent Document 2), succinate esters (Patent Document 3), 2,4-pentanediol diesters (Patent Document 4), naphthalenediol diesters (Patent Document 5), and catechol diesters (Patent Document 6). Even now, this is a field in which research and development is being actively conducted, primarily by private companies.

[0006] Furthermore, many methods have been disclosed for elementary reactions for synthesizing various ester compounds (for example, Patent Documents 7 to 11, Non-Patent Documents 1 to 19). [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2005-226076 A [Patent Document 2] Special Publication No. 2000-516987 [Patent Document 3] Special Publication No. 2002-542347 [Patent Document 4] Special Publication No. 2005-517746 [Patent Document 5] Special Publication No. 2011-529888 [Patent Document 6] Special Publication No. 2014-500390 [Patent Document 7] JP 2008-247796 A [Patent Document 8] International Publication No. 2008 / 062553 [Patent Document 9] US Patent Application Publication No. 2018 / 0149973 [Patent Document 10] US Patent Application Publication No. 2002 / 0162991 [Patent Document 11] JP 2008-037756 A [Non-patent literature]

[0008] [Non-licensed document 1] Journal of the American Chemical Society,1952,74,1027-1029

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Non-licensed literature 9

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Non-licensed Document 11

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Non-licensed Document 13

[0009] Propylene polymers have heat resistance and rigidity similar to those of general-purpose engineering plastics, while being composed almost entirely of carbon and hydrogen, and therefore have the advantage of producing less toxic gases even when burned.

[0010] Due to recent advances in molding technology, it is possible to achieve higher physical properties (rigidity, heat resistance, etc.) by using propylene polymers with higher stereoregularity than ever before. Therefore, the market demands propylene polymers with higher stereoregularity. In addition, from the viewpoints of resource conservation and environmental protection, there is also a demand for a method for producing propylene polymers with high productivity.

[0011] Therefore, an object of the present invention is to provide an internal donor component suitable for a solid titanium catalyst component, which can produce a propylene polymer with extremely high stereoregularity with high productivity (high activity) when used in the solid titanium catalyst component. [Means for solving the problem]

[0012] As a result of intensive research aimed at solving the above problems, the present inventors have found that an ester compound having a specific cyclic structure is suitable as, for example, a Lewis base for a solid titanium catalyst component, and have completed the present invention. The present invention relates to, for example, the following items [1] to

[28] .

[0013] [1] An ester compound represented by the following general formula (1):

[0014] [ka]

[0015] [In formula (1), R 1 ~R 24 R is independently a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 1 ~R 10 , R 23 and R 24 may be bonded to each other to form a ring, or adjacent substituents may be directly bonded to each other to form a multiple bond. 11 ~R 24 may be bonded to each other to form a ring, or adjacent substituents may be bonded to each other to form a multiple bond. 1 ~R 24 At least one pair of n2 to n5 are bonded to each other to form a ring structure. n2 to n5 each independently represent an integer of 0 to 2. n1 and n6 each independently represent an integer of 0 or 1. L 1 and L 2 are each independently a hydrocarbon group or a heteroatom-containing hydrocarbon group. [2] L 1 and L 2and each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a heteroatom-containing hydrocarbon group.

[0016] [3] L 1 and L 2 and each independently represent a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group. [4] The ester compound according to [1], represented by any one of the following general formulas (2) to (4):

[0017] [ka]

[0018] [In formulas (2) to (4), R 1 ~R 24 R is independently a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 1 ~R 10 , R 23 and R 24 may be bonded to each other to form a ring, or adjacent substituents may be directly bonded to each other to form a multiple bond. 11 ~R 24 may be bonded to each other to form a ring, or adjacent substituents may be bonded to each other to form a multiple bond. X and Y each independently represent a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. n2 to n5 each independently represent an integer of 0 to 2. n1 and n6 each independently represent an integer of 0 or 1. L 1 and L 2 are each independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group. [5] The ester compound according to [3] or [4], wherein n1 and n6 are 1, and n2 to n5 are all 0.

[0019] [6] The ester compound according to [1], represented by the following general formula (5) or (6):

[0020] [ka]

[0021] [In formula (5), R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group, R 4 and R 9 are each independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group; R 11 , R 15 , R 17 and R 21 R is independently a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 11 , R 15 , R 17 and R 21 may be bonded to each other to form a ring. X is a hydrocarbon group, a heteroatom or a heteroatom-containing hydrocarbon group. 1 and L 2 are each independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group.

[0022] [ka]

[0023] [In formula (6), R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group, R 4 , R 9 , R 11 , R 12 , R 15 ~R 18 , R 21 and R 22 R is independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 11 , R 12 , R 15 ~R 18 , R 21 and R 22may be bonded to each other to form a ring, or adjacent substituents may be bonded to each other to form a multiple bond. X is a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. 1 and L 2 are each independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group. [7] The ester compound according to [1], represented by the following general formula (7) or (8):

[0024] [ka]

[0025] [In formula (7), R 4 , R 9 , R 12 , R 15 ~R 18 and R 21 R is independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 15 ~R 18 may be bonded to each other to form a ring, or adjacent substituents may be bonded to each other to form a multiple bond. Y is a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. 1 and L 2 are each independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group.

[0026] [ka]

[0027] [In formula (8), R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group, R 3 , R 4 , R 9 , R 10 , R 12 , R 15 ~R 18 and R 21R is independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 15 ~R 18 may be bonded to each other to form a ring, or adjacent substituents may be bonded to each other to form a multiple bond. Y is a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. 1 and L 2 are each independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group. [8] The ester compound according to [1], represented by the following general formula (9):

[0028] [ka]

[0029] [In formula (9), R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group, R 4 , R 9 , R 12 , R 15 ~R 18 and R 21 R is independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 15 ~R 18 may be bonded to each other to form a ring, or adjacent substituents may be bonded to each other to form a multiple bond. X and Y are each independently a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. 1 and L 2 are each independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group. [9] The ester compound according to [1], represented by the following general formula (31):

[0030] [ka]

[0031] [In formula (31), R 31 ~R 34are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group; R 4 , R 9 , R 21 and R 22 are each independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group; R 4 , R 9 , R 21 , R 22 , and R 31 ~R 34 may be bonded to each other to form a ring. 1 and L 2 are each independently a hydrocarbon group or a heteroatom-containing hydrocarbon group. X is a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group.

[10] The ester compound according to any one of [4] and [6] to [9], wherein X and Y are each independently a divalent group selected from the groups represented by the following general formula group (10):

[0032] [ka]

[0033] [Group (10), R 1' ~R 7' are each independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group; R 2' ~R 7' may be bonded to each other to form a ring, or adjacent substituents may be directly bonded to each other to form a multiple bond.

[11] The ester compound according to any one of [4] and [6] to [9], wherein X and Y are divalent groups selected from the groups represented by the following general formula group (11):

[0034] [ka]

[0035] [In group (11), R 1' ~R 5'are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 20 carbon atoms; R 2' ~R 5' may be bonded to each other to form a ring, or adjacent substituents may be directly bonded to each other to form a multiple bond.

[12] The ester compound according to [9], wherein X is a divalent group represented by the following general formula (13):

[0036] [ka]

[0037] [In formula (13), R 2' and R 3' are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 20 carbon atoms; R 2' and R 3' may be bonded to each other to form a ring.

[13] R 1' ~R 7' are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0038]

[14] R 1' ~R 5' are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[15] R 2' and R 3' each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0039]

[16] R 2' and R 3' The ester compound according to

[12] , wherein all of are hydrogen atoms.

[17] R 1 ~R 24each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 20 carbon atoms.

[0040]

[18] R 1 ~R 24 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 10 carbon atoms.

[0041]

[19] R 31 ~R 34 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 20 carbon atoms.

[0042]

[20] R 31 ~R 34 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 10 carbon atoms.

[21] R 31 ~R 34 are all hydrogen atoms, and R 4 , R 9 , R 21 and R 22 are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 6 carbon atoms; L 1 and L 2 are each independently a hydrocarbon group having 1 to 10 carbon atoms or a heteroatom-containing hydrocarbon group having 1 to 10 carbon atoms.

[0043]

[22] R 31 ~R 34 , R 21 and R 22 are all hydrogen atoms, and R 4 and R 9 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and L 1 and L2 are each independently selected from a hydrocarbon group having 1 to 10 carbon atoms.

[0044]

[23] R 1 and R 2 The ester compound according to any one of [1] to [8], wherein

[24] R 1 , R 2 , R 23 , R 24 are all hydrogen atoms, and R 3 ~R 22 are each independently a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.

[0045]

[25] L 1 and L 2 each independently represents a hydrocarbon group having 4 to 20 carbon atoms or a heteroatom-containing hydrocarbon group.

[26] L 1 and L 2 each independently represents a hydrocarbon group having 4 to 10 carbon atoms or a heteroatom-containing hydrocarbon group.

[0046]

[27] R 4 and / or R 9 is a hydrocarbon group or a heteroatom-containing hydrocarbon group.

[28] R 4 and / or R 9 is a hydrocarbon group or an oxygen atom-containing hydrocarbon group. Effect of the Invention

[0047] The ester compound of the present invention can be used, for example, in resin additives, cosmetics and external skin preparations, bactericidal compositions, antioxidants, chelating agents, and Ziegler-Natta catalysts. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0048] The ester compound according to the present invention will be described in more detail below. The ester compound according to the present invention (hereinafter also referred to as "ester compound (A)") is represented by the following general formula (1).

[0049] [ka]

[0050] In formula (1), R 1 ~R 24 R is independently a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 1 ~R 10 , R 23 and R 24 may be bonded to each other to form a ring, or adjacent substituents may be directly bonded to each other to form a multiple bond. 11 ~R 24 may be bonded to each other to form a ring, or adjacent substituents may be bonded to each other to form a multiple bond. 1 ~R 24 At least one pair of n2 to n5 are bonded to each other to form a ring structure. n2 to n5 each independently represent an integer of 0 to 2. n1 and n6 each independently represent an integer of 0 or 1. L 1 and L 2 are each independently a hydrocarbon group or a heteroatom-containing hydrocarbon group. Among the above, it is preferable that any of n4, n5, and n6 is 1 or 2. In particular, R 11 ~R 24 When any two or more of these are bonded to form an aromatic ring structure, it is preferable that any of n4, n5, and n6 is 1 or 2.

[0051] Preferred examples of the ester compound (A) of the present invention include compounds represented by the following general formulas (2) to (4).

[0052] [ka]

[0053] In formulas (2) to (4), R 1 ~R 24 R is independently a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 1 ~R 10 , R 23 and R 24 may be bonded to each other to form a ring, or adjacent substituents may be directly bonded to each other to form a multiple bond. 11 ~R 24 may be bonded to each other to form a ring, or adjacent substituents may be bonded to each other to form a multiple bond. X and Y each independently represent a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. n2 to n5 each independently represent an integer of 0 to 2. n1 and n6 each independently represent an integer of 0 or 1. L 1 and L 2 are each independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group.

[0054] Moreover, examples of more preferred embodiments of the ester compound (A) of the present invention include compounds represented by the following general formulas (5) to (9).

[0055] [ka]

[0056] In formula (5), R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group, R 4 and R 9 are each independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group; R 11 , R 15 , R 17 and R 21 R is independently a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group.11 , R 15 , R 17 and R 21 may be bonded to each other to form a ring. X is a hydrocarbon group, a heteroatom or a heteroatom-containing hydrocarbon group. 1 and L 2 are each independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group.

[0057] [ka]

[0058] In formula (6), R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group, R 4 , R 9 , R 11 , R 12 , R 15 ~R 18 , R 21 and R 22 R is independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 11 , R 12 , R 15 ~R 18 , R 21 and R 22 may be bonded to each other to form a ring, or adjacent substituents may be bonded to each other to form a multiple bond. X is a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. 1 and L 2 are each independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group.

[0059] [ka]

[0060] In formula (7), R 4 , R 9 , R 12 , R 15 ~R 18 and R 21R is independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 15 ~R 18 may be bonded to each other to form a ring, or adjacent substituents may be bonded to each other to form a multiple bond. Y is a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. 1 and L 2 are each independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group.

[0061] [ka]

[0062] In formula (8), R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group, R 3 , R 4 , R 9 , R 10 , R 12 , R 15 ~R 18 and R 21 R is independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 15 ~R 18 may be bonded to each other to form a ring, or adjacent substituents may be bonded to each other to form a multiple bond. Y is a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. 1 and L 2 are each independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group.

[0063] In the case of the structure of formula (8), R 3 , R 4 , R 9 and R 10are each preferably independently a substituent selected from a hydrogen atom, a halogen atom, a hydrocarbon group, and a halogen-containing hydrocarbon group, more preferably selected from a hydrogen atom, a hydrocarbon group, and a halogen-containing hydrocarbon group, and particularly preferably selected from hydrogen and a hydrocarbon group. More specifically, preferred examples of the above-mentioned hydrocarbon group include a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Preferred examples of the halogen-containing hydrocarbon group include a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, in which one or more hydrogen atoms have been substituted with a halogen atom.

[0064] [ka]

[0065] In formula (9), R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group, R 4 , R 9 , R 12 , R 15 ~R 18 and R 21 R is independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 15 ~R 18 may be bonded to each other to form a ring, or adjacent substituents may be bonded to each other to form a multiple bond. X and Y are each independently a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. 1 and L 2 are each independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group.

[0066] Among these ester compounds, the ester compounds represented by the formulae (5), (8) and (9) are preferred, the compounds represented by the formulae (5) and (9) are more preferred, and the ester compound represented by the formula (5) is most preferred.

[0067] Moreover, a more preferred embodiment of the ester compound (A) of the present invention is a compound represented by the following general formula (31).

[0068] [ka]

[0069] The structure of the substituent in the above formula (31) will be described in detail later. <R 1 ~R 24 > In the above formula (1), R 1 ~R 24 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group.

[0070] Examples of the hydrocarbon group include a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, and a substituted or unsubstituted aryl group.

[0071] Examples of the heteroatom-containing hydrocarbon group include a substituted or unsubstituted heteroatom-containing alkyl group and a substituted or unsubstituted heteroaryl group. Examples of the hydrocarbon group and the heteroatom-containing hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroatom-containing alkyl group, and a heteroaryl group. The number of carbon atoms in these groups is preferably 1 to 20. The lower limit is preferably 2, more preferably 3, and particularly preferably 4. However, the preferred lower limit in the case of an aryl group is 6. On the other hand, the upper limit is preferably 18, more preferably 15, even more preferably 10, and particularly preferably 6. In the case of a heteroaryl group, it is preferred that the heteroaryl group has one or more ring structures having 5 or more members, more preferably has one or more 5- to 7-membered ring structures, and even more preferably has one or more 5- or 6-membered ring structures.

[0072] R 1 ~R 24 At least one of the substituents may be a substituent other than hydrogen. Furthermore, it may be preferable that one or more of the carbon atoms forming the cyclic structure are quaternary carbons. In the above-mentioned embodiment, for example, when the ester compound of the present invention is used as a component of an olefin polymerization catalyst, the performance balance may be improved.

[0073] As mentioned above, R 1 ~R 10 , R 23 and R 24 may be bonded to each other to form a ring, and R 11 ~R 24 may be bonded to each other to form a ring. The moiety forming the ring may be formed by a single bond or may contain a double bond. A structure containing a carbon-carbon double bond may be preferred. The moiety forming the ring may be preferably a structure further containing a ring structure, and the ring structure may be preferably further containing a double bond, particularly preferably a carbon-carbon double bond. Specific structural examples of the moiety forming such a ring are the same as the structural examples of X and Y described later. In the present invention, the carbon-carbon double bond contains an aromatic structure.

[0074] The carbon atom to which the substituents bonded to each other to form a ring (hereinafter sometimes referred to as "BC") is usually bonded to "another substituent" (hereinafter sometimes referred to as "BS") (for example, R 3 R 10 When directly bonded to form a ring, R 4 Or R 9 (The above-mentioned examples correspond to the above-mentioned examples.) In the present invention, the "other substituent" may preferably be a hydrocarbon group and / or a heteroatom-containing hydrocarbon group, which will be described later. As the heteroatom-containing hydrocarbon group, an oxygen-containing hydrocarbon group is particularly preferable. More specifically, the hydrocarbon group is an aliphatic group, an alicyclic group, or an aromatic group having 1 to 10 carbon atoms, more preferably an aliphatic group, an alicyclic group, or an aromatic group having 1 to 6 carbon atoms, and the heteroatom-containing hydrocarbon group is more specifically an aliphatic group, an alicyclic group, or an aromatic group having 1 to 10 carbon atoms, more preferably an aliphatic group, an alicyclic group, or an aromatic group having 1 to 6 carbon atoms. The heteroatom is preferably oxygen. The oxygen-containing hydrocarbon group is more preferably an alkoxy group. More specifically, the position of such a substituent may be R in the above formulas (2), (4), (5), (6), and (9). 4 and / or R 9 and R in the above formulas (3), (4), (7), and (8). 12 and / or R 21 More preferably, the above-mentioned R 4 and / or R 9 When the substituent at such a position is a group having the above-mentioned structure, when the compound is used as a component of an olefin polymerization catalyst, it may become easier to control the polymerization activity, stereoregularity, and also the molecular weight of the resulting polymer with hydrogen.

[0075] Also, R 1 ~R 24 In the formula (1), adjacent substituents may be directly bonded to each other to form a multiple bond, such as a double bond or a triple bond. Furthermore, aromatic ring structures to which these substituents are bonded are also within the scope of the present invention. For example, aromatic ring structures represented by formulas (5) and (7) can be mentioned.

[0076] R 1 When R etc. form a ring structure, the substituents forming the ring are selected from the substituents other than hydrogen atoms and halogen atoms, and are preferably hydrocarbon groups. 1 ~R 24 At least one pair of the substituents bond to each other to form a ring structure. Of the rings formed, at least one pair of the substituents forming the ring is preferably separated by 2 carbon atoms or more, more preferably 3 carbon atoms or more. As such a structure, a ring structure containing X or Y in formulae (2) to (4) is preferable, and a ring structure containing X or Y in formulae (5) to (9) is more preferable.

[0077] When adjacent substituents are bonded to form a ring, R 3 ~R 6 , R 7 ~R 10 , R 11 ~R 22 It is preferable that the substituents selected from the group consisting of X and R are bonded to each other to form a ring. In this case, from the viewpoint of synthesis, it is preferable that the substituents forming the ring do not contain a bridgehead carbon atom. A bridgehead carbon atom refers to a carbon atom that shares two or more rings. For example, in the case of formula (2), X and R 4 A carbon atom with X and R bonded to it. 9 A carbon atom to which R is attached 23 A carbon atom to which R is attached 24 As such a structure, preferred examples include structures included in formulae (5) to (9). As the structure included in formula (5), R 11 and R 15 are bonded together to form a ring, R 15 and R 17 are bonded together to form a ring, R 17 and R 21 Particularly preferred are structures in which R are bonded to each other to form a ring, and structures consisting of a combination thereof. 11 or R 12 and R 15 or R 16 A structure in which R is bonded to form a ring 15 or R 16and R 17 or R 18 A structure in which R is bonded to form a ring 17 or R 18 and R 21 or R 22 Particularly preferred are structures in which R is bonded to form a ring, and structures formed from a combination thereof. 15 or R 16 and R 17 or R 18 are bonded to form a ring is particularly preferred.

[0078] In formula (5), R 11 and R 15 An example of the ester compound (A) having a structure in which the groups are bonded to each other to form a ring is shown below.

[0079] [ka]

[0080] In formula (5), R 15 and R 17 An example of the ester compound (A) having a structure in which the groups are bonded to each other to form a ring is shown below.

[0081] [ka]

[0082] In formula (5), R 17 and R 21 An example of the ester compound (A) having a structure in which the groups are bonded to each other to form a ring is shown below.

[0083] [ka]

[0084] In formula (6), R 11 or R 12 and R 15 or R 16An example of the ester compound (A) having a structure in which the groups are bonded to form a ring is shown below.

[0085] [ka]

[0086] In formula (6), R 15 or R 16 and R 17 or R 18 An example of the ester compound (A) having a structure in which the groups are bonded to form a ring is shown below.

[0087] [ka]

[0088] In formula (6), R 17 or R 18 and R 21 or R 22 An example of the ester compound (A) having a structure in which the groups are bonded to form a ring is shown below.

[0089] [ka]

[0090] In formula (6), R 11 or R 12 and R 15 or R 16 A structure in which R is bonded to form a ring, 17 or R 18 and R 21 or R 22 An example of the ester compound (A) having both a structure in which the groups are bonded to form a ring is shown below.

[0091] [ka]

[0092] In formula (7), R 15 or R16 and R 17 or R 18 An example of the ester compound (A) having a structure in which the groups are bonded to form a ring is shown below.

[0093] [ka]

[0094] In formula (8), R 15 or R 16 and R 17 or R 18 An example of the ester compound (A) having a structure in which the groups are bonded to form a ring is shown below.

[0095] [ka]

[0096] In formula (9), R 15 or R 16 and R 17 or R 18 An example of the ester compound (A) having a structure in which the groups are bonded to form a ring is shown below.

[0097] [ka]

[0098] Preferred R 15 ~R 18 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms. 3 , R 4 , R 9 and R 10are each independently preferably a substituent selected from a hydrogen atom, a halogen atom, a hydrocarbon group, and a halogen-containing hydrocarbon group, more preferably a hydrogen atom, a hydrocarbon group, and a halogen-containing hydrocarbon group, and particularly preferably a hydrogen atom and a hydrocarbon group. Preferred examples of the above-mentioned hydrocarbon group include a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Preferred examples of the halogen-containing hydrocarbon group include substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, and substituted or unsubstituted aryl groups having 6 to 20 carbon atoms in which one or more hydrogen atoms have been substituted with a halogen atom.

[0099] Also preferably, R 1 ~R 24 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

[0100] More preferably, R 1 ~R 24are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 10 carbon atoms.

[0101] More preferably, R 1 ~R 24 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 10 carbon atoms.

[0102] Even more preferably, R 1 ~R 24 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. Particularly preferably, R 1 , R 2 , R 23 , R 24 are all hydrogen atoms, and R 3 ~R 22 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.

[0103] In addition, R 1 ~R 24 The carbon atoms to which are bonded form two or more ring structures as shown in the general formula (1). It is preferable that one or more of the ring structures is an alicyclic ring structure. In other words, it is preferable that at least all of the rings are not aromatic ring structures.

[0104] <R 31 ~R 34 > In the above formula (31), R 31~R 34 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group.

[0105] Examples of the hydrocarbon group include a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, and a substituted or unsubstituted aryl group.

[0106] Examples of the heteroatom-containing hydrocarbon group include a substituted or unsubstituted heteroatom-containing alkyl group and a substituted or unsubstituted heteroaryl group. Examples of the hydrocarbon group and the heteroatom-containing hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroatom-containing alkyl group, and a heteroaryl group. The number of carbon atoms in these groups is preferably 1 to 20. The lower limit is preferably 2, more preferably 3, and particularly preferably 4. However, the preferred lower limit in the case of an aryl group is 6. On the other hand, the upper limit is preferably 18, more preferably 15, even more preferably 10, and particularly preferably 6. In the case of a heteroaryl group, it is preferred that the heteroaryl group has one or more ring structures having 5 or more members, more preferably has one or more 5- to 7-membered ring structures, and even more preferably has one or more 5- or 6-membered ring structures.

[0107] Preferred R 31 ~R 34 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

[0108] More preferred R31 ~R 34 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 10 carbon atoms.

[0109] More preferred R 31 ~R 34 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 6 carbon atoms.

[0110] R 31 ~R 34 may be bonded to each other to form a ring. Particularly preferred R 31 ~R 34 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and most preferably R 31 ~R 34 are all hydrogen atoms. 31 ~R 34 , R 21 , R 22 , R 4 , R 9 may be bonded to each other to form a ring, or adjacent substituents may be bonded directly to each other to form a multiple bond.

[0111] The structure of the ester compound represented by the above formula (31) will be described in detail below. As mentioned above, R 31 ~R 34 , R 21 , R 22 , R 4 , R9 may be bonded to each other to form a ring, or adjacent substituents may be directly bonded to each other to form a multiple bond, such as a double bond or a triple bond. Furthermore, aromatic ring structures to which these substituents are bonded are also within the scope of the present invention. For example, R 34 , R 21 , R 22 Examples of such aromatic ring structures include those having an aromatic ring structure to which

[0112] R 31 ~R 34 , R 21 , R 22 , R 4 , R 9 When R are bonded to each other to form a ring structure, the substituents forming the ring are selected from the group consisting of hydrogen atoms and halogen atoms, and are preferably hydrocarbon groups. 31 ~R 34 , R 21 , R 22 are preferably bonded to each other to form a ring, and more preferably R 31 and R 32 are bonded together to form a ring, R 32 and R 33 are bonded together to form a ring, R 33 and R 34 are bonded together to form a ring, R 21 and R 22 are bonded together to form a ring, R 34 , R 21 , R 22 are bonded to each other, and combinations thereof.

[0113] R 31 and R 32 An example of the ester compound (A) having a structure in which the groups are bonded to each other to form a ring is shown below.

[0114] [ka]

[0115] R 32 and R 33An example of the ester compound (A) having a structure in which the groups are bonded to each other to form a ring is shown below.

[0116] [ka]

[0117] R 33 and R 34 An example of the ester compound (A) having a structure in which the groups are bonded to each other to form a ring is shown below.

[0118] [ka]

[0119] R 21 and R 22 An example of the ester compound (A) having a structure in which the groups are bonded to each other to form a ring is shown below.

[0120] [ka]

[0121] R 34 , R 21 , R 22 An example of the ester compound (A) having a structure in which the groups are bonded to each other to form a ring is shown below.

[0122] [ka]

[0123] Also, the preferred R 21 , R 22 , R 4 , R 9are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

[0124] More preferred R 21 , R 22 , R 4 , R 9 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 10 carbon atoms.

[0125] More preferred R 21 , R 22 , R 4 , R 9 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 6 carbon atoms.

[0126] R 21 , R 22 , R 4 , R 9 may be bonded to each other to form a ring, for example, R 21 and R 22 and a ring structure in which the ring structures are bonded to each other. Particularly preferred R 21 , R 22 , R 4 , R 9 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and most preferably R 21 , R 22 , R 4 , R 9 are all hydrogen atoms.

[0127] <L 1 and L 2 > In the above formula (1), L 1 and L 2 are each independently a hydrocarbon group or a heteroatom-containing hydrocarbon group.

[0128] Examples of the hydrocarbon group include a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, and a substituted or unsubstituted aryl group.

[0129] Examples of the heteroatom-containing hydrocarbon group include a substituted or unsubstituted heteroatom-containing alkyl group and a substituted or unsubstituted heteroaryl group. Examples of the hydrocarbon group and the heteroatom-containing hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroatom-containing alkyl group, and a heteroaryl group. The number of carbon atoms in these groups is preferably 1 to 20. The lower limit is preferably 2, more preferably 3, and particularly preferably 4. However, in the case of an aryl group, the preferred lower limit is 6. On the other hand, the upper limit is preferably 18, more preferably 15, even more preferably 10, and particularly preferably 6. In the case of a heteroaryl group, it is preferred that the heteroaryl group has one or more ring structures having 5 or more members, more preferably has one or more 5- to 7-membered ring structures, and even more preferably has one or more 5- or 6-membered ring structures.

[0130] The preferred range of the number of carbon atoms is selected from 4 or more, or 1 to 20. In the latter case, it is more preferably 1 to 10. In the former case, it is more preferably 4 to 20.

[0131] In the former case, L is preferred. 1 and L 2 are each independently a substituted or unsubstituted alkyl group having 4 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 4 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 4 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 4 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having 4 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 4 to 20 carbon atoms.

[0132] More preferred L 1 and L 2 are each independently a substituted or unsubstituted alkyl group having 4 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having 4 to 10 carbon atoms, or a substituted or unsubstituted heteroaryl group having 4 to 15 carbon atoms.

[0133] More preferred L 1 and L 2are each independently a substituted or unsubstituted aryl group having 6 to 10 carbon atoms and a substituted or unsubstituted heteroaryl group having 4 to 10 carbon atoms, and particularly preferably a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. An aryl group containing a substituent other than hydrogen is particularly preferred. The substituent other than hydrogen is a hydrocarbon group having 1 to 10 carbon atoms or a heteroatom-containing hydrocarbon group having 1 to 10 carbon atoms. The heteroatom is specifically an element in Group 16 of the periodic table, and more specifically oxygen. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, an isopropyl group, an n-butyl group, an s-butyl group, and a t-butyl group, and specific examples of the heteroatom-containing hydrocarbon group include a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, and a t-butoxy group.

[0134] <n1~n6> In the above formula (1) etc., n2 to n5 represent an integer of 0 to 2, and n1 and n6 represent an integer of 0 or 1.

[0135] n2 to n5 are preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0. Each of n1 and n6 is preferably 0 or 1, and more preferably 1.

[0136] <XおよびY> In the above formulas (2) to (9) and (31), X and Y are each independently a hydrocarbon group, a hetero atom or a hetero atom-containing hydrocarbon group, and preferably are each independently a divalent group selected from the groups shown in the following general formula group (10).

[0137] [ka]

[0138] In group (10), R 1' ~R 7' are each independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group; R2' ~R 7' may be bonded to each other to form a ring, or adjacent substituents may be directly bonded to each other to form a multiple bond.

[0139] Preferred R 1' ~R 7' are each independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, or a substituted or unsubstituted heteroatom-containing hydrocarbon group having 1 to 10 carbon atoms.

[0140] More preferred R 1' ~R 7' are each independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms, and most preferably R 1' ~R 7' are all hydrogen atoms. As mentioned above, R 2' ~R 7' may be bonded to each other to form a monocyclic or polycyclic ring. 1' ~R 7' is the above R 1 ~R 24 can be linked to form a ring structure.

[0141] X and Y are preferably divalent groups selected from the groups represented by the following general formula group (11).

[0142] [ka]

[0143] In group (11), R 1' ~R 5' are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 20 carbon atoms; R 2' ~R 5' may be bonded to each other to form a ring, or adjacent substituents may be directly bonded to each other to form a multiple bond.

[0144] When X and Y are divalent groups selected from the groups represented by the general formula group (11), R1' ~R 5' are preferably each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. It is more preferable that X and Y each represent a divalent group selected from the groups represented by the following general formula group (12).

[0145] [ka]

[0146] In formula (12), R 2' ~R 5' are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 20 carbon atoms; R 2' ~R 5' may be bonded to each other to form a ring.

[0147] It is particularly preferable that X and Y are divalent groups represented by the following general formula (13).

[0148] [ka]

[0149] In formula (13), R 2' and R 3' are each independently selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 20 carbon atoms; R 2' and R 3' may be bonded to each other to form a ring.

[0150] In the ester compound (A) represented by formula (31), when X is a divalent group represented by formula (13), R 2' and R 3' are preferably each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and more preferably all are hydrogen atoms.

[0151] As mentioned above, in equations (10), (11), and (12), R 2' ~R7' In some cases, it is preferable that the R are bonded to each other to form a ring, or that adjacent substituents are directly bonded to each other to form a multiple bond. The multiple bond is preferably a carbon-carbon double bond. 2' ~R 7' More preferably, R is a structure containing a carbon-carbon double bond at a site where R are bonded to each other to form a ring. 2' ~R 5' are preferably bonded to each other to form a ring, and more preferably contain a substituted or unsubstituted aryl group in the multiple bond. An example of such a substituent for X and Y is shown below.

[0152] [ka]

[0153] Examples of the hydrocarbon group include a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted aryl group.

[0154] Examples of the heteroatom-containing hydrocarbon group include a substituted or unsubstituted heteroatom-containing alkyl group and a substituted or unsubstituted heteroaryl group. Examples of the hydrocarbon group and the heteroatom-containing hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroatom-containing alkyl group, and a heteroaryl group. The number of carbon atoms in these groups is preferably 1 to 20. The lower limit is preferably 2, more preferably 3, and particularly preferably 4. However, in the case of an aryl group, the lower limit is preferably 6, and the upper limit is preferably 20, more preferably 15, even more preferably 10, and particularly preferably 6. In the case of a heteroaryl group, it is preferable that the heteroaryl group has one or more ring structures having 5 or more members, more preferably has one or more 5- to 7-membered ring structures, and even more preferably has one or more 5- or 6-membered ring structures.

[0155] Below, R 1 ~R 24 , R 31 ~R 34 , L 1 , L 2 , R 1' ~R 7' More specific examples of the groups and atoms exemplified in are shown below. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Examples of the hydrocarbon group include various structures such as aliphatic, branched aliphatic, alicyclic, and aromatic, as shown below.

[0156] Examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, a thexyl group, a cumyl group, and a trityl group.

[0157] Examples of the substituted or unsubstituted alkenyl group include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, and a hexenyl group.

[0158] Examples of the substituted or unsubstituted alkynyl group include an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, and an octynyl group.

[0159] Examples of the substituted or unsubstituted cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a cyclopentadienyl group, an indenyl group, and a fluorenyl group.

[0160] Examples of the substituted or unsubstituted aryl group include aromatic hydrocarbon groups such as a phenyl group, a methylphenyl group, a dimethylphenyl group, a diisopropylphenyl group, a dimethylisopropylphenyl group, a tert-butylphenyl group, a di-tert-butylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group, and heteroatom-substituted aryl groups such as a methoxyphenyl group, a dimethylaminophenyl group, a nitrophenyl group, and a trifluoromethylphenyl group.

[0161] Examples of the substituted or unsubstituted heteroatom-containing hydrocarbon group include heteroatom-containing alkyl groups such as methoxymethyl, methoxyethyl, benzyloxy, ethoxymethyl, and ethoxyethyl groups, and heteroaryl groups such as furyl, pyrrolyl, thienyl, pyrazolyl, pyridyl, carbazolyl, imidazolyl, dimethylfuryl, N-methylpyrrolyl, N-phenylpyrrolyl, diphenylpyrrolyl, thiazolyl, quinolyl, benzofuryl, triazolyl, and tetrazolyl groups. The number of carbon atoms contained in the above-mentioned carbon-containing substituent is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6, and particularly preferably 1 to 4, as described above. When the above-mentioned substituent has an aryl group structure, the number of carbon atoms is preferably 4 to 20, more preferably 4 to 10, and even more preferably 6 to 10. R 1 ~R 24 When is a substituent other than a hydrogen atom, it is preferably selected from the above-mentioned hydrocarbon groups and oxygen-containing hydrocarbon substituents. The oxygen-containing hydrocarbon group is more preferably an alkoxy group. When such a structure is used as an internal donor in an olefin polymerization catalyst, an effect such as the production of an olefin polymer with a broader molecular weight distribution may be exhibited.

[0162] <Specific examples of ester compound (A)> Specific examples of the ester compound (A) of the present invention are shown below, but the ester compound (A) of the present invention is not limited to these.

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[0210] R 1 ~R 24 Examples of compounds in which the moiety forming a ring by bonding further has a double bond or a ring structure, particularly a ring structure containing a double bond, include compounds having the following structures.

[0211] [ka]

[0212] [ka]

[0213] [ka]

[0214] [ka]

[0215] [ka]

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[0221] In the above structural formulas, the methyl group is represented as "Me", the ethyl group as "Et", the propyl group as "Pr", the butyl group as "Bu", and the phenyl group as "Ph", and [n] stands for "normal", [i] for "iso", and "t" for "tertiary".

[0222] In addition, the ester compound (A) of the present invention contains OCOL bonded to an alicyclic structure. 1 Group and OCOL 2 Although the group may form a cis or trans structure derived from the alicyclic structure, it is preferable that the ester compound has a cis structure as the main component, where the main component means that the content of the compound having a cis structure exceeds 50 mol %, preferably 70 mol % or more.

[0223] The reason why the ester compound (A) of the present invention is suitable as a Lewis base (internal donor) component of a solid titanium catalyst component is unclear at present, but the present inventors speculate as follows. The ester compound (A) of the present invention has a structure in which rings are linked, and preferably also has a crosslinked structure (a structure corresponding to the above X or Y). This requirement restricts the conformation, and the distance and orientation of two adjacent ester groups bonded to the ring are fixed. As a result, it is presumed that when an ester is coordinated to magnesium chloride, the coordination mode of the ester is restricted, and a rigid polymerization environment consisting of titanium atoms, magnesium chloride, and an ester compound is formed. It is considered that when polymerization proceeds under such an environment, the orientation of the polymer chain and the direction of insertion of propylene are highly controlled, and a catalyst suitable for highly stereoregular polymerization is formed. A skeleton in which an ester is bonded to a ring containing a crosslinked structure (e.g., formula (5), (6), and (9)) is a better skeleton as an internal donor for Ziegler catalysts because the distance and orientation of the ester moiety are restricted. In addition, even if the ester moiety is directly bonded to the cyclohexane skeleton (e.g., formula (8)), the conformation of the cyclohexane skeleton is restricted by the ring structure containing a crosslinked structure being condensed to the cyclohexane skeleton, and it is considered that the same effect is ultimately obtained. As described above, the structure having a 6-membered ring structure has been described here. Based on this inference, however, the same effect can be expected from an ester compound having a structure represented by formula (1), more preferably a polycyclic structure represented by formulae (2) to (4), even if it is an ester compound other than the specifically exemplified compounds, and it is clear that the same effect can be expressed even if it has a 5- to 10-membered ring structure.

[0224] Since the ester compound (A) of the present invention has a structure in which rings are linked as described above, it is presumed that the compound has a moderate rigidity and relatively little structural displacement. Therefore, when used in an olefin polymerization catalyst described later, when the ester group-containing compound (A) is coordinated to a titanium compound or a magnesium compound, it is expected to maintain a stable structure while having a moderate interaction. Therefore, it is considered to have a favorable effect on stereospecificity and activity. On the other hand, the alicyclic structure as described above will show various structures that are easily displaced, for example, chair-shaped or boat-shaped at a micro-site. From this, it is expected that a polymer with a wide molecular weight distribution can be produced.

[0225] In addition, the ester compound (A) of the present invention represented by the above formula (31) has a specific polycyclic structure as described above. It also has a unique asymmetric structure. By having such a structure, it has a moderate rigidity as a compound, so it is thought that there is a possibility that there is little displacement or shaking as a structure when forming an active species of olefin polymerization by interaction with a magnesium compound or a titanium compound and a polymerization reaction occurs. On the other hand, in the case of an ester compound (A) having an asymmetric structure such as the above formula (31), since the conformation when interacting with a magnesium compound or a titanium compound is likely to be more than that of a symmetric compound, it is possible to form active species with various microstructures. This point is thought to be advantageous for obtaining an embodiment including a polymer with a wide molecular weight distribution or a polymer with high stereoregularity. In addition, since it has a unique asymmetric structure preferably including an aryl structure, it may be possible to take a strong coordination structure with a magnesium compound or a titanium compound.

[0226] From the above viewpoints, it is presumed that the ester compound (A) of the present invention is suitable as a Lewis base (internal donor) component of a solid titanium catalyst component. <Method for producing ester compound (A)> The method for producing the ester compound (A) of the present invention is not particularly limited, and for example, the corresponding olefin can be obtained through a diolation reaction or a diesterification reaction. In addition, for example, the ester compound (A) can be obtained through a carbonation reaction, a diolation reaction, or a diesterification reaction using a specific polycyclic compound such as anthracene. More specifically, the ester compound (A) can be produced as follows.

[0227] <Olefin synthesis> The olefin shown in the following formula (21) can be synthesized, for example, by the Diels-Alder reaction of cyclopentadiene and norbornene (Non-Patent Document 1). The olefin shown in the following general formula (33) can be synthesized, for example, by the Diels-Alder reaction of substituted indene and substituted diene (Patent Document 11). The diene can also be used as a raw material from a precursor diene dimer (e.g., dicyclopentadiene). The product obtained by the Diels-Alder reaction is often a mixture of endo and exo isomers (see the following formulas (22) and (34)), but either isomer can be applied to the present invention. That is, it may be a mixture, or it may be only the endo isomer, or it may be only the exo isomer. These endo and exo isomer structures are often reflected in the target ester compound.

[0228] In addition, olefins can be obtained by reacting benzyne with dienes (Non-Patent Documents 2, 3, 14), and cycloolefins can be obtained by decarbonylating and decarboxylating alicyclic dicarboxylic anhydrides in the presence of a compound that can act as a ligand (e.g., triphenylphosphine) using a nickel complex (e.g., tetrakistriphenylphosphine nickel) as a catalyst (Patent Documents 7 and 8). <Synthesis of anthracenes> In addition, the R 1 ~R 24 A compound in which the moiety at which the ring is formed by bonding further has a double bond or a ring structure, particularly a ring structure containing a double bond, can be synthesized, for example, by converting an anthracene into a carbonate compound through a Diels-Alder reaction with vinylene carbonate, followed by a diol reaction and a diesterification reaction.

[0229] Anthracenes can be synthesized, for example, by reacting anthraquinone with an organometallic reagent (e.g., an alkyllithium or a Grignard reagent) followed by reduction (e.g., a reaction using tin(II) chloride or sodium hypophosphite) (see formula (14(1)) below; Patent Document 9, Non-Patent Documents 15 and 16).

[0230] Dihalogen anthracene can also be synthesized by a substitution reaction of a metal reactant (e.g., lithium or magnesium) with an alkyl halide, or by a coupling reaction of a transition metal catalyst (e.g., nickel or palladium) with an organometallic reactant (e.g., a boronic acid ester or a Grignard reactant) (see formulas (14(2)) and (14(3)), Patent Document 10, and Non-Patent Document 17). Dialkoxyanthracene can also be obtained by reacting anthraquinone with a reducing agent (e.g., zinc) and an electrophile (e.g., an alkyl halide or a sulfonic acid ester) (see formula (14(4)), Non-Patent Document 18).

[0231] [ka]

[0232] In formula (14(1)), R 25 M represents an organometallic reactant, R 25 represents an alkyl group, and M represents a metal or metal halide. Examples of M include Li, MgBr, MgCl, and MgI.

[0233] [ka]

[0234] In formula (14(2)), R 26 Z represents an electrophile, Z represents a halogen atom, R 26 represents an alkyl group.

[0235] [ka]

[0236] In formula (14(3)), Z represents a halogen atom, R 27 represents an alkyl group or an aryl group, and A and A' represent a hydroxyl group or a crosslinked structure formed by bonding A and A'. 27Examples of the structural formula of the boron-containing compound having a structure containing A, A, and A', i.e., a boric acid compound or a boric acid ester (preferably, a cyclic boric acid ester compound), include the structures represented by the following formula group (15).

[0237] [ka]

[0238] [ka]

[0239] In formula 14(4), R 28 Z represents an electrophile, Z represents a halogen atom, R 28 represents an alkyl group. <Synthesis of diol> The diols (formulae (23) and (35)), which are precursors of esters, can be produced from the corresponding olefins (formulae (21) and (33)). For example, the diols (formulae (23) and (35)) can be directly obtained by reacting the olefins with potassium permanganate (Non-Patent Document 4) or osmium tetroxide (Non-Patent Document 5).

[0240] Alternatively, the olefin moiety can be epoxidized using metachloroperbenzoic acid (Non-Patent Document 6); tert-butyl peroxide (Non-Patent Document 7); dimethyldioxirane (Non-Patent Document 8); formic acid and hydrogen peroxide (Non-Patent Document 9); hydrogen peroxide and a molybdenum catalyst; or hydrogen peroxide and a tungsten catalyst (Non-Patent Document 10), followed by acid or alkali hydrolysis to give the diol (formula (23) and formula (35)).

[0241] [ka]

[0242] [ka]

[0243] In addition, the diene or anthracene compound can be cyclically carbonated and then hydrolyzed to obtain a diol compound. The details are as follows. Cyclic carbonates (formula (24)), which are precursors of diols (formula (23)), can be produced by the Diels-Alder reaction of the corresponding dienes with vinylene carbonate (Non-Patent Document 19). As above, the precursor diene dimer can also be used as a raw material. In addition, the product obtained by the Diels-Alder reaction is often a mixture of endo and exo isomers, but this Diels-Alder product can also be used. This reaction can also be used to obtain polycyclic carbonates of specific structures as shown in the examples below, using polycyclic aromatic compounds such as anthracene instead of dienes.

[0244] The diol form (formula (23)) can be obtained by hydrolyzing the cyclic carbonate of formula (24) with an acid or an alkali (Non-Patent Document 19).

[0245] [ka]

[0246] <Synthesis of ester> The ester corresponding to the above formula (1) can be synthesized by reacting a diol (formula (23)) with an acid chloride in the presence of a base (formula 25). The base is not particularly limited, but for example, sodium hydroxide, potassium hydroxide, or an amine base can be used. In addition, it can be synthesized by reacting a diol with a carboxylic acid in the presence of an acid catalyst, or by using a condensing agent such as DCC (Non-Patent Document 11) (formula (26)). When one equivalent of an acid chloride or carboxylic acid is reacted with a diol (formula (3')), an isomer corresponding to formula (24) may be generated, but if the acid chloride or carboxylic acid is subsequently reacted, a compound corresponding to formula (1) can be obtained. At this time, L 1 and L2 may be the same or different. Alternatively, the diol may be reacted with a carboxylic acid in the presence of an azocarboxylate and triphenylphosphine to synthesize the diol (Non-Patent Document 12).

[0247] The ester corresponding to the above formula (31) can be synthesized by reacting a diol (formula (35)) with an acid chloride in the presence of a base, as shown in the following formula (37). The base is not particularly limited, but for example, sodium hydroxide, potassium hydroxide, and amine bases can be used. In addition, the ester can be synthesized by reacting a diol with a carboxylic acid in the presence of an acid catalyst, or by using a condensing agent such as DCC (Non-Patent Document 11) (see formula (38)). When one equivalent of an acid chloride or carboxylic acid is reacted with a diol (formula (35)), an isomer corresponding to formula (36) may be produced, but if the diol is subsequently reacted with an acid chloride or carboxylic acid, a compound corresponding to formula (31) can be obtained. At this time, L 1 and L 2 may be the same or different. Alternatively, the diol may be reacted with a carboxylic acid in the presence of an azocarboxylate and triphenylphosphine to synthesize the diol (Non-Patent Document 12).

[0248] [ka]

[0249] [ka]

[0250] In the above-mentioned synthesis method of an ester compound, as described above, a mixture of endo and exo isomers may be obtained. From a structural viewpoint, the endo isomer tends to be easily generated. There is no particular limitation on the isomer ratio when the mixture is obtained, but a preferred example is when the endo / exo isomer ratio is 100 / 0 to 50 / 50, preferably 95 / 5 to 60 / 40, and more preferably 90 / 10 to 65 / 35.

[0251] These endo and exo isomers can often be separated by known column chromatography using silica gel, so the endo and exo isomers can be isolated separately. It is also possible to change the isomer ratio by an isomerization reaction using a solid acid catalyst such as zeolite. Of course, it is also possible to combine the isolated compounds in a specific ratio to adjust the isomer ratio to a desired ratio. Depending on the application of the ester compound of the present invention, it is expected that either the endo or exo isomer may show a suitable effect, or a specific isomer ratio may show a suitable effect. In such cases, the isomer ratio may be adjusted to 100 / 0 to 0 / 100 by, for example, the above-mentioned method.

[0252] As described above, the ester compound (A) of the present invention can be used for various applications in the form of either the endo isomer or the exo isomer, either singly or as a mixture of isomers. As described above, the ester compound (A) of the present invention is suitable as a Lewis base component of a solid titanium catalyst component, but is not limited to this use. Needless to say, it may be applicable to known additive uses such as additives for various resins, cosmetics and skin external preparations, bactericidal compositions, antioxidants, chelating agents, etc. EXAMPLES

[0253] The synthesis method of the ester compound of the present invention is illustrated in the following examples. Note that the compounds of the structural formulas disclosed in the following examples and comparative examples show the structures of the main components of stereoisomers, and may contain other stereoisomers. In the present invention, the main component refers to more than 50 mol%, preferably 70 mol% or more.

[0254] (Method for measuring the melting behavior of compounds) When the obtained ester compound was solid, a suitable amount of the sample was placed in an aluminum pan and the melting behavior was measured under the following conditions using a DSC7020 differential scanning calorimeter manufactured by Hitachi High-Tech Science Corporation.

[0255] Starting temperature: 25℃, End temperature: 300℃, Heating rate: 10℃ / min The peak temperature considered to be the melting point was observed. When it was difficult to identify the peak temperature considered to be due to the influence of an isomer mixture or a compound that decomposes at high temperatures, the temperature at which the end of heat absorption ended was regarded as the melting completion temperature.

[0256] (Method of determining isomer composition) The isomers were separated by conventional silica column chromatography. From the results of NMR analysis of the isolated isomers and the mixture, the chemical shifts specific to the isomers were identified, and the isomer ratio was determined from the absorption intensity ratio.

[0257] ( 1 H NMR structural analysis method) The nuclear magnetic resonance spectrometer used was a JNM-EX270 model manufactured by JEOL Ltd. The solvent was deuterated chloroform, and a small amount of tetramethylsilane was added. The measurement temperature was room temperature, and the observation nuclei were 1 The conditions were H (270 MHz), sequence was single pulse, 45° pulse, repetition time was 5.5 seconds or more, and the number of accumulations was 16 to 64 times or more. The reference chemical shift was set to 0 ppm for hydrogen of tetramethylsilane. 1 Peaks such as H were assigned by standard methods.

[0258] [Example A1] <Synthesis of Compound 1> Compound 1 shown below was synthesized according to the reaction scheme below and by the method described below.

[0259] [ka]

[0260] In a 1L three-neck flask, 8.62g (53.8mmol) of endo-tetracyclododecene, 240mL of tert-butyl alcohol, and 50mL of water were added, and the internal temperature was cooled to 0°C while stirring. In another flask, 12.0g of potassium permanganate, 250mL of water, and 2.68g of sodium hydroxide were added and stirred to prepare an aqueous potassium permanganate solution. The aqueous potassium permanganate solution was slowly added dropwise to the previously prepared tetracyclododecene solution so that the internal temperature did not exceed 5°C. After the addition, stirring was continued at 0°C for 1 hour. A saturated aqueous sodium pyrosulfite solution was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed. The formed precipitate was removed by filtration, and the filtrate was extracted three times with ethyl acetate. The organic layer was washed with saturated saline and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the obtained organic layer was concentrated using a rotary evaporator to obtain 7.24g of crude product of compound 1. The obtained compound 1 was used in the next <Synthesis of compound 2> without further purification.

[0261] <Synthesis of compound 2> Compound 2 shown below was synthesized according to the reaction scheme below and by the method described below.

[0262] [ka]

[0263] Under a nitrogen atmosphere, 5 g (25.7 mmol) of compound 1 and 31 mL of dehydrated pyridine were added to a 100 mL three-neck flask and stirred. The mixture was cooled in an ice bath, and 6.3 mL of benzoyl chloride was slowly added. After the addition, the mixture was warmed to room temperature and stirred overnight. The mixture was cooled again in an ice bath, and 5 mL of methanol was added. Chloroform and water were added to the reaction liquid, and the organic layer was separated. The organic layer was washed three times with water, a saturated aqueous solution of ammonium chloride, and saturated saline, and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the obtained organic layer was concentrated using a rotary evaporator to obtain 10.37 g of a crude product. The product was purified by silica gel column chromatography to obtain 6.67 g (16.6 mmol, white solid) of compound 2. The obtained compound 2 1 The H-NMR data is shown below.

[0264] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ0.97-1.28 (m, 3H), 1.32-1.70 (m, 4H), 1.90 (br s, 2H), 2.15 (d, J=10.2 Hz, 1H), 2.39 (br s, 2H), 2.53 (br s, 2H), 5.53-5.59 (m, 2H), 7.19-7.33 (m, 4H), 7.40-7.49 (m, 2H), 7.80-7.92 (m, 4H). The resulting compound 2 had a melting completion temperature of 141°C.

[0265] [Example A2] <Synthesis of compound 3> Compound 3 shown below was synthesized by the method described below.

[0266] [ka]

[0267] In a 1L three-neck flask, 10.18g (63.5mmol) of exo-tetracyclododecene, 240mL of tert-butyl alcohol, and 60mL of water were added, and the internal temperature was cooled to 0°C while stirring. In another flask, 13.81g of potassium permanganate, 300mL of water, and 3.00g of sodium hydroxide were added and stirred to prepare an aqueous potassium permanganate solution. The aqueous potassium permanganate solution was slowly added dropwise to the previously prepared tetracyclododecene solution so that the internal temperature did not exceed 5°C. After the addition, stirring was continued at 0°C for 1 hour. A saturated aqueous sodium pyrosulfite solution was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed. The formed precipitate was removed by filtration, and the filtrate was extracted three times with ethyl acetate. The organic layer was washed with saturated saline and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the resulting organic layer was concentrated using a rotary evaporator to obtain 3.42 g (17.6 mmol) of crude product of compound 3. The obtained compound 3 was used in the next <Synthesis of compound 4> without further purification.

[0268] <Synthesis of compound 4> Compound 4 shown below was synthesized by the method described below.

[0269] [ka]

[0270] In a nitrogen atmosphere, 4.0 g (20.6 mmol) of compound 3, 4.2 mL of dehydrated pyridine, and 100 mL of dehydrated chloroform were added to a 200 mL three-neck flask and stirred. The mixture was cooled in an ice bath, and 4.9 mL of benzoyl chloride was slowly added. After the addition, the mixture was warmed to room temperature and stirred overnight. The mixture was cooled again in an ice bath, and 5 mL of methanol was added. Chloroform and water were added to the reaction liquid, and the organic layer was separated. The organic layer was washed three times with water, a saturated aqueous solution of ammonium chloride, and saturated saline, and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the obtained organic layer was concentrated using a rotary evaporator to obtain 11.3 g of a crude product. The mixture was purified by silica gel column chromatography to obtain 4.44 g (11.0 mmol, white solid) of compound 4. 1 The H-NMR data is shown below.

[0271] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ0.96 (d, J=10.6 Hz 1H), 1.13-1.22 (m, 2H), 1.43-1.60 (m, 5H), 1.77-2.05 (m, 2H), 2.23 (br s, 2H), 2.41 (br s, 2H), 4.99-5.01 (m, 2H), 7.21-7.29 (m, 4H), 7.42-7.49 (m, 2H), 7.81-7.87 (m, 4H). The resulting compound 4 had a melting completion temperature of 163°C.

[0272] [Example A3] <Synthesis of compound 5> Compound 5 shown below was synthesized by the method described below.

[0273] [ka]

[0274] 15.53 g (110.8 mmol) of benzonorbornadiene, 425 mL of tert-butyl alcohol, and 105 mL of water were added to a 2 L three-neck flask, and the internal temperature was cooled to 0°C while stirring. 23.7 g of potassium permanganate, 527 mL of water, and 5.07 g of sodium hydroxide were added to another flask and stirred to prepare an aqueous potassium permanganate solution. The aqueous potassium permanganate solution was slowly added dropwise to the previously prepared benzonorbornadiene solution so that the internal temperature did not exceed 5°C. After the addition, stirring was continued at 0°C for 1 hour. A saturated aqueous sodium pyrosulfite solution was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed. The formed precipitate was removed by filtration, and the filtrate was extracted three times with ethyl acetate. The organic layer was washed with saturated saline and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the obtained organic layer was concentrated using a rotary evaporator to obtain 8.19 g of compound 5. The obtained compound 5 1 The H-NMR data is shown below.

[0275] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ1.89-1.97 (m, 1H), 2.20-2.27 (m, 1H), 2.74-2.82 (m, 2H), 3.20-3.25 (m, 2H), 3.80-3.87 (m, 2H), 7.06-7.13 (m, 2H), 7.15-7.22 (m, 2H). <Synthesis of compound 6> Compound 6 shown below was synthesized by the method described below.

[0276] [ka]

[0277] Under a nitrogen atmosphere, 9.57 g (54.3 mmol) of compound 5 and 70 mL of dehydrated pyridine were added to a 300 mL three-neck flask and stirred. The mixture was cooled in an ice bath, and 13.4 mL of benzoyl chloride was slowly added. After the addition, the mixture was warmed to room temperature and stirred overnight. The mixture was cooled again in an ice bath, and 5 mL of methanol was added. 200 mL of water was added to a beaker, and the reaction liquid was added while stirring, and the resulting precipitate was filtered. The precipitate was washed with hexane and then recrystallized from ethanol to obtain 16.36 g of a solid. A small amount of residual pyridine was removed by silica gel column chromatography, and 15.48 g (40.3 mmol, white solid) of compound 6 was obtained. 1 The H-NMR data is shown below.

[0278] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ2.12-2.20 (m, 1H), 2.57-2.64 (m, 1H), 3.57 (br s, 2H), 5.18 (d, J=1.6 Hz, 2H), 7.12-7.22 (m, 2H), 7.24-7.37(m, 6H), 7.44-7.53 (m, 4H), 7.87-7.96 (m, 2H). The resulting compound 6 had a melting completion temperature of 139°C.

[0279] [Example A4] <Synthesis of compound 7> Compound 7 shown below was synthesized according to the reaction scheme below and by the method described below.

[0280] [ka]

[0281] Under a nitrogen atmosphere, 200 mL of dehydrated toluene, 6.36 mL of 1-bromo-2-iodobenzene, and 10.5 mL of 2,5-dimethylfuran were added to a 1 L three-neck flask and cooled to -20°C while stirring. 47 mL of n-butyllithium hexane solution (1.6 M) was slowly added dropwise, and after the dropwise addition, the mixture was stirred at -20°C for 1 hour. The temperature was gradually raised to room temperature and stirring was continued overnight. Water was slowly added dropwise while cooling in an ice bath, and ethyl acetate was added to separate the organic layer. The organic layer was washed with saturated saline and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the obtained organic layer was concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography to obtain 4.05 g (23.5 mmol) of compound 7. 1 The H-NMR data is shown below.

[0282] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ1.90 (s, 6H), 6.77 (s, 2H), 6.97 (dd, J=5.3, 3.0 Hz, 2H), 7.13 (dd, J=5.3, 3.0 Hz, 2H). <Synthesis of compound 8> Compound 8 shown below was synthesized by the method described below.

[0283] [ka]

[0284] Compound 7 (4.05 g, 23.5 mmol), tert-butyl alcohol (129 mL), and water (32 mL) were added to a 2 L three-neck flask, and the internal temperature was cooled to 0°C while stirring. Potassium permanganate (7.23 g), water (161 mL), and sodium hydroxide (1.61 g) were added to another flask and stirred to prepare an aqueous potassium permanganate solution. The aqueous potassium permanganate solution was slowly added dropwise to the previously prepared solution of compound 7 so that the internal temperature did not exceed 5°C. After the addition, stirring was continued at 0°C for 1 hour. A saturated aqueous sodium pyrosulfite solution was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed. The formed precipitate was removed by filtration, and the filtrate was extracted three times with ethyl acetate. The organic layer was washed with saturated saline and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the obtained organic layer was concentrated with a rotary evaporator to obtain 3.03 g of a crude product. The mixture was purified by silica gel column chromatography to obtain 2.02 g (10.7 mmol) of compound 8. 1 The H-NMR data is shown below.

[0285] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ1.76 (s, 6H), 2.84 (br s, 2H), 3.76 (br s, 2H), 7.15-7.25 (m, 4H). <Synthesis of compound 9> Compound 9 shown below was synthesized by the method described below.

[0286] [ka]

[0287] In a nitrogen atmosphere, 2.15 g (10.4 mmol) of compound 8 and 10 mL of dehydrated pyridine were added to a 50 mL three-neck flask and stirred. The mixture was cooled in an ice bath, and 2.8 mL of benzoyl chloride was slowly added. After the addition, the mixture was warmed to room temperature and stirred overnight. The mixture was cooled again in an ice bath, and 5 mL of methanol was added. 100 mL of water and 100 mL of ethyl acetate were added to a beaker, and the organic layer was separated. The organic layer was washed three times with water, washed with a saturated aqueous solution of ammonium chloride and saturated saline, and dried over magnesium sulfate. The magnesium sulfate was filtered, and the mixture was concentrated using a rotary evaporator to obtain 4.78 g of a crude product. The mixture was purified by silica gel column chromatography to obtain 3.29 g (7.9 mmol, white solid) of compound 9. The obtained compound 9 was 1 The H-NMR data is shown below.

[0288] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 1.85 (s, 6H), 5.34 (s, 2H), 7.22-7.55 (m, 10H), 7.91-8.02 (m, 4H). The resulting compound 9 had a melting completion temperature of 196°C.

[0289] [Example A5] <Synthesis of compound 10> Compound 10 shown below was synthesized according to the reaction scheme shown below and by the method described below.

[0290] [ka]

[0291] In a nitrogen atmosphere, 16.0 g of 3,4-dibromotoluene, 120 mL of dehydrated toluene, and 4.23 g of cyclopentadiene were added to a 500 mL three-neck flask and stirred. The cyclopentadiene used in the reaction was prepared by pyrolyzing dicyclopentadiene at 160-170°C with reference to Non-Patent Document 13, and the component distilled at 40°C-67°C was used immediately. The internal temperature was cooled to 0°C, and 40 mL of n-butyllithium hexane solution (1.6 M) was slowly added dropwise. After the addition, the temperature was gradually raised to room temperature and stirred at room temperature for 4 hours. After the reaction, a saturated aqueous ammonium chloride solution was added, and then diethyl ether was added. The organic layer was separated, and the organic layer was washed with water and saturated saline. The organic layer was dried over magnesium sulfate, and the magnesium sulfate was filtered off. The obtained organic layer was concentrated with a rotary evaporator to obtain 14.32 g of a crude product. The crude product was purified by silica gel column chromatography to obtain 4.19 g (26.8 mmol) of compound 10. 1 The H-NMR data is shown below.

[0292] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ2.19-2.24(m, 1H), 2.27-2.33 (m, 4H), 3.85 (s, 2H), 6.71-6.81 (m, 2H), 7.06-7.12 (m, 3H). <Synthesis of compound 11> Compound 11 shown below was synthesized by the method described below.

[0293] [ka]

[0294] In a 500mL three-neck flask, 4.19g (26.8mmol) of compound 10, 107mL of tert-butyl alcohol, and 27mL of water were added, and the internal temperature was cooled to 0°C while stirring. In another flask, 6.40g of potassium permanganate, 135mL of water, and 1.42g of sodium hydroxide were added and stirred to prepare an aqueous potassium permanganate solution. The aqueous potassium permanganate solution was slowly added dropwise to the previously prepared solution of compound 10 so that the internal temperature did not exceed 5°C. After the dropwise addition, stirring was continued at 0°C for 1 hour. A saturated aqueous sodium pyrosulfite solution was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed. The formed precipitate was removed by filtration, and the filtrate was extracted four times with ethyl acetate. The organic layer was washed with saturated saline and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the obtained organic layer was concentrated with a rotary evaporator to obtain 3.80g of a crude product. The mixture was purified by silica gel column chromatography to obtain 3.04 g (16.0 mmol) of compound 11. 1 The H-NMR data is shown below.

[0295] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ1.86-1.93 (m, 1H), 2.18-2.24 (m, 1H), 2.30 (s, 3H), 2.78-2.86 (m, 2H), 3.15-3.19 (m, 2H), 3.78-3.84 (m, 2H), 6.90 (d, J=7.3 Hz, 1H), 7.02 (s, 1H), 7.07 (d, J=7.3 Hz, 1H). <Synthesis of compound 12> Compound 12 shown below was synthesized by the method described below.

[0296] [ka]

[0297] In a nitrogen atmosphere, 2.94 g (15.5 mmol) of compound 11, 80 mL of dehydrated chloroform, and 4.6 g of benzoyl chloride were added to a 200 mL three-neck flask and stirred. The mixture was cooled in an ice bath, and 2.6 mL of dehydrated pyridine was slowly added dropwise. After the addition, the mixture was warmed to room temperature and stirred overnight, cooled again in an ice bath, and 5 mL of methanol was added. Water and chloroform were added to the reaction solution and stirred, and the organic layer was separated. The organic layer was washed with saturated saline and then dried over magnesium sulfate. The magnesium sulfate was filtered off, and the obtained organic layer was concentrated using a rotary evaporator to obtain 7.91 g of a crude product. The mixture was purified by silica gel column chromatography to obtain 4.82 g (12.1 mmol, white solid) of compound 12. The obtained compound 12 1 The H-NMR data is shown below.

[0298] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ2.08-2.17 (m, 1H), 2.35 (s, 3H), 2.55-2.63 (m, 1H), 3.49-3.55 (m, 2H), 5.13-5.18 (m, 2H), 6.96-7.04 (m, 1H), 7.15-7.39 (m, 6H), 7.44-7.52 (m, 2H), 7.87-7.95 (m, 4H). The resulting compound 12 had a melting completion temperature of 155°C.

[0299] [Example A6] <Synthesis of compound 13> Compound 13 shown below was synthesized according to the reaction scheme below and by the method described below.

[0300] [ka]

[0301] Under a nitrogen atmosphere, 21.7 g of sodium hydride (64.6% liquid paraffin dispersion) was added to a 200 mL three-neck flask, and 135 mL of dehydrated tetrahydrofuran was added and stirred. 19.3 g of cyclopentadiene was slowly dropped while cooling in an ice bath. The cyclopentadiene used in the reaction was obtained by thermally decomposing dicyclopentadiene at 160 to 170 ° C. with reference to Non-Patent Document 13, and the component distilled at 40 ° C. to 67 ° C. was promptly used. After dropping, the mixture was stirred at room temperature for 20 minutes, and then 28.9 g of 1,2-dichloroethane was slowly dropped while cooling in an ice bath. After dropping, the mixture was heated to room temperature and stirred for 8 hours. 100 mL of tetrahydrofuran and 10.5 g of water were added to a beaker to prepare hydrous THF. After the reaction, the flask was cooled in an ice bath, and hydrous tetrahydrofuran was slowly dropped. Ice water was prepared in another flask, and the previous reaction liquid was transferred into the ice water. Then, pentane was added, and the organic layer was separated. The organic layer was then washed twice with 0.5N hydrochloric acid, twice with water, and once with saturated saline, and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the obtained organic layer was distilled, and the components at 664 to 665 torr and distillation temperature of 88 to 92°C were collected, and 18.09 g of compound 13 was obtained.

[0302] <Synthesis of compound 14> Compound 14 shown below was synthesized according to the reaction scheme below and by the method described below.

[0303] [ka]

[0304] In a nitrogen atmosphere, 15.1 g (64.0 mmol) of 1,2-dibromobenzene, 130 mL of dehydrated toluene, and 5.90 g of compound 13 were added to a 500 mL three-neck flask and stirred. The internal temperature was cooled to 0°C, and 40 mL of n-butyllithium hexane solution (1.6 M) was slowly added dropwise. After the addition, the temperature was gradually raised to room temperature and stirred at room temperature for 4 hours. After the reaction, a saturated aqueous ammonium chloride solution was added, followed by diethyl ether. The organic layer was separated and washed with water and saturated saline in that order. The organic layer was dried over magnesium sulfate, and the magnesium sulfate was filtered off, and the obtained organic layer was concentrated with a rotary evaporator to obtain 15.44 g of crude product. The crude product was purified by silica gel column chromatography to obtain 7.70 g (45.8 mmol) of compound 14.

[0305] <Synthesis of compound 14-2> Compound 14-2 shown below was synthesized by the method described below.

[0306] [ka]

[0307] Compound 14 (7.7 g, 45.8 mmol), tert-butyl alcohol (178 mL), and water (44 mL) were added to a 500 mL three-neck flask, and the internal temperature was cooled to 0° C. while stirring. Potassium permanganate (10.6 g), water (222 mL), and sodium hydroxide (2.32 g) were added to another flask and stirred to prepare an aqueous potassium permanganate solution. The aqueous potassium permanganate solution was slowly added dropwise to the previously prepared solution of compound 14 so that the internal temperature did not exceed 5° C. After the addition, stirring was continued at 0° C. for 1 hour. A saturated aqueous sodium pyrosulfite solution was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed. The formed precipitate was removed by filtration, and the filtrate was extracted four times with ethyl acetate. The organic layer was washed with saturated saline and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the obtained organic layer was concentrated with a rotary evaporator to obtain 5.63 g of a crude product. The mixture was purified by silica gel column chromatography to obtain 3.85 g (19.0 mmol) of compound 14-2. 1 The H-NMR data is shown below.

[0308] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ0.29-0.35 (m, 2H), 0.89-0.95 (m, 2H), 2.69-2.79 (m, 4H), 3.91-3.96 (m, 2H), 7.08-7.22 (m, 4H). <Synthesis of compound 15> Compound 15 shown below was synthesized by the method described below.

[0309] [ka]

[0310] In a nitrogen atmosphere, 4.06 g (24.1 mmol) of compound 14-2, 105 mL of dehydrated chloroform, and 5.95 g of benzoyl chloride were added to a 200 mL three-neck flask and stirred. The mixture was cooled in an ice bath, and 3.4 mL of dehydrated pyridine was slowly added dropwise. After the addition, the mixture was warmed to room temperature and stirred overnight, cooled again in an ice bath, and 5 mL of methanol was added. Water and chloroform were added to the reaction solution and stirred, and the organic layer was separated. The organic layer was washed with saturated saline and then dried over magnesium sulfate. The magnesium sulfate was filtered off, and the obtained organic layer was concentrated using a rotary evaporator to obtain 9.65 g of a crude product. The mixture was purified by silica gel column chromatography to obtain 3.88 g (9.5 mmol, white solid) of compound 15. 1 The H-NMR data is shown below.

[0311] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ0.46-0.56 (m, 2H), 1.05-1.14 (m, 2H), 3.04 (s, 2H), 5.28 (s, 2H), 7.17-7.37 (m, 8H), 7.44-7.53 (m, 2H), 7.88-7.96 (m, 4H). The resulting compound 15 had a melting completion temperature of 111°C.

[0312] [Example A7] <Synthesis of compound 16> Compound 16 shown below was synthesized according to the reaction scheme below and by the method described below.

[0313] [ka]

[0314] In a nitrogen atmosphere, 20.0 g (68.5 mmol) of 1,2-dibromo-4-tert-butylbenzene, 130 mL of dehydrated toluene, and 4.54 g of cyclopentadiene were added to a 500 mL three-neck flask and stirred. The cyclopentadiene used in the reaction was prepared by pyrolyzing dicyclopentadiene at 160-170°C with reference to Non-Patent Document 13, and the component distilled at 40°C-67°C was used immediately. The internal temperature was cooled to 0°C, and 43 mL of n-butyllithium hexane solution (1.6 M) was slowly dripped in. After dripping, the temperature was gradually raised to room temperature and stirred at room temperature for 12 hours. After the reaction, a saturated aqueous ammonium chloride solution was added, followed by diethyl ether. The organic layer was separated and washed with water and saturated saline in that order. The organic layer was dried over magnesium sulfate, and the magnesium sulfate was filtered off. The obtained organic layer was concentrated with a rotary evaporator to obtain 19.67 g of a crude product. The crude product was purified by silica gel column chromatography to obtain 5.57 g (28.1 mmol) of compound 16. 1 The H-NMR data is shown below.

[0315] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ1.30 (s, 9H), 2.21-2.33 (m, 2H), 3.83-3.87 (m, 2H), 6.76-6.80 (m, 2H), 6.93 (dd, J=7.2, 1.6 Hz, 1H), 7.13 (d, J=7.2 Hz, 1H), 7.29 (d, J=1.6 Hz, 1H). <Synthesis of compound 17> Compound 17 shown below was synthesized by the method described below.

[0316] [ka]

[0317] In a 500mL three-neck flask, 5.57g (28.1mmol) of compound 16, 109mL of tert-butyl alcohol, and 27mL of water were added, and the internal temperature was cooled to 0°C while stirring. In another flask, 6.55g of potassium permanganate, 135mL of water, and 1.55g of sodium hydroxide were added and stirred to prepare an aqueous potassium permanganate solution. The aqueous potassium permanganate solution was slowly added dropwise to the previously prepared solution of compound 16 so that the internal temperature did not exceed 5°C. After the addition, stirring was continued at 0°C for 1 hour. A saturated aqueous sodium pyrosulfite solution was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed. The formed precipitate was removed by filtration, and the filtrate was extracted four times with ethyl acetate. The organic layer was washed with saturated saline and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the obtained organic layer was concentrated using a rotary evaporator. The crude product was purified by silica gel column chromatography to obtain 4.11 g (17.7 mmol) of compound 17. 1 The H-NMR data is shown below.

[0318] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ1.29 (s, 9H), 1.88-1.95 (m, 1H), 2.19-2.25 (m, 1H), 2.89 (br s, 2H), 3.17-3.20 (m, 2H), 3.80-3.84 (m, 2H), 7.09-7.12 (m, 2H), 7.22-7.24 (m, 1H). <Synthesis of compound 18> Compound 18 shown below was synthesized by the method described below.

[0319] [ka]

[0320] In a nitrogen atmosphere, 4.11 g (9.3 mmol) of compound 17 and 17.7 mL of dehydrated pyridine were added to a 50 mL three-neck flask and stirred. The mixture was cooled in an ice bath, and 4.3 mL of benzoyl chloride was slowly added. After the addition, the mixture was warmed to room temperature and stirred overnight. The mixture was cooled again in an ice bath, and 5 mL of methanol was added. 100 mL of water and 100 mL of ethyl acetate were added to a beaker, and the organic layer was separated. The organic layer was washed three times with water, once with a saturated aqueous solution of ammonium chloride, and once with saturated saline, and then dried over magnesium sulfate. The magnesium sulfate was filtered, and the mixture was concentrated using a rotary evaporator to obtain 9.34 g of a crude product. The product was purified by silica gel column chromatography to obtain 6.13 g of a solid component. The obtained solid was recrystallized with hexane to obtain 4.0 g (9.0 mmol, white solid) of compound 18. The obtained compound 18 1 The H-NMR data is shown below.

[0321] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ1.33 (s, 9H), 2.11-2.19 (m, 1H), 2.56-2.63 (m, 1H), 3.53 (s, 2H), 5.15-5.19 (m, 2H), 7.18-7.32 (m, 6H), 7.37-7.39 (m, 1H), 7.44-7.53 (m, 2H), 7.88-7.94 (m, 4H). The resulting compound 18 had a melting completion temperature of 115°C.

[0322] [Example A8] <Synthesis of compound 19> Compound 19 shown below was synthesized by the method described below.

[0323] [ka]

[0324] In a nitrogen atmosphere, 20.0 g (75.8 mmol) of 1,2-dibromo-4,5-dimethylbenzene, 150 mL of dehydrated toluene, and 5.01 g of cyclopentadiene were added to a 500 mL three-neck flask and stirred. The cyclopentadiene used in the reaction was prepared by pyrolyzing dicyclopentadiene at 160-170°C with reference to Non-Patent Document 13, and the component distilled at 40°C-67°C was used immediately. The internal temperature was cooled to 0°C, and 47.5 mL of n-butyllithium hexane solution (1.6 M) was slowly dripped. After dripping, the temperature was gradually raised to room temperature and stirred at room temperature for 12 hours. After the reaction, a saturated aqueous ammonium chloride solution was added, followed by diethyl ether. The organic layer was separated and washed with water and saturated saline in that order. The organic layer was dried over magnesium sulfate, and the magnesium sulfate was filtered off. The obtained organic layer was concentrated with a rotary evaporator to obtain 18.64 g of a crude product. The crude product was purified by silica gel column chromatography to obtain 3.89 g (22.8 mmol) of compound 19. 1 The H-NMR data is shown below.

[0325] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ2.17-2.22 (m, 7H), 2.29 (dt, J=6.9, 1.6 Hz, 1H), 3,81-3.85 (m, 2H), 6.77 (t, J=2.0 Hz, 2H), 7.03 (s, 2H). <Synthesis of compound 20> Compound 20 shown below was synthesized by the method described below.

[0326] [ka]

[0327] In a 500mL three-neck flask, 5.57g (22.8mmol) of compound 19, 89mL of tert-butyl alcohol, and 22mL of water were added, and the internal temperature was cooled to 0°C while stirring. In another flask, 5.33g of potassium permanganate, 111mL of water, and 1.22g of sodium hydroxide were added and stirred to prepare an aqueous potassium permanganate solution. The aqueous potassium permanganate solution was slowly added dropwise to the previously prepared solution of compound 19 so that the internal temperature did not exceed 5°C. After the addition, stirring was continued at 0°C for 1 hour. A saturated aqueous sodium pyrosulfite solution was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed. The formed precipitate was removed by filtration, and the filtrate was extracted four times with ethyl acetate. The organic layer was washed with saturated saline and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the obtained organic layer was concentrated using a rotary evaporator. The crude product was purified by silica gel column chromatography to obtain 2.25 g (11.0 mmol) of compound 20. 1 The H-NMR data is shown below.

[0328] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ1.83-1.90 (m, 1H), 2.17-2.23 (m, 7H), 2.70-2.77 (m, 2H), 3.12-3.17 (m, 2H), 3.77-3.83 (m, 2H), 6.98 (s, 2H). <Synthesis of compound 21> Compound 21 shown below was synthesized by the method described below.

[0329] [ka]

[0330] In a nitrogen atmosphere, 2.25 g (11.0 mmol) of compound 20 and 11.0 mL of dehydrated pyridine were added to a 50 mL three-neck flask and stirred. The mixture was cooled in an ice bath, and 2.7 mL of benzoyl chloride was slowly added. After the addition, the mixture was warmed to room temperature and stirred overnight. The mixture was cooled again in an ice bath, and 5 mL of methanol was added. 100 mL of water and 100 mL of ethyl acetate were added to a beaker, and the organic layer was separated. The organic layer was washed three times with water, once each with a saturated aqueous ammonium chloride solution and once each with saturated saline, and dried over magnesium sulfate. The magnesium sulfate was filtered, and the mixture was concentrated using a rotary evaporator to obtain 4.82 g of a crude product. The mixture was purified by silica gel column chromatography to obtain 4.44 g (10.8 mmol, pale yellow solid) of compound 21. 1 The H-NMR data is shown below.

[0331] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ2.09 (d, J = 9.8 Hz, 1H), 2.26 (s, 6H), 2.57 (d, J = 9.8 Hz, 1H), 3.49 (s, 2H), 5.13 (d, J = 1.3 Hz, 2H), 7.13 (s, 2H), 7.20-7.31 (m, 4H), 7.44-7.52 (m, 2H), 7.87-7.93 (m, 4H). The resulting compound 21 had a melting completion temperature of 152°C.

[0332] [Example A9] <Synthesis of compound 22> Compound 22 shown below was synthesized by the method described below.

[0333] [ka]

[0334] A 1L three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a dropping funnel, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 6.00mL (44.1mmol, 1 equivalent) of 2-isopropylphenol was charged, followed by 100mL of dichloromethane and 0.62mL (4.41mmol, 0.1 equivalent). Next, under a nitrogen atmosphere, 8.21g (46.1mmol, 1.05 equivalent) of N-bromosuccinimide (NBS) dissolved in 400mL of dichloromethane was slowly dropped into the reaction solution prepared above at room temperature, and the reaction solution after the dropwise addition was stirred at room temperature for 1 hour. After the reaction was completed, hydrochloric acid (2M) was added until the pH became 1, and 100mL of water was added, followed by extraction with dichloromethane three times. The collected organic layer was dried over sodium sulfate and concentrated using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane) to obtain 9.40 g (43.7 mmol, 91% yield) of compound 22. The spectrum of the compound obtained was in good agreement with that of the same compound synthesized in "J. Med. Chem. 2017, 60, 3618-3625". 1 The H-NMR data is shown below.

[0335] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ1.24 (d, J=6.9 Hz, 6H), 3.32 (sep, J=6.9 Hz, 1H), 5.57 (s, 1H), 6.77 (t, J=7.5 Hz, 1H), 7.14 (dd, J=7.5, 1.7 Hz, 1H) 7.29 (dd, J=7.5, 1.7 Hz, 1H). Synthesis reference: Bull. Chem. Soc. Jpn. 1993, 66, 1576-1579. <Synthesis of compound 23> Compound 23 shown below was synthesized by the method described below.

[0336] [ka]

[0337] A 500mL three-neck flask containing a stirrer that had been thoroughly dried by heating was equipped with a reflux condenser, a flat stopper, and a three-way cock. Under a nitrogen atmosphere, 9.40g (43.7mmol, 1 equivalent) of compound 22, 85mL of THF, and 12.0mL (56.8mmol, 1.3 equivalents) of 1,1,1,3,3,3-hexamethyldisilazane (HMDS) were added, and the flat stopper was replaced with a thermometer, followed by heating and stirring at 80°C in an oil bath. After stirring overnight, the mixture was allowed to cool to room temperature, then reduced pressure was applied under a nitrogen atmosphere, and THF and unreacted HMDS were removed from the reaction system. The product of this reaction was used as is in the following reaction without purification.

[0338] The product vessel from the above reaction was fitted with an addition funnel and 120 mL of THF was added and then cooled to -78°C. n 38.3mL (1.6M, 61.2mmol, 1.4eq) of BuLi hexane solution was slowly added dropwise, and after completion of the addition, the mixture was stirred at -78°C for 30 minutes. Subsequently, 10.0mL (61.0mmol, 1.4eq) of trifluoromethanesulfonic anhydride (Tf2O) was slowly added dropwise under -78°C conditions, and after completion of the addition, the mixture was stirred at -78°C for 30 minutes, and the reaction solution was then allowed to reach room temperature. The reaction solution was cooled again to 0°C, and saturated aqueous sodium bicarbonate solution was slowly added until the pH was about 7-8. The mixture was extracted three times with ethyl acetate, and the collected organic layer was dried over sodium sulfate and then concentrated with a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (developing solvent: hexane), and 9.93g (29.2mmol, yield 67%) of compound 23 was obtained. The spectrum of the obtained compound 23 was in good agreement with that of the same compound synthesized in Angew. Chem. Int. Ed. 2011, 50, 5674-5677. 1 The H-NMR data is shown below.

[0339] 1H NMR (270 MHz, CDCl3, TMS as internal standard): δ 0.38 (s, 9H), 1.24 (d, J=6.9 Hz, 6H), 3.31 (sep, J=6.9 Hz, 1H), 7.31-7.43 (m, 3H). Synthesis reference: Org. Lett. 2013, 15, 5722-5725. <Synthesis of compound 24> Compound 24 shown below was synthesized by the method described below.

[0340] [ka]

[0341] A 1L three-necked flask with a stirrer that had been thoroughly dried by heating was equipped with a reflux condenser, a flat stopper, and a three-way cock, and 22.2g (146mmol, 5 equivalents) of cesium fluoride and 290mL of acetonitrile were charged under a nitrogen atmosphere. Next, 12.3mL (146mmol, 5 equivalents) of cyclopentadiene obtained immediately before by thermal decomposition of dicyclopentadiene was added to the reaction solution, and immediately thereafter, 9.93g (29.2mmol, 1 equivalent) of compound 23 was added. After replacing the flat stopper with a thermometer, the mixture was heated to 40°C in an oil bath and stirred for 16 hours. After the reaction was completed, the mixture was allowed to cool to room temperature, and the reaction solution was passed through silica gel (developing solvent: ethyl acetate) and concentrated using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (developing solvent: hexane), and 5.32g of a solution containing compound 24 and a small amount of impurities was obtained. It was used in the next reaction without further purification. The obtained compound 24 1 The H-NMR data is shown below.

[0342] 1H NMR (270 MHz, CDCl3, TMS as internal standard): δ1.20 (d, J =6.9 Hz, 3H), 1.28 (d, J=6.9 Hz, 3H), 2.17-2.21 (m, 1H), 2.26-2.30 (m, 1H), 3.13 (sep, J=6.9 Hz, 1H), 3.86-3.88 (m, 1H), 4.08-4.09 (m, 1H), 6.77-6.93 (m, 4H), 7.07 (d, J=6.3 Hz, 1H). Synthesis reference: Macromolecules 2017, 50, 580-586. <Synthesis of compound 25> Compound 25 shown below was synthesized by the method described below.

[0343] [ka]

[0344] A 500 mL three-neck flask with a stirrer was equipped with a dropping funnel, a thermometer, and a three-way cock. t BuOH 120mL, water 35mL, and a mixed solution of compound 24 obtained in <Synthesis of compound 24> (5.32g (1 equivalent)) were charged, and the reaction solution was cooled to 0℃. NaOH 1.45g (36.2mmol, 1.25 equivalent) and KMnO4 6.86g (43.4mmol, 1.5 equivalent) were dissolved in water 130mL, and slowly added dropwise to the reaction solution. After the addition was completed, the mixture was stirred for another 30 minutes under the condition of 0℃, and then unreacted KMnO4 was quenched using a saturated aqueous solution of sodium pyrosulfite. After stirring at room temperature for a while, sodium bicarbonate was added until the pH of the reaction solution became about 7-8, and the resulting white precipitate was removed by filtration. The filtered solution was extracted three times with ethyl acetate, and the collected organic layer was dried over sodium sulfate and then concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (developed with 1 L of hexane, then developed with hexane:ethyl acetate = 3:1) to obtain 5.31 g (24.3 mmol, yield 84%) of compound 25. 1The H-NMR data is shown below.

[0345] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ1.22 (d, J =6.9 Hz, 3H), 1.27 (d, J = 6.9 Hz, 3H),1.86-1.92 (m, 1H), 2.20-2.24 (m, 1H), 2.71 (d, J = 4.9 Hz, 1H), 2.86 (d, J = 4.9 Hz, 1H), 3.09 (sep, J = 6.9 Hz,1H), 3.20 (br s, 1H), 3.40 (br s, 1H), 3.78-3.87 (m, 2H), 6.99-7.10 (m, 3H). Synthesis reference: J. Org. Chem. 2017, 82, 9715-9730. <Synthesis of compound 26> Compound 26 shown below was synthesized by the method described below.

[0346] [ka]

[0347] A 100mL three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 5.31g (24.3mmol, 1 equivalent) of compound 25 and about 10mL of pyridine were added, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 7.0mL (60.3mmol, 2.5 equivalents) of benzoyl chloride was slowly added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature and stirred overnight. After the reaction was completed, the solution was cooled to 0°C, 10mL of methanol was added, and the mixture was stirred for 1 hour. After adding about 20mL of water and about 30mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous ammonium chloride solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate=20:1) and recrystallization with hexane to obtain 5.19 g (12.2 mmol, yield 50%, white solid) of compound 26. 1 The H-NMR data is shown below.

[0348] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 1.32 (d, J = 6.9 Hz, 3H), 1.33 (d, J = 6.9 Hz, 3H), 2.10-2.15 (m, 1H), 2.57-2.61 (m, 1H), 3.19 (sep, J = 6.9 Hz,1H), 3.56 (br s, 1H), 3.75 (br s, 1H), 5.12-5.19 (m, 2H), 7.08-7.17 (m, 3H), 7.22-7.35 (overlapped with CHCl3 signals, m, 4H), 7.45-7.54 (m, 2H), 7.87-7.96 (m, 4H). The resulting compound 26 had a melting completion temperature of 114°C.

[0349] [Example A10] <Synthesis of compound 27> Compound 27 shown below was synthesized by the method described below.

[0350] [ka]

[0351] In the synthesis of compound 23, 7.26 g (23.2 mmol, 48% yield) of compound 27 was obtained according to the procedure and equivalent relationship described in the synthesis of compound 23, except that 6.00 mL (48.4 mmol) of 6-bromo-o-cresol was used instead of 9.40 g (43.7 mmol) of compound 22. The spectrum of compound 27 obtained was in good agreement with that of the same compound synthesized in "J. Org. Chem. 2015, 80, 11618-11623". 1 The H-NMR data is shown below.

[0352] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 0.38 (s, 9H), 2.38 (s, 3H), 7.28-7.30 (m, 2H), 7.38-7.47 (m, 1H). <Synthesis of compound 28> Compound 28 shown below was synthesized by the method described below.

[0353] [ka]

[0354] In the synthesis of compound 24, 3.39 g (17 mmol, 74% yield) of compound 28 containing a small amount of hexane was obtained in accordance with the procedure and equivalent relationship described in the synthesis of compound 24, except that 7.26 g (23.2 mmol) of compound 27 was used instead of 9.93 g (29.2 mmol) of compound 23. 1 The H-NMR data is shown below.

[0355] 1H NMR (270 MHz, CDCl3, TMS as internal standard): δ2.17-2.21 (m, 1H), 2.26-2.31 (m,4H), 3.85-3.88 (m, 1H), 3.99-4.00 (m, 1H), 6.73-6.85 (m, 4H), 7.05 (d, J = 6.9 Hz, 1H). <Synthesis of compound 29> Compound 29 shown below was synthesized by the method described below.

[0356] [ka]

[0357] A 500 mL three-neck flask with a stirrer was equipped with a dropping funnel, a thermometer, and a three-way cock. t BuOH 70mL, water 20mL, and 3.39g (17mmol, 1 equivalent) of compound 28 obtained in <Synthesis of compound 28> with a small amount of hexane were added, and the reaction solution was cooled to 0℃. NaOH 0.85g (21.3mmol, 1.25 equivalent) and KMnO4 4.03g (25.5mmol, 1.5 equivalent) were dissolved in water 80mL, and slowly added dropwise to the reaction solution. After the addition was completed, the mixture was stirred for another 30 minutes under the condition of 0℃, and then unreacted KMnO4 was quenched using a saturated aqueous solution of sodium pyrosulfite. After stirring at room temperature for a while, sodium bicarbonate was added until the pH of the reaction solution was about 7-8, and the resulting white precipitate was removed by filtration. The filtered solution was extracted three times with ethyl acetate, and the collected organic layer was dried over sodium sulfate and then concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate=3:1) to obtain 2.19 g (11.5 mmol, yield 68%) of compound 29. 1 The H-NMR data is shown below.

[0358] 1H NMR (270 MHz, CDCl3, TMS as internal standard): δ1.86-1.91 (m, 1H), 2.19-2.24 (m, 1H), 2.31 (s, 3H), 2.72-2.74 (m, 1H), 2.83-2.85 (m, 1H), 3.19-3.20 (m, 1H), 3.31-3.32 (m, 1H), 3.77-3.84 (m, 2H), 6.89-7.07 (m, 3H). <Synthesis of compound 30> Compound 30 shown below was synthesized by the method described below.

[0359] [ka]

[0360] A 100mL three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.19g (11.5mmol, 1 equivalent) of compound 29 and about 10mL of pyridine were added, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 2.94mL (25.3mmol, 2.2 equivalents) of benzoyl chloride was slowly added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature and stirred for 3 hours. After the reaction was completed, the solution was cooled to 0°C, 20mL of methanol was added, and the mixture was stirred for 1 hour. After adding about 20mL of water and about 30mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous ammonium chloride solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (developing solvent: hexane:ethyl acetate=10:1) to obtain 3.19 g (8.01 mmol, yield 70%, white solid) of compound 30. 1 The H-NMR data is shown below.

[0361] 1H NMR (270 MHz, CDCl3, TMS as internal standard): δ 2.09-2.14 (m, 1H), 2.41 (s, 3H), 2.56-2.60 (m, 1H), 3.55 (br s, 1H), 3.67 (br s, 1H), 5.10-5.18 (m, 2H), 6.99-7.17 (m, 3H), 7.24-7.33 (overlapped with CHCl3 signals, m, 4H), 7.45-7.53 (m, 2H), 7.88-7.95 (m, 4H). The resulting compound 30 had a melting completion temperature of 131°C.

[0362] [Example A11] <Synthesis of Compound 31> Compound 31 shown below was synthesized by the method described below.

[0363] [ka]

[0364] In the synthesis of compound 22, 10.8 g (53.9 mmol, 90% yield) of compound 31 was obtained according to the procedure and equivalent relationship described in the synthesis of compound 22, except that 7.33 g (60.0 mmol) of 2,5-dimethylphenol was used instead of 6.00 mL (44.1 mmol) of 2-isopropylphenol. The spectrum of the obtained compound was in good agreement with that of the same compound synthesized in "Adv. Synth. Catal. 2008, 350, 1309-1315". 1 The H-NMR data is shown below.

[0365] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 2.27 (s, 3H), 2.36 (s, 3H), 5.65 (s, 1H), 6.71 (d, J = 7.6 Hz, 1H), 6.95 (d, J = 7.6 Hz, 1H). <Synthesis of compound 32> Compound 32 shown below was synthesized by the method described below.

[0366] [ka]

[0367] In the synthesis of compound 23, 10.8 g (53.9 mmol) of compound 31 was used instead of 9.40 g (43.7 mmol) of compound 22, and the procedure and equivalent relationship described in the synthesis of compound 23 were followed to obtain 13.0 g of compound 32 containing a small amount of impurity. The product of this reaction was not further purified or identified, and was used in the next reaction.

[0368] <Synthesis of compound 33> Compound 33 shown below was synthesized by the method described below.

[0369] [ka]

[0370] In the synthesis of compound 24, 5.58 g (32.8 mmol) of compound 33 was obtained in accordance with the procedure and equivalent relationship described in the synthesis of compound 24, except that 13.0 g (39.9 mmol is 1 equivalent) of compound 32 containing a small amount of impurity was used instead of 9.93 g (29.2 mmol) of compound 23. 1 The H-NMR data is shown below.

[0371] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ2.13-2.17 (m, 1H), 2.23-2.27 (m, 7H), 3.97-4.00 (m, 2H), 6.66 (s, 2H), 6.78-6.79 (m, 2H). <Synthesis of compound 34> Compound 34 shown below was synthesized by the method described below.

[0372] [ka]

[0373] A 500 mL three-neck flask with a stirrer was equipped with a dropping funnel, a thermometer, and a three-way cock. t BuOH 135mL, water 40mL, and compound 33 5.58g (32.8mmol, 1eq) were added, and the reaction solution was cooled to 0℃. NaOH 1.64g (41.0mmol, 1.25eq) and KMnO4 7.78g (49.2mmol, 1.5eq) were dissolved in water 150mL, and slowly added dropwise to the reaction solution. After the addition, the mixture was stirred for another 30 minutes at 0℃, and then unreacted KMnO4 was quenched using a saturated aqueous solution of sodium pyrosulfite. After stirring at room temperature for a while, sodium bicarbonate was added until the pH of the reaction solution reached about 7-8, and the resulting white precipitate was removed by filtration. The filtered solution was extracted three times with ethyl acetate, and the collected organic layer was dried over sodium sulfate and then concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate=5:1) to obtain 5.29 g (25.9 mmol, yield 79%) of compound 34. 1 The H-NMR data is shown below.

[0374] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ1.82-1.87 (m, 1H), 2.18-2.22 (m, 1H), 2.27 (s, 6H), 2.73-2.78 (m, 2H), 3.29-3.03 (m, 2H), 3.76-3.80 (m, 2H), 6.81 (s, 2H). <Synthesis of compound 35> Compound 35 shown below was synthesized by the method described below.

[0375] [ka]

[0376] A 100mL three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 5.29g (25.9mmol, 1 equivalent) of compound 34 and about 10mL of pyridine were added, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 6.60mL (57.0mmol, 2.2 equivalents) of benzoyl chloride was slowly added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature and stirred for 4 hours. After the reaction was completed, the solution was cooled to 0°C, 20mL of methanol was added, and the mixture was stirred for 1 hour. After adding about 20mL of water and about 30mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous ammonium chloride solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate=20:1) and recrystallization with hexane to obtain 5.49 g (13.3 mmol, yield 51%, white solid) of compound 35. 1 The H-NMR data is shown below.

[0377] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 2.04-2.10 (m, 1H), 2.36 (s, 6H), 2.54-2.58 (m, 1H), 3.66 (br s, 2H), 5.10-5.11 (m, 2H), 6.91 (s, 2H), 7.26-7.32 (overlapped with CHCl3 signals, m, 4H), 7.46-7.53 (m, 2H), 7.91-7.94 (m, 4H). The resulting compound 35 had a melting completion temperature of 138°C.

[0378] [Example A12] <Synthesis of compound 36> Compound 36 shown below was synthesized by the method described below.

[0379] [ka]

[0380] A 500 mL three-neck flask with a stirrer was equipped with a dropping funnel, a thermometer, and a three-way cock. t BuOH 110mL, water 35mL, 1,4-Dihydro-1,4-methanoanthracene 5.00g (26.0mmol, 1eq) were charged, and the reaction solution was cooled to 0℃. NaOH 1.30g (32.5mmol, 1.25eq) and KMnO4 6.16g (39.0mmol, 1.5eq) were dissolved in water 120mL, and slowly added dropwise to the reaction solution. After the addition, the mixture was stirred for another hour under 0℃ conditions, and then unreacted KMnO4 was quenched using a saturated aqueous solution of sodium pyrosulfite. After stirring at room temperature for a while, sodium bicarbonate was added until the pH of the reaction solution was about 7-8, and the resulting white precipitate was removed by filtration. The filtered solution was extracted three times with ethyl acetate, and the collected organic layer was dried over sodium sulfate and then concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate=10:1) to obtain 2.57 g (11.4 mmol, yield 44%) of compound 36. 1 The H-NMR data is shown below.

[0381] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ1.94-1.99 (m, 1H), 2.33-2.37 (m, 1H), 2.82 (br s, 2H), 3.37 (s, 2H), 3.92 (br s, 2H), 7.39-7.43 (m, 2H), 7.60 (br s, 2H), 7.74-7.77 (m, 2H). <Synthesis of compound 37> Compound 37 shown below was synthesized by the method described below.

[0382] [ka]

[0383] A 100mL three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.57g (11.4mmol, 1 equivalent) of compound 36 and about 10mL of pyridine were added, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 2.90mL (25.1mmol, 2.2 equivalents) of benzoyl chloride was slowly added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature and stirred overnight. After the reaction was completed, the solution was cooled to 0°C, 10mL of methanol was added, and the mixture was stirred for 1 hour. After adding about 20mL of water and about 30mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous ammonium chloride solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified by two silica gel column chromatography runs (eluent: 1st run: hexane:ethyl acetate = 20:1, then ethyl acetate only, 2nd run: hexane:ethyl acetate = 5:1) and washing with hexane, resulting in 3.09 g (7.1 mmol, yield 62%, pale yellow solid) of compound 37. 1 The H-NMR data is shown below.

[0384] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ2.19 (d, J =9.9 Hz, 1H), 2.71 (d, J = 9.2 Hz, 1H), 3.72 (br s, 2H), 5.26 (m, 2H), 7.27-7.32 (m, 4H), 7.45-7.53 (m, 4H), 7.76 (br s, 2H), 7.80-7.83 (m, 2H), 7.91-7.94 (m, 4H). The resulting compound 37 had a melting completion temperature of 164°C.

[0385] [Example A13] <Synthesis of compound 38> Compound 38 shown below was synthesized by the method described below.

[0386] [ka]

[0387] A 500 mL three-neck flask with a stirrer was equipped with a dropping funnel, a thermometer, and a three-way cock. t 150mL of BuOH, 50mL of water, and 4.33g (30.0mmol, 1eq) of 1,4-epoxy-1,4-dihydronaphthalene were added, and the reaction solution was cooled to 0℃. 1.50g (37.5mmol, 1.25eq) of NaOH and 7.11g (45.0mmol, 1.5eq) of KMnO4 were dissolved in 150mL of water, and slowly added dropwise to the reaction solution. After the addition, the mixture was stirred for another hour at 0℃, and then unreacted KMnO4 was quenched using a saturated aqueous solution of sodium pyrosulfite. After stirring at room temperature for a while, sodium bicarbonate was added until the pH of the reaction solution reached about 7-8, and the resulting white precipitate was removed by filtration. The filtered solution was extracted three times with ethyl acetate, and the collected organic layer was dried over sodium sulfate and then concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: ethyl acetate) to obtain 2.79 g (15.7 mmol, yield 53%) of compound 38. 1 The H-NMR data is shown below.

[0388] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ2.71-2.77 (m, 2H), 3.93-3.98 (m, 2H), 5.17 (s, 2H), 7.19-7.24 (m, 2H), 7.27-7.31 (m, 2H). <Synthesis of compound 39> Compound 39 shown below was synthesized by the method described below.

[0389] [ka]

[0390] A 100mL three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 3.10g (17.4mmol, 1 equivalent) of compound 38 and about 10mL of pyridine were added, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 4.50mL (38.3mmol, 2.2 equivalents) of benzoyl chloride was slowly added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature and stirred overnight. After the reaction was completed, the solution was cooled to 0°C, 10mL of methanol was added, and the mixture was stirred for 30 minutes. After adding about 20mL of water and about 30mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous ammonium chloride solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified by recrystallization from acetone to obtain 3.92 g (10.1 mmol, yield 58%, colorless transparent crystals) of compound 39. 1 The H-NMR data is shown below.

[0391] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 5.30 (s, 2H), 5.55 (s, 2H), 7.26-7.33 (overlapped by CHCl3 signals, m, 6H), 7.43-7.54 (m, 4H), 7.94-7.97 (m, 4H). The resulting compound 39 had a melting completion temperature of 188°C.

[0392] [Example A14] <Synthesis of compound 40> Compound 40 shown below was synthesized by the method described below.

[0393] [ka]

[0394] A 100mL three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.13g (12.1mmol, 1 equivalent) of compound 5 and about 10mL of pyridine were added, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 3.42mL (26.8mmol, 2.2 equivalents) of o-toluoyl chloride was slowly added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature and stirred overnight. After the reaction was completed, the solution was cooled to 0°C, 10mL of methanol was added, and the mixture was stirred for 30 minutes. After adding about 20mL of water and about 30mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous ammonium chloride solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 5:1, followed by ethyl acetate alone) to obtain 3.75 g (9.08 mmol, yield 75%, white solid) of compound 40. 1 The H-NMR data is shown below.

[0395] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ2.13-2.17 (m, 1H), 2.49 (s, 6H), 2.54-2.59 (m, 1H), 3.55 (s, 2H), 5.15-5.16 (m, 2H), 7.02 (t, J = 7.6 Hz, 2H), 7.15-7.20 (m, 4H), 7.30-7.36 (m, 4H), 7.77-7.80 (m, 2H). The resulting compound 40 had a melting completion temperature of 119°C.

[0396] [Example A15] <Synthesis of compound 41> Compound 41 shown below was synthesized by the method described below.

[0397] [ka]

[0398] A 100mL three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.15g (12.2mmol, 1 equivalent) of compound 5 and about 10mL of pyridine were added, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 3.54mL (26.8mmol, 2.2 equivalents) of m-toluoyl chloride was slowly added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature and stirred overnight. After the reaction was completed, the solution was cooled to 0°C, 10mL of methanol was added, and the mixture was stirred for 30 minutes. After adding about 20mL of water and about 30mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous ammonium chloride solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified by two silica gel column chromatography runs (eluent: hexane:ethyl acetate=5:1) and recrystallization from ethanol to obtain 2.60 g (6.30 mmol, yield 52%, white solid) of compound 41. 1 The H-NMR data is shown below.

[0399] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 2.13-2.21 (m, 7H), 2.59-2.63 (m, 1H), 3.57 (s, 2H), 5.15-5.16 (m, 2H), 7.17-7.24 (m, 4H), 7.29-7.36 (m, 4H), 7.68 (br s, 2H), 7.76-7.79 (m, 2H). The resulting compound 41 had a melting completion temperature of 84°C.

[0400] [Example A16] <Synthesis of compound 42> Compound 42 shown below was synthesized by the method described below.

[0401] [ka]

[0402] A 100mL three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.23g (12.6mmol, 1 equivalent) of compound 5 and about 10mL of pyridine were added, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 4.20mL (28.4mmol, 2.3 equivalents) of 3,5-dimethylbenzoyl chloride was slowly added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature and stirred overnight. After the reaction was completed, the solution was cooled to 0°C, 10mL of methanol was added, and the mixture was stirred for 1 hour. After adding about 20mL of water and about 30mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous ammonium chloride solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified twice by silica gel column chromatography (developing solvent: 1st time: hexane:ethyl acetate=10:1, 2nd time: hexane:ethyl acetate=20:1) to obtain 5.13 g (11.6 mmol, yield 92%, white solid) of compound 42. 1 The H-NMR data is shown below.

[0403] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ2.12-2.19 (m, 13H), 2.59-2.63 (m, 1H), 3.56 (s, 2H), 5.11-5.12 (m, 2H), 7.12 (br s, 2H), 7.17-7.20 (m, 2H), 7.32-7.35 (m, 2H), 7.53 (br s, 4H). The resulting compound 42 had a melting completion temperature of 118°C.

[0404] [Example A17] <Synthesis of compound 43> Compound 43 shown below was synthesized by the method described below.

[0405] [ka]

[0406] A 100mL three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.26g (12.8mmol, 1 equivalent) of compound 5 and about 10mL of pyridine were added. After cooling the reaction solution to 0°C, 5.00g (29.3mmol, 2.3 equivalents) of 4-methoxybenzoyl chloride was slowly added. After the addition was completed, the temperature was raised to room temperature and stirred overnight. After the reaction was completed, the solution was cooled to 0°C, 10mL of methanol was added, and the mixture was stirred for 1 hour. After adding about 20mL of water and about 30mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride, dried over sodium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified by washing with ethanol, and 4.67 g (10.5 mmol, yield 82%, pale yellow solid) of compound 43 was obtained. 1 The H-NMR data is shown below.

[0407] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ2.11-2.16 (m, 1H), 2.56-2.61 (m, 1H), 3.54 (s, 2H), 3.83 (s, 6H), 5.12-5.13 (m, 2H), 6.75-6.80 (m, 4H), 7.16-7.19 (m, 2H), 7.31-7.34 (m, 2H), 7.84-7.89 (m, 4H). The resulting compound 43 had a melting completion temperature of 167°C.

[0408] [Example A18] <Synthesis of compound 44> Compound 44 shown below was synthesized by the method described below.

[0409] [ka]

[0410] A 100mL three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.26g (12.8mmol, 1 equivalent) of compound 5 and about 10mL of pyridine were added, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 3.81mL (27.9mmol, 2.2 equivalents) of 3-methoxybenzoyl chloride was slowly added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature and stirred overnight. After the reaction was completed, the solution was cooled to 0°C, 10mL of methanol was added, and the mixture was stirred for 1 hour. After adding about 20mL of water and about 30mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous ammonium chloride solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate=10:1) and recrystallization in a two-layer system of acetone-hexane, yielding 3.07 g (6.91 mmol, yield 54%, white solid) of compound 44. 1 The H-NMR data is shown below.

[0411] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ2.13-2.18 (m, 1H), 2.57-2.61 (m, 1H), 3.56 (s, 2H), 3.66 (s, 6H), 5.16-5.17 (m, 2H), 7.01-7.06 (m, 2H), 7.17-7.23 (m, 4H), 7.32-7.35 (m, 2H), 7.41-7.42 (m, 2H), 7.52-7.56 (m, 2H). The resulting compound 44 had a melting completion temperature of 113°C.

[0412] [Example A19] <Synthesis of compound 45> Compound 45 shown below was synthesized by the method described below.

[0413] [ka]

[0414] A 100mL three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 1.78g (10.1mmol, 1 equivalent) of compound 5 and about 10mL of pyridine were added, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 3.30mL (22.3mmol, 2.2 equivalents) of 3-(trifluoromethyl)benzoyl chloride was slowly added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature and stirred overnight. After the reaction was completed, the solution was cooled to 0°C, 10mL of methanol was added, and the mixture was stirred for 1 hour. After adding about 20mL of water and about 30mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous ammonium chloride solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate=10:1) and recrystallization with hexane to obtain 3.63 g (6.98 mmol, yield 70%, colorless transparent crystals) of compound 45. 1 The H-NMR data is shown below.

[0415] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ2.19-2.24 (m, 1H), 2.60-2.65 (m, 1H), 3.59 (br s, 2H), 5.22-5.23 (m, 2H), 7.19-7.24 (m, 2H), 7.34-7.37 (m, 2H), 7.46 (t, J = 7.6 Hz, 2H), 7.73-7.77 (m, 2H), 8.09-8.12 (m, 4H). The resulting compound 45 had a melting completion temperature of 124°C.

[0416] [Example A20] <Synthesis of compound 46> Compound 46 shown below was synthesized by the method described below.

[0417] [ka]

[0418] A 100mL three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.06g (11.7mmol, 1 equivalent) of compound 5 and about 10mL of pyridine were added, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 3.80mL (25.3mmol, 2.2 equivalents) of 1-naphthoyl chloride was slowly added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature and stirred overnight. After the reaction was completed, the solution was cooled to 0°C, 10mL of methanol was added, and the mixture was stirred for 1 hour. After adding about 20mL of water and about 30mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous ammonium chloride solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate=10:1) and washed with hexane to obtain 4.73 g (9.76 mmol, yield 85%, white solid) of compound 46. 1 The H-NMR data is shown below.

[0419] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ2.19-2.24 (m, 1H), 2.65-2.69 (m, 1H), 3.67 (s, 2H), 5.34-5.35 (m, 2H), 7.06-7.12 (m, 2H), 7.21-7.24 (m, 2H), 7.33-7.46 (m, 6H), 7.76-7.80 (m, 2H), 7.86 (d, J = 8.2, 2H), 8.01-8.05 (m, 2H), 8.79-8.82 (m, 2H). The resulting compound 46 had a melting completion temperature of 158°C.

[0420] [Example A21] <Synthesis of compound 47> Compound 47 shown below was synthesized by the method described below.

[0421] [ka]

[0422] A 100mL three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.03g (11.5mmol, 1 equivalent) of compound 5 and about 10mL of pyridine were added. After cooling the reaction solution to 0°C, 4.80g (25.2mmol, 2.2 equivalents) of 2-naphthoyl chloride was slowly added. After the addition was completed, the temperature was raised to room temperature and stirred overnight. After the reaction was completed, about 10mL of dichloromethane was added and stirred for another 3 hours, the solution was cooled to 0°C, 10mL of methanol was added, and stirred for 1 hour. After adding about 20mL of water and about 30mL of dichloromethane, the solution was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous ammonium chloride solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified by two silica gel column chromatography runs (eluent: hexane:ethyl acetate=7:1 for the first run, hexane:ethyl acetate=5:1 for the second run) and washing with hexane to obtain 2.05 g (4.23 mmol, yield 37%, white solid) of compound 47. 1 The H-NMR data is shown below.

[0423] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ2.21-2.26 (m, 1H), 2.71-2.76 (m, 1H), 3.67 (br s, 2H), 5.26-5.27 (m, 2H), 7.20-7.23 (m, 2H), 7.30-7.40 (m, 6H), 7.48-7.54 (m, 2H), 7.71 (d, J = 8.6 Hz, 2H), 7.77-7.80 (m, 2H), 7.96-8.00 (m, 2H), 8.39 (br s, 2H). The resulting compound 47 had a melting completion temperature of 201°C.

[0424] [Example A22] <Synthesis of compound 48> Compound 48 shown below was synthesized by the method described below.

[0425] [ka]

[0426] A 100mL three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.15g (12.2mmol, 1 equivalent) of compound 5 and about 10mL of pyridine were added, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 4.00mL (26.8mmol, 2.2 equivalents) of 2-ethylbenzoyl chloride was slowly added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature and stirred overnight. After the reaction was completed, the solution was cooled to 0°C, 10mL of methanol was added, and the mixture was stirred for 30 minutes. After adding about 20mL of water and about 30mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous ammonium chloride solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate=20:1) to obtain 4.34 g (9.85 mmol, yield 81%, white solid) of compound 48. 1 The H-NMR data is shown below.

[0427] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ1.15 (t, J = 7.3 Hz, 6H), 2.13-2.17 (m, 1H), 2.54-2.57 (m, 1H), 2.89 (q, J = 7.3 Hz, 4H), 3.54 (br s, 2H), 5.16 (br s, 2H), 7.01 (t, J = 7.6 Hz, 2H), 7.17-7.21 (m, 4H), 7.33-7.38 (m, 4H), 7.73 (d, J = 8.2Hz, 2H). The resulting compound 48 had a melting completion temperature of 52°C.

[0428] [Example A23] <Synthesis of compound 49> Compound 49 shown below was synthesized by the method described below.

[0429] [ka]

[0430] A 100mL three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.19g (12.4mmol, 1 equivalent) of compound 5 and about 10mL of pyridine were added, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 4.50g (26.7mmol, 2.2 equivalents) of 2,3-dimethylbenzoyl chloride was slowly added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature and stirred overnight. After the reaction was completed, the solution was cooled to 0°C, 10mL of methanol was added, and the mixture was stirred for 1 hour. After adding about 20mL of water and about 30mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous ammonium chloride solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate=20:1) and recrystallization with hexane to obtain 4.62 g (10.5 mmol, yield 85%, white solid) of compound 49. 1 The H-NMR data is shown below.

[0431] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ2.10-2.31 (m, 13H), 2.51-2.55 (m, 1H), 3.53-3.54 (m, 2H), 5.13-5.14 (m, 2H), 6.88-6.95 (m, 2H), 7.17-7.23 (m, 4H), 7.33-7.36 (m, 2H), 7.49-7.52 (m, 2H). The resulting compound 49 had a melting completion temperature of 107°C.

[0432] [Example A24] <Synthesis of compound 50> Compound 50 shown below was synthesized by the method described below.

[0433] [ka]

[0434] In the synthesis of compound 6, 10 g of p-dimethylaminobenzoyl chloride was used instead of 13.4 mL of benzoyl chloride, and the reaction temperature after the addition of the reagent was 115° C. for 7 days. The procedure and equivalent relationship described in the synthesis of compound 6 were followed to obtain 4.34 g of compound 50 (light yellow solid). 1 The H-NMR data is shown below.

[0435] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ2.07-2.12 (m, 1H), 2.57-2.60 (m, 1H), 3.00 (s, 12H), 3.52 (br s, 2H), 5.10-5.11 (m, 2H), 6.52 (d, J = 8.9 Hz, 4H), 7.14-7.17 (m, 2H), 7.30-7.33 (m, 2H), 7.81 (d, J = 8.9 Hz, 4H). The resulting compound 50 had a melting completion temperature of 252°C.

[0436] [Example A25] <Synthesis of compound 51> Compound 51 shown below was synthesized by the method described below.

[0437] [ka]

[0438] A 100mL three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.80g (15.9mmol, 1 equivalent) of compound 5 and about 10mL of pyridine were added, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 4.38mL (32.3mmol, 2 equivalents) of cyclohexanecarbonyl chloride was slowly added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature and stirred overnight. After the reaction was completed, the solution was cooled to 0°C, 20mL of methanol was added, and the mixture was stirred for 1 hour. After adding about 20mL of water and about 30mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous ammonium chloride solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate=20:1) to obtain 4.57 g (11.5 mmol, yield 72%, white solid) of compound 51. 1 The H-NMR data is shown below.

[0439] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 1.19-1.53 ​​(m, 10H), 1.62-1.83 (m, 6H), 1.89-2.01 (m, 5H), 2.26-2.35 (m, 3H), 3.31-3.32 (m, 2H), 4.75-4.76 (m, 2H), 7.10-7.13 (m, 2H), 7.23-7.27 (overlapping with CHCl3 signals, m, 2H). The resulting compound 51 had a melting completion temperature of 80°C.

[0440] [Example A26] <Synthesis of compound 52> Compound 52 shown below was synthesized by the method described below.

[0441] [ka]

[0442] A 100mL three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 3.22g (18.3mmol, 1 equivalent) of compound 5 and about 10mL of pyridine were added, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 4.25mL (40.3mmol, 2.2 equivalents) of isobutyryl chloride was slowly added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature and stirred overnight. After the reaction was completed, the solution was cooled to 0°C, 20mL of methanol was added, and the mixture was stirred for 40 minutes. After adding about 20mL of water and about 30mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous ammonium chloride solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate=15:1) to obtain 5.70 g (18.0 mmol, yield 98%, pale yellow liquid) of compound 52. 1 The H-NMR data is shown below.

[0443] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 1.17-1.22 (m, 12H), 1.98-2.03 (m, 1H), 2.30-2.34 (m, 1H), 2.57 (sep, J = 6.9 Hz, 2H), 3.32-3.33 (m, 2H), 4.77-4.78 (m, 2H), 7.11-7.16 (m, 2H), 7.23-7.27 (overlapping with CHCl3 signals, m, 2H). [Example A27] <Synthesis of compound 53> Compound 53 shown below was synthesized according to the reaction scheme below and by the method described below.

[0444] [ka]

[0445] In a 1L three-neck flask, 14.8g of tricyclo[6,2,1,0(2,7)]undec-4-ene, 500mL of tert-butyl alcohol, and 100mL of water were added and cooled to 0°C while stirring. In another flask, 23.7g of potassium permanganate, 400mL of water, and 4.8g of sodium hydroxide were added and stirred to prepare an aqueous potassium permanganate solution. The aqueous potassium permanganate solution was added dropwise to the previously prepared tricycloundecene solution so that the internal temperature did not exceed 5°C. After the addition, stirring was continued at 0°C for 1 hour. Then, a saturated aqueous sodium thiosulfate solution was added dropwise until the red-purple color of the aqueous layer disappeared. The resulting precipitate was removed by filtration, and tert-butyl alcohol was distilled off from the filtrate under reduced pressure. The filtrate was then extracted three times with ethyl acetate. The organic layer was washed with saturated saline, dried over sodium sulfate, and concentrated with a rotary evaporator. Compound 53 was reacted without purification.

[0446] <Synthesis of compound 54> Compound 54 shown below was synthesized according to the reaction scheme below and by the method described below.

[0447] [ka]

[0448] In a nitrogen atmosphere, 5.5 g of compound 53, 6.4 g of triethylamine, and 100 mL of chloroform were added to a 300 mL three-neck flask, and the mixture was cooled to 0°C using an ice bath while stirring. 8.9 g of benzoyl chloride was added so that the internal temperature did not exceed 5°C. After the addition, the mixture was warmed to room temperature and stirred overnight. After confirming the disappearance of the raw materials by liquid chromatography, the mixture was cooled again in an ice bath and 5 mL of methanol was added. Chloroform and water were added to the reaction solution, the organic layer was separated, and the aqueous layer was extracted three times with chloroform. The organic layer was washed with saturated saline, dried over sodium sulfate, and then concentrated using a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 10 / 1) to obtain 3.7 g of compound 54 (yield: 31%, liquid). The obtained compound 54 1The H-NMR data is shown below.

[0449] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ7.97-7.91(m,4H), 7.55-7.47(m,2H), 7.39-7.33(m,4H), 5.49-5.47(m,2H), 2.19-1.14(m,14H). [Example A28] <Synthesis of compound 55> Compound 55 shown below was synthesized according to the reaction scheme below and by the method described below.

[0450] [ka]

[0451] In a nitrogen atmosphere, 3 g of compound 5, 5.2 g of triethylamine, 0.21 g of 4-dimethylaminopyridine (DMAP), and 100 mL of chloroform were added to a 300 mL three-neck flask, and the mixture was cooled to 0°C using an ice bath while stirring. 7.9 g of 4-methylbenzoyl chloride was added so that the internal temperature did not exceed 5°C. After the addition, the mixture was warmed to room temperature and stirred overnight. After confirming the disappearance of the raw materials by liquid chromatography, the mixture was cooled again in an ice bath and 5 mL of methanol was added. Chloroform and water were added to the reaction solution, the organic layer was separated, and the aqueous layer was extracted three times with chloroform. The organic layer was washed with saturated saline, dried over sodium sulfate, and then concentrated using a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 10 / 1) to obtain 4.3 g of compound 55 (10.4 mmol, yield: 61%, white powder). The obtained compound 55 1 The H-NMR data is shown below.

[0452] 1H NMR(270 MHz, CDCl3, TMS as internal standard): δ7.80(d,J=8.4Hz,4H), 7.33(dd,J=5.1Hz,3.2Hz,2H), 7.18(dd,J=5.4Hz,3.0Hz,2H), 7.09(d, J=8.4Hz,4H), 5.14(d,J=1.6Hz,2H), 3.55(s,2H), 2.59(d,J=9.5Hz,1H), 2.38(s,6H), 2.14(d,J=9.7Hz,1H). The resulting compound 55 had a melting completion temperature of 186°C.

[0453] [Example A29] <Synthesis of compound 56> Compound 56 shown below was synthesized according to the reaction scheme below and by the method described below.

[0454] [ka]

[0455] In a nitrogen atmosphere, 3 g of compound 5, 5.2 g of triethylamine, 0.21 g of 4-dimethylaminopyridine (DMAP), and 100 mL of chloroform were added to a 300 mL three-neck flask, and the mixture was cooled to 0°C using an ice bath while stirring. 10.7 g of 4-trifluoromethylbenzoyl chloride was added so that the internal temperature did not exceed 5°C. After the addition, the mixture was warmed to room temperature and stirred overnight. After confirming the disappearance of the raw materials by liquid chromatography, the mixture was cooled again in an ice bath and 5 mL of methanol was added. Chloroform and water were added to the reaction solution, the organic layer was separated, and the aqueous layer was extracted three times with chloroform. The organic layer was washed with saturated saline, dried over sodium sulfate, and then concentrated using a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 10 / 1) to obtain 4.8 g of compound 56 (9.2 mmol, yield: 54%, white powder). The obtained compound 56 1 The H-NMR data is shown below.

[0456] 1H NMR(270 MHz, CDCl3, TMS as internal standard): δ7.96(d,J=8.4Hz,4H), 7.54(d,J=8.4Hz,4H), 7.35(dd,J=5.4Hz,3.0Hz,2H), 7.21(dd,J =5.4Hz,3.0Hz,2H), 5.22(d,J=1.4Hz,2H), 3.58(s,2H), 2.60(d,J=10.0Hz,1H), 2.14(d,J=10.3Hz,1H). The resulting compound 56 had a melting completion temperature of 146°C.

[0457] [Example A30] <Synthesis of compound 57> Compound 57 shown below was synthesized according to the reaction scheme below and by the method described below.

[0458] [ka]

[0459] In a nitrogen atmosphere, 3 g of compound 5, 5.17 g of triethylamine, 0.21 g of 4-dimethylaminopyridine (DMAP), and 100 mL of chloroform were added to a 300 mL three-neck flask, and the mixture was cooled to 0°C using an ice bath while stirring. 10.0 g of 4-butylbenzoyl chloride was added so that the internal temperature did not exceed 5°C. After the addition, the mixture was warmed to room temperature and stirred overnight. After confirming the disappearance of the raw materials by liquid chromatography, the mixture was cooled again in an ice bath and 5 mL of methanol was added. Chloroform and water were added to the reaction solution, the organic layer was separated, and the aqueous layer was extracted three times with chloroform. The organic layer was washed with saturated saline, dried over sodium sulfate, and then concentrated using a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 10 / 1) to obtain 3.8 g of compound 57 (7.7 mmol, yield: 45%, white powder). The obtained compound 57 1 The H-NMR data is shown below.

[0460] 1H NMR(270 MHz, CDCl3, TMS as internal standard): δ7.81(d,J=8.4Hz,4H), 7.33(dd,J=5.1Hz,3.2Hz,2H), 7.18(dd,J=5.4Hz,3.2Hz,2H), 7.07(d,J=8.4Hz,4H), 5.14(d ,J=1.6Hz,2H), 3.55(s,2H), 2.65-2.57(m,5H), 2.14(d,J=9.7Hz,1H), 1.64-1.53(m,4H), 1.41-1.27(m,4H), 0.93(t,J=7.3Hz,6H). The resulting compound 57 had a melting completion temperature of 86°C.

[0461] [Example A31] <Synthesis of compound 58> Compound 58 shown below was synthesized according to the reaction scheme below and by the method described below.

[0462] [ka]

[0463] In a nitrogen atmosphere, 3 g of compound 5, 5.2 g of triethylamine, 0.21 g of 4-dimethylaminopyridine (DMAP), and 100 mL of chloroform were added to a 300 mL three-neck flask, and the mixture was cooled to 0°C using an ice bath while stirring. 9.3 g of 2,4,6-trimethylbenzoyl chloride was added so that the internal temperature did not exceed 5°C. After the addition, the mixture was warmed to room temperature and stirred overnight. After confirming the disappearance of the raw materials by liquid chromatography, the mixture was cooled again in an ice bath and 5 mL of methanol was added. Chloroform and water were added to the reaction solution, the organic layer was separated, and the aqueous layer was extracted three times with chloroform. The organic layer was washed with saturated saline, dried over sodium sulfate, and then concentrated using a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 10 / 1) to obtain 4.6 g of compound 58 (9.8 mmol, yield: 58%, white powder). The obtained compound 58 1 The H-NMR data is shown below.

[0464] 1H NMR(270 MHz, CDCl3, TMS as internal standard): δ7.34(dd,J=5.4Hz,3.2Hz,2H), 7.17(dd,J=5.4Hz,3.0Hz,2H), 6.76(s,4H), 5.10(d,J=1.6Hz,2H), 3.55(s,2H), 2.42(d,J=9.5Hz,1H), 2.28-2.25(m,7H), 2.13(s,12H). The resulting compound 58 had a melting completion temperature of 173°C.

[0465] [Example A32] <Synthesis of compound 59> Compound 59 shown below was synthesized according to the reaction scheme below and by the method described below.

[0466] [ka]

[0467] 15 mL of 30% hydrogen peroxide and 60 mL of 88% formic acid were added to a 300 mL three-neck flask and heated to 40 ° C. using an oil bath while stirring. 14.8 g of tricyclo[6,2,1,0(2,7)]undec-4-ene was added dropwise to the reaction solution so that the internal temperature did not exceed 50 ° C. After the dropwise addition, stirring was continued at 40 ° C. for 1 hour. Then, it was allowed to cool to room temperature and stirred for 17 hours. The reaction solution was concentrated under reduced pressure, and 20 mL of 2 mol / L aqueous sodium hydroxide solution and 50 mL of ethyl acetate were added at 50 ° C. or less, and stirred at 50 ° C. for 1 hour. The organic layer was separated, and the aqueous layer was extracted three times with ethyl acetate. The organic layer was washed with saturated saline, dried over sodium sulfate, and then concentrated with a rotary evaporator. Compound 59 was reacted without purification.

[0468] <Synthesis of Compound 60> Compound 60 shown below was synthesized according to the reaction scheme below and by the method described below.

[0469] [ka]

[0470] In a nitrogen atmosphere, 3.3 g of compound 59, 3.8 g of triethylamine, 0.22 g of 4-dimethylaminopyridine (DMAP), and 100 mL of chloroform were added to a 300 mL three-neck flask, and the mixture was cooled to 0°C using an ice bath while stirring. 5.3 g of benzoyl chloride was added so that the internal temperature did not exceed 5°C. After the addition, the mixture was warmed to room temperature and stirred overnight. After confirming the disappearance of the raw materials by liquid chromatography, the mixture was cooled again in an ice bath and 5 mL of methanol was added. Chloroform and water were added to the reaction solution, and the organic layer was separated, and the aqueous layer was extracted three times with chloroform. The organic layer was washed with saturated saline, dried over sodium sulfate, and then concentrated using a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 10 / 1) to obtain 5.3 g of compound 60 (13.6 mmol, yield: 74%, white powder). The obtained compound 60 1 The H-NMR data is shown below.

[0471] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 8.06-8.01 (m, 4H), 7.55-7.39 (m, 6H), 5.50-5.45 (m, 1H), 5.21-5.13 (m, 1H), 2.06-1.09 (m, 14H). The resulting compound 60 had a melting completion temperature of 125°C.

[0472] [Example A33] <Synthesis of Compound 61> Compound 61 shown below was synthesized according to the reaction scheme below and by the method described below.

[0473] [ka]

[0474] 15 mL of 30% hydrogen peroxide and 60 mL of 88% formic acid were added to a 300 mL three-neck flask and heated to 40 ° C. using an oil bath while stirring. 14.2 g of 1,4-dihydro-1,4-methanonaphthalene was added dropwise to the reaction solution so that the internal temperature did not exceed 50 ° C. After the dropwise addition, stirring was continued at 40 ° C. for 1 hour. Then, it was allowed to cool to room temperature and stirred for 17 hours. The reaction solution was concentrated under reduced pressure, and 20 mL of 2 mol / L aqueous sodium hydroxide solution and 50 mL of ethyl acetate were added at 50 ° C. or less, and stirred at 50 ° C. for 1 hour. The organic layer was separated, and the aqueous layer was extracted three times with ethyl acetate. The organic layer was washed with saturated saline, dried with sodium sulfate, and then concentrated with a rotary evaporator. Compound 61 was reacted without purification.

[0475] <Synthesis of Compound 62> Compound 62 shown below was synthesized according to the reaction scheme below and by the method described below.

[0476] [ka]

[0477] In a nitrogen atmosphere, 8.8 g of compound 61, 10.63 g of triethylamine, and 100 mL of chloroform were added to a 300 mL three-neck flask, and the mixture was cooled to 0°C using an ice bath while stirring. 14.8 g of benzoyl chloride was added so that the internal temperature did not exceed 5°C. After the addition, the mixture was warmed to room temperature and stirred overnight. After confirming the disappearance of the raw materials by liquid chromatography, the mixture was cooled again in an ice bath and 5 mL of methanol was added. Chloroform and water were added to the reaction solution, the organic layer was separated, and the aqueous layer was extracted three times with chloroform. The organic layer was washed with saturated saline, dried over sodium sulfate, and then concentrated using a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 10 / 1) to obtain 4.1 g of compound 62 (10.7 mmol, yield: 21%, white powder). The obtained compound 62 1 The H-NMR data is shown below.

[0478] 1H NMR(270 MHz, CDCl3, TMS as internal standard): δ8.09-8.05(m,2H), 7.83-7.79(m,2H), 7.57-7.15(m,10H), 5.09-5 .02(m,2H), 3.94(s,1H), 3.65-3.63(m,1H), 2.45-2.38(m,1H), 2.27-2.19(m,1H). The resulting compound 62 had a melting completion temperature of 192°C.

[0479] [Example A34] <Synthesis of Compound 63> Compound 63 shown below was synthesized by the method described below.

[0480] [ka]

[0481] In a nitrogen atmosphere, 35.2 g (149 mmol) of 1,2-dibromobenzene, 300 mL of dehydrated toluene, and 12.0 g of 1,3-cyclohexadiene were added to a 500 mL three-neck flask and stirred. The internal temperature was cooled to 0°C, and 83 mL of n-butyllithium hexane solution (1.6 M) was slowly added dropwise. After the addition, the temperature was gradually raised to room temperature and stirred at room temperature for 12 hours. After the reaction, a saturated aqueous ammonium chloride solution was added, followed by diethyl ether. The organic layer was separated and washed with water and saturated saline in that order. The organic layer was dried over magnesium sulfate, and then the magnesium sulfate was filtered off. The obtained organic layer was concentrated using a rotary evaporator to obtain 15.42 g of a crude product. The crude product was purified by silica gel column chromatography to obtain 4.9 g of compound 63 as a mixture with impurities.

[0482] <Synthesis of compound 64> Compound 64 shown below was synthesized by the method described below.

[0483] [ka]

[0484] In a 1000mL three-neck flask, 4.9g of compound 63 containing impurities obtained in <Synthesis of compound 63>, 125mL of tert-butyl alcohol, and 31mL of water were added, and the internal temperature was cooled to 0°C while stirring. In another flask, 7.35g of potassium permanganate, 150mL of water, and 1.70g of sodium hydroxide were added and stirred to prepare an aqueous potassium permanganate solution. The aqueous potassium permanganate solution was slowly added dropwise to the solution containing compound 63 prepared previously, so that the internal temperature did not exceed 5°C. After the dropwise addition, stirring was continued at 0°C for 1 hour. A saturated aqueous sodium pyrosulfite solution was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed. The formed precipitate was removed by filtration, and the filtrate was extracted four times with ethyl acetate. The organic layer was washed with saturated saline and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the obtained organic layer was concentrated using a rotary evaporator. The crude product was purified by silica gel column chromatography to obtain 0.72 g of compound 64 as an isomer mixture.

[0485] <Synthesis of compounds 65-1 and 65-2> Compounds 65-1 and 65-2 shown below were synthesized by the method described below.

[0486] [ka]

[0487] In a nitrogen atmosphere, 0.65 g (3.3 mmol) of compound 64 and 10.0 mL of dehydrated pyridine were added to a 50 mL three-neck flask and stirred. The mixture was cooled in an ice bath, and 0.82 mL of benzoyl chloride was slowly added. After the addition, the mixture was warmed to room temperature and stirred overnight. The mixture was cooled again in an ice bath, and 5 mL of methanol was added. 100 mL of water and 100 mL of ethyl acetate were added to a beaker, and the organic layer was separated. The organic layer was washed three times with water, washed with a saturated aqueous solution of ammonium chloride and saturated saline, and dried over magnesium sulfate. The magnesium sulfate was filtered, and the mixture was concentrated using a rotary evaporator to obtain a crude product. The mixture was purified by silica gel column chromatography to obtain 0.41 g of compound 65-1 (white solid) and 0.53 g of compound 65-2 (white solid). The stereostructures of compounds 65-1 and 65-2 were determined by NOESY. 1 The H-NMR data is shown below.

[0488] (Compound 65-1) 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ1.40-1.50 (m, 2H), 2.36-2.45 (m, 2H), 3.45 (s, 2H), 5.19 (s, 2H), 7.25-7.32 (m, 8H), 7.44-7.53 (m, 2H), 7.90-7.96 (m, 4H). (Compound 65-2) 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ1.52-1.62 (m, 2H), 1.92-2.00 (m, 2H), 3.41 (s, 2H), 5.55-5.57 (m, 2H), 7.08-7.16 (m, 4H), 7.22-7.38 (m, 6H), 7.52-7.57 (m, 4H). The resulting compound 65-1 had a melting completion temperature of 143° C. The resulting compound 65-2 had a melting completion temperature of 193° C.

[0489] [Example A35] <Synthesis of Compound 66> Compound 66 shown below was synthesized by the method described below.

[0490] [ka]

[0491] In a nitrogen atmosphere, 3.8 g of anthracene, 2.9 g of vinylene carbonate, and 15 mL of toluene were added to a 30 mL pressure vessel, and the mixture was heated and stirred so that the internal temperature reached 180° C., and stirring was continued for 45 hours. After cooling to room temperature, the mixture was concentrated and the solid was filtered off. The solid obtained was washed with hexane and then dried to obtain 3.85 g of compound 66. 1 The H-NMR data is shown below.

[0492] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): 7.40-7.37 (m, 4H), 7.27-7.22 (m, 4H), 4.88 (m, 2H), 4.70 (m, 2H). <Synthesis of compound 67> Compound 67 shown below was synthesized by the method described below.

[0493] [ka]

[0494] In a 100 mL three-neck flask, 3.8 g of compound 66, 7.2 mL of 4 mol / L sodium hydroxide solution, and 28 mL of methanol were added. After the addition, the mixture was stirred at room temperature for 30 minutes. After the methanol was distilled off, 20 mL of water was added, and the mixture was extracted with 30 mL of chloroform, and the organic layer was dried over sodium sulfate. The chloroform was distilled off, and the mixture was dried to obtain 2.88 g of compound 67. 1 The H-NMR data is shown below.

[0495] 1H NMR (270 MHz, CDCl3, TMS as internal standard): 7.39-7.30 (m, 4H), 7.23-7.14 (m, 4H), 4.42 (s, 2H), 4.06 (s, 2H), 2.10 (s, 2H). <Synthesis of compound 68> Compound 68 shown below was synthesized by the method described below.

[0496] [ka]

[0497] Under a nitrogen atmosphere, 2.9 g of compound 67, 3.51 mL of triethylamine, and 12 mL of chloroform were added and stirred at room temperature for 10 minutes. 2.92 mL of benzoyl chloride was added at room temperature, and the mixture was heated and stirred so that the internal temperature reached 85°C, and stirring was continued for 12 hours. After cooling in an ice bath, 5 mL of saturated sodium bicarbonate was added, and the mixture was extracted with 10 mL of chloroform. The organic layer was dried over magnesium sulfate and then concentrated. The obtained solid was filtered, washed with hexane, and dried to obtain 5.0 g of compound 68 (11.2 mmol, yield: 92%, white powder). The obtained compound 68 1 The H-NMR data is shown below.

[0498] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): 7.59-7.56 (m, 4H), 7.44-7.36 (m, 6H), 7.26-7.21 (m, 4H), 7.18-7.12 (m, 4H), 5.52 (s, 2H), 4.68 (s, 2H). The resulting compound 68 had a melting completion temperature of 174°C.

[0499] [Example A36] <Synthesis of Compound 69> Compound 69 shown below was synthesized by the method described below.

[0500] [ka]

[0501] In a nitrogen atmosphere, 3.8 g of 9-methylanthracene and 5.2 g of vinylene carbonate were added to a 30 mL pressure vessel, and the mixture was heated and stirred so that the internal temperature reached 220°C, and the stirring was continued for 9 hours. After cooling to room temperature, 5 mL of methanol was added and stirred, and the solid was filtered off. The obtained solid was washed with methanol and then dried to obtain 5.6 g of compound 69.

[0502] <Synthesis of compound 70> Compound 70 shown below was synthesized by the method described below.

[0503] [ka]

[0504] In a 50 mL three-neck flask, 5.6 g of compound 69, 8.0 g of sodium hydroxide, and 30 mL of pure water were added, and the mixture was heated and stirred until the internal temperature reached 100° C., and the stirring was continued for 6 hours. After cooling to room temperature, 12 mol / L concentrated hydrochloric acid was added at 50° C. or less to neutralize the mixture. The solid was filtered off, washed with pure water, and dried to obtain 5.0 g of compound 70.

[0505] <Synthesis of Compound 71> Compound 71 shown below was synthesized by the method described below.

[0506] [ka]

[0507] In a nitrogen atmosphere, 5.0 g of compound 70, 8.4 g of benzoyl chloride, and 50 mL of pyridine were added to a 200 mL three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 60°C, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the solid was filtered off, washed with hexane, and dried to obtain 6.4 g of compound 71 (14.0 mmol, yield: 70%, white powder). The amount of the obtained compound 71 was 1 The H-NMR data is shown below.

[0508] 1 H NMR (270 MHz, CDCl3, TMS as internal standard):7.64-7.61 (m, 2H), 7.49-7.17 (m, 14H), 7.08-7.02 (m, 2H), 5.57 (dd, J = 7.8 Hz, 3.0 Hz, 1H), 5.29 (d, J = 7.6 Hz, 1H), 4.68 (d, J = 3.0 Hz, 1H), 2.02 (s, 3H). The resulting compound 71 had a melting completion temperature of 173°C.

[0509] [Example A37] <Synthesis of compound 72> Compound 72 shown below was synthesized by the method described below.

[0510] [ka]

[0511] In a nitrogen atmosphere, 4.0 g of 9,10-dimethylanthracene and 5.0 g of vinylene carbonate were added to a 30 mL pressure vessel, and the mixture was heated and stirred so that the internal temperature reached 220°C, and the stirring was continued for 9 hours. After cooling to room temperature, 5 mL of methanol was added and stirred, and the solid was filtered off. The obtained solid was washed with methanol and then dried to obtain 5.6 g of compound 72.

[0512] <Synthesis of Compound 73> Compound 73 shown below was synthesized by the method described below.

[0513] [ka]

[0514] In a 50 mL three-neck flask, 5.6 g of compound 72, 7.6 g of sodium hydroxide, and 30 mL of pure water were added, and the mixture was heated and stirred until the internal temperature reached 100° C., and the stirring was continued for 6 hours. After cooling to room temperature, 12 mol / L concentrated hydrochloric acid was added at 50° C. or less to neutralize the mixture. The solid was filtered off, washed with pure water, and then dried to obtain 5.0 g of compound 73.

[0515] <Synthesis of compound 74> Compound 74 shown below was synthesized by the method described below.

[0516] [ka]

[0517] In a nitrogen atmosphere, 5.0 g of compound 73, 8.0 g of benzoyl chloride, and 50 mL of pyridine were added to a 200 mL three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 60°C, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the solid was filtered off, washed with hexane, and dried to obtain 5.2 g (11.0 mmol, yield 58%, white powder) of compound 74. 1 The H-NMR data is shown below.

[0518] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): 7.52-7.49 (m, 4H), 7.46-7.42 (m, 4H), 7.35-7.27 (m, 6H), 7.12-7.06 (m, 4H), 5.40 (s, 2H), 2.00 (s, 6H). The resulting compound 74 had a melting completion temperature of 218°C.

[0519] [Example A38] <Synthesis of Compound 75> Compound 75 shown below was synthesized by the method described below.

[0520] [ka]

[0521] In a nitrogen atmosphere, 8.0 g of 9,10-diethoxyanthracene and 7.7 g of vinylene carbonate were added to a 30 mL pressure vessel, and the mixture was heated and stirred so that the internal temperature reached 220°C, and the stirring was continued for 9 hours. After cooling to room temperature, 5 mL of methanol was added and stirred, and the solid was filtered off. The obtained solid was washed with methanol and then dried to obtain 10.5 g of compound 75.

[0522] <Synthesis of Compound 76> Compound 76 shown below was synthesized by the method described below.

[0523] [ka]

[0524] In a 50 mL three-neck flask, 10.5 g of compound 75, 12.0 g of sodium hydroxide, and 30 mL of pure water were added, and the mixture was heated and stirred so that the internal temperature reached 100°C, and stirring was continued for 6 hours. After cooling to room temperature, 12 mol / L concentrated hydrochloric acid was added at 50°C or less to neutralize. The solid was filtered off, washed with pure water, and dried to obtain 9.8 g of compound 76.

[0525] <Synthesis of Compound 77> Compound 77 shown below was synthesized by the method described below.

[0526] [ka]

[0527] In a nitrogen atmosphere, 9.8 g of compound 76, 12.6 g of benzoyl chloride, and 50 mL of pyridine were added to a 200 mL three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 60°C, and stirring was continued for 6 hours. After distilling off the pyridine, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the solid was filtered off, washed with hexane, and dried to obtain 9.4 g of compound 77 (17.6 mmol, yield: 59%, white powder). The amount of the obtained compound 77 was 1 The H-NMR data is shown below.

[0528] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): 7.76-7.73 (m, 2H), 7.51-7.46 (m, 6H), 7.39-7.26 (m, 6H), 7.10-7.04 (m, 4H), 5.98 (s, 2H), 4.20 (dq, J = 8.4 Hz, 7.0 Hz,2H), 3.93 (dq, J = 8.4 Hz, 7.0 Hz,2H), 1.46 (t, J = 7.0 Hz, 6H). The resulting compound 77 had a melting completion temperature of 175°C.

[0529] [Example A39] <Synthesis of compound 78> Compound 78 shown below was synthesized by the method described below.

[0530] [ka]

[0531] In a nitrogen atmosphere, 7.0 g of 9,10-diethylanthracene and 7.7 g of vinylene carbonate were added to a 30 mL pressure vessel, and the mixture was heated and stirred so that the internal temperature reached 220°C, and the stirring was continued for 9 hours. After cooling to room temperature, 5 mL of methanol was added and stirred, and the solid was filtered off. The obtained solid was washed with methanol and then dried to obtain 9.6 g of compound 78.

[0532] <Synthesis of Compound 79> Compound 79 shown below was synthesized by the method described below.

[0533] [ka]

[0534] 9.6 g of compound 78, 12.0 g of sodium hydroxide, and 30 mL of pure water were added to a 50 mL three-neck flask, and stirring was continued for 6 hours so that the internal temperature reached 100° C. After cooling to room temperature, 12 mol / L concentrated hydrochloric acid was added at 50° C. or less to neutralize. The solid was filtered off, washed with pure water, and dried to obtain 3.2 g of compound 79.

[0535] <Synthesis of Compound 80> Compound 80 shown below was synthesized by the method described below.

[0536] [ka]

[0537] In a nitrogen atmosphere, 3.2 g of compound 79, 4.6 g of benzoyl chloride, and 50 mL of pyridine were added to a 200 mL three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 60°C, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the solid was filtered off, washed with hexane, and dried to obtain 2.1 g of compound 80 (4.2 mmol, yield: 38%, white powder). The amount of the obtained compound 80 was 1 The H-NMR data is shown below.

[0538] 1 H NMR (270 MHz, CDCl3, TMS as internal standard):7.47-7.44 (m, 8H), 7.33-7.22 (m, 6H), 7.09-7.03 (m, 4H),5.65 (s, 2H), 2.58 (q, J = 7.3 Hz, 4H), 1.37 (t, J = 7.3 Hz, 6H). The resulting compound 80 had a melting completion temperature of 184°C.

[0539] [Example A40] <Synthesis of Compound 81> Compound 81 shown below was synthesized by the method described below.

[0540] [ka]

[0541] In a nitrogen atmosphere, 8.7 g of 9,10-di-n-butylanthracene and 7.7 g of vinylene carbonate were added to a 30 mL pressure vessel, and the mixture was heated and stirred so that the internal temperature reached 220°C, and the stirring was continued for 9 hours. After cooling to room temperature, 5 mL of methanol was added and stirred, and the solid was filtered off. The obtained solid was washed with methanol and then dried to obtain 11.3 g of compound 81.

[0542] <Synthesis of Compound 82> Compound 82 shown below was synthesized by the method described below.

[0543] [ka]

[0544] In a 50 mL three-neck flask, 11.3 g of compound 81, 12.0 g of sodium hydroxide, and 30 mL of pure water were added, and the mixture was heated and stirred so that the internal temperature reached 100° C., and stirring was continued for 6 hours. After cooling to room temperature, 12 mol / L concentrated hydrochloric acid was added at 50° C. or less to neutralize. The solid was filtered off, washed with pure water, and dried to obtain 4.1 g of compound 82.

[0545] <Synthesis of Compound 83> Compound 83 shown below was synthesized by the method described below.

[0546] [ka]

[0547] In a nitrogen atmosphere, 4.1 g of compound 82, 4.9 g of benzoyl chloride, and 50 mL of pyridine were added to a 200 mL three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 60°C, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the solid was filtered off, washed with hexane, and dried to obtain 5.4 g of compound 83 (9.7 mmol, yield: 83%, white powder). The amount of the obtained compound 83 was 1 The H-NMR data is shown below.

[0548] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): 7.48-7.21 (m, 14H), 7.08-7.02 (m, 4H), 5.62 (s, 2H), 2.55-2.35 (m, 4H), 1.98-1.47 (m, 8H), 0.99 (t, J = 7.3Hz, 6H). The resulting compound 83 had a melting completion temperature of 176°C.

[0549] [Example A41] <Synthesis of compound 84> Compound 84 shown below was synthesized by the method described below.

[0550] [ka]

[0551] In a nitrogen atmosphere, 7.2 g of 9,10-dimethoxyanthracene and 7.7 g of vinylene carbonate were added to a 30 mL pressure vessel, and the mixture was heated and stirred so that the internal temperature reached 220°C, and the stirring was continued for 9 hours. After cooling to room temperature, 5 mL of methanol was added and stirred, and the solid was filtered off. The obtained solid was washed with methanol and then dried to obtain 9.7 g of compound 84.

[0552] <Synthesis of Compound 85> Compound 85 shown below was synthesized by the method described below.

[0553] [ka]

[0554] In a 50 mL three-neck flask, 9.7 g of compound 84, 12.0 g of sodium hydroxide, and 30 mL of pure water were added, and the mixture was heated and stirred so that the internal temperature reached 100° C., and stirring was continued for 6 hours. After cooling to room temperature, 12 mol / L concentrated hydrochloric acid was added at 50° C. or less to neutralize. The solid was filtered off, washed with pure water, and dried to obtain 6.4 g of compound 85.

[0555] <Synthesis of Compound 86> Compound 86 shown below was synthesized by the method described below.

[0556] [ka]

[0557] In a nitrogen atmosphere, 6.4 g of compound 85, 9.1 g of benzoyl chloride, and 50 mL of pyridine were added to a 200 mL three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 60°C, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the solid was filtered off, washed with hexane, and dried to obtain 7.4 g of compound 86 (14.6 mmol, yield: 68%, white powder). The amount of the obtained compound 86 was 1 The H-NMR data is shown below.

[0558] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): 7.71-7.56 (m, 4H), 7.51-7.05 (m, 14H), 5.98 (s, 2H), 3.87 (s, 6H). The resulting compound 86 had a melting completion temperature of 227°C.

[0559] [Example A42] <Synthesis of Compound 87> Compound 87 shown below was synthesized by the method described below.

[0560] [ka]

[0561] In a nitrogen atmosphere, 4.1 g of compound 85, 6.4 g of 4-methylbenzoyl chloride, and 50 mL of pyridine were added to a 200 mL three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 60°C, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the solid was filtered off, washed with hexane, and dried to obtain 1.3 g of compound 87 (2.4 mmol, yield: 18%, white powder). The amount of the obtained compound 87 was 1 The H-NMR data is shown below.

[0562] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): 7.70-7.53 (m, 4H), 7.39-7.26 (m, 8H), 6.90-6.87 (m, 4H), 5.95 (s, 2H), 3.85 (s, 6H) 2.24 (s, 6H). The resulting compound 87 had a melting completion temperature of 220°C.

[0563] [Example A43] <Synthesis of compound 88> Compound 88 shown below was synthesized by the method described below.

[0564] [ka]

[0565] In a nitrogen atmosphere, 4.1 g of compound 85, 8.1 g of 4-n-butylbenzoyl chloride, and 50 mL of pyridine were added to a 200 mL three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 60°C, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the solid was filtered off, washed with hexane, and dried to obtain 1.9 g of compound 88 (3.1 mmol, yield: 22%, white powder). The amount of the obtained compound 88 was 1 The H-NMR data is shown below.

[0566] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): 7.70-7.55 (m, 4H), 7.39-7.25 (m, 8H), 6.89-6.86 (m, 4H), 5.95 (s, 2H), 3.86 (s, 6H) 2.51-2.45 (m, 4H), 1.56-1.19 (m, 8H), 0.88 (t, J = 7.0 Hz, 6H). The resulting compound 88 had a melting completion temperature of 158°C.

[0567] [Example A44] <Synthesis of Compound 89> Compound 89 shown below was synthesized by the method described below.

[0568] [ka]

[0569] In a nitrogen atmosphere, 15 g of compound 85 (50.3 mmol) and 117 mL of dehydrated pyridine were added to a 200 mL three-neck flask and cooled in an ice bath. 18.0 g (105.5 mmol) of 4-methoxybenzoyl chloride was added dropwise over about 5 minutes, and the mixture was heated and stirred for 20 hours in an oil bath heated to 100 ° C. After the reaction was completed, the mixture was allowed to cool, and 10 mL of dehydrated methanol was added to quench the mixture at room temperature. After stirring at room temperature for about 30 minutes, the reaction solution was dropped into a mixed solution of hexane and water (hexane: water = 5: 1) to obtain fine crystals. The obtained crystals were collected by filtration, washed with hexane, and then dissolved in 100 mL of dichloromethane. The mixture was washed twice with 100 mL of 1 N hydrochloric acid, followed by one each of 100 mL of saturated aqueous sodium bicarbonate and saturated saline, and then the obtained organic layer was dried over magnesium sulfate. After removing magnesium sulfate by filtration and concentrating with an evaporator, the resulting solid was dissolved again in 30 mL of chloroform and added dropwise to 150 mL of methanol to obtain a solid. The resulting solid was purified by silica gel column chromatography (developing solvent: dichloromethane:methanol = gradient from 100:0 to 97:3) to obtain 20.17 g of compound 89 (yield 71%, white solid). 1 The H-NMR data is shown below.

[0570] 1 H NMR (270 MHz, CDCl3, TMS as internal standard):7.70-7.67 (m, 2H), 7.58-7.55 (m, 2H), 7.46-7.43 (m, 4H), 7.37-7.33 (m, 2H), 7.31-7.28 (m, 2H), 6.59-6.56 (m, 4H), 5.94 (s, 2H), 3.86 (s, 6H) 3.73 (s, 6H). The resulting compound 89 had a melting completion temperature of 221°C.

[0571] [Example A45] <Synthesis of Compound 90> Compound 90 shown below was synthesized by the method described below.

[0572] [ka]

[0573] In a nitrogen atmosphere, 5.0 g of compound 85 (16.8 mmol) and 13 mL of dehydrated pyridine were added to a 100 mL three-neck flask and stirred at room temperature. 7.0 g (35.6 mmol) of 4-tert-butylbenzoyl chloride was added dropwise, and the mixture was stirred at 100°C for 24 hours using an oil bath. After the reaction was completed, 26 mL of methanol was added, and the precipitated solid was collected by filtration. The obtained solid was washed with 13 mL of 2N hydrochloric acid, suspended in 20 mL of methanol, and stirred at 60°C for about 1 hour. After cooling, the white solid was collected by filtration, and 10.2 g of compound 90 (yield 98%, white solid) was obtained. 1 The H-NMR data is shown below.

[0574] 1 H NMR (270 MHz, CDCl3, TMS as internal standard):7.71-7.67 (m, 2H), 7.58-7.55 (m, 2H), 7.46-7.28 (m, 8H), 7.12-7.09 (4H), 5.96 (s, 2H), 3.86 (s, 6H), 1.19 (s, 18H). The resulting compound 90 had a melting completion temperature of 178°C.

[0575] [Example A46] <Synthesis of Compound 91> Compound 91 shown below was synthesized by the method described below.

[0576] [ka]

[0577] A 300mL three-neck flask containing a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 3.08g of 3-isopropylbenzoic acid (18.8mmol), 60mL of dichloromethane, and 2 drops of DMF were added. The reaction solution was cooled to 0°C, and then 2.57mL of oxalyl chloride (30mmol) was slowly added dropwise. After the addition was completed, the temperature was raised to room temperature and the mixture was stirred at room temperature for 3 hours. The volatile compounds in the reaction system were removed under reduced pressure to obtain compound 91. This was used in <Synthesis of compound 92> without further purification.

[0578] <Synthesis of Compound 92> Compound 92 shown below was synthesized by the method described below.

[0579] [ka]

[0580] A 100mL three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. 1.6g of compound 5 and 10mL of dehydrated pyridine were added under a nitrogen atmosphere. After cooling the reaction solution to 0°C, 20mL of a dichloromethane solution of compound 91 synthesized in <Synthesis of compound 91> was slowly added to the pyridine solution of compound 5 and stirred overnight. After the reaction was completed, the solution was cooled to 0°C, 20mL of methanol was added, and the mixture was stirred for 1 hour. After adding 20mL of water and 30mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous ammonium chloride solution. The organic layer was dried over sodium sulfate and concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (developing solvent: hexane:ethyl acetate=10:1) and recrystallization using hexane, and 1.54g of compound 92 (yield 34%, white solid) was obtained. The obtained compound 92 1 The H-NMR data is shown below.

[0581] 1H NMR (270 MHz, CDCl3, TMS as internal standard): δ 1.12 (d, J = 6.9 Hz, 12H), 2.13-2.17 (m, 1H), 2.59-2.63 (m, 1H), 2.73 (sep, J = 6.9 Hz, 2H), 3.57 (s, 2H), 5.16 (s, 2H), 7.13-7.26 (overlapped with CHCl3 signals, m, 4H), 7.33-7.36 (m, 4H), 7.76-7.79 (m, 4H). The resulting compound 92 had a melting completion temperature of 93°C.

[0582] [Example A47] <Synthesis of Compound 93> Compound 93 shown below was synthesized by the method described below.

[0583] [ka]

[0584] Compound 93 was synthesized according to the procedure and equivalent relationship described in <Synthesis of Compound 91>, except that 4.21 g (28.0 mmol) of 3,4-dimethylbenzoic acid was used instead of 3-isopropylbenzoic acid in <Synthesis of Compound 91>. The obtained compound 93 was used as it was in <Synthesis of Compound 94>.

[0585] <Synthesis of Compound 94> Compound 94 shown below was synthesized by the method described below.

[0586] [ka]

[0587] A 100mL three-neck flask containing a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. 2.13g of compound 5 (12.1mmol) and 10mL of dehydrated pyridine were added under a nitrogen atmosphere. After cooling the reaction solution to 0°C, 20mL of a dichloromethane solution of compound 93 synthesized in <Synthesis of compound 93> was slowly added to the pyridine solution of compound 5 and stirred overnight. After the reaction was completed, the solution was cooled to 0°C, 20mL of methanol was added, and the mixture was stirred for 1 hour. After adding 20mL of water and 30mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous ammonium chloride solution. The organic layer was dried over sodium sulfate and concentrated using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (developing solvent: hexane:ethyl acetate=10:1), and 2.64g of compound 94 (6.0mmol, yield 50%, pale yellow solid) was obtained. The obtained compound 94 1 The H-NMR data is shown below.

[0588] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ2.07 (s, 6H), 2.11-2.17 (m, 1H), 2.27 (s, 6H), 2.58-2.62 (m, 1H), 3.56 (s, 2H), 5.12-5.13 (m, 2H), 7.09 (d, J = 7.9 Hz, 2H), 7.16-7.19 (m, 2H), 7.32-7.35 (m, 2H), 7.62 (br s, 2H), 7.70-7.72 (m, 2H). The resulting compound 94 had a melting completion temperature of 158°C.

[0589] [Example A48] <Synthesis of Compound 95> Compound 95 shown below was synthesized according to the reaction scheme below and the method described below.

[0590] [ka]

[0591] Under a nitrogen atmosphere, 200 mL of dehydrated acetonitrile, 6.36 g of 1-phenylpyrrole, and 6.74 g of cesium fluoride were added to a 1 L three-neck flask and stirred at room temperature. Then, 4.3 g of 2-(trimethylsilyl)phenyl triflate was slowly added, and the reaction solution was heated and stirred at 40°C for 16 hours. The reaction solution was passed through a silica gel short column (developing solvent: ethyl acetate) and concentrated with a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (developing solvent: hexane:ethyl acetate = 5:1), and 2.31 g (10.5 mmol, yield 71%) of compound 95 was obtained.

[0592] <Synthesis of Compound 96> Compound 96 shown below was synthesized by the method described below.

[0593] [ka]

[0594] A 500mL three-neck flask with a stirrer was equipped with a dropping funnel, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 60mL of a mixed solution of tert-butyl alcohol and acetone, 20mL of water, and 2.51g (11.4mmol) of compound 95 were added, and the reaction solution was cooled to 0°C. 0.57g (14.3mmol) of sodium hydroxide and 2.70g (17.1mmol) of potassium permanganate were dissolved in 60mL of water and slowly dropped into the reaction solution prepared above. After the dropwise addition, the mixture was stirred for another hour under the condition of 0°C, and then the unreacted potassium permanganate was quenched using a saturated aqueous solution of sodium pyrosulfite. After stirring at room temperature for a while, sodium bicarbonate was added until the pH of the reaction solution reached about 7 to 8, and the resulting white precipitate was removed by filtration. The filtered solution was extracted three times with ethyl acetate, and the collected organic layer was dried over sodium sulfate and then concentrated using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (developing solvent: hexane:ethyl acetate=1:1) to obtain 2.04 g (8.1 mmol, yield 71%) of compound 96.

[0595] <Synthesis of Compound 97> Compound 97 shown below was synthesized by the method described below.

[0596] [ka]

[0597] A 100mL three-neck flask with a stirrer that had been thoroughly dried by heating was equipped with a flat stopper, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.18g (8.6mmol) of compound 96 and 10mL of dehydrated pyridine were added, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 2.20mL (18.9mmol) of benzoyl chloride was slowly added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature and stirred overnight. After the reaction was completed, the solution was cooled to 0°C, 10mL of methanol was added, and the mixture was stirred for 30 minutes. After adding 20mL of water and 30mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. The organic layer was dried over sodium sulfate and then concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate=10:1) to obtain 1.80 g (3.9 mmol, yield 45%, white solid) of compound 97. 1 The H-NMR data is shown below.

[0598] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 5.27-5.29 (m, 4H), 6.77-6.82 (m, 1H), 6.89-6.92 (m, 2H), 7.11-7.17 (m, 2H), 7.20-7.30 (overlapped with CHCl3 signals, m, 6H), 7.41-7.51 (m, 4H), 7.90-7.94 (m, 4H). The resulting compound 97 had a melting completion temperature of 158°C.

[0599] [Example A49] <Synthesis of Compound 98> Compound 98 shown below was synthesized according to the reaction scheme below and the method described below.

[0600] [ka]

[0601] In a nitrogen atmosphere, 14.0 g of p-benzoquinone (0.130 mol) and 17.6 g of α-terpinene (0.129 mol) were added to a 2 L three-neck flask, followed by the addition of 700 mL of water and stirring at room temperature. 420 mL of acetone was slowly added dropwise, and stirring was continued at room temperature overnight. 700 mL of ethyl acetate was added and stirred, after which the organic layer and the aqueous layer were separated. The organic layer was washed with saturated saline and then dried over magnesium sulfate. The mixture was concentrated using a rotary evaporator to obtain a crude product. The obtained crude product was combined with a crude product obtained by the same procedure and in an equivalent relationship using 5.0 g of p-benzoquinone (total 41.87 g) and purified by silica gel column chromatography to obtain 30.0 g of compound 98.

[0602] <Synthesis of Compound 99> Compound 99 shown below was synthesized according to the reaction scheme below and the method described below.

[0603] [ka]

[0604] In a nitrogen atmosphere, 28.0 g (0.115 mol) of compound 98 was added to a 500 mL three-neck flask, followed by the addition of 1078 mL of dehydrated methanol, and the mixture was stirred at room temperature for a while. 92.9 g of cerium chloride heptahydrate (0.249 mol) was added, followed by ice cooling, and 9.92 g of sodium borohydride (0.262 mol) was slowly added. After the addition was completed, the mixture was stirred for 1 hour under ice cooling, and quenched with 1N hydrochloric acid. A saturated aqueous solution of sodium bicarbonate was added to neutralize the mixture, and the volatile substances were removed using a rotary evaporator. The remaining aqueous solution was extracted with ethyl acetate, and the obtained organic layer was washed with a saturated aqueous solution of sodium bicarbonate and saturated saline, and dried over magnesium sulfate. After filtering off the magnesium sulfate, the mixture was concentrated using a rotary evaporator. The product was purified by recrystallization from ethanol and silica gel column chromatography (hexane:ethyl acetate=90:10→60:40) to obtain 24.9 g (yield 88%) of an isomer mixture, Compound 99.

[0605] <Synthesis of Compound 100> Compound 100 shown below was synthesized according to the reaction scheme below and by the method described below.

[0606] [ka]

[0607] In a nitrogen atmosphere, 21.3 g (85.8 mmol) of compound 99 was added to a 100 mL three-neck flask, followed by 25.7 g of sodium iodide (171.5 mmol) and 326 mL of acetonitrile, and the mixture was stirred at room temperature for a while. 21.7 mL of chlorotrimethylsilane (171.0 mmol) was added dropwise thereto, and the mixture was stirred at room temperature after the completion of the dropwise addition. The mixture was quenched with a sodium thiosulfate solution, and the resulting solution was extracted with chloroform. The organic layer was washed with water and saturated saline, and then dried with magnesium sulfate. After filtering off the magnesium sulfate, the mixture was concentrated with a rotary evaporator. The crude product was purified together with another lot of the crude product by silica gel column chromatography (developing solvent: hexane), and 9.13 g of compound 100 containing a small amount of impurities was obtained. No further purification was performed, and the product was used in the following <Synthesis of Compounds 101-1 and 101-2>.

[0608] <Synthesis of Compounds 101-1 and 101-2> Compounds 101-1 and 101-2 shown below were synthesized by the method described below.

[0609] [ka]

[0610] In a nitrogen atmosphere, 9.13 g of the product obtained in <Synthesis of Compound 100> was added to a 1L three-neck flask, followed by 167 mL of tert-butyl alcohol and 42 mL of water, and cooled to 0°C in an ice bath. In a separate flask, an aqueous solution consisting of 10.0 g of potassium permanganate (63.2 mmol), 2.18 g of sodium hydroxide (54.5 mol), and 209 mL of water was prepared and slowly added dropwise to the reaction solution previously prepared. After the addition was completed, stirring was continued for 20 minutes while cooling in an ice bath. While cooling in an ice bath, sodium pyrosulfite was slowly added until the color of potassium permanganate in the reaction solution disappeared. Ethyl acetate was added to the reaction solution, and the operation of separating only the supernatant organic layer was repeated four times, and the collected organic layer was dried over magnesium sulfate and then concentrated using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (hexane:ethyl acetate=100:0→60:40) to obtain 1.74 g (yield 16%) of compounds 101-1 and 101-2, respectively.

[0611] <Synthesis of Compound 102> Compound 102 shown below was synthesized by the method described below.

[0612] [ka]

[0613] In a nitrogen atmosphere, 1.74 g of compound 101-1 (7.06 mmol) was added to a 200 mL three-neck flask and dissolved in 7 mL of dehydrated pyridine. While cooling in an ice bath, 1.72 mL of benzoyl chloride (14.8 mmol) was slowly added dropwise so that the internal temperature did not exceed 5°C. After the dropwise addition, the temperature was raised to room temperature and stirred for a while. After cooling the reaction solution on ice, methanol was slowly added to quench it. Then, water and dichloromethane were added, and the organic layer side was washed three times with 1N hydrochloric acid, once with a saturated aqueous sodium bicarbonate solution, and once with saturated saline, in that order. The organic layer after washing was dried over magnesium sulfate, filtered, and concentrated with a rotary evaporator. The obtained crude product was purified by silica gel column chromatography to obtain 1.10 g of compound 102 (yield 35%, white solid). The obtained compound 102 1 The H-NMR data is shown below.

[0614] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ1.19-1.47 (m, 11 H), 2.27-2.58 (m, 3H), 5.15 (dd, J = 1.6, 8.6 Hz, 1H), 5.29 (dd, J = 1.6, 8.6 Hz, 1H), 7.11-7.17 (m, 2H), 7.29-7.40 (m, 6H), 7.43-7.50 (m, 2H), 7.77-7.80 (m, 2H), 7.88-7.92 (m, 2H). Peaks believed to be the melting points of the obtained compound 102 were observed at 143°C and 150°C.

[0615] <Synthesis of compound 103> Compound 103 shown below was synthesized by the method described below.

[0616] [ka]

[0617] In the synthesis of compound 102, 1.74 g of compound 101-1 was replaced by 1.77 g of compound 102-2 (7.18 mmol) in place of the compound 101-1. The procedure and the equivalent relationship described in the synthesis of compound 102 were followed to obtain 2.36 g of compound 103 (yield 73%, white solid). 1 The H-NMR data is shown below. 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 1.04 (d, J = 6.9 Hz, 3H), 1.16 (d, J = 6.9 Hz, 3H), 1.41 (s, 3H), 1.48-1.58 (m, 2H), 1.77-1.94 (m, 2H), 2.73-2.83 (m, 1H), 5.55 (d, J = 7.9 Hz, 1H), 5.62 (d, J = 7.9 Hz, 1H), 6.94-7.00 (m, 2H), 7.09-7.15 (m, 2H), 7.21-7.52 (overlapped with CHCl3 signals, m, 10H). The resulting compound 103 had a melting completion temperature of 149°C.

[0618] [Example A50] <Synthesis of compound 104> Compound 104 shown below was synthesized according to the reaction scheme below and by the method described below.

[0619] [ka]

[0620] In a nitrogen atmosphere, 70g (0.85mol) of 2-cyclopenten-1-one and 900mL of dehydrated diethyl ether were added to a 2L four-neck flask, and the mixture was stirred while cooling the internal temperature to 0℃. Next, 94g (1.42mol) of cyclopentadiene was added. The cyclopentadiene used in the reaction was quickly prepared by pyrolyzing dicyclopentadiene in tetradecane at 160℃ or higher. 48.4g (0.34mol) of boron trifluoride-ethyl ether complex was added dropwise over 10 minutes while the internal temperature was kept at 0-5℃. After the dropwise addition, the temperature was raised to room temperature and stirring was continued for 17 hours. After the reaction was completed, 900mL of pure water was added and the mixture was stirred for 30 minutes. The organic layer and aqueous layer were separated, and the collected aqueous layer was extracted three times with 500mL of diethyl ether. After the organic layer was collected, it was washed with 1L of saturated saline. The organic layer was dried over magnesium sulfate, filtered, and then concentrated using a rotary evaporator. The crude product was purified by silica gel column chromatography (hexane:ethyl acetate=50:1) to obtain 82.9 g of compound 104 (yield 66%).

[0621] <Synthesis of compound 105> Compound 105 shown below was synthesized according to the reaction scheme below and by the method described below.

[0622] [ka]

[0623] In a nitrogen atmosphere, 24 g of compound 104 (162 mmol), 41.7 g (178 mmol) of 50% 4-methylmorpholine N-oxide (hereinafter referred to as "NMO") aqueous solution, 60 mL of pure water, 60 mL of acetone, and 120 mL of tert-butyl alcohol were added to a 500 mL four-neck flask and stirred. 124 mg (0.5 mmol) of osmium oxide was added and stirred at room temperature for 2 days. After the reaction was completed, 2 g of sodium hydrosulfite, 24 g of Florisil, and 160 mL of pure water were added and stirred for 30 minutes. The filtrate was collected by vacuum filtration and adjusted to a pH of 7 using 1N sulfuric acid. The organic solvent was removed from the filtrate under reduced pressure at an external temperature of 40°C, and the remaining aqueous solution was adjusted to a pH of 3 again using 1N sulfuric acid. Excess sodium chloride and 500 mL of ethyl acetate were added and stirred, and the mixture was filtered under reduced pressure to remove the sodium chloride that had not dissolved. The organic layer and the aqueous layer were separated by liquid separation, and the collected aqueous layer was extracted three times with 400 mL of ethyl acetate. The organic layers were collected, dried over sodium sulfate, filtered, and then concentrated using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (ethyl acetate:dichloromethane=1:1) to obtain 13.2 g of compound 105 (yield 45%).

[0624] <Synthesis of compound 106> Compound 106 shown below was synthesized by the method described below.

[0625] [ka]

[0626] In a nitrogen atmosphere, 3.33 g of compound 105 (18.3 mmol) was added to a three-neck flask, followed by the addition of 10 mL of dehydrated pyridine and stirring. The mixture was cooled in an ice bath, and 4.68 mL of benzoyl chloride (40.3 mmol) was slowly added. After the addition, the mixture was warmed to room temperature and stirred for 5 hours. The mixture was cooled again in an ice bath, and 10 mL of methanol was added to quench the reaction. Then, water and dichloromethane were added, and the mixture was transferred to a separatory funnel. The mixture was washed with water and a saturated aqueous solution of ammonium chloride, and the organic layer was dried over magnesium sulfate and concentrated using a rotary evaporator. The obtained crude product (8.29 g) was purified by silica gel column chromatography (developing solvent: hexane:ethyl acetate = 85:15 → 65:35) and recrystallization with acetone solvent, and 3.16 g of compound 106 (yield 44%, pale yellow solid) was obtained. The obtained compound 106 1 The H-NMR data is shown below.

[0627] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ1.63-1.67 (m, 1H), 2.08-2.62 (m, 6H), 2.76-2.82 (m, 1H), 2.89-2.99 (m, 2H), 5.11-5.13 (m, 1H), 5.45-5.48 (m, 1H), 7.17 (t, J = 7.6 Hz, 2H), 7.33 (t, J = 7.6 Hz, 2H), 7.42 (t, J = 7.6 Hz, 1H), 7.52 (t, J = 7.6 Hz, 1H). 7.74-7.77 (m, 2H), 7.90-7.92 (m, 2H). The resulting compound 106 had a melting completion temperature of 127°C.

[0628] [Example A51] <Synthesis of compound 107> Compound 107 shown below was synthesized according to the reaction scheme below and by the method described below.

[0629] [ka]

[0630] In a nitrogen atmosphere, 1.5 L of dehydrated diethyl ether was added to a 5 L four-neck flask and cooled until the internal temperature reached 0°C. Then, 22.2 g (585 mmol) of lithium aluminum hydride was added. 51 g of compound 104 (344 mmol) was dissolved in 500 mL of dehydrated diethyl ether and added dropwise to the previously prepared solution over 30 minutes. At this time, the liquid temperature was adjusted to be in the range of 0 to 5°C. After the dropwise addition was completed, the temperature was raised to room temperature and stirring was continued for 1 hour. After the reaction was completed, the liquid temperature was cooled again to 0°C, and 200 mL of methanol was added dropwise over 1 hour while paying attention to the generation of hydrogen. Then, 2 L of saturated aqueous potassium sodium tartrate solution was slowly added and stirred at room temperature for 2 hours. The organic layer and aqueous layer were separated, and the collected aqueous layer was extracted three times with 500 mL of diethyl ether. The organic layer was collected and washed with 1 L of saturated saline solution. The organic layer was dried over sodium sulfate, filtered, concentrated using a rotary evaporator, and vacuum dried at an external temperature of 40° C. for 2 hours to obtain 48.0 g of compound 107 (yield 93%).

[0631] <Synthesis of compound 108> Compound 108 shown below was synthesized according to the reaction scheme below and by the method described below.

[0632] [ka]

[0633] In a nitrogen atmosphere, 47.9 g of compound 107 (319 mmol), 48.5 g of triethylamine (479 mmol), and 1 L of dichloromethane were added to a 2 L four-neck flask, and the mixture was cooled to an internal temperature of 0°C. Next, 40.2 g (351 mmol) of methanesulfonyl chloride was added dropwise over 30 minutes, while being careful to keep the internal temperature at 0 to 5°C. After the addition was completed, the mixture was stirred for 30 minutes while keeping the internal temperature at 5°C. After the reaction was completed, 500 mL of pure water was added and stirred for 30 minutes. The organic layer was separated and added to 500 mL of 10% hydrochloric acid cooled in an ice bath, and stirred. Next, the organic layer was separated and added to 500 mL of saturated aqueous sodium bicarbonate solution, and stirred. The organic layer was separated again, and washed with 500 mL of saturated saline. The organic layer was dried over sodium sulfate, filtered, concentrated using a rotary evaporator, and vacuum dried at an external temperature of 40° C. for 2 hours to obtain 70.4 g of compound 108 (yield 97%).

[0634] <Synthesis of compound 109> Compound 109 shown below was synthesized according to the reaction scheme below and by the method described below.

[0635] [ka]

[0636] In a nitrogen atmosphere, 1 L of dehydrated diethyl ether was added to a 5 L four-neck flask, and the internal temperature was adjusted to 0°C. Then, 17.5 g (460 mmol) of lithium aluminum hydride was added. 70.0 g of compound 108 (307 mmol) was dissolved in 500 mL of dehydrated diethyl ether, and this solution was added dropwise to the previously prepared solution over 30 minutes. At this time, the internal temperature was adjusted to be in the range of 0 to 5°C. After the addition was completed, the mixture was stirred at room temperature for 3 hours. After the reaction was completed, the internal temperature was cooled again to 0°C, and 2 L of a saturated aqueous solution of potassium sodium tartrate was added dropwise over 2 hours while paying attention to the generation of hydrogen, and then the mixture was stirred at room temperature for another 2 hours. The organic layer and the aqueous layer were separated, and the collected aqueous layer was extracted four times with 400 mL of diethyl ether. The collected organic layer was washed with 1 L of saturated saline solution. The organic layer was dried over sodium sulfate, filtered, and then concentrated at normal pressure at an external temperature of 50°C. After concentration, the mixture was distilled under reduced pressure at 10 mmHg at an external temperature of 60° C. The components distilled at 40° C. were collected to obtain 37 g of compound 109 (yield 90%, colorless transparent liquid).

[0637] <Synthesis of Compound 110> Compound 110 shown below was synthesized by the method described below.

[0638] [ka]

[0639] In a 2L four-neck flask, 15g of compound 109 (112mmol), 108mL of pure water, and 600mL of tert-butyl alcohol were added and cooled on ice. 5.87g (145mmol) of sodium hydroxide and 19.43g (123mmol) of potassium permanganate were dissolved in 660mL of water, placed in a dropping funnel, and slowly dropped into the previously prepared mixed solution so that the internal temperature was 3℃ or less. After the completion of the dropping, the reaction completion was confirmed by GC analysis, and then a saturated aqueous solution of sodium pyrosulfite was added until the color of potassium permanganate disappeared, and then celite filtration was performed. The filtrate was concentrated, and the obtained aqueous layer was extracted three times with ethyl acetate. The collected organic layer was dried and filtered with sodium sulfate, and then concentrated with a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (dichloromethane:ethyl acetate=2:1) ​​to obtain 11.95g of compound 110 (yield 64%, white solid).

[0640] <Synthesis of Compound 111> Compound 111 shown below was synthesized by the method described below.

[0641] [ka]

[0642] In a nitrogen atmosphere, 3.0 g of compound 110 (17.8 mmol) was added to a three-neck flask, followed by the addition of 10 mL of dehydrated pyridine and stirring. The mixture was cooled in an ice bath, and 4.25 mL of benzoyl chloride (36.6 mmol) was slowly added over 10 minutes. After the addition, the mixture was warmed to room temperature and stirred overnight. The mixture was cooled again in an ice bath, and 3 mL of methanol was added to quench the reaction. Water and ethyl acetate were then added, and the mixture was transferred to a separatory funnel. The mixture was washed with water, a saturated aqueous solution of ammonium chloride, and saturated saline, in that order, and the organic layer was dried over magnesium sulfate and concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (hexane:ethyl acetate=10:1) to obtain 6.47 g of compound 111 (yield 96%, white solid). The obtained compound 111 1 The H-NMR data is shown below.

[0643] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 1.58-1.87 (m, 7H), 2.22-2.26 (m, 1H), 2.44 (br s, 2H), 2.58 (br s, 2H), 5.38 (d, J = 1.6 H, 2H), 7.22-7.28 (overlapped with CHCl3 signals, m, 4H), 7.46 (t, J = 7.6 Hz, 2H), 7.84-7.87 (m, 4H). The resulting compound 111 had a melting completion temperature of 97°C.

[0644] [Example A52] <Synthesis of Compound 112> Compound 112 shown below was synthesized according to the reaction scheme below and by the method described below.

[0645] [ka]

[0646] Under a nitrogen atmosphere, 33.3g (0.25mol) of aluminum chloride and 1.5L of dehydrated toluene were added to a 5L four-neck flask and stirred at room temperature. 41g (0.50mol) of 2-cyclopenten-1-one was dissolved in 1L of dehydrated toluene, and then added to the reaction solution prepared above and stirred at room temperature for 40 minutes. Then, 240.4g (3.0mol) of 1,3-cyclohexadiene was added, and the internal temperature was raised to 60°C and heated and stirred for 12 hours. After the reaction was completed, the mixture was cooled using an ice bath, 2L of 1N hydrochloric acid was added, and then stirred at room temperature for 30 minutes. The organic layer and the aqueous layer were separated, and the collected aqueous layer was extracted twice with 500mL of toluene. The collected organic layer was washed once with 1L of saturated saline and once with 1L of saturated aqueous sodium bicarbonate. The organic layer was dried and filtered with sodium sulfate, and then concentrated with a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (hexane:ethyl acetate=20:1) to obtain 36 g (yield 44%) of compound 112, which was an isomer mixture.

[0647] <Synthesis of compound 113> Compound 113 shown below was synthesized by the method described below.

[0648] [ka]

[0649] In a nitrogen atmosphere, 35.5 g of compound 112 (219 mmol), 50 mL (241 mmol) of 50% NMO aqueous solution, 81 mL of pure water, 81 mL of acetone, and 162 mL of tert-butyl alcohol were added to a 500 mL four-neck flask and stirred. Then, 170 mg (0.66 mmol) of osmium oxide was added and heated and stirred at an internal temperature of 40 ° C for 40 hours. After the reaction was completed, 2.7 g of sodium hydrosulfite, 33 g of Florisil, and 216 mL of pure water were added and stirred for 30 minutes. The filtrate was collected by vacuum filtration, and the pH of the filtrate was adjusted to 7 using 1 N sulfuric acid. The organic solvent was removed from the filtrate under reduced pressure at an external temperature of 40 ° C, and the remaining aqueous solution was adjusted again to 3 using 1 N sulfuric acid. Excess sodium chloride and 600 mL of ethyl acetate were added and stirred, and the mixture was filtered under reduced pressure to filter out the sodium chloride that remained dissolved. The organic layer and the aqueous layer were separated by separation, and the collected aqueous layer was extracted three times with 600 mL of ethyl acetate. The organic layers were collected, dried over sodium sulfate, filtered, and then concentrated using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (ethyl acetate:dichloromethane=1:1) and washed with hexane solvent to obtain 27.0 g of compound 113 (yield 64%).

[0650] <Synthesis of compound 114> Compound 114 shown below was synthesized by the method described below.

[0651] [ka]

[0652] In a nitrogen atmosphere, 4.0 g of compound 113 (20.4 mmol) was added to a 100 mL three-neck flask, followed by the addition of 10 mL of dehydrated pyridine and stirring. The mixture was cooled in an ice bath, and 4.89 mL of benzoyl chloride (42.1 mmol) was slowly added. After the addition, the mixture was warmed to room temperature and stirred overnight. The mixture was cooled again in an ice bath, and 5 mL of methanol was added to quench the reaction. Then, water and ethyl acetate were added to separate the aqueous layer and the organic layer, and the organic layer was washed once each with a saturated aqueous ammonium chloride solution, a saturated aqueous sodium bicarbonate solution, and saturated saline. The organic layer was dried over magnesium sulfate and filtered, and then concentrated using a rotary evaporator. The crude product was purified by silica gel column chromatography (hexane:ethyl acetate = 10:1 → 5:1) to obtain 7.49 g of compound 114 (yield 91%, pale yellow solid). The obtained compound 114 1 The H-NMR data is shown below.

[0653] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 1.48-1.55 (overlapping with H2O signals, m, 2H), 1.98-2.54 (m, 9H), 2.68-2.81 (m, 1H), 5.01-5.05 (m, 1H), 5.52-5.56 (m, 1H), 7.18-7.34 (overlapping with CHCl3 signals, m, 4H), 7.41-7.52 (m, 2H), 7.79-7.92 (m, 4H). The resulting compound 114 had a melting completion temperature of 122°C.

[0654] [Example A53] <Synthesis of compound 115> Compound 115 shown below was synthesized by the method described below.

[0655] [ka]

[0656] In a nitrogen atmosphere, 2.68 g of 5,6-dihydrodicyclopentadiene (20 mmol), 100 mL of tert-butyl alcohol, and 40 mL of water were added to a 1 L three-neck flask, and the reaction solution was cooled to 0 ° C. 1.0 g of sodium hydroxide (25 mmol) and 4.74 g of potassium permanganate (30 mmol) were dissolved in 100 mL of water, and slowly added dropwise to the reaction solution previously prepared. After the addition was completed, the mixture was stirred at the same temperature for 1 hour, and then a saturated aqueous solution of sodium pyrosulfite was added dropwise until the color of the unreacted potassium permanganate disappeared. After stirring at room temperature for a while, sodium bicarbonate was added until the pH of the reaction solution was about 7 to 8, and the resulting white precipitate was removed by filtration. The filtered solution was extracted three times with ethyl acetate, and the collected organic layer was dried over sodium sulfate and then concentrated with a rotary evaporator. The crude product (2.51 g) containing compound 115 was used in the next step, <Synthesis of compound 116>, without further purification.

[0657] <Synthesis of compound 116> Compound 116 shown below was synthesized by the method described below.

[0658] [ka]

[0659] Under a nitrogen atmosphere, 2.51 g of the crude product obtained in <Synthesis of Compound 115> was added to a 100 mL three-neck flask, followed by the addition of 10 mL of dehydrated pyridine and stirring. The mixture was cooled in an ice bath, and 4.04 mL of benzoyl chloride (34.8 mmol) was slowly added. After the addition, the mixture was warmed to room temperature and stirred overnight. The mixture was cooled again in an ice bath, and 10 mL of methanol was added to quench the mixture. Then, water and dichloromethane were added to separate the aqueous layer and the organic layer, and the organic layer was washed twice with a saturated aqueous ammonium chloride solution. The organic layer was dried over sodium sulfate and filtered, and then concentrated using a rotary evaporator. The crude product was purified by two silica gel column chromatography runs (first run: hexane:ethyl acetate=10:1, second run: hexane:ethyl acetate=20:1) to obtain 3.03 g of compound 116 (colorless, transparent liquid). The obtained compound 116 1 The H-NMR data is shown below.

[0660] 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 1.50-1.61 (overlapped by H2O signals, m, 6H), 1.97-2.14 (m, 2H), 2.25 (br s, 1H), 2.44 (br s, 1H), 2.61-2.69 (m, 1H), 2.72-2.83 (m, 1H), 5.47 (t, J = 4.0 Hz, 1H), 5.61-5.67 (m, 1H), 7.32-7.40 (m, 4H), 7.48-7.55 (m, 2H), 7.92-7.98 (m, 4H). [Example A54] <Preparation of solid titanium catalyst component [α1]> After thoroughly replacing the atmosphere in a 1L glass vessel with nitrogen, 85.8g of anhydrous magnesium chloride, 321g of decane, and 352g of 2-ethylhexyl alcohol were added and reacted at 130°C for 3 hours to obtain a homogeneous solution. 241g of this solution and 6.43g of ethyl benzoate were added to a glass vessel and stirred and mixed at 50°C for 1 hour. After cooling the homogeneous solution thus obtained to room temperature, 38.3mL of this homogeneous solution was added dropwise to 100mL of titanium tetrachloride kept at -20°C over a period of 45 minutes while stirring at a stirring speed of 350 rpm. After the addition, the temperature of this mixture was raised to 80°C over a period of 3.8 hours, and when it reached 80°C, 0.97g of the compound 6 was added to the mixture. The temperature was again raised to 120°C over a period of 40 minutes, and the mixture was kept at the same temperature for 35 minutes while stirring. After the reaction was completed, the solid portion was collected by hot filtration, and this solid portion was resuspended in 100 mL of titanium tetrachloride, and then the reaction was again heated at 120°C for 35 minutes. After the reaction was completed, the solid portion was collected by hot filtration again, and thoroughly washed with 100°C decane and room temperature decane until no free titanium compounds were detected in the washings. The solid titanium catalyst component [α1] prepared by the above operations was stored as a decane slurry, and a part of it was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component [α1] obtained in this way was 0.28 mass% titanium, 1.7 mass% magnesium, and 0.12 mass% 2-ethylhexyl alcohol residue.

[0661] <Main Polymerization> 500g of propylene and 1NL of hydrogen were added to a 2L polymerization vessel at room temperature, and then a mixture of 7mL of heptane, 0.5mmol of triethylaluminum, 0.08mmol of cyclohexylmethyldimethoxysilane, and 0.004mmol (titanium atom equivalent) of solid titanium catalyst component [α1] mixed for 10 minutes at 25°C was added, and the temperature inside the polymerization vessel was quickly raised to 70°C. After polymerization at 70°C for 1.5 hours, the reaction was stopped with a small amount of methanol, and propylene was purged. The obtained polymer particles were further dried under reduced pressure at 80°C overnight. The polymerization results are as follows.

[0662] Activity: 48.6kg-PP / g-catalyst Bulk density: 490kg / m 3 MFR (ASTM1238E standard, 230℃, 2.16kg load): 0.57g / 10min Decane insolubles: 1.87wt% Tm:163.92℃ Tmf:172.08℃ Mw / Mn: 10.64 Mz / Mw: 4.85 The methods for measuring the above physical properties are as follows.

[0663] (1) Bulk density: Measurements were performed in accordance with JIS K-6721. (2)Melt flow rate (MFR): The method was based on ASTM D1238E, and the measurement temperature was 230° C. for propylene polymers.

[0664] (3) Amount of decane soluble (insoluble) components: Put about 3 g (10 -4 The weight was measured to the nearest g. This weight was represented as b(g) in the formula below. 500 mL of decane, 500 mL of decane, and a small amount of a heat-resistant stabilizer soluble in decane were added, and the mixture was heated to 150°C over 2 hours while stirring with a stirrer under a nitrogen atmosphere to dissolve the propylene polymer. The mixture was then held at 150°C for 2 hours and then slowly cooled to 23°C over 8 hours. The resulting liquid containing the precipitate of the propylene polymer was filtered under reduced pressure using a 25G-4 standard glass filter manufactured by Tokyo Glass Instruments Co., Ltd. 100 mL of the filtrate was collected and dried under reduced pressure to obtain a portion of the decane-soluble component, and the weight of this was calculated by multiplying the weight of the propylene polymer by 100 mL. -4 (This weight is represented as a(g) in the formula below.) After this operation, the amount of decane soluble components was determined by the formula below.

[0665] Decane soluble component content = 100 × (500 × a) / (100 × b) Decane insoluble content = 100 - 100 × (500 × a) / (100 × b) (4) Molecular weight distribution: Gel permeation chromatograph: Tosoh Corporation HLC-8321 GPC / HT type Detector: Differential refractometer Columns: Two TSKgel GMH6-HT columns and two TSKgel GMH6-HTL columns manufactured by Tosoh Corporation were connected in series.

[0666] Mobile phase medium: o-dichlorobenzene Flow rate: 1.0mL / min Measurement temperature: 140℃ How to create a calibration curve: Standard polystyrene samples were used Sample concentration: 0.1% (w / w) Sample volume: 0.4mL The measurement was performed under the above conditions, and the obtained chromatogram was analyzed by a known method to calculate the weight average molecular weight (Mw), number average molecular weight (Mn), Z average molecular weight (Mz), and the Mw / Mn and Mz / Mw values, which are indices of molecular weight distribution (MWD). The measurement time for one sample was 60 minutes.

[0667] (5) Melting point of polymer (Tm): The melting point (Tm), crystallization temperature (Tc), and heat of fusion (ΔH) of the polymer in the present invention were measured by differential scanning calorimetry (DSC) using a Seiko Instruments Inc. DSC220C device. 3 to 10 mg of sample was sealed in an aluminum pan and heated from room temperature to 200°C at 100°C / min. The sample was held at 200°C for 5 minutes and then cooled to 30°C at 10°C / min. In this cooling test, the peak temperature was taken as the crystallization temperature (Tc). After being left at 30°C for 5 minutes, the sample was heated a second time to 200°C at 10°C / min. In this second heating test, the peak temperature was taken as the melting point (Tm) and the heat generated was taken as the heat of fusion (ΔH).

[0668] The final melting point (Tmf) of the polymer in the present invention was measured by differential scanning calorimetry (DSC) using a Seiko Instruments DSC220C device. 3 to 10 mg of the sample was sealed in an aluminum pan and heated from room temperature to 240°C at 80°C / min. The sample was held at 240°C for 1 minute and then cooled to 0°C at 80°C / min. After holding at 0°C for 1 minute, the sample was heated to 150°C at 80°C / min and held for 5 minutes. Finally, the sample was heated to 180°C at 1.35°C / min, and the intersection of the tangent of the inflection point on the high temperature side of the peak obtained in this final heating test and the baseline was adopted as the final melting point (Tmf).

[0669] Tmf can be considered as one parameter for evaluating the crystallization ease and crystal structure of a polymer in the ultra-high molecular weight region, which is considered to have a tendency to be difficult to crystallize. More specifically, it can be considered that the higher the Tmf value, the easier it is for the ultra-high molecular weight polymer component to form strong, heat-resistant crystals.

[0670] [Example B1] <Synthesis of Compounds 201 and 202> Compounds 201 and 202 shown below were synthesized by the method described below.

[0671] [ka]

[0672] [In (Compound 201), the thick line represents the front side of the paper, and the dotted line represents the back side of the paper. Compound 201 corresponds to the diol compound derived from the endo isomer shown in formula (34) above.]

[0673] [ka]

[0674] [In (Compound 202), the thick line represents the front side of the paper, and Compound 202 corresponds to the exo-form-derived diol compound shown in the above formula (34).] A 2-liter flask was equipped with a mechanical stirrer and the inside of the flask was replaced with nitrogen. An olefin (R in formula (33)) was added to the flask. 4 , R 9 , R 31 ~R 34 25.4 grams of a compound in which X is a hydrogen atom and X is CH2, 440 ml of tert-butyl alcohol, and 110 ml of water were added, and the internal temperature was cooled to 0°C. 30 grams of potassium permanganate, 600 ml of water, and 6.60 grams of sodium hydroxide were added to another 1L beaker to prepare an aqueous solution of potassium permanganate alkali. A dropping funnel was attached to the 2L flask, the prepared aqueous solution of potassium permanganate alkali was charged into the dropping funnel, and the aqueous solution of potassium permanganate alkali was slowly dropped so that the internal temperature did not exceed 5°C. After the dropping was completed, the mixture was stirred at an internal temperature of 0°C for 1 hour. A saturated aqueous solution of sodium pyrosulfite was prepared in another flask, and slowly dropped into the reaction solution until a white precipitate was formed. After the dropping, the temperature was raised to room temperature to precipitate a white solid. After collecting the supernatant organic layer, extraction was performed twice from the aqueous layer with ethyl acetate. The organic layers were combined, washed with water and saturated saline, and dried over magnesium sulfate. The organic layer was then concentrated to obtain 27.41 grams of a crude product. The obtained crude product was purified by silica gel column chromatography to obtain 22.71 grams of the target product (mixture of isomers). The obtained product was purified again by a silica gel column to separate the isomers, and 10.9 grams of compound 201 and 2.9 grams of compound 202 were isolated. 1 The H-NMR data is shown below.

[0675] (Compound 201) 1H NMR (270 MHz, CDCl3, TMS as internal standard): δ 1.39-1.51 (m, 1 H), 1.89-2.01 (m,1 H), 2.19-2.27 (m, 1 H), 2.30-2.38 (m, 1 H), 2.47-2.58 (m, 2 H), 2.70-3.08 (m,3H), 3.21-3.32 (m, 1H), 3.58-3.76 (m, 2 H), 7.06-7.36 (m, 4 H). (Compound 202) 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 1.00-1.10 (m, 1 H), 1.55-1.64 (m,1 H), 2.07(br s, 1 H), 2.23-2.35 (m, 2 H), 2.50 (dd, J = 14.5, 5.3 Hz, 2 H) 2.63 (dd, J = 17.1, 3.6 Hz, 1H), 3.06 (d, J = 7.9, 1 H), 3.28 (dd, J = 17.4, 10.5Hz, 1 H), 3.79-3.87 (m, 1 H), 3.88-3.96 (m, 1 H), 7.09-7.20 (m, 4 H). <Synthesis of compound 203> Compound 203 shown below was synthesized by the method described below.

[0676] [ka]

[0677] The inside of a 200 ml flask was replaced with nitrogen, and 5 grams of compound 201 was added, followed by 30 ml of dehydrated pyridine. 5.69 ml of benzoyl chloride was slowly added dropwise while cooling in an ice bath. After the addition, the mixture was warmed to room temperature and stirred overnight. It was again cooled in an ice bath, and quenched by adding methanol. After adding chloroform and water and stirring, the organic layer was separated. The organic layer was washed with a saturated aqueous ammonium chloride solution and saturated saline, and then dried over magnesium sulfate. The organic layer was then concentrated to obtain 10.61 grams of a crude product. Purification was performed by silica gel column chromatography to obtain 6.83 grams of compound 203. The obtained compound 203 was 1 The H-NMR data is shown below.

[0678] (Compound 203) 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 1.68-1.74 (m, 1 H), 2.29-2.34 (m,1 H), 2.57-2.59 (m, 1 H), 2.90-3.20 (m, 4 H), 3.83 (dd, J = 10.2, 5.6 Hz, 1 H) 4.66 (dd, J = 5.9, 1.3 Hz, 1H), 5.03 (dd, J = 5.9, 1.7 Hz, 1 H), 7.20-7.49 (m, 10 H), 7.79-7.86 (m, 4 H). The melting completion temperature of compound 203 was 108.7°C.

[0679] <Synthesis of compound 204> Compound 204 shown below was synthesized by the method described below.

[0680] [ka]

[0681] In the synthesis of compound 203, 3.85 g of compound 204 was obtained (yield 89%) according to the procedure and equivalent relationship described in the synthesis of compound 203, except that 2.2 g of compound 202 was used instead of compound 201. 1 The H-NMR data is shown below.

[0682] (Compound 204) 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 1.27-1.33 (m, 1 H), 1.92-1.98 (m,1 H), 2.44 (br s, 1 H), 2.57-2.76 (m, 3 H), 3.34-3.45 (m, 2 H) 5.19-5.23 (m, 1 H), 5.30-5.35 (m, 1 H), 7.17-7.32 (m, 8 H), 7.43-7.52 (m, 2 H), 7.84-7.92 (m, 4 H). The melting completion temperature of compound 204 was 168.2°C.

[0683] [Example B2] <Preparation of solid titanium catalyst component [α1]> After thoroughly replacing the atmosphere in a 1L glass vessel with nitrogen, 85.8g of anhydrous magnesium chloride, 321g of decane, and 352g of 2-ethylhexyl alcohol were added and reacted at 130°C for 3 hours to obtain a homogeneous solution. 241g of this solution and 6.43g of ethyl benzoate were added to a glass vessel and stirred and mixed at 50°C for 1 hour. After cooling the homogeneous solution thus obtained to room temperature, 38.3ml of this homogeneous solution was added dropwise to 100ml of titanium tetrachloride kept at -20°C over a period of 45 minutes while stirring at a stirring speed of 350 rpm. After the addition, the temperature of this mixture was raised to 80°C over a period of 3.8 hours, and when it reached 80°C, 0.91g of the compound 203 was added to the mixture. The temperature was again raised to 120°C over a period of 40 minutes, and the mixture was kept at the same temperature for 35 minutes while stirring. After the reaction was completed, the solid portion was collected by hot filtration, resuspended in 100 ml of titanium tetrachloride, and then heated again at 120°C for 35 minutes. After the reaction was completed, the solid portion was collected by hot filtration again, and thoroughly washed with decane at 100°C and room temperature until no free titanium compounds were detected in the washings. The solid titanium catalyst component [α1] prepared by the above procedure was stored as a decane slurry.

[0684] <Main Polymerization> 500g of propylene and 1NL of hydrogen were added to a 2L pressure-resistant polymerization vessel at room temperature, and then a mixture of 7ml of heptane, 0.5mmol of triethylaluminum, 0.08mmol of cyclohexylmethyldimethoxysilane, and 0.004mmol of solid titanium catalyst component [α1] (titanium atom equivalent) mixed for 10 minutes at 25°C was added, and the temperature inside the polymerization vessel was quickly raised to 70°C. After polymerization at 70°C for 1.5 hours, the reaction was stopped with a small amount of methanol, and the propylene was purged. The obtained polymer particles were further dried under reduced pressure at 80°C overnight. The polymerization results are as follows.

[0685] Activity: 72.7kg-PP / g-catalyst Bulk density: 490kg / m 3 MFR (ASTM1238e standard, 230℃, 2.16kg load): 0.45g / 10min Decane insolubles: 0.49wt% Tm: 165.39℃ Tmf:172.33℃ Mw / Mn: 11.25 Mz / Mw: 4.41 The methods for measuring the above physical properties are as described in Example A54.

[0686] [Example B3] <Synthesis of compound 205> Compound 205 shown below was synthesized by the method described below.

[0687] [ka]

[0688] The inside of a 100 ml flask was replaced with nitrogen, and 3.0 g (1 equivalent) of a mixture of compound 201 and compound 202 was added, followed by the addition of 15 ml of dehydrated pyridine and 15 ml of chloroform. While cooling in an ice bath, 4.5 g (2.1 equivalents) of 3-methylbenzoyl chloride was slowly added dropwise. After the addition, the mixture was warmed to room temperature and stirred overnight. It was again cooled in an ice bath, and quenched by adding methanol. After adding chloroform and water and stirring, the organic layer was separated. The organic layer was washed with a saturated aqueous ammonium chloride solution and saturated saline, and then dried over magnesium sulfate. The organic layer was then concentrated to obtain 6.78 g of a crude product. The product was purified by silica gel column chromatography to obtain 5.94 g (yield 95%) of compound 205, which is an isomer mixture of endo and exo isomers (endo:exo = 86:14). The obtained compound 205 1 The H-NMR data is shown below.

[0689] (Compound 205) 1H NMR (270 MHz, CDCl3, TMS as internal standard): endo: δ 1.68-1.73 (m, 1 H), 2.13-2.19 (m, 6 H), 2.30-2.35 (m, 1 H), 2.57-2.59 (m, 1 H), 2.89-3.20 (m, 4 H), 3.80-3.86 (dd, J = 10.6, 5.9 Hz, 1 H), 4.63-4.65 (m, 1 H), 5.00-5.03 (m, 1 H), 7.14-7.34 (m, 8 H), 7.56-7.76 (m, 4 H); exo: 1.26-1.32 (m, 1 H), 1.92-1.96 (m, 1 H), 2.13-2.19 (m, 6 H), 2.42 (br s, 1 H), 2.61-2.74 (m, 3 H), 3.33-3.43 (m, 2 H), 5.16-5.18 (m, 1 H), 5.27-5.30 (m, 1 H), 7.14-7.34 (m, 8 H), 7.56-7.76 (m, 4 H). The melting completion temperature of compound 205 was 116.0°C.

[0690] [Example B4] <Synthesis of compound 206> Compound 206 shown below was synthesized by the method described below.

[0691] [ka]

[0692] In the synthesis of compound 205, 4.91 grams (2.1 equivalents) of 3,5-dimethylbenzoyl chloride was used instead of 3-methylbenzoyl chloride, and the procedure and equivalent relationship described in the synthesis of compound 205 were followed to obtain 6.37 grams (96% yield) of compound 206, which is an isomer mixture of endo and exo isomers (endo:exo=85:15). 1 The H-NMR data is shown below.

[0693] (Compound 206) 1 H NMR (270 MHz, CDCl3, TMS as internal standard): endo: δ 1.68-1.72 (m, 1 H), 2.13-2.18 (m, 12 H), 2.31-2.34 (m, 1 H), 2.56-2.58 (m, 1 H), 2.88-3.19 (m, 4 H), 3.79-3.85 (dd, J = 10.6, 5.6 Hz, 1 H), 4.60-4.63 (m, 1 H), 4.98-5.00 (m, 1 H), 7.07-7.09 (m, 2 H), 7.17-7.32 (m, 4 H), 7.42-7.50 (m, 4 H); exo: 1.24-1.29 (m, 1 H), 1.90-1.96 (m, 1 H), 2.13-2.18 (m, 12 H), 2.42 (br s, 1 H), 2.60-2.74 (m, 3 H), 3.33-3.43 (m, 2 H), 5.14-5.16 (m, 1 H), 5.24-5.27 (m, 1 H), 7.07-7.09 (m, 2 H), 7.17-7.32 (m, 4 H), 7.42-7.50 (m, 4 H). Peaks believed to be the melting point of compound 206 were observed at 153.0°C and 191.4°C.

[0694] [Example B5] <Synthesis of compound 207> Compound 207 shown below was synthesized by the method described below.

[0695] [ka]

[0696] In the synthesis of compound 205, 3.80 grams (2.1 equivalents) of 2-furoyl chloride was used instead of 3-methylbenzoyl chloride, but in accordance with the procedure and equivalent relationship described in the synthesis of compound 205, 5.40 grams (94% yield) of compound 207 (endo:exo=86:14), which is an isomer mixture of endo and exo isomers, was obtained.1 The H-NMR data is shown below.

[0697] (Compound 207) 1 H NMR (270 MHz, CDCl3, TMS as internal standard): endo: δ 1.66-1.70 (m, 1 H), 2.24-2.28 (m, 1 H), 2.54-2.55 (m, 1 H), 2.85-3.08 (m, 4 H), 3.78-3.83 (dd, J = 10.6, 5.6 Hz, 1 H), 4.55-4.57 (m, 1 H), 4.95-4.97 (m, 1 H), 6.37-6.42 (m, 2 H), 6.86-6.97 (m, 2 H), 7.16-7.30 (m, 4 H), 7.44-7.49 (m, 2 H); exo: 1.23-1.28 (m, 1 H), 1.86-1.91 (m, 1 H), 2.39 (br s, 1 H), 2.57-2.72 (m, 3 H), 3.31-3.42 (m, 2 H), 5.11-5.13 (m, 1 H), 5.22-5.24 (m, 1 H), 6.37-6.42 (m, 2 H), 6.86-6.97 (m, 2 H), 7.16-7.30 (m, 4 H), 7.44-7.49 (m, 2 H). Peaks believed to be the melting points of compound 207 were observed at 107.6°C and 120.5°C.

[0698] [Example B6] <Synthesis of compound 208> Compound 208 shown below was synthesized by the method described below.

[0699] [ka]

[0700] In the synthesis of compound 205, 4.27 grams (2.1 equivalents) of 2-thenoyl chloride was used instead of 3-methylbenzoyl chloride, but in accordance with the procedure and equivalent relationship described in the synthesis of compound 205, 5.72 grams (94% yield) of compound 208, an isomer mixture of endo and exo isomers (endo:exo=86:14), was obtained. 1 The H-NMR data is shown below.

[0701] (Compound 208) 1 H NMR (270 MHz, CDCl3, TMS as internal standard): endo: δ 1.66-1.70 (m, 1 H), 2.24-2.29 (m, 1 H), 2.55-2.56 (m, 1 H), 2.87-3.14 (m, 4 H), 3.78-3.84 (dd, J = 10.2, 5.6 Hz, 1 H), 4.57-4.59 (m, 1 H), 4.94-4.97 (m, 1 H), 6.95-7.01 (m, 2 H), 7.16-7.32 (m, 4 H), 7.43-7.48 (m, 2 H), 7.58-7.67 (m, 2 H); exo: 1.24-1.28 (m, 1 H), 1.87-1.92 (m, 1 H), 2.40 (br s, 1 H), 2.56-2.73 (m, 3 H), 3.32-3.42 (m, 2 H), 5.11-5.14 (m, 1 H), 5.23-5.25 (m, 1 H), 6.95-7.01 (m, 2 H), 7.16-7.32 (m, 4 H), 7.43-7.48 (m, 2 H), 7.58-7.67 (m, 2 H). Peaks believed to be the melting point of compound 208 were observed at 110.9°C and 141.5°C.

[0702] [Example B7] <Synthesis of compound 209> Compound 209 shown below was synthesized by the method described below.

[0703] [ka]

[0704] In the synthesis of compound 205, 5.77 g (88% yield) of compound 209 (endo:exo=88:12), which is an isomer mixture of endo and exo isomers, was obtained in the same manner as in the synthesis of compound 205, except that 5.0 g (2.1 equivalents) of 1-naphthoyl chloride was used instead of 3-methylbenzoyl chloride. 1 The H-NMR data is shown below.

[0705] (Compound 209) 1 H NMR (270 MHz, CDCl3, TMS as internal standard): endo: δ 1.75-1.79 (m, 1 H), 2.36-2.40 (m, 1 H), 2.69-2.70 (m, 1 H), 2.96-3.29 (m, 4 H), 3.86-3.92 (dd, J = 10.2, 5.6 Hz, 1 H), 4.82-4.85 (m, 1 H), 5.19-5.22 (m, 1 H), 6.98-7.43 (m, 10 H), 7.73-7.98 (m, 6 H), 8.70-8.80 (m, 2 H); exo: 1.33-1.37 (m, 1 H), 1.99-2.03 (m, 1 H), 2.53 (br s, 1 H), 2.70-2.79 (m, 3 H), 3.38-3.47 (m, 2 H), 5.36-5.38 (m, 1 H), 5.48-5.50 (m, 1 H), 6.98-7.43 (m, 10 H), 7.73-7.98 (m, 6 H), 8.70-8.80 (m, 2 H). The melting completion temperature of compound 209 was 149.8°C.

[0706] [Example B8] <Synthesis of compound 210> Compound 210 shown below was synthesized by the method described below.

[0707] [ka]

[0708] In the synthesis of compound 205, 5.0 grams (2.1 equivalents) of 2-naphthoyl chloride was used instead of 3-methylbenzoyl chloride, but the procedure and equivalent relationship described in the synthesis of compound 205 were followed to obtain 4.89 grams (75% yield) of compound 210, which is only the endo isomer. 1 The H-NMR data is shown below.

[0709] (Compound 210) 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 1.76-1.80 (m, 1 H), 2.43-2.47 (m, 1 H), 2.67-2.68 (m, 1 H), 2.95-3.25 (m, 4 H), 3.85-3.91 (dd, J = 10.6, 5.9 Hz, 1 H), 4.74-4.76 (m, 1 H), 5.11-5.14 (m, 1 H), 7.21-7.54 (m, 10 H), 7.64-7.80 (m, 4 H), 7.88-7.95 (m, 2 H), 8.27-8.35 (m, 2 H). The melting completion temperature of compound 210 was 173.8°C.

[0710] [Example B9] <Synthesis of compound 211> Compound 211 shown below was synthesized by the method described below.

[0711] [ka]

[0712] In the synthesis of compound 205, 5.0 grams (2.1 equivalents) of 3-methoxybenzoyl chloride was used instead of 3-methylbenzoyl chloride, and the procedure and equivalent relationship described in the synthesis of compound 205 were followed to obtain 4.70 grams (70% yield) of compound 211, which is an isomer mixture of endo and exo isomers (endo:exo=80:20). 1 The H-NMR data is shown below.

[0713] (Compound 211) 1 H NMR (270 MHz, CDCl3, TMS as internal standard): endo: δ 1.69-1.72 (m, 1 H), 2.28-2.32 (m, 1 H), 2.57-2.58 (m, 1 H), 2.88-3.18 (m, 4 H), 3.60-3.66 (m, 6 H), 3.80-3.86 (dd, J = 10.2, 5.6 Hz, 1 H), 4.64-4.66 (m, 1 H), 5.01-5.03 (m, 1 H), 6.98-7.03 (m, 2 H), 7.13-7.37 (m, 8 H), 7.44-7.53 (m, 2 H); exo: 1.26-1.30 (m, 1 H), 1.91-1.95 (m, 1 H), 2.42 (br s, 1 H), 2.60-2.73 (m, 3 H), 3.33-3.43 (m, 2 H), 3.60-3.66 (m, 6 H), 5.18-5.20 (m, 1 H), 5.29-5.31 (m, 1 H), 6.98-7.03 (m, 2 H), 7.13-7.37 (m, 8 H), 7.44-7.53 (m, 2 H). The melting completion temperature of compound 211 was 124.3°C.

[0714] [Example B10] <Synthesis of compound 212> Compound 212 shown below was synthesized by the method described below.

[0715] [ka]

[0716] In the synthesis of compound 205, 5.75 grams (2.7 equivalents) of phenylacetyl chloride was used instead of 3-methylbenzoyl chloride, but in accordance with the procedure and equivalent relationship described in the synthesis of compound 205, 1.32 grams (yield 21%) of compound 212, an isomer mixture of endo and exo isomers (endo:exo=78:22), was obtained as a colorless, transparent liquid. 1 The H-NMR data is shown below.

[0717] (Compound 212) 1 H NMR (270 MHz, CDCl3, TMS as internal standard): endo: δ 1.52-1.55 (m, 1 H), 1.98-2.02 (m, 1 H), 2.29-2.33 (m, 1 H), 2.63-2.65 (m, 1 H), 2.75-2.97 (m, 3 H), 3.17-3.26 (m, 4 H), 3.66-3.72 (dd, J = 10.6, 5.6 Hz, 1 H), 4.27-4.30 (m, 1 H), 4.64-4.67 (m, 1 H), 7.13-7.33 (m, 14 H); exo: 1.09-1.13 (m, 1 H), 1.60-1.64 (m, 1 H), 2.15 (br s, 1 H), 2.33-2.57 (m, 3 H), 3.17-3.26 (m, 6 H), 5.20-5.22 (m, 1 H), 5.31-5.33 (m, 1 H), 7.13-7.33 (m, 14 H). [Example B11] <Synthesis of compound 213> Compound 213 shown below was synthesized by the method described below.

[0718] [ka]

[0719] In the synthesis of compound 205, 5.14 grams (2.1 equivalents) of 3,5-difluorobenzoyl chloride was used instead of 3-methylbenzoyl chloride, and the procedure and equivalent relationship described in the synthesis of compound 205 were followed to obtain 6.02 grams (87% yield) of compound 213, which is an isomer mixture of endo and exo isomers (endo:exo=96:4). 1 The H-NMR data is shown below.

[0720] (Compound 213) 1 H NMR (270 MHz, CDCl3, TMS as internal standard): endo: δ 1.74-1.77 (m, 1 H), 2.24-2.29 (m, 1 H), 2.57-2.59 (m, 1 H), 2.89-3.11 (m, 4 H), 3.82-3.88 (dd, J = 10.6, 5.6 Hz, 1 H), 4.62-4.64 (m, 1 H), 5.00-5.02 (m, 1 H), 6.87-6.99 (m, 2 H), 7.18-7.38 (m, 8 H); exo: 1.30-1.35 (m, 1 H), 1.87-1.91 (m, 1 H), 2.43 (br s, 1 H), 2.60-2.75 (m, 3 H), 3.35-3.45 (m, 2 H), 5.17-5.20 (m, 1 H), 5.29-5.31 (m, 1 H), 6.87-6.99 (m, 2 H), 7.18-7.38 (m, 8 H). The melting completion temperature of compound 213 was 127.7°C.

[0721] [Example B12] <Synthesis of compound 214> Compound 214 shown below was synthesized by the method described below.

[0722] [ka]

[0723] The inside of a 100 ml flask was replaced with nitrogen, and 5.95 g (1 equivalent) of 3-phenylbenzoic acid was added, followed by 60 ml of dichloromethane and 2 drops of dimethylformamide. 3.09 ml (1.2 equivalents) of oxalyl chloride was slowly added dropwise while cooling in an ice bath. After the addition, the temperature was raised to room temperature and the mixture was stirred for 2 hours. The volatile compounds in the reaction system were removed under reduced pressure to obtain compound 214. This was used in the synthesis of compound 215 without further purification.

[0724] <Synthesis of compound 215> Compound 215 shown below was synthesized by the method described below.

[0725] [ka]

[0726] To a 100 ml flask containing the entire amount (2.2 equivalents) of compound 214 synthesized in <Synthesis of compound 214> under nitrogen atmosphere, 3 ml of dehydrated pyridine was added. While cooling in an ice bath, 10 ml of dichloromethane solution containing 2.92 g (1 equivalent) of a mixture of compound 201 and compound 202 was slowly added. After the dropwise addition, the mixture was warmed to room temperature and stirred overnight. It was cooled again in an ice bath and quenched by adding methanol. After adding chloroform and water and stirring, the organic layer was separated. The organic layer was washed with a saturated aqueous ammonium chloride solution and saturated saline, and then dried with magnesium sulfate. The organic layer was then concentrated to obtain 9.87 g of a crude product. The product was purified by silica gel column chromatography to obtain 6.82 g (yield 88%) of compound 215, which is an isomer mixture of endo and exo isomers (endo:exo=88:12). The obtained compound 215 1 The H-NMR data is shown below.

[0727] (Compound 215) 1H NMR (270 MHz, CDCl3, TMS as internal standard): endo: δ 1.72-1.75 (m, 1 H), 2.33-2.37 (m, 1 H), 2.60-2.61 (m, 1 H), 2.92-3.21 (m, 4 H), 3.82-3.88 (dd, J = 9.9, 5.3 Hz, 1 H), 4.69-4.72 (m, 1 H), 5.08-5.11 (m, 1 H), 7.17-7.39 (m, 16 H), 7.59-7.64 (m, 2 H), 7.81-7.85 (m, 2 H), 8.02-8.07 (m, 2 H); exo: 1.26-1.33 (m, 1 H), 1.96-1.99 (m, 1 H), 2.45 (br s, 1 H), 2.63-2.75 (m, 3 H), 3.35-3.45 (m, 2 H), 5.25-5.38 (m, 1 H), 5.36-5.38 (m, 1 H), 7.17-7.39 (m, 16 H), 7.59-7.64 (m, 2 H), 7.81-7.85 (m, 2 H), 8.02-8.07 (m, 2 H). Compound 215 exhibited a gradual melting behavior from 62.5°C.

[0728] [Example B13] <Synthesis of compound 216> Compound 216 shown below was synthesized by the method described below.

[0729] [ka]

[0730] In the synthesis of compound 205, 5.36 grams (2.2 equivalents) of 3-chlorobenzoyl chloride was used instead of 3-methylbenzoyl chloride, and only 10 ml of pyridine was used as the solvent. The procedure and equivalent relationship described in the synthesis of compound 205 were followed, but an isomeric mixture of endo and exo isomers, compound 216 (endo:exo=83:17), was obtained in an amount of 2.22 grams (yield 32%). 1The H-NMR data is shown below.

[0731] (Compound 216) 1 H NMR (270 MHz, CDCl3, TMS as internal standard): endo: δ 1.71-1.75 (m, 1 H), 2.28-2.32 (m, 1 H), 2.57-2.58 (m, 1 H), 2.89-3.10 (m, 4 H), 3.80-3.86 (dd, J = 10.2, 5.6 Hz, 1 H), 4.63-4.65 (m, 1 H), 5.01-5.04 (m, 1 H), 7.16-7.33 (m, 6 H), 7.40-7.45 (m, 2 H), 7.71-7.80 (m, 4 H); exo: 1.28-1.32 (m, 1 H), 1.90-1.95 (m, 1 H), 2.42 (br s, 1 H), 2.60-2.74 (m, 3 H), 3.32-3.42 (m, 2 H), 5.17-5.20 (m, 1 H), 5.29-5.31 (m, 1 H), 7.16-7.33 (m, 6 H), 7.40-7.45 (m, 2 H), 7.71-7.80 (m, 4 H). The melting completion temperature of compound 216 was 139.4°C.

[0732] [Example B14] <Synthesis of compound 217> Compound 217 shown below was synthesized by the method described below.

[0733] [ka]

[0734] In the synthesis of compound 205, 6.41 g (2.2 equivalents) of 3,5-dichlorobenzoyl chloride was used instead of 3-methylbenzoyl chloride, and only 10 ml of pyridine was used as the solvent. The procedure and the equivalent relationship described in the synthesis of compound 205 were followed, and 4.50 g (yield 58%) of compound 217, which is only the endo isomer, was obtained.1 The H-NMR data is shown below.

[0735] (Compound 217) 1 H NMR (270 MHz, CDCl3, TMS as internal standard): δ 1.74-1.78 (m, 1 H), 2.26-2.30 (m, 1 H), 2.57-2.58 (m, 1 H), 2.89-3.10 (m, 4 H), 3.82-3.88 (dd, J = 9.9, 5.6 Hz, 1 H), 4.60-4.62 (m, 1 H), 4.98-5.01 (m, 1 H), 7.23-7.32 (m, 4 H), 7.45-7.48 (m, 2 H), 7.62-7.67 (m, 4 H). The melting completion temperature of compound 217 was 208.2°C.

[0736] [Example B15] <Synthesis of compound 218> Compound 218 shown below was synthesized by the method described below.

[0737] [ka]

[0738] Compound 218 was synthesized according to the procedure and equivalent relationship described in <Synthesis of Compound 214>, except that 4.63 g (1 equivalent) of 3,4-dimethylbenzoic acid was used instead of 3-phenylbenzoic acid in <Synthesis of Compound 214>. The obtained compound 218 was used as it is in the synthesis of compound 219.

[0739] <Synthesis of compound 219> Compound 219 shown below was synthesized by the method described below.

[0740] [ka]

[0741] The inside of a 100 ml flask was replaced with nitrogen, and 2.57 g (1 equivalent) of a mixture of compound 201 and compound 202 was added, followed by 20 ml of a dichloromethane solution of the total amount (2.2 equivalents) of compound 218 synthesized in <Synthesis of compound 218>. While cooling in an ice bath, 10 ml of dehydrated pyridine was slowly added dropwise. After the addition, the mixture was warmed to room temperature and stirred overnight. It was cooled again in an ice bath, and quenched by adding methanol. After adding dichloromethane and water and stirring, the organic layer was separated. The organic layer was washed with a saturated aqueous ammonium chloride solution and saturated saline, and then dried over magnesium sulfate. The organic layer was then concentrated to obtain 10.3 g of a crude product. The product was purified by silica gel column chromatography to obtain 4.80 g (83% yield) of compound 219, which is an isomer mixture of endo and exo isomers (endo:exo = 87:13). The obtained compound 219 1 The H-NMR data is shown below.

[0742] (Compound 219) 1H NMR (270 MHz, CDCl3, TMS as internal standard):endo: δ 1.66-1.70 (m, 1 H), 2.07-2.08 (m, 6 H), 2.23-2.25 (m, 6 H), 2.29-2.33 (m, 1 H), 2.56-2.57 (m, 1 H), 2.88-3.18 (m, 4 H), 3.79-3.85 (dd, J = 10.9, 5.6 Hz, 1 H), 4.61-4.63 (m, 1 H), 4.97-5.00 (m, 1 H), 7.02-7.08 (m, 2 H), 7.16-7.34 (m, 4 H), 7.51-7.66 (m, 4 H); exo body: 1.24-1.27 (m, 1 H), 1.91-1.95 (m, 1 H), 2.07-2.08 (m, 6 H), 2.23-2.25 (m, 6 H), 2.41 (br s, 1 H), 2.59-2.74 (m, 3 H), 3.30-3.42 (m, 2 H), 5.14-5.16 (m, 1 H), 5.25-5.28 (m, 1 H), 7.02-7.08 (m, 2 H), 7.16-7.34 (m, 4 H), 7.51-7.66 (m, 4 H). The melting completion temperature of compound 219 was 131.1°C.

[0743] [Example B16] <Synthesis of compound 220> Compound 220 shown below was synthesized by the method described below.

[0744] [ka]

[0745] Compound 220 was synthesized according to the procedure and equivalent relationship described in <Synthesis of Compound 214>, except that 4.85 g (1 equivalent) of 5,6,7,8-tetrahydro-2-naphthoic acid was used instead of 3-phenylbenzoic acid in <Synthesis of Compound 214>. The obtained compound 220 was used as it was in the synthesis of compound 221.

[0746] <Synthesis of compound 221> Compound 221 shown below was synthesized by the method described below.

[0747] [ka]

[0748] In the synthesis of compound 219, compound 220 (2.2 equivalents) was used instead of compound 218, and the procedure and equivalent relationship described in the synthesis of compound 219 were followed to obtain 4.30 g (yield 74%) of compound 221, which is an isomer mixture of endo and exo isomers (endo:exo=86:14). 1 The H-NMR data is shown below.

[0749] (Compound 221) 1 H NMR (270 MHz, CDCl3, TMS as internal standard): endo: δ 1.66-1.73 (m, 9 H), 2.28-2.32 (m, 1 H), 2.37-2.77 (m, 9 H), 2.88-3.19 (m, 4 H), 3.78-3.84 (dd, J = 10.2, 5.3 Hz, 1 H), 4.60-4.62 (m, 1 H), 4.97-4.99 (m, 1 H), 6.96-7.01 (m, 2 H), 7.14-7.32 (m, 4 H), 7.41-7.50 (m, 2 H), 7.58-7.63 (m, 2 H); exo: 1.23-1.27 (m, 1 H), 1.66-1.73 (m, 8 H), 1.90-1.94 (m, 1 H), 2.37-2.77 (m, 12 H), 3.30-3.42 (m, 2 H), 5.13-5.15 (m, 1 H), 5.24-5.27 (m, 1 H), 6.96-7.01 (m, 2 H), 7.14-7.32 (m, 4 H), 7.41-7.50 (m, 2 H), 7.58-7.63 (m, 2 H). The melting completion temperature of compound 221 was 151.2°C.

[0750] [Example B17] <Synthesis of compound 222> Compound 222 shown below was synthesized by the method described below.

[0751] [ka]

[0752] Compound 222 was synthesized according to the procedure and equivalent relationship described in <Synthesis of Compound 214>, except that 5.0 g (1 equivalent) of 4-methoxy-3-methylbenzoic acid was used instead of 3-phenylbenzoic acid in <Synthesis of Compound 214>. The obtained compound 222 was used as it is in the synthesis of compound 223.

[0753] <Synthesis of compound 223> Compound 223 shown below was synthesized by the method described below.

[0754] [ka]

[0755] In the synthesis of compound 219, 2.10 g (yield 33%) of compound 223, which is only the endo isomer, was obtained in accordance with the procedure and equivalent relationship described in the synthesis of compound 219, except that compound 222 (2.2 equivalents) was used instead of compound 218. 1 The H-NMR data is shown below.

[0756] (Compound 223) 1H NMR (270 MHz, CDCl3, TMS as internal standard): δ 1.66-1.70 (m, 1 H), 1.95 (s, 3 H), 2.02 (s, 3 H), 2.29-2.33 (m, 1 H), 2.55-2.56 (m, 1 H), 2.87-3.19 (m, 4 H), 3.78-3.88 (m, 7 H), 4.59-4.61 (m, 1 H), 4.96-4.98 (m, 1 H), 6.67-6.73 (m, 2 H), 7.21-7.33 (m, 4 H), 7.51-7.58 (m, 2 H), 7.72-7.79 (m, 2 H). The melting completion temperature of compound 223 was 187.1°C. [Industrial Applicability]

[0757] The novel ester compound according to the present invention is useful for the production of resin additives, cosmetics, skin care products, antibacterial compositions, antioxidants, chelating agents, and Ziegler-Natta catalysts. In particular, it can be used as a catalyst component for Ziegler-Natta catalysts, and can produce catalysts that give excellent stereoregularity and productivity when polypropylene is polymerized, making it extremely valuable industrially.

Claims

1. An ester compound represented by the following general formula (1): [Formula 1] [In formula (1), R 1 ~R 24 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 1 ~R 10 , R 23 and R 24 may be bonded to each other to form a ring, or adjacent substituents may be directly bonded to each other to form a multiple bond. 11 ~R 24 may be bonded to each other to form a ring, or adjacent substituents may be bonded to each other to form a multiple bond. 1 ~R 24 At least one pair of n2 to n5 are bonded to each other to form a ring structure. n2 to n5 each independently represent an integer of 0 to 2. n1 and n6 each independently represent an integer of 0 or 1. L 1 and L 2 are each independently a hydrocarbon group or a heteroatom-containing hydrocarbon group.

2. L 1 and L 2 and each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a heteroatom-containing hydrocarbon group.

3. L 1 and L 2 and each independently represent a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group.

4. The ester compound according to claim 1, represented by any one of the following general formulas (2) to (4): [Case 2] [In formulas (2) to (4), R 1 ~R 24 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 1 ~R 10 , R 23 and R 24 may be bonded to each other to form a ring, or adjacent substituents may be directly bonded to each other to form a multiple bond. 11 ~R 24 may be bonded to each other to form a ring, or adjacent substituents may be bonded to each other to form a multiple bond. X and Y each independently represent a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. n2 to n5 each independently represent an integer of 0 to 2. n1 and n6 each independently represent an integer of 0 or 1. L 1 and L 2 are each independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group.

5. The ester compound according to claim 3 or 4, wherein n1 and n6 are 1, and n2 to n5 are all 0.

6. The ester compound according to claim 1, represented by the following general formula (5) or (6): [C3] [In formula (5), R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group; R 4 and R 9 are each independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group; R 11 , R 15 , R 17 and R 21 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 11 , R 15 , R 17 and R 21 may be bonded to each other to form a ring. X is a hydrocarbon group, a heteroatom or a heteroatom-containing hydrocarbon group. 1 and L 2 are each independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group. [C4] [In formula (6), R 1and R 2 are each independently a hydrogen atom or a hydrocarbon group; R 4 , R 9 , R 11 , R 12 , R 15 ~R 18 , R 21 and R 22 are each independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 11 , R 12 , R 15 ~R 18 , R 21 and R 22 may be bonded to each other to form a ring, or adjacent substituents may be bonded to each other to form a multiple bond. X is a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. 1 and L 2 are each independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group.

7. The ester compound according to claim 1, represented by the following general formula (7) or (8): [C5] [In formula (7), R 4 , R 9 , R 12 , R 15 ~R 18 and R 21 are each independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 15 ~R 18 may be bonded to each other to form a ring, or adjacent substituents may be bonded to each other to form a multiple bond. Y is a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. 1 and L 2 are each independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group. [C6] [In formula (8), R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group; R 3 , R 4 , R 9 , R 10 , R 12 , R 15 ~R 18 and R 21 are each independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 15 ~R 18 may be bonded to each other to form a ring, or adjacent substituents may be bonded to each other to form a multiple bond. Y is a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. 1 and L 2 are each independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group.

8. The ester compound according to claim 1, represented by the following general formula (9): [C7] [In formula (9), R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group; R 4 , R 9 , R 12 , R 15 ~R 18 and R 21 are each independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 15 ~R 18 may be bonded to each other to form a ring, or adjacent substituents may be bonded to each other to form a multiple bond. X and Y are each independently a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. 1 and L 2 are each independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group.

9. The ester compound according to claim 1, represented by the following general formula (31): [C8] [In formula (31), R 31 ~R 34are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group; R 4 , R 9 , R 21 and R 22 are each independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group; R 4 , R 9 , R 21 , R 22 , and R 31 ~R 34 may be bonded to each other to form a ring. 1 and L 2 are each independently a hydrocarbon group or a heteroatom-containing hydrocarbon group. X is a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group.

10. The ester compound according to any one of claims 4 and 6 to 9, wherein X and Y are each independently a divalent group selected from the groups represented by the following general formula group (10): [C9] [In group (10), R 1' ~R 7' are each independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group; R 2' ~R 7' may be bonded to each other to form a ring, or adjacent substituents may be directly bonded to each other to form a multiple bond.

11. The ester compound according to any one of claims 4 and 6 to 9, wherein X and Y are divalent groups selected from groups represented by the following general formula group (11): [C10] [In group (11), R 1' ~R 5' are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 20 carbon atoms; R 2' ~R 5' may be bonded to each other to form a ring, or adjacent substituents may be directly bonded to each other to form a multiple bond.

12. The ester compound according to claim 9, wherein X is a divalent group represented by the following general formula (13): [C11] [In formula (13), R 2' and R 3' are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 20 carbon atoms; R 2' and R 3' may be bonded to each other to form a ring.

13. R 1' ~R 7' are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

14. R 1' ~R 5' are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

15. R 2' and R 3' and each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

16. R 2' and R 3' The ester compound according to claim 12, wherein all of are hydrogen atoms.

17. R 1 ~R 24 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 20 carbon atoms.

18. R 1 ~R 24 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 10 carbon atoms.

19. R 31 ~R 34 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 20 carbon atoms.

20. R 31 ~R 34 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 10 carbon atoms.

21. R 31 ~R 34 are all hydrogen atoms, and R 4 , R 9 , R 21 and R 22 are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 6 carbon atoms; L 1 and L 2 are each independently a hydrocarbon group having 1 to 10 carbon atoms or a heteroatom-containing hydrocarbon group having 1 to 10 carbon atoms.

22. R 31 ~R 34 , R 21 and R 22 are all hydrogen atoms, and R 4 and R 9 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; L 1 and L 2 are each independently selected from hydrocarbon groups having 1 to 10 carbon atoms.

23. R 1 and R 2 The ester compound according to any one of claims 1 to 8, wherein is a hydrogen atom.

24. R 1 , R 2 , R 23 , R 24 are all hydrogen atoms, and R 3 ~R 22 and each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.

25. L 1 and L 2 and each independently represent a hydrocarbon group having 4 to 20 carbon atoms or a heteroatom-containing hydrocarbon group.

26. L 1 and L 2 and each independently represent a hydrocarbon group having 4 to 10 carbon atoms or a heteroatom-containing hydrocarbon group.

27. The R 4 and / or R 9 The ester compound according to claim 4, 6 or 8, wherein is a hydrocarbon group or a heteroatom-containing hydrocarbon group.

28. The R 4 and / or R 9 The ester compound according to claim 4, 6 or 8, wherein is a hydrocarbon group or an oxygen atom-containing hydrocarbon group.

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