Ester compounds

Abstract

The objective is to provide an internal donor component suitable for solid titanium catalyst components, which, when used primarily in solid titanium catalyst components, can produce propylene polymers with extremely high stereoregularity with high productivity (high activity). [Solution] For example, an ester compound represented by the following formula (7). TIFF2026086704000258.tif70135

Description

[Technical Field]

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

[0002] Prior art concerning ester compounds includes many disclosures relating to additive applications such as resin additives, cosmetics and topical skin preparations, bactericidal compositions, antioxidants, and chelating agents. One such application is its use in Mg compound-supported titanium catalysts used in olefin polymerization.

[0003] Catalysts for olefin polymerization are one of the technologies that have undergone significant development 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 and an organoaluminum compound, followed by Natta's report of the first propylene polymerization using a combination of titanium trichloride and a halogen-containing organoaluminum compound. Within this context, it was discovered that catalysts containing titanium tetrachloride, a magnesium compound, and a Lewis base, known as third-generation catalysts, could achieve both high polymerization activity (high productivity) and high stereoregularity in propylene polymerization. This was one of the opportunities that led to the widespread use of propylene polymers (polypropylene) worldwide.

[0004] Furthermore, it has been discovered 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"), greatly influence catalytic performance, and various Lewis bases have been developed to date.

[0005] Lewis bases used in Ziegler-Natta catalysts include, for example, ethyl benzoate, phthalate ester, 1,3-diketone (Patent Document 1), malonic acid ester (Patent Document 2), succinate ester (Patent Document 3), 2,4-pentanediol diester (Patent Document 4), naphthalenediol diester (Patent Document 5), and catechol diester (Patent Document 6). This is a field in which research and development is still being actively pursued, mainly by companies.

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

[0007] [Patent Document 1] Japanese Patent Publication No. 2005-226076 [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] Japanese Patent Publication No. 2008-247796 [Patent Document 8] International Publication No. 2008 / 062553 [Patent Document 9] U.S. Patent Application Publication No. 2018 / 0149973 [Patent Document 10] U.S. Patent Application Publication No. 2002 / 0162991 [Patent Document 11] Japanese Patent Publication No. 2008-037756 [Non-patent literature]

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

Non-licensed Document 2

Non-licensed Document 4

Non-licensed Document 5

Non-licensed Document 6

Non-licensed Document 7

Non-licensed literature 9

Non-licensed literature 10

Non-licensed Document 11

Non-licensed Document 12

Non-licensed Document 13

[0009] Propylene polymers possess heat resistance and rigidity similar to general-purpose engineering plastics, while having the advantage of producing fewer toxic gases when incinerated, due to their composition consisting almost entirely of carbon and hydrogen.

[0010] Recent advances in molding technology suggest that using propylene polymers with higher stereoregularity than before could potentially lead to superior physical properties (such as rigidity and heat resistance). Therefore, there is a market demand for propylene polymers with higher stereoregularity. Furthermore, from the perspective of resource conservation and environmental protection, there is a need for highly productive methods for manufacturing propylene polymers.

[0011] Therefore, the problem of the present invention is mainly to provide an internal donor component suitable for a solid titanium catalyst component that can produce a highly stereoregular propylene polymer with high productivity (high activity) when used in the solid titanium catalyst component.

Means for Solving the Problems

[0012] As a result of intensive studies to solve 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 of a solid titanium catalyst component, and have completed the present invention. The present invention relates to, for example, the following [1] to

[28] .

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

[0014] [Chemical Formula]

[0015] [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. R 1 ~R 10 , R 23 and R 24 may be bonded to each other to form a ring, or may form a multiple bond in which adjacent substituents are directly bonded. R 11 ~R 24 may be bonded to each other to form a ring, or may form a multiple bond in which adjacent substituents are bonded to each other. At least one set of R 1 ~R 24 is 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 2The ester compound described in [1], which is independently a hydrocarbon group or a heteroatom-containing hydrocarbon group having 1 to 20 carbon atoms.

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

[0017]

Chemical formula

[0018] 〔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. R 1 ~R 10 , R 23 and R 24 may combine with each other to form a ring, or may form a multiple bond in which adjacent substituents are directly bonded. R 11 ~R 24 may combine with each other to form a ring, or may combine with each other to form a multiple bond in which adjacent substituents are bonded. X and Y are each independently 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 or a heteroatom-containing hydrocarbon group having 4 or more carbon atoms. 〕 [5] The ester compound described in [3] or [4], in which n1 and n6 are 1 and n2 to n5 are all 0.

[0019] [6] The ester compound described in [1], which is represented by the following general formula (5) or (6).

[0020] [Chemical]

[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 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or a heteroatom-containing hydrocarbon group. R 11 , R 15 , R 17 and R 21 may combine with each other to form a ring. X is a hydrocarbon group, a heteroatom or a heteroatom-containing hydrocarbon group. L 1 and L 2 are each independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group.〕

[0022] [Chemical]

[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[[ID=6|6]] 22 are each independently a hydrogen atom, a hydrocarbon group or a heteroatom-containing hydrocarbon group. R 11 , R 12 , R 15 ~R 18 , R 21 and R 22The substituents may bond to each other to form a ring, or adjacent substituents may bond 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 Each of these is independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group. [7] The ester compound described in [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 Each of these is independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 15 ~R 18 The substituents may bond to each other to form a ring, or adjacent substituents may bond 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 Each of these is 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 Each is independently a hydrogen atom or a hydrocarbon group, and R 3 , R 4 , R 9 , R 10 , R 12 , R 15 ~R 18 and R 21is each independently a hydrogen atom, a hydrocarbon group or a heteroatom-containing hydrocarbon group. R 15 ~R 18 may combine with each other to form a ring, or adjacent substituents may combine with each other to form a multiple bond. Y is a hydrocarbon group, a heteroatom or a heteroatom-containing hydrocarbon group. L 1 and L 2 are each independently a hydrocarbon group or a heteroatom-containing hydrocarbon group having 4 or more carbon atoms. ] [8] The ester compound according to [1], which is represented by the following general formula (9).

[0028]

Chemical formula

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

[0030]

Chemical formula

[0031] [In formula (31), R 31 ~R 34is 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 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 combine with each other to form a ring. L 1 and L 2 are 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]

Chemical formula

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

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

[0034]

Chemical formula

[0035] [In group (11), R 1' ~R 5'Each of these is 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, and R 2' ~R 5' These substituents may bond to each other to form a ring, or adjacent substituents may directly bond to each other to form a multiple bond.

[12] The ester compound described in [9], wherein X is a divalent group shown in the following general formula (13).

[0036] [ka]

[0037] [In formula (13), R 2' and R 3' Each of these is 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, and R 2' and R 3' They may be joined to each other to form a ring.

[13] R 1' ~R 7' The ester compound described in

[10] , wherein each is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0038]

[14] R 1' ~R 5' The ester compound described in

[11] , wherein each is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[15] R 2' and R 3' The ester compound described in

[12] , wherein each is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0039]

[16] R 2' and R 3' The ester compounds described in

[12] , wherein all atoms are hydrogen atoms.

[17] R 1 ~R 24The ester compound according to any one of items [1] to

[16] , wherein each is 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.

[0040]

[18] R 1 ~R 24 The ester compound according to any one of items [1] to

[16] , wherein each is 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.

[0041]

[19] R 31 ~R 34 The ester compound described in [9], wherein each is independently 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 The ester compound described in [9], wherein each is 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 All are hydrogen atoms, R 4 , R 9 , R 21 and R 22 However, each is independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a hydrocarbon group containing a heteroatom having 1 to 6 carbon atoms, L 1 and L 2 The ester compound described in [9], wherein each is 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 All are hydrogen atoms, R 4 and R 9 However, each is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, L 1 and L2 However, each is independently selected from hydrocarbon groups having 1 to 10 carbon atoms, as described in [9].

[0044]

[23] R 1 and R 2 An ester compound as described in any one of items [1] to [8], wherein is a hydrogen atom.

[24] R 1 , R 2 , R 23 , R 24 All are hydrogen atoms, R 3 ~R 22 However, each is independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, as described in any one of items [1] to [8].

[0045]

[25] L 1 and L 2 The ester compound according to any one of items [1] to [8], wherein each is independently a hydrocarbon group having 4 to 20 carbon atoms or a heteroatom-containing hydrocarbon group.

[26] L 1 and L 2 However, each is independently a hydrocarbon group having 4 to 10 carbon atoms or a heteroatom-containing hydrocarbon group, as described in any one of items [1] to [8].

[0046]

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

[28] The aforementioned R 4 and / or R 9 The ester compound according to [4], [6], or [8], wherein the ester compound is a hydrocarbon group or an oxygen atom-containing hydrocarbon group. [Effects of the Invention]

[0047] The ester compounds of the present invention can be used, for example, as resin additives, cosmetics and topical skin preparations, antibacterial compositions, antioxidants, chelating agents, and Ziegler-Natta catalysts. [Modes for carrying out the invention]

[0048] The ester compounds 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 Each of these 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 R may bond to each other to form a ring, or adjacent substituents may form a multiple bond by direct bonding. 11 ~R 24 R may bond to each other to form a ring, or adjacent substituents may bond to each other to form a multiple bond. 1 ~R 24 In this structure, at least one pair is linked to each other to form a ring structure. n2 to n5 each independently represent integers from 0 to 2. n1 and n6 each independently represent integers of 0 or 1. 1 and L 2 Each of these is independently a hydrocarbon group or a heteroatom-containing hydrocarbon group. Among the above, it is preferable that one or two of n4, n5, and n6 are present. In particular, R 11 ~R 24 When any two or more of these are bonded together to form an aromatic ring structure, it is preferable that one of n4, n5, and n6 is either 1 or 2.

[0051] Examples of preferred embodiments 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 Each of these 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 R may bond to each other to form a ring, or adjacent substituents may form a multiple bond by direct bonding. 11 ~R 24 The substituents may bond to each other to form a ring, or adjacent substituents may bond 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. n2 to n5 each independently represent an integer from 0 to 2. n1 and n6 each independently represent an integer of 0 or 1. L 1 and L 2 Each of these is independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group.

[0054] Furthermore, as an example of a more preferred embodiment of the ester compound (A) of the present invention, there are compounds represented by the following general formulas (5) to (9).

[0055] [ka]

[0056] In formula (5), R 1 and R 2 Each is independently a hydrogen atom or a hydrocarbon group, and R 4 and R 9 Each of these is independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group, and R 11 , R 15 , R 17 and R 21 Each of these 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 They may bond to each other to form a ring. X is a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. 1 and L 2 Each of these is 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 Each is independently a hydrogen atom or a hydrocarbon group, and R 4 , R 9 , R 11 , R 12 , R 15 ~R 18 , R 21 and R 22 Each of these 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 The substituents may bond to each other to form a ring, or adjacent substituents may bond 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 Each of these is 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 21Each of these is independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 15 ~R 18 The substituents may bond to each other to form a ring, or adjacent substituents may bond 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 Each of these is 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 Each is independently a hydrogen atom or a hydrocarbon group, and R 3 , R 4 , R 9 , R 10 , R 12 , R 15 ~R 18 and R 21 Each of these is independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 15 ~R 18 The substituents may bond to each other to form a ring, or adjacent substituents may bond 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 Each of these is independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group.

[0063] In the case of the structure of equation (8), R 3 , R 4 , R 9 and R 10Preferably, each substituent is independently 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 hydrocarbon group are 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. Furthermore, preferred examples of halogen-containing hydrocarbon groups include substituents in which one or more hydrogen atoms in a C1-C20 substituted or unsubstituted alkyl group, a C1-C20 substituted or unsubstituted cycloalkyl group, a C2-C20 substituted or unsubstituted alkenyl group, a C2-C20 substituted or unsubstituted alkynyl group, or a C6-C20 substituted or unsubstituted aryl group are replaced by halogen atoms.

[0064] [ka]

[0065] In formula (9), R 1 and R 2 Each is independently a hydrogen atom or a hydrocarbon group, and R 4 , R 9 , R 12 , R 15 ~R 18 and R 21 Each of these is independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 15 ~R 18 The substituents 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 Each of these is independently a hydrocarbon group having 4 or more carbon atoms or a heteroatom-containing hydrocarbon group.

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

[0067] Furthermore, as an example of a more preferred embodiment of the ester compound (A) of the present invention, a compound represented by the following general formula (31) can be mentioned.

[0068] [ka]

[0069] A detailed explanation of the structure of the substituents in formula (31) will be given later. <R 1 ~R 24 > In the above formula (1), etc., R 1 ~R 24 These are, independently, a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group.

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

[0071] Examples of the heteroatom-containing hydrocarbon group include substituted or unsubstituted heteroatom-containing alkyl groups and substituted or unsubstituted heteroaryl groups. Examples of the hydrocarbon group and the heteroatom-containing hydrocarbon group include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroatom-containing alkyl groups, and heteroaryl groups. 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 preferable to have one or more ring structures of 5 or more members, more preferably one or more 5 to 7 member ring structures, and even more preferably one or more 5-membered or 6-membered ring structures.

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

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

[0074] The carbon atoms to which the substituents described above, which bond together to form a ring, are attached (hereinafter sometimes referred to as "B4C") usually have "other substituents" (hereinafter sometimes referred to as "B4S") attached (for example, R 3 R 10 When R directly bonds to form a ring, 4 Ya R 9 This applies.) In the present invention, it is preferable that the "other substituent" is a hydrocarbon group and / or a heteroatom-containing hydrocarbon group, as described later. As the heteroatom-containing hydrocarbon group, an oxygen-containing hydrocarbon group is particularly preferred. The hydrocarbon group is more specifically an aliphatic group, alicyclic group, or aromatic group having 1 to 10 carbon atoms, and more preferably an aliphatic group, alicyclic group, or aromatic group having 1 to 6 carbon atoms. The heteroatom-containing hydrocarbon group is more specifically an aliphatic group, alicyclic group, or aromatic group having 1 to 10 carbon atoms, and more preferably an aliphatic group, alicyclic group, or aromatic group having 1 to 6 carbon atoms. The heteroatom is preferably oxygen. The oxygen-containing hydrocarbon group is even more preferably an alkoxy group. As for the position of such substituents, more specifically, R in formulas (2), (4), (5), (6), and (9) above. 4 and / or R 9 Or, R in the above equations (3), (4), (7), (8) 12 and / or R 21 We can give examples, and more preferably the above R 4 and / or R 9 Therefore, when substituents in such positions are groups with the structure described above, using them as components of an olefin polymerization catalyst can make it easier to control the polymerization activity, stereoregularity, and the molecular weight of the resulting polymer with hydrogen.

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

[0076] R 1 When such molecules form a ring structure, the substituents forming the ring are selected from substituents other than hydrogen atoms and halogen atoms, and are preferably hydrocarbon groups. 1 ~R 24 In this structure, at least one pair of substituents are bonded to each other to form a ring structure. In the formed ring, it is preferable that at least one pair of substituents forming the ring are separated by 2 or more carbon atoms, and more preferably by 3 or more carbon atoms. Such a structure is preferably a ring structure containing X or Y from formulas (2) to (4), and more preferably a ring structure containing X or Y from formulas (5) to (9).

[0077] When adjacent substituents bond to form a ring, R 3 ~R 6 , R 7 ~R 10 , R 11 ~R 22 It is preferable that substituents selected from the above bond to each other to form a ring. In this case, from a synthetic viewpoint, it is preferable that the substituents forming the ring do not include carbon atoms in the bridgehead position. A carbon atom in the bridgehead position refers to a carbon atom that shares two or more rings, for example, in formula (2), X and R 4 The carbon atoms bonded together are X and R 9 A carbon atom bonded to R 23 A carbon atom bonded to R 24 This refers to a carbon atom to which R is bonded. Preferably, such structures can be found in formulas (5) to (9), and a structure included in formula (5) is R 11 and R 15 A structure in which these are bonded to each other to form a ring, R 15 and R 17 A structure in which these are bonded to each other to form a ring, R 17 and R 21 Structures in which R is bonded to each other to form a ring, and structures consisting of combinations thereof, are particularly preferred. Structures included in formula (6) include R 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 Structures in which R is bonded to form a ring, and structures consisting of combinations thereof, are particularly preferred. Structures included in formulas (7) to (9) include R 15 or R 16 and R 17 or R 18 A structure in which these elements are joined to form a ring is particularly preferred.

[0078] In formula (5), R 11 and R 15 An example of an ester compound (A) having a structure in which these molecules 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 an ester compound (A) having a structure in which these molecules 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 an ester compound (A) having a structure in which these molecules 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 an ester compound (A) having a structure in which atoms 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 an ester compound (A) having a structure in which atoms 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 an ester compound (A) having a structure in which atoms 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 an ester compound (A) having both a structure in which a ring is formed by bonding is shown below.

[0091] [ka]

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

[0097] [ka]

[0098] Preferred R 15 ~R 18 Each of these is 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 10Preferably, each substituent is independently 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. Preferred examples of the 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. Furthermore, preferred examples of the halogen-containing hydrocarbon groups mentioned above include substituents in which one or more hydrogen atoms in a C1-C20 substituted or unsubstituted alkyl group, a C1-C20 substituted or unsubstituted cycloalkyl group, a C2-C20 substituted or unsubstituted alkenyl group, a C2-C20 substituted or unsubstituted alkynyl group, or a C6-C20 substituted or unsubstituted aryl group are replaced by halogen atoms.

[0099] Also, preferably, R 1 ~R 24 Each of these is 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] Comfortable, R 1 ~R 24Each of these is 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 Each of these is 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] Furthermore, R 1 ~R 24 Each of these is independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. Particularly preferred, R 1 , R 2 , R 23 , R 24 All are hydrogen atoms, R 3 ~R 22 However, each is independently either a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.

[0103] Note, R 1 ~R 24 The carbon atoms to which the compound is bonded form two or more ring structures, as shown in the general formula (1) above. Preferably, one or more of these ring structures are alicyclic ring structures. That is, it is preferable that at least all of the rings are not aromatic ring structures.

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

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

[0106] Examples of the heteroatom-containing hydrocarbon group include substituted or unsubstituted heteroatom-containing alkyl groups and substituted or unsubstituted heteroaryl groups. Examples of the hydrocarbon group and the heteroatom-containing hydrocarbon group include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroatom-containing alkyl groups, and heteroaryl groups. 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 preferable to have one or more ring structures of 5 or more members, more preferably one or more 5 to 7 member ring structures, and even more preferably one or more 5-membered or 6-membered ring structures.

[0107] Preferred R 31 ~R 34 Each of these is 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] A more preferred R31 ~R 34 Each of these is 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] A more preferable R 31 ~R 34 Each of these is 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 These may be structures in which elements are bonded to each other to form a ring. Particularly preferred R 31 ~R 34 Each is independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and the most preferred R 31 ~R 34 These are all hydrogen atoms. 31 ~R 34 , R 21 , R 22 , R 4 , R 9 These substituents may bond to each other to form a ring, or adjacent substituents may directly bond to each other to form a multiple bond.

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

[0112] R 31 ~R 34 , R 21 , R 22 , R 4 , R 9 When these atoms bond to each other to form a ring structure, the substituents forming the ring are selected from substituents other than hydrogen atoms and halogen atoms, and are preferably hydrocarbon groups. 31 ~R 34 , R 21 , R 22 It is preferable that they bond to each other to form a ring, and more preferably R 31 and R 32 A structure in which R is bonded to each other to form a ring. 32 and R 33 A structure in which R is bonded to each other to form a ring. 33 and R 34 A structure in which R is bonded to each other to form a ring. 21 and R 22 A structure in which R is bonded to each other to form a ring. 34 , R 21 , R 22 These are structures formed by the bonding of elements with each other, and structures selected from combinations thereof.

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

[0114] [ka]

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

[0116] [ka]

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

[0118] [ka]

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

[0120] [ka]

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

[0122] [ka]

[0123] Also, preferred R 21 , R 22 , R 4 , R 9Each of these is 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] A more preferred R 21 , R 22 , R 4 , R 9 Each of these is 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] A more preferable R 21 , R 22 , R 4 , R 9 Each of these is 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 These may be structures in which elements are bonded to each other to form a ring, for example, R 21 and R 22 One example is a ring structure in which these are linked to each other. Particularly preferred R 21 , R 22 , R 4 , R 9 Each is independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and the most preferred R 21 , R 22 , R 4 , R 9 These are all hydrogen atoms.

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

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

[0129] Examples of the heteroatom-containing hydrocarbon group include substituted or unsubstituted heteroatom-containing alkyl groups and substituted or unsubstituted heteroaryl groups. Examples of the hydrocarbon group and the heteroatom-containing hydrocarbon group include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroatom-containing alkyl groups, and heteroaryl groups. 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 preferable to have one or more ring structures of 5 or more members, more preferably one or more 5 to 7 member ring structures, and even more preferably one or more 5-membered or 6-membered ring structures.

[0130] The preferred range for 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 preferable. 1 and L 2 Each of these is 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] A more preferable L 1 and L 2 These are, 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] A more preferable L 1 and L 2These are, 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 are particularly preferably substituted or unsubstituted aryl groups having 6 to 10 carbon atoms. Particularly preferably are aryl groups containing substituents other than hydrogen. The substituents other than hydrogen include hydrocarbon groups having 1 to 10 carbon atoms and heteroatom-containing hydrocarbon groups having 1 to 10 carbon atoms. Specifically, the heteroatom is a group 16 element of the periodic table, and more specifically, oxygen. Specific examples of hydrocarbon groups include methyl, ethyl, isopropyl, n-butyl, s-butyl, and t-butyl groups, and preferred examples of heteroatom-containing hydrocarbon groups include methoxy, ethoxy, isopropoxy, n-butoxy, s-butoxy, and t-butoxy groups.

[0134] <n1~n6> In equation (1) above, n2 to n5 represent integers from 0 to 2, and n1 and n6 represent integers of 0 or 1.

[0135] n2 to n5 are preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0. n1 and n6 are 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 heteroatom, or a heteroatom-containing hydrocarbon group, and preferably each is 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' Each of these is independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group, and R2' ~R 7' These substituents may bond to each other to form a ring, or adjacent substituents may directly bond to each other to form a multiple bond.

[0139] Preferred R 1' ~R 7' These are, 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] A more preferred R 1' ~R 7' Each is independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms, with the most preferred R 1' ~R 7' These are all hydrogen atoms. As mentioned above, R 2' ~R 7' These may be bonded to each other to form a monocycle or polycycle. Also, R 1' ~R 7' This is the aforementioned R 1 ~R 24 It can combine with other elements to form a ring structure.

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

[0142] [ka]

[0143] In group (11), R 1' ~R 5' Each of these is 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, and R 2' ~R 5' These substituents may bond to each other to form a ring, or adjacent substituents may directly bond to each other to form a multiple bond.

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

[0145] [ka]

[0146] In formula (12), R 2' ~R 5' Each of these is 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, and R 2' ~R 5' They may be joined together to form a ring.

[0147] X and Y are particularly preferably divalent groups as shown in the following general formula (13).

[0148] [ka]

[0149] In formula (13), R 2' and R 3' Each is 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' They may be joined together to form a ring.

[0150] In the ester compound (A) represented by formula (31), if X is the divalent group shown in formula (13), then R 2' and R 3' Preferably, each is 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, the substituents may bond to each other to form a ring, or it may be preferable for adjacent substituents to bond directly to each other to form a multiple bond. A carbon-carbon double bond is preferred as the multiple bond. 2' ~R 7' It is even more preferable that the structures include carbon-carbon double bonds in the regions that bond to each other to form a ring. Among the above, R 2' ~R 5' It is preferable that the atoms bond to each other to form a ring, and more preferably that the multiple bond contains substituted or unsubstituted aryl groups. Examples of such substituents on X and Y are shown below.

[0152] [ka]

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

[0154] Examples of the heteroatom-containing hydrocarbon group include substituted or unsubstituted heteroatom-containing alkyl groups and substituted or unsubstituted heteroaryl groups. Examples of the hydrocarbon group and the heteroatom-containing hydrocarbon group include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroatom-containing alkyl groups, and heteroaryl groups. 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, 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 to have one or more ring structures of 5 or more members, more preferably one or more 5 to 7 member ring structures, and even more preferably one or more 5-membered 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 above are shown. Examples of the halogen atoms include fluorine, chlorine, bromine, and iodine. Examples of hydrocarbon groups include various structures such as aliphatic, branched aliphatic, alicyclic, and aromatic groups, as shown below.

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

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

[0158] Examples of the substituted or unsubstituted alkynyl groups include ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, and octinyl groups.

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

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

[0161] Examples of the substituted or unsubstituted heteroatom-containing hydrocarbon groups 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 in the above-mentioned substituents containing carbon is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6, and particularly preferably 1 to 4. When the 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. 1 ~R 24 If the substituent is not a hydrogen atom, it is preferably selected from the above-mentioned hydrocarbon groups and oxygen-containing hydrocarbon substituents. An alkoxy group is even more preferred as the oxygen-containing hydrocarbon group. With such a structure, when used as an internal donor for an olefin polymerization catalyst, effects such as obtaining an olefin polymer with a broader molecular weight distribution may occur.

[0162] <Specific examples of ester compounds (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] The aforementioned R 1 ~R 24 Examples of compounds in which the sites where molecules bond to form a ring further contain double bonds or ring structures, particularly ring structures containing double bonds, include compounds with the following structures.

[0211] [ka]

[0212] [ka]

[0213] [ka]

[0214] [ka]

[0215] [ka]

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[0220] [ka]

[0221] In the structural formulas above, methyl groups are denoted as "Me", ethyl groups as "Et", propyl groups as "Pr", butyl groups as "Bu", and phenyl groups as "Ph". [n] indicates "normal", [i] indicates "iso", and [t] indicates "tertiary".

[0222] Furthermore, the ester compound (A) of the present invention is OCOL bonded to an alicyclic structure. 1 Base and OCOL 2 The group may form a cis or trans structure derived from its alicyclic structure, but it is preferable that the cis-structured ester compound is the main component. Here, "main component" means that the content of the cis-structured compound 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 currently unknown, but the inventors speculate as follows. The ester compound (A) of the present invention has a ring-linked structure, preferably also possessing a crosslinked structure (a structure corresponding to X or Y above). This requirement restricts the conformation, fixing the distance and orientation of two adjacent ester groups bonded to the ring. As a result, it is hypothesized that when the ester coordinates to magnesium chloride, the coordination mode of the ester is restricted, forming a rigid polymerization environment consisting of titanium atoms, magnesium chloride, and the ester compound. When polymerization proceeds under such an environment, the orientation of the polymer chain and the insertion direction of propylene are highly controlled, and it is thought that a catalyst suitable for highly stereoregular polymerization is formed. A skeleton in which the ester is bonded to a ring containing a crosslinked structure (e.g., formulas (5), (6), and (9)) is a superior skeleton as an internal donor for Ziegler catalysts because the distance and orientation of the ester moiety are restricted. Furthermore, even if the ester moiety is directly bonded to a cyclohexane skeleton (e.g., formula (8)), the conformation of the cyclohexane skeleton is restricted by the ring structure containing the crosslinked structure fused to the cyclohexane skeleton, and it is thought that a similar effect is consequently achieved. As described above, although we have explained structures having a 6-membered ring structure, based on this inference, similar effects can be expected from ester compounds having the structure represented by formula (1), or more preferably the polycyclic structures represented by formulas (2) to (4), even if they are not the compounds specifically exemplified, and it is clear that similar effects will be exhibited even with 5-membered to 10-membered ring structures.

[0224] As described above, the ester compound (A) of the present invention has a ring-linked structure, and is therefore presumed to have appropriate rigidity as a compound, with relatively little structural displacement. Therefore, when used as a catalyst for olefin polymerization, as described later, it is expected that when the ester group-containing compound (A) coordinates with titanium compounds or magnesium compounds, it will maintain a stable structure while exhibiting appropriate interactions. Thus, it is thought to have a favorable effect on stereospecificity and activity. On the other hand, such alicyclic structures will likely exhibit diverse structures, such as chair-shaped or boat-shaped displacements at the microscopic level. From this, it is expected that polymers with a broad molecular weight distribution can be produced.

[0225] Furthermore, the ester compound (A) of the present invention, represented by formula (31) above, has a specific bicyclic structure as described above. It also has a unique asymmetric structure. Because it has such a structure, the compound has appropriate rigidity, and it is thought that when it forms active species for olefin polymerization through interaction with magnesium compounds and titanium compounds and polymerization reactions occur, there is a possibility that there will be little displacement or shaking of the structure. On the other hand, in the case of an ester compound (A) with an asymmetric structure like that of formula (31) above, the conformations when interacting with magnesium compounds and titanium compounds are likely to be more numerous than those of symmetric compounds, so there is a possibility that it can form active species with diverse microstructures. This point is thought to be advantageous in obtaining embodiments that include polymers with a wide molecular weight distribution and polymers with high stereoregularity. In addition, because it preferably has a unique asymmetric structure that includes an aryl structure, it may be able to take on a strong coordination structure with magnesium compounds and titanium compounds.

[0226] From the above viewpoint, 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, it can be obtained by diolation and diesterification reactions of the corresponding olefin. Alternatively, it can be obtained by carbonate, diolation, and diesterification reactions using specific polycyclic compounds such as anthracenes. More specifically, it can be produced as follows.

[0227] ≪Synthesis of Olefins≫ The olefin shown in formula (21) below can be synthesized, for example, by the Diels-Alder reaction of cyclopentadiene and norbornene (Non-Patent Literature 1). The olefin shown in general formula (33) below can also be synthesized, for example, by the Diels-Alder reaction of substituted indene and substituted diene (Patent Literature 11). The diene can also be used as a starting material in the form of a diene dimer (e.g., dicyclopentadiene). Furthermore, the product obtained by the Diels-Alder reaction is often a mixture of endo and exo isomers (see formulas (22) and (34) below), but either isomer can be applied to the present invention. That is, it may be a mixture, the endo isomer alone, or the exo isomer alone. These endo and exo structures are often reflected in the target ester compound.

[0228] Furthermore, olefins can be obtained by reacting benzyne with a diene (Non-Patent Documents 2, 3, 14), and cyclic olefins can be obtained by decarbonylating and decarboxylating alicyclic dicarboxylic acid anhydrides using a nickel complex (e.g., tetrakistriphenylphosphine nickel) as a catalyst in the presence of a ligand-capable compound (e.g., triphenylphosphine) (Patent Documents 7, 8). <<Synthracene synthesis>> Furthermore, the R 1 ~R 24Compounds in which the ring-forming site is further composed of a double bond or a ring structure, particularly a ring structure containing a double bond, can be synthesized, for example, by first converting anthracenes into carbonate compounds through a Diels-Alder reaction with vinylene carbonate, followed by diolation and diesterification reactions.

[0229] Anthracenes can be synthesized, for example, by reacting anthraquinone with an organometallic reagent (e.g., alkyllithium or 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] Furthermore, dihalogenated anthracenes can also be synthesized by substitution reactions with metal reagents (e.g., lithium or magnesium) and alkyl halides, or by coupling reactions using transition metal catalysts (e.g., nickel or palladium) and organometallic reagents (e.g., boronic acid esters or Grignard reagents) (see formulas (14(2)), (14(3)), Patent Document 10, Non-Patent Document 17). Dialkoxyanthracenes can also be obtained by reacting anthraquinone with a reducing agent (e.g., zinc) and an electrophile (e.g., alkyl halides or sulfonic acid esters) (see formula (14(4)), Non-Patent Document 18).

[0231] [ka]

[0232] In formula (14(1)), R 25 M represents an organometallic reagent, 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 equation (14(3)), Z represents a halogen atom, and R 27 The first character represents an alkyl group or aryl group, and A and A' represent a hydroxyl group or a cross-linked structure formed by the bonding of A and A'. 27 Examples of structural formulas for boric acid compounds and boric acid esters (preferably cyclic boric acid ester compounds) that are boron-containing compounds with structures containing A and A' can be found in the following group of formulas (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 Diols>> The diol compounds (formulas (23) and (35)), which are precursors to esters, can be produced using the corresponding olefins (formulas (21) and (33)) as raw materials. For example, the diol compounds (formulas (23) and (35)) can be directly obtained by the reaction of an olefin with potassium permanganate (Non-Patent Literature 4) or osmium tetroxide (Non-Patent Literature 5).

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

[0241] [ka]

[0242] [ka]

[0243] Furthermore, diol compounds can also be obtained by cyclic carbonate the aforementioned dienes or anthracene compounds and then hydrolyzing them. Details are as follows. The cyclic carbonate (formula (24)), which is a precursor of the diol (formula (23)), can be produced by the Diels-Alder reaction of the corresponding diene and vinylene carbonate (Non-Patent Literature 19). Similarly, the diene can also be used as a dimer of the precursor diene as a starting material. Furthermore, although the product obtained by the Diels-Alder reaction is often a mixture of the endo and exo forms, this reaction can also be applied to the Diels-Alder compound. This reaction can also be used with polycyclic aromatic compounds such as anthracene instead of the diene to obtain polycyclic carbonates with specific structures as shown in the examples described later.

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

[0245] [ka]

[0246] ≪Synthesis of Esters≫ The ester corresponding to formula (1) above can be synthesized by reacting the 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 amine bases can be used. Alternatively, it can be synthesized by reacting the diol with a carboxylic acid in the presence of an acid catalyst, or by using a condensing agent such as DCC (Non-Patent Literature 11) (formula (26)). When the diol (formula (3')) is reacted with 1 equivalent amount of acid chloride or carboxylic acid, an isomer corresponding to formula (24) can be produced, but if acid chloride or carboxylic acid is reacted thereafter, a compound corresponding to formula (1) can be obtained. At this time, L 1 and L 2 These may be the same or different. Furthermore, the diol compound can also be synthesized by reacting it with a carboxylic acid in the presence of an azocarboxylic acid ester and triphenylphosphine (Non-Patent Document 12).

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

[0248] [ka]

[0249] [ka]

[0250] As mentioned above, the synthesis method of ester compounds may result in a mixture of endo and exo isomers. From a structural standpoint, the endo isomer tends to be more readily formed. There are no particular restrictions on the isomer ratio when these mixtures are 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 even more preferably 90 / 10 to 65 / 35.

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

[0252] As described above, the ester compound (A) of the present invention can be used individually as the endo and exo forms or as an isomer mixture for various applications. 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 its use is not limited to this. It goes without saying that it has potential applications in known additive applications such as additives to various resins, cosmetics and topical skin preparations, antibacterial compositions, antioxidants, and chelating agents. [Examples]

[0253] The following examples illustrate the synthesis method of the ester compounds of the present invention. Note that the compounds with structural formulas disclosed in the following examples and comparative examples represent the structure of the main component of the stereoisomer and may contain other stereoisomers. Furthermore, in the present invention, the main component refers to a component exceeding 50 mol%, preferably 70 mol% or more.

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

[0255] Starting temperature: 25℃, End temperature: 300℃, Heating rate: 10°C / min The peak temperature considered to be the melting point was observed. When it was difficult to identify the peak temperature due to the influence of isomer mixtures or compounds that decompose at high temperatures, the temperature at which endothermic reaction ended was defined as the melting completion temperature.

[0256] (Method for determining isomer composition) Isomers were separated by conventional silica column chromatography. NMR analysis of the isolated isomers and the mixture revealed the chemical shifts specific to each isomer, and the isomer ratio was determined by the absorption intensity ratio.

[0257] ( 1 (Structural analysis method using 1H NMR) A JEOL Ltd. JNM-EX270 nuclear magnetic resonance spectrometer was used, with deuterated chloroform as the solvent and a small amount of tetramethylsilane added. The measurement temperature was room temperature, and the observed nuclei were 1 The conditions were as follows: H (270MHz), sequence was single pulse, 45° pulse, repetition time of 5.5 seconds or more, and integration count of 16 to 64 times or more. The reference chemical shift was set to 0 ppm for hydrogen in tetramethylsilane.1 Peaks such as H were assigned using conventional methods.

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

[0259] [ka]

[0260] 8.62 g (53.8 mmol) of endo-type tetracyclododecene, 240 mL of tert-butyl alcohol, and 50 mL of water were added to a 1 L three-necked flask, and the internal temperature was cooled to 0°C while stirring. In another flask, 12.0 g of potassium permanganate, 250 mL of water, and 2.68 g 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, ensuring that the internal temperature did not exceed 5°C. After 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 mixture until a white precipitate formed. The precipitate was removed by filtration, and the filtrate was extracted three times with ethyl acetate. The organic layer was washed with saturated brine and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the resulting organic layer was concentrated using a rotary evaporator to obtain 7.24 g of the crude product of compound 1. The resulting compound 1 was not purified further and was used in the next step, the synthesis of compound 2.

[0261] <Synthesis of Compound 2> Compound 2, shown below, was synthesized according to the reaction equation below and the method described later.

[0262] [ka]

[0263] Under a nitrogen atmosphere, 5 g (25.7 mmol) of compound 1 and 31 mL of anhydrous pyridine were added to a 100 mL three-necked 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 heated 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 mixture to separate the organic layer. The organic layer was washed three times with water, saturated ammonium chloride aqueous solution, and saturated brine, and dried over magnesium sulfate. Magnesium sulfate was filtered off, and the obtained organic layer was concentrated using a rotary evaporator to obtain 10.37 g of crude product. Purification by silica gel column chromatography yielded 6.67 g (16.6 mmol, white solid) of 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 melting temperature of the obtained compound 2 was 141°C.

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

[0266] [ka]

[0267] In a 1 L three-necked flask, 10.18 g (63.5 mmol) of exo-tetracyclododecene, 240 mL of tert-butyl alcohol, and 60 mL of water were added, and the mixture was cooled to 0°C while stirring. In another flask, 13.81 g of potassium permanganate, 300 mL of water, and 3.00 g 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, ensuring that the internal temperature did not exceed 5°C. After adding the solution, stirring was continued at 0°C for 1 hour. A saturated aqueous sodium pyrosulfite solution was prepared and slowly added dropwise to the reaction mixture until a white precipitate formed. The precipitate was removed by filtration, and the filtrate was extracted three times with ethyl acetate. The organic layer was washed with saturated brine and dried over magnesium sulfate. 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 compound 3. The obtained compound 3 was used in the following synthesis of compound 4 without further purification.

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

[0269] [ka]

[0270] Under a nitrogen atmosphere, 4.0 g (20.6 mmol) of compound 3, 4.2 mL of anhydrous pyridine, and 100 mL of anhydrous chloroform were added to a 200 mL three-necked 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 heated 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 mixture and the organic layer was separated. The organic layer was washed three times with water, saturated aqueous ammonium chloride solution, and saturated brine, and dried over magnesium sulfate. Magnesium sulfate was filtered off, and the obtained organic layer was concentrated using a rotary evaporator to obtain 11.3 g of crude product. Purification by silica gel column chromatography yielded 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 melting completion temperature of the obtained compound 4 was 163°C.

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

[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-necked flask, and the mixture was cooled to 0°C while stirring. In a separate flask, 23.7 g of potassium permanganate, 527 mL of water, and 5.07 g 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 benzonorbornadiene solution, ensuring that the internal temperature did not exceed 5°C. After addition, stirring was continued at 0°C for 1 hour. An aqueous saturated sodium pyrosulfite solution was prepared and slowly added dropwise to the reaction mixture until a white precipitate formed. The precipitate was removed by filtration, and the filtrate was extracted three times with ethyl acetate. The organic layer was washed with saturated brine and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the resulting 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 later.

[0276] [ka]

[0277] Under a nitrogen atmosphere, 9.57 g (54.3 mmol) of compound 5 and 70 mL of anhydrous pyridine were added to a 300 mL three-necked 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 heated 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 mixture was added while stirring. The resulting precipitate was filtered. The precipitate was washed with hexane, and then recrystallized with ethanol to obtain 16.36 g of solid. A small amount of residual pyridine was removed by silica gel column chromatography to obtain 15.48 g (40.3 mmol, white solid) of compound 6. 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 melting temperature of the obtained compound 6 was 139°C.

[0279] [Example A4] <Synthesis of Compound 7> Compound 7, shown below, was synthesized according to the reaction equation below and the method described later.

[0280] [ka]

[0281] Under a nitrogen atmosphere, 200 mL of anhydrous toluene, 6.36 mL of 1-bromo-2-iodobenzene, and 10.5 mL of 2,5-dimethylfuran were added to a 1 L three-necked flask and cooled to -20°C while stirring. 47 mL of n-butyllithium hexane solution (1.6 M) was slowly added dropwise, and the mixture was stirred at -20°C for 1 hour after addition. The temperature was gradually raised to room temperature and stirred continuously 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 brine and dried over magnesium sulfate. Magnesium sulfate was filtered off, and the obtained organic layer was concentrated using a rotary evaporator. The resulting 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 later.

[0283] [ka]

[0284] 4.05 g (23.5 mmol) of compound 7, 129 mL of tert-butyl alcohol, and 32 mL of water were added to a 2 L three-necked flask, and the mixture was cooled to 0°C while stirring. In a separate flask, 7.23 g of potassium permanganate, 161 mL of water, and 1.61 g 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 compound 7 solution, ensuring that the internal temperature did not exceed 5°C. After 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 mixture until a white precipitate formed. The precipitate was removed by filtration, and the filtrate was extracted three times with ethyl acetate. The organic layer was washed with saturated brine and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the resulting organic layer was concentrated using a rotary evaporator to obtain 3.03 g of crude product. The compound 8 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 later.

[0286] [ka]

[0287] Under a nitrogen atmosphere, 2.15 g (10.4 mmol) of compound 8 and 10 mL of anhydrous pyridine were added to a 50 mL three-necked 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 heated 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, then washed with saturated ammonium chloride aqueous solution and saturated brine, 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 crude product. The crude product was purified by silica gel column chromatography to obtain 3.29 g (7.9 mmol, white solid) of compound 9. 1 The H-NMR data is shown below.

[0288] 1 1H 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 melting temperature of the obtained compound 9 was 196°C.

[0289] [Example A5] <Synthesis of Compound 10> Compound 10, shown below, was synthesized according to the reaction equation below and the method described later.

[0290] [ka]

[0291] Under a nitrogen atmosphere, 16.0 g of 3,4-dibromotoluene, 120 mL of anhydrous toluene, and 4.23 g of cyclopentadiene were added to a 500 mL three-necked flask and stirred. The cyclopentadiene used in the reaction was obtained by thermally decomposing dicyclopentadiene at 160-170°C, referring to Non-Patent Literature 13, and using the component distilled off at 40-67°C 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 addition, the temperature was gradually raised to room temperature and stirred at room temperature for 4 hours. After the reaction, saturated ammonium chloride aqueous solution was added, followed by diethyl ether. The organic layer was separated and washed with water and saturated brine. After drying the organic layer over magnesium sulfate, the magnesium sulfate was filtered off, and the resulting organic layer was concentrated using a rotary evaporator to obtain 14.32 g of 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 later.

[0293] [ka]

[0294] In a 500 mL three-necked flask, 4.19 g (26.8 mmol) of compound 10, 107 mL of tert-butyl alcohol, and 27 mL of water were added, and the mixture was cooled to 0°C while stirring. In another flask, 6.40 g of potassium permanganate, 135 mL of water, and 1.42 g 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, ensuring that the internal temperature did not exceed 5°C. After 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 mixture until a white precipitate formed. The precipitate was removed by filtration, and the filtrate was extracted four times with ethyl acetate. The organic layer was washed with saturated brine and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the resulting organic layer was concentrated using a rotary evaporator to obtain 3.80 g of crude product. The compound 11 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 later.

[0296] [ka]

[0297] Under a nitrogen atmosphere, 2.94 g (15.5 mmol) of compound 11, 80 mL of anhydrous chloroform, and 4.6 g of benzoyl chloride were added to a 200 mL three-necked flask and stirred. The mixture was cooled in an ice bath, and 2.6 mL of anhydrous pyridine was slowly added dropwise. After the addition, the mixture was heated to room temperature and stirred overnight, then cooled again in an ice bath, and 5 mL of methanol was added. Water and chloroform were added to the reaction mixture and stirred, after which the organic layer was separated. The organic layer was washed with saturated brine and dried over magnesium sulfate. Magnesium sulfate was filtered off, and the obtained organic layer was concentrated using a rotary evaporator to obtain 7.91 g of crude product. Purification by silica gel column chromatography yielded 4.82 g (12.1 mmol, white solid) of 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 melting temperature of the obtained compound 12 was 155°C.

[0299] [Example A6] <Synthesis of Compound 13> Compound 13, shown below, was synthesized according to the reaction equation below and the method described later.

[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-necked flask, and 135 mL of anhydrous tetrahydrofuran was added and stirred. 19.3 g of cyclopentadiene was slowly added dropwise while cooling in an ice bath. The cyclopentadiene used in the reaction was obtained by thermally decomposing dicyclopentadiene at 160-170°C, referring to Non-Patent Literature 13, and using the component distilled at 40-67°C immediately. After addition, the mixture was stirred at room temperature for 20 minutes, and then 28.9 g of 1,2-dichloroethane was slowly added dropwise while cooling in an ice bath. After addition, the temperature was raised to room temperature and the mixture was stirred for 8 hours. 100 mL of tetrahydrofuran and 10.5 g of water were added to a beaker to prepare hydrated THF. The hydrated tetrahydrofuran was slowly added dropwise to the flask after the reaction while cooling in an ice bath. Ice water was prepared in another flask, and the reaction solution was transferred to the ice water. Subsequently, 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 brine, and dried over magnesium sulfate. After filtering off the magnesium sulfate, the resulting organic layer was distilled, and the component with a distillation temperature of 88-92°C and a yield of 664-665 torr was collected, yielding 18.09 g of compound 13.

[0302] <Synthesis of Compound 14> Compound 14, shown below, was synthesized according to the reaction equation below and the method described later.

[0303] [ka]

[0304] Under a nitrogen atmosphere, 15.1 g (64.0 mmol) of 1,2-dibromobenzene, 130 mL of anhydrous toluene, and 5.90 g of compound 13 were added to a 500 mL three-necked 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 addition, the temperature was gradually raised to room temperature and stirred for 4 hours at room temperature. After the reaction, saturated aqueous ammonium chloride solution was added, followed by diethyl ether. The organic layer was separated and washed with water and then saturated brine. The organic layer was dried over magnesium sulfate, and the magnesium sulfate was filtered off. The resulting organic layer was concentrated using 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 later.

[0306] [ka]

[0307] 7.7 g (45.8 mmol) of compound 14, 178 mL of tert-butyl alcohol, and 44 mL of water were added to a 500 mL three-necked flask, and the mixture was cooled to 0°C while stirring. In a separate flask, 10.6 g of potassium permanganate, 222 mL of water, and 2.32 g 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 14, ensuring that the internal temperature did not exceed 5°C. After 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 mixture until a white precipitate formed. The precipitate was removed by filtration, and the filtrate was extracted four times with ethyl acetate. The organic layer was washed with saturated brine and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the resulting organic layer was concentrated using a rotary evaporator to obtain 5.63 g of crude product. The compound 14-2 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 later.

[0309] [ka]

[0310] Under a nitrogen atmosphere, 4.06 g (24.1 mmol) of compound 14-2, 105 mL of anhydrous chloroform, and 5.95 g of benzoyl chloride were added to a 200 mL three-necked flask and stirred. The mixture was cooled in an ice bath, and 3.4 mL of anhydrous pyridine was slowly added dropwise. After the addition, the mixture was heated to room temperature and stirred overnight, then cooled again in an ice bath, and 5 mL of methanol was added. Water and chloroform were added to the reaction mixture and stirred, after which the organic layer was separated. The organic layer was washed with saturated brine and dried over magnesium sulfate. Magnesium sulfate was filtered off, and the obtained organic layer was concentrated using a rotary evaporator to obtain 9.65 g of crude product. Purification by silica gel column chromatography yielded 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 melting temperature of the obtained compound 15 was 111°C.

[0312] [Example A7] <Synthesis of Compound 16> Compound 16, shown below, was synthesized according to the reaction equation below and the method described later.

[0313] [ka]

[0314] Under a nitrogen atmosphere, 20.0 g (68.5 mmol) of 1,2-dibromo-4-tert-butylbenzene, 130 mL of anhydrous toluene, and 4.54 g of cyclopentadiene were added to a 500 mL three-necked flask and stirred. The cyclopentadiene used in the reaction was obtained by thermally decomposing dicyclopentadiene at 160-170°C, referring to Non-Patent Literature 13, and using the component distilled off at 40-67°C immediately. The internal temperature was cooled to 0°C, and 43 mL of n-butyllithium hexane solution (1.6 M) was slowly added dropwise. After addition, the temperature was gradually raised to room temperature and stirred at room temperature for 12 hours. After the reaction, saturated ammonium chloride aqueous solution was added, followed by diethyl ether. The organic layer was separated and washed with water and then saturated brine. After drying the organic layer over magnesium sulfate, the magnesium sulfate was filtered off, and the resulting organic layer was concentrated using a rotary evaporator to obtain 19.67 g of 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 later.

[0316] [ka]

[0317] 5.57 g (28.1 mmol) of compound 16, 109 mL of tert-butyl alcohol, and 27 mL of water were added to a 500 mL three-necked flask, and the mixture was cooled to 0°C while stirring. In a separate flask, 6.55 g of potassium permanganate, 135 mL of water, and 1.55 g 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 compound 16 solution, ensuring that the internal temperature did not exceed 5°C. After 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 mixture until a white precipitate formed. The precipitate was removed by filtration, and the filtrate was extracted four times with ethyl acetate. The organic layer was washed with saturated brine and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the resulting 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 later.

[0319] [ka]

[0320] Under a nitrogen atmosphere, 4.11 g (9.3 mmol) of compound 17 and 17.7 mL of anhydrous pyridine were added to a 50 mL three-necked 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 heated 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 saturated ammonium chloride aqueous solution and saturated brine, and dried over magnesium sulfate. The magnesium sulfate was filtered and the mixture was concentrated using a rotary evaporator to obtain 9.34 g of crude product. The product was purified by silica gel column chromatography to obtain 6.13 g of solid component. The obtained solid was recrystallized on hexane to obtain 4.0 g (9.0 mmol, white solid) of 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 melting temperature of the obtained compound 18 was 115°C.

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

[0323] [ka]

[0324] Under a nitrogen atmosphere, 20.0 g (75.8 mmol) of 1,2-dibromo-4,5-dimethylbenzene, 150 mL of anhydrous toluene, and 5.01 g of cyclopentadiene were added to a 500 mL three-necked flask and stirred. The cyclopentadiene used in the reaction was obtained by thermally decomposing dicyclopentadiene at 160-170°C, as described in Non-Patent Literature 13, and using the component distilled off at 40-67°C immediately. The internal temperature was cooled to 0°C, and 47.5 mL of n-butyllithium hexane solution (1.6 M) was slowly added dropwise. After addition, the temperature was gradually raised to room temperature and stirred at room temperature for 12 hours. After the reaction, saturated ammonium chloride aqueous solution was added, followed by diethyl ether. The organic layer was separated and washed with water and then saturated brine. After drying the organic layer over magnesium sulfate, the magnesium sulfate was filtered off, and the resulting organic layer was concentrated using a rotary evaporator to obtain 18.64 g of 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 later.

[0326] [ka]

[0327] In a 500 mL three-necked flask, 5.57 g (22.8 mmol) of compound 19, 89 mL of tert-butyl alcohol, and 22 mL of water were added, and the mixture was cooled to 0°C while stirring. In another flask, 5.33 g of potassium permanganate, 111 mL of water, and 1.22 g 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, ensuring that the internal temperature did not exceed 5°C. After 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 mixture until a white precipitate formed. The precipitate was removed by filtration, and the filtrate was extracted four times with ethyl acetate. The organic layer was washed with saturated brine and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the resulting 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 later.

[0329] [ka]

[0330] Under a nitrogen atmosphere, 2.25 g (11.0 mmol) of compound 20 and 11.0 mL of anhydrous pyridine were added to a 50 mL three-necked 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 heated 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, and once each with saturated ammonium chloride aqueous solution and saturated brine, 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 crude product. The crude product 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 melting temperature of the obtained compound 21 was 152°C.

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

[0333] [ka]

[0334] A 1 L three-necked flask, thoroughly heated and dried, was fitted with a stirring bar, a dropping funnel, a thermometer, and a three-way stopcock. Under a nitrogen atmosphere, 6.00 mL (44.1 mmol, 1 equivalent) of 2-isopropylphenol was added, followed by 100 mL of dichloromethane and 0.62 mL (4.41 mmol, 0.1 equivalent) of diisopropylamine. Next, under a nitrogen atmosphere, 8.21 g (46.1 mmol, 1.05 equivalent) of N-bromosuccinimide (NBS), dissolved in 400 mL of dichloromethane, was slowly added dropwise to the previously prepared reaction solution at room temperature. After the addition was complete, the reaction solution was stirred at room temperature for 1 hour. After the reaction was complete, hydrochloric acid (2 M) was added until the pH became 1, then 100 mL of water was added, followed by three extractions with dichloromethane. The collected organic layer was dried over sodium sulfate, concentrated using a rotary evaporator, and the resulting crude product was purified by silica gel column chromatography (eluent: hexane) to obtain 9.40 g (43.7 mmol, yield 91%) of compound 22. The obtained compound showed good agreement with the spectrum 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 later.

[0336] [ka]

[0337] A 500 mL three-necked flask, thoroughly heated and dried, was fitted with a reflux condenser, a stopper, and a three-way stopcock. Under a nitrogen atmosphere, 9.40 g (43.7 mmol, 1 equivalent) of compound 22, 85 mL of THF, and 12.0 mL (56.8 mmol, 1.3 equivalents) of 1,1,1,3,3,3-hexamethyldisilazane (HMDS) were added. The stopper was replaced with a thermometer, and the mixture was heated and stirred in an oil bath at 80°C. After stirring overnight, the mixture was allowed to cool to room temperature, and then the system was reduced under a nitrogen atmosphere to remove the THF and unreacted HMDS from the reaction system. The product of this reaction was not purified and was used directly in the following reactions.

[0338] A dropping funnel was attached to the container containing the reaction product, 120 mL of THF was added, and the mixture was cooled to -78°C. n 38.3 mL of BuLi-hexane solution (1.6 M, 61.2 mmol, 1.4 equivalents) was slowly added dropwise, and after the addition was complete, the mixture was stirred at -78°C for 30 minutes. Subsequently, 10.0 mL of trifluoromethanesulfonic anhydride (Tf2O) (61.0 mmol, 1.4 equivalents) was slowly added dropwise under -78°C conditions, and after the addition was complete, the mixture was stirred at -78°C for 30 minutes, after which the reaction solution was allowed to cool to room temperature. The reaction solution was cooled again to 0°C, and saturated sodium bicarbonate aqueous solution was slowly added until the pH was approximately 7-8. The mixture 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 (eluent: hexane), yielding 9.93 g (29.2 mmol, yield 67%) of compound 23. The obtained compound 23 showed good agreement with the spectrum of the same compound synthesized in "Angew. Chem. Int. Ed. 2011, 50, 5674-5677". 1 The H-NMR data is shown below.

[0339] 1¹H 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 later.

[0340] [ka]

[0341] A 1 L three-necked flask, thoroughly heated and dried, was fitted with a reflux condenser, a stopper, and a three-way stopcock. Under a nitrogen atmosphere, 22.2 g (146 mmol, 5 equivalents) of cesium fluoride and 290 mL of acetonitrile were added. Subsequently, 12.3 mL (146 mmol, 5 equivalents) of cyclopentadiene, obtained by the thermal decomposition of dicyclopentadiene immediately beforehand, was added to the reaction solution, followed immediately by the addition of 9.93 g (29.2 mmol, 1 equivalent) of compound 23. After replacing the stopper with a thermometer, the mixture was heated to 40°C in an oil bath and stirred for 16 hours. After the reaction was complete, the mixture was allowed to cool to room temperature, and the reaction solution was passed through silica gel (eluent: ethyl acetate) and concentrated using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane), yielding 5.32 g of a solution containing compound 24 and a small amount of impurities. This solution 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, Synthesis reference: Macromolecules 2017, 50, 580-586. <Synthesis of Compound 25> Compound 25, shown below, was synthesized by the method described later.

[0343] [ka]

[0344] A 500 mL three-necked flask containing a stirring bar was equipped with a dropping funnel, thermometer, and three-way stopcock. Under a nitrogen atmosphere... t 120 mL of BuOH, 35 mL of water, and 5.32 g (1 equivalent) of a mixed solution of compound 24 obtained in <Synthesis of Compound 24> were charged, and the reaction solution was cooled to 0°C. 1.45 g (36.2 mmol, 1.25 equivalents) of NaOH and 6.86 g (43.4 mmol, 1.5 equivalents) of KMnO4 were dissolved in 130 mL of water and slowly added dropwise to the reaction solution. After the addition was complete, the mixture was stirred for a further 30 minutes under conditions of 0°C, and the unreacted KMnO4 was quenched with 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 approximately 7-8, and the resulting white precipitate was filtered off. The filtered solution was extracted three times with ethyl acetate, and the collected organic layer was dried with sodium sulfate and then concentrated using a rotary evaporator. The crude product obtained was purified by silica gel column chromatography (development solvent: hexane, followed by development in hexane:ethyl acetate = 3:1), yielding 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 later.

[0346] [ka]

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

[0348] 1 ¹H 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 (overlaps with CHCl3 signal, m, 4H), 7.45-7.54 (m, 2H), 7.87-7.96 (m, 4H). The melting temperature of the obtained compound 26 was 114°C.

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

[0350] [ka]

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

[0352] 1 ¹H 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 later.

[0353] [ka]

[0354] In the synthesis of compound 24, 3.39 g (17 mmol, yield 74%) of compound 28, which contained a small amount of hexane, was obtained by following the procedure and equivalence relationships 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. The obtained compound 28 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 later.

[0356] [ka]

[0357] A 500 mL three-necked flask containing a stirring bar was equipped with a dropping funnel, thermometer, and three-way stopcock. Under a nitrogen atmosphere... t 70 mL of BuOH and 20 mL of water were added, along with 3.39 g (17 mmol, 1 equivalent) of compound 28, which had a small amount of hexane mixed in as obtained in <Synthesis of Compound 28>, and the reaction solution was cooled to 0°C. 0.85 g (21.3 mmol, 1.25 equivalents) of NaOH and 4.03 g (25.5 mmol, 1.5 equivalents) of KMnO4 were dissolved in 80 mL of water and slowly added dropwise to the reaction solution. After the addition was complete, the mixture was stirred for a further 30 minutes at 0°C, and the unreacted KMnO4 was quenched with 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 approximately 7-8, and the resulting white precipitate was filtered off. 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 crude product obtained was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 3:1), yielding 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 later.

[0359] [ka]

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

[0361] 1¹H 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 (overlaps with CHCl3 signal, m, 4H), 7.45–7.53 (m, 2H), 7.88–7.95 (m, 4H). The melting temperature of the obtained compound 30 was 131°C.

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

[0363] [ka]

[0364] In the synthesis of compound 22, 10.8 g (53.9 mmol, 90% yield) of compound 31 was obtained by following the procedure and stoichiometric relationships 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 obtained compound showed good agreement with the spectrum of the same compound synthesized in "Adv. Synth. Catal. 2008, 350, 1309-1315". 1 The H-NMR data is shown below.

[0365] 1 ¹H 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 later.

[0366] [ka]

[0367] In the synthesis of compound 23, 13.0 g of compound 32 containing a small amount of impurities was obtained by following the procedure and equivalence relationships described in the synthesis of compound 23, except that 10.8 g (53.9 mmol) of compound 31 was used instead of 9.40 g (43.7 mmol) of compound 22. 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 later.

[0369] [ka]

[0370] In the synthesis of compound 24, instead of using 9.93 g (29.2 mmol) of compound 23, 13.0 g (39.9 mmol as 1 equivalent) of compound 32 containing a small amount of impurities was used. Except for this, the procedure and equivalent relationships described in the synthesis of compound 24 were followed to obtain 5.58 g (32.8 mmol) of compound 33. The obtained compound 33 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 later.

[0372] [ka]

[0373] A 500 mL three-necked flask containing a stirring bar was equipped with a dropping funnel, thermometer, and three-way stopcock. Under a nitrogen atmosphere... t 135 mL of BuOH, 40 mL of water, and 5.58 g (32.8 mmol, 1 equivalent) of compound 33 were added, and the reaction solution was cooled to 0°C. 1.64 g (41.0 mmol, 1.25 equivalents) of NaOH and 7.78 g (49.2 mmol, 1.5 equivalents) of KMnO4 were dissolved in 150 mL of water and slowly added dropwise to the reaction solution. After the addition was complete, the mixture was stirred for a further 30 minutes at 0°C, and the unreacted KMnO4 was quenched with 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 approximately 7-8, and the resulting white precipitate was filtered off. 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 crude product obtained was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 5:1), yielding 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 later.

[0375] [ka]

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

[0377] 1 ¹H 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 (overlaps with CHCl3 signal, m, 4H), 7.46–7.53 (m, 2H), 7.91–7.94 (m, 4H). The melting temperature of the obtained compound 35 was 138°C.

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

[0379] [ka]

[0380] A 500 mL three-necked flask containing a stirring bar was equipped with a dropping funnel, thermometer, and three-way stopcock. Under a nitrogen atmosphere... t 110 mL of BuOH, 35 mL of water, and 5.00 g (26.0 mmol, 1 equivalent) of 1,4-Dihydro-1,4-methanoanthracene were added, and the reaction solution was cooled to 0°C. 1.30 g (32.5 mmol, 1.25 equivalent) of NaOH and 6.16 g (39.0 mmol, 1.5 equivalent) of KMnO4 were dissolved in 120 mL of water and slowly added dropwise to the reaction solution. After the addition was complete, the mixture was stirred for another hour at 0°C, and the unreacted KMnO4 was quenched with 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 approximately 7-8, and the resulting white precipitate was filtered off. 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 crude product obtained was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 10:1), yielding 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 later.

[0382] [ka]

[0383] A 100 mL three-necked flask, thoroughly heated and dried, was fitted with a stopper, thermometer, and three-way stopcock. Under a nitrogen atmosphere, 2.57 g (11.4 mmol, 1 equivalent) of compound 36 and approximately 10 mL of pyridine were added, and the stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 2.90 mL (25.1 mmol, 2.2 equivalents) of benzoyl chloride was slowly added dropwise. After the addition was complete, the temperature was raised to room temperature and the mixture was stirred overnight. After the reaction was complete, the solution was cooled to 0°C, 10 mL of methanol was added, and the mixture was stirred for 1 hour. Approximately 20 mL of water and approximately 30 mL of dichloromethane were added, and the mixture was extracted three times with dichloromethane. The collected organic layer was washed twice with saturated ammonium chloride aqueous solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The crude product obtained was purified by two silica gel column chromatography cycles (eluent: 1st cycle: hexane:ethyl acetate = 20:1 followed by ethyl acetate only; 2nd cycle: hexane:ethyl acetate = 5:1) and washing with hexane, yielding 3.09 g of compound 37 (7.1 mmol, yield 62%, pale yellow solid). 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 melting temperature of the obtained compound 37 was 164°C.

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

[0386] [ka]

[0387] A 500 mL three-necked flask containing a stirring bar was equipped with a dropping funnel, thermometer, and three-way stopcock. Under a nitrogen atmosphere... t 150 mL of BuOH, 50 mL of water, and 4.33 g (30.0 mmol, 1 equivalent) of 1,4-epoxy-1,4-dihydronaphthalene were added, and the reaction solution was cooled to 0°C. 1.50 g (37.5 mmol, 1.25 equivalent) of NaOH and 7.11 g (45.0 mmol, 1.5 equivalent) of KMnO4 were dissolved in 150 mL of water and slowly added dropwise to the reaction solution. After the addition was complete, the mixture was stirred for another hour at 0°C, and the unreacted KMnO4 was quenched with 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 approximately 7-8, and the resulting white precipitate was filtered off. 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 crude product obtained was purified by silica gel column chromatography (eluent: ethyl acetate), yielding 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 later.

[0389] [ka]

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

[0391] 1 ¹H NMR (270 MHz, CDCl3, TMS as internal standard): δ 5.30 (s, 2H), 5.55 (s, 2H), 7.26-7.33 (overlaps with CHCl3 signal, m, 6H), 7.43-7.54 (m, 4H), 7.94-7.97 (m, 4H). The melting temperature of the obtained compound 39 was 188°C.

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

[0393] [ka]

[0394] A 100 mL three-necked flask, thoroughly heated and dried, was fitted with a stopper, thermometer, and three-way stopcock. Under a nitrogen atmosphere, 2.13 g (12.1 mmol, 1 equivalent) of compound 5 and approximately 10 mL of pyridine were added, and the stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 3.42 mL (26.8 mmol, 2.2 equivalents) of o-tol oil chloride was slowly added dropwise. After the addition was complete, the temperature was raised to room temperature and the mixture was stirred overnight. After the reaction was complete, the solution was cooled to 0°C, 10 mL of methanol was added, and the mixture was stirred for 30 minutes. Approximately 20 mL of water and approximately 30 mL of dichloromethane were added, and the mixture was extracted three times with dichloromethane. The collected organic layer was washed twice with saturated ammonium chloride aqueous solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The crude product obtained was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 5:1, followed by ethyl acetate only), yielding 3.75 g of compound 40 (9.08 mmol, yield 75%, white solid). 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 melting temperature of the obtained compound 40 was 119°C.

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

[0397] [ka]

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

[0399] 1 ¹H 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 melting temperature of the obtained compound 41 was 84°C.

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

[0401] [ka]

[0402] A 100 mL three-necked flask, thoroughly heated and dried, was fitted with a stopper, thermometer, and three-way stopcock. Under a nitrogen atmosphere, 2.23 g (12.6 mmol, 1 equivalent) of compound 5 and approximately 10 mL of pyridine were added, and the stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 4.20 mL (28.4 mmol, 2.3 equivalents) of 3,5-dimethylbenzoyl chloride was slowly added dropwise. After the addition was complete, the temperature was raised to room temperature and the mixture was stirred overnight. After the reaction was complete, the solution was cooled to 0°C, 10 mL of methanol was added, and the mixture was stirred for 1 hour. Approximately 20 mL of water and approximately 30 mL of dichloromethane were added, and the mixture was extracted three times with dichloromethane. The collected organic layer was washed twice with saturated ammonium chloride aqueous solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The crude product obtained was purified by two silica gel column chromatography cycles (eluent: 1st cycle: hexane:ethyl acetate = 10:1, 2nd cycle: hexane:ethyl acetate = 20:1), yielding 5.13 g of compound 42 (11.6 mmol, yield 92%, white solid). 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 melting temperature of the obtained compound 42 was 118°C.

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

[0405] [ka]

[0406] A 100 mL three-necked flask, thoroughly heated and dried, was fitted with a stopper, thermometer, and three-way stopcock. Under a nitrogen atmosphere, 2.26 g (12.8 mmol, 1 equivalent) of compound 5 and approximately 10 mL of pyridine were added. After cooling the reaction solution to 0°C, 5.00 g (29.3 mmol, 2.3 equivalents) of 4-methoxybenzoyl chloride was slowly added. After the addition was complete, the temperature was raised to room temperature and the mixture was stirred overnight. After the reaction was complete, the solution was cooled to 0°C, 10 mL of methanol was added, and the mixture was stirred for 1 hour. Approximately 20 mL of water and approximately 30 mL of dichloromethane were added, and the mixture was extracted three times with dichloromethane. The collected organic layer was washed twice with saturated ammonium chloride aqueous solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The crude product obtained was purified by washing with ethanol, yielding 4.67 g of compound 43 (10.5 mmol, yield 82%, pale yellow solid). 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 melting temperature of the obtained compound 43 was 167°C.

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

[0409] [ka]

[0410] A 100 mL three-necked flask, thoroughly heated and dried, was fitted with a stopper, thermometer, and three-way stopcock. Under a nitrogen atmosphere, 2.26 g (12.8 mmol, 1 equivalent) of compound 5 and approximately 10 mL of pyridine were added, and the stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 3.81 mL (27.9 mmol, 2.2 equivalents) of 3-methoxybenzoyl chloride was slowly added dropwise. After the addition was complete, the temperature was raised to room temperature and the mixture was stirred overnight. After the reaction was complete, the solution was cooled to 0°C, 10 mL of methanol was added, and the mixture was stirred for 1 hour. Approximately 20 mL of water and approximately 30 mL of dichloromethane were added, and the mixture was extracted three times with dichloromethane. The collected organic layer was washed twice with saturated ammonium chloride aqueous solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The crude product obtained was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 10:1) and recrystallization in a two-layer acetone-hexane system, yielding 3.07 g of compound 44 (6.91 mmol, yield 54%, white solid). 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 melting temperature of the obtained compound 44 was 113°C.

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

[0413] [ka]

[0414] A 100 mL three-necked flask, thoroughly heated and dried, was fitted with a stopper, thermometer, and three-way stopcock. Under a nitrogen atmosphere, 1.78 g (10.1 mmol, 1 equivalent) of compound 5 and approximately 10 mL of pyridine were added, and the stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 3.30 mL (22.3 mmol, 2.2 equivalents) of 3-(trifluoromethyl)benzoyl chloride was slowly added dropwise. After the addition was complete, the temperature was raised to room temperature and the mixture was stirred overnight. After the reaction was complete, the solution was cooled to 0°C, 10 mL of methanol was added, and the mixture was stirred for 1 hour. Approximately 20 mL of water and approximately 30 mL of dichloromethane were added, and the mixture was extracted three times with dichloromethane. The collected organic layer was washed twice with saturated ammonium chloride aqueous solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The crude product obtained was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 10:1) and recrystallization with hexane, yielding 3.63 g of compound 45 (6.98 mmol, yield 70%, colorless transparent crystals). 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 melting temperature of the obtained compound 45 was 124°C.

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

[0417] [ka]

[0418] A 100 mL three-necked flask, thoroughly heated and dried, was fitted with a stopper, thermometer, and three-way stopcock. Under a nitrogen atmosphere, 2.06 g (11.7 mmol, 1 equivalent) of compound 5 and approximately 10 mL of pyridine were added, and the stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 3.80 mL (25.3 mmol, 2.2 equivalents) of 1-naphthoyl chloride was slowly added dropwise. After the addition was complete, the temperature was raised to room temperature and the mixture was stirred overnight. After the reaction was complete, the solution was cooled to 0°C, 10 mL of methanol was added, and the mixture was stirred for 1 hour. Approximately 20 mL of water and approximately 30 mL of dichloromethane were added, and the mixture was extracted three times with dichloromethane. The collected organic layer was washed twice with saturated ammonium chloride aqueous solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The crude product obtained was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 10:1) and washing with hexane, yielding 4.73 g of compound 46 (9.76 mmol, yield 85%, white solid). 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 melting temperature of the obtained compound 46 was 158°C.

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

[0421] [ka]

[0422] A 100 mL three-necked flask, thoroughly heated and dried, was fitted with a stopper, thermometer, and three-way stopcock. Under a nitrogen atmosphere, 2.03 g (11.5 mmol, 1 equivalent) of compound 5 and approximately 10 mL of pyridine were added. After cooling the reaction solution to 0°C, 4.80 g (25.2 mmol, 2.2 equivalents) of 2-naphthoyl chloride was slowly added. After the addition was complete, the temperature was raised to room temperature and the mixture was stirred overnight. After the reaction was complete, approximately 10 mL of dichloromethane was added and the mixture was stirred for a further 3 hours. The solution was then cooled to 0°C, 10 mL of methanol was added, and the mixture was stirred for 1 hour. Approximately 20 mL of water and approximately 30 mL of dichloromethane were added, and the mixture was extracted three times with dichloromethane. The collected organic layer was washed twice with saturated ammonium chloride aqueous solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The crude product obtained was purified by two silica gel column chromatography cycles (eluent: 1st cycle: hexane:ethyl acetate = 7:1, 2nd cycle: hexane:ethyl acetate = 5:1) and washing with hexane, yielding 2.05 g of compound 47 (4.23 mmol, yield 37%, white solid). 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 melting temperature of the obtained compound 47 was 201°C.

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

[0425] [ka]

[0426] A 100 mL three-necked flask, thoroughly heated and dried, was fitted with a stopper, thermometer, and three-way stopcock. Under a nitrogen atmosphere, 2.15 g (12.2 mmol, 1 equivalent) of compound 5 and approximately 10 mL of pyridine were added, and the stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 4.00 mL (26.8 mmol, 2.2 equivalents) of 2-ethylbenzoyl chloride was slowly added dropwise. After the addition was complete, the temperature was raised to room temperature and the mixture was stirred overnight. After the reaction was complete, the solution was cooled to 0°C, 10 mL of methanol was added, and the mixture was stirred for 30 minutes. Approximately 20 mL of water and approximately 30 mL of dichloromethane were added, and the mixture was extracted three times with dichloromethane. The collected organic layer was washed twice with saturated ammonium chloride aqueous solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The crude product obtained was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 20:1), yielding 4.34 g of compound 48 (9.85 mmol, yield 81%, white solid). 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 melting temperature of the obtained compound 48 was 52°C.

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

[0429] [ka]

[0430] A 100 mL three-necked flask, thoroughly heated and dried, was fitted with a stopper, thermometer, and three-way stopcock. Under a nitrogen atmosphere, 2.19 g (12.4 mmol, 1 equivalent) of compound 5 and approximately 10 mL of pyridine were added, and the stopper was replaced with a dropping funnel. After cooling the reaction solution to 0°C, 4.50 g (26.7 mmol, 2.2 equivalents) of 2,3-dimethylbenzoyl chloride was slowly added dropwise. After the addition was complete, the temperature was raised to room temperature and the mixture was stirred overnight. After the reaction was complete, the solution was cooled to 0°C, 10 mL of methanol was added, and the mixture was stirred for 1 hour. Approximately 20 mL of water and approximately 30 mL of dichloromethane were added, and the mixture was extracted three times with dichloromethane. The collected organic layer was washed twice with saturated ammonium chloride aqueous solution, dried over sodium sulfate, and concentrated using a rotary evaporator. The crude product obtained was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 20:1) and recrystallization with hexane, yielding 4.62 g of compound 49 (10.5 mmol, yield 85%, white solid). 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 melting temperature of the obtained compound 49 was 107°C.

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

[0433] [ka]

[0434] In the synthesis of compound 6, instead of using 13.4 mL of benzoyl chloride, 10 g of p-dimethylaminobenzoyl chloride was used, and the reaction temperature after reagent addition was maintained at 115°C for 7 days. Except for these differences, the procedure and stoichiometric relationships described in the synthesis of compound 6 were followed to obtain 4.34 g (pale yellow solid) of compound 50. 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 melting temperature of the obtained compound 50 was 252°C.

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

[0437] [ka]

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

[0439] 1 ¹H 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 (overlaps with CHCl3 signal, m, 2H). The melting temperature of the obtained compound 51 was 80°C.

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

[0441] [ka]

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

[0443] 1 ¹H 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 (overlaps with CHCl3 signal, m, 2H). [Example A27] <Synthesis of Compound 53> Compound 53, shown below, was synthesized according to the reaction equation below and the method described later.

[0444] [ka]

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

[0446] <Synthesis of Compound 54> Compound 54, shown below, was synthesized according to the reaction equation below and the method described later.

[0447] [ka]

[0448] Under 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-necked flask and 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 addition, the temperature was raised to room temperature and stirred overnight. After confirming the disappearance of the starting material 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 mixture, and the organic layer was separated. The aqueous layer was extracted three times with chloroform. The organic layer was washed with saturated brine, dried over sodium sulfate, and 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). 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 equation below and the method described later.

[0450] [ka]

[0451] Under 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-necked flask and 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 addition, the temperature was raised to room temperature and stirred overnight. After confirming the disappearance of the starting 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 mixture, and the organic layer was separated. The aqueous layer was extracted three times with chloroform. The organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated using a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 10 / 1) to obtain 4.3 g of compound 55 (10.4 mmol, yield: 61%, white powder). 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 melting temperature of the obtained compound 55 was 186°C.

[0453] [Example A29] <Synthesis of Compound 56> Compound 56, shown below, was synthesized according to the reaction equation below and the method described later.

[0454] [ka]

[0455] Under 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-necked flask and 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 addition, the temperature was raised to room temperature and stirred overnight. After confirming the disappearance of the starting 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 mixture, and the organic layer was separated. The aqueous layer was extracted three times with chloroform. The organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated using a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 10 / 1) to obtain 4.8 g of compound 56 (9.2 mmol, yield: 54%, white powder). 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 melting temperature of the obtained compound 56 was 146°C.

[0457] [Example A30] <Synthesis of Compound 57> Compound 57, shown below, was synthesized according to the reaction equation below and the method described later.

[0458] [ka]

[0459] Under 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-necked flask and 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 addition, the temperature was raised to room temperature and stirred overnight. After confirming the disappearance of the starting 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 mixture, and the organic layer was separated. The aqueous layer was extracted three times with chloroform. The organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated using a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 10 / 1) to obtain 3.8 g of compound 57 (7.7 mmol, yield: 45%, white powder). 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 melting temperature of the obtained compound 57 was 86°C.

[0461] [Example A31] <Synthesis of Compound 58> Compound 58, shown below, was synthesized according to the reaction equation below and the method described later.

[0462] [ka]

[0463] Under 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-necked flask and 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 addition, the temperature was raised to room temperature and stirred overnight. After confirming the disappearance of the starting 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 mixture, and the organic layer was separated. The aqueous layer was extracted three times with chloroform. The organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated using a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 10 / 1) to obtain 4.6 g of compound 58 (9.8 mmol, yield: 58%, white powder). 1 The H-NMR data is shown below.

[0464] 1 H 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 melting temperature of the obtained compound 58 was 173°C.

[0465] [Example A32] <Synthesis of Compound 59> Compound 59, shown below, was synthesized according to the reaction equation below and the method described later.

[0466] [ka]

[0467] 15 mL of 30% hydrogen peroxide solution and 60 mL of 88% formic acid were added to a 300 mL three-necked flask and heated to 40 °C using an oil bath while stirring. 14.8 g of tricyclo[6,2,1,0(2,7)]undeca-4-ene was added dropwise to the reaction mixture, ensuring the internal temperature did not exceed 50 °C. After addition, stirring was continued at 40 °C for 1 hour. The mixture was then allowed to cool to room temperature and stirred for 17 hours. The reaction mixture was concentrated under reduced pressure, and 20 mL of 2 mol / L sodium hydroxide aqueous solution and 50 mL of ethyl acetate were added at a temperature below 50 °C, and the mixture was 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 brine, dried over sodium sulfate, and then concentrated using a rotary evaporator. Compound 59 was proceeded to the reaction without purification.

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

[0469] [ka]

[0470] Under 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-necked flask and 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 addition, the temperature was raised to room temperature and stirred overnight. After confirming the disappearance of the starting 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 mixture, and the organic layer was separated. The aqueous layer was extracted three times with chloroform. The organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated using a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 10 / 1) to obtain 5.3 g of compound 60 (13.6 mmol, yield: 74%, white powder). 1 The H-NMR data is shown below.

[0471] 1 ¹H 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 melting temperature of the obtained compound 60 was 125°C.

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

[0473] [ka]

[0474] 15 mL of 30% hydrogen peroxide solution and 60 mL of 88% formic acid were added to a 300 mL three-necked 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 mixture, ensuring the internal temperature did not exceed 50°C. After addition, stirring was continued at 40°C for 1 hour. The mixture was then allowed to cool to room temperature and stirred for 17 hours. The reaction mixture was concentrated under reduced pressure, and 20 mL of 2 mol / L sodium hydroxide aqueous solution and 50 mL of ethyl acetate were added at a temperature below 50°C, and the mixture was 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 brine, dried over sodium sulfate, and then concentrated using a rotary evaporator. Compound 61 was proceeded to the reaction without purification.

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

[0476] [ka]

[0477] Under 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-necked flask and 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 addition, the temperature was raised to room temperature and stirred overnight. After confirming the disappearance of the starting 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 mixture, and the organic layer was separated. The aqueous layer was extracted three times with chloroform. The organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated using a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 10 / 1) to obtain 4.1 g of compound 62 (10.7 mmol, yield: 21%, white powder). 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 melting temperature of the obtained compound 62 was 192°C.

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

[0480] [ka]

[0481] Under a nitrogen atmosphere, 35.2 g (149 mmol) of 1,2-dibromobenzene, 300 mL of anhydrous toluene, and 12.0 g of 1,3-cyclohexadiene were added to a 500 mL three-necked 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 addition, the temperature was gradually raised to room temperature and stirred at room temperature for 12 hours. After the reaction, saturated aqueous ammonium chloride solution was added, followed by diethyl ether. The organic layer was separated and washed with water and then saturated brine. The organic layer was dried over magnesium sulfate, and the magnesium sulfate was filtered off. The resulting organic layer was concentrated using a rotary evaporator to obtain 15.42 g of 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 later.

[0483] [ka]

[0484] In a 1000 mL three-necked flask, 4.9 g of compound 63 containing impurities obtained in <Synthesis of Compound 63>, 125 mL of tert-butyl alcohol, and 31 mL of water were added, and the mixture was cooled to 0°C while stirring. In another flask, 7.35 g of potassium permanganate, 150 mL of water, and 1.70 g 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 containing compound 63, ensuring that the internal temperature did not exceed 5°C. After 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 mixture until a white precipitate formed. The precipitate was removed by filtration, and the filtrate was extracted four times with ethyl acetate. The organic layer was washed with saturated brine and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the resulting 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 later.

[0486] [ka]

[0487] Under a nitrogen atmosphere, 0.65 g (3.3 mmol) of compound 64 and 10.0 mL of anhydrous pyridine were added to a 50 mL three-necked 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 heated 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, then washed with saturated ammonium chloride aqueous solution and saturated brine, and dried over magnesium sulfate. The magnesium sulfate was filtered, and the crude product was concentrated using a rotary evaporator. The crude product 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 stereochemistry of compounds 65-1 and 65-2 was 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 melting temperature of compound 65-1 was 143°C. The melting temperature of compound 65-2 was 193°C.

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

[0490] [ka]

[0491] Under 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. The mixture was heated and stirred until 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 obtained solid was washed with hexane and 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 later.

[0493] [ka]

[0494] 3.8 g of compound 66, 7.2 mL of 4 mol / L sodium hydroxide solution, and 28 mL of methanol were added to a 100 mL three-necked flask. After addition, the mixture was stirred at room temperature for 30 minutes. After removing the methanol by distillation, 20 mL of water was added, and the mixture was extracted with 30 mL of chloroform. The organic layer was dried over sodium sulfate. After removing the chloroform by distillation and drying, 2.88 g of compound 67 was obtained. 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 later.

[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. At room temperature, 2.92 mL of benzoyl chloride was added and the mixture was heated and stirred until 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 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). 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 melting temperature of the obtained compound 68 was 174°C.

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

[0500] [ka]

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

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

[0503] [ka]

[0504] 5.6 g of compound 69, 8.0 g of sodium hydroxide, and 30 mL of pure water were added to a 50 mL three-necked flask. The mixture was heated and stirred until 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 a temperature below 50 °C 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 later.

[0506] [ka]

[0507] Under 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-necked flask. The mixture was heated and stirred until 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 sodium hydroxide aqueous solution. The organic layer was then 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). 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 melting temperature of the obtained compound 71 was 173°C.

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

[0510] [ka]

[0511] Under 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. The mixture was heated and stirred until the internal temperature reached 220°C, and 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 dried to obtain 5.6 g of compound 72.

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

[0513] [ka]

[0514] 5.6 g of compound 72, 7.6 g of sodium hydroxide, and 30 mL of pure water were added to a 50 mL three-necked flask. The mixture was heated and stirred until 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 a temperature below 50 °C to neutralize the mixture. The solid was filtered off, washed with pure water, and dried to obtain 5.0 g of compound 73.

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

[0516] [ka]

[0517] Under 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-necked flask. The mixture was heated and stirred until 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 sodium hydroxide aqueous solution. The organic layer was then dried over magnesium sulfate. After concentration, the solid was filtered off, washed with hexane, and dried to obtain 5.2 g of compound 74 (11.0 mmol, yield 58%, white powder). 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 melting temperature of the obtained compound 74 was 218°C.

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

[0520] [ka]

[0521] Under 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. The mixture was heated and stirred until the internal temperature reached 220 °C, and stirring was continued for 9 hours. After cooling to room temperature, 5 mL of methanol was added and the mixture was stirred, and the solid was filtered off. The obtained solid was washed with methanol and dried to obtain 10.5 g of compound 75.

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

[0523] [ka]

[0524] 10.5 g of compound 75, 12.0 g of sodium hydroxide, and 30 mL of pure water were added to a 50 mL three-necked flask. The mixture was heated and stirred until 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 a temperature below 50 °C to neutralize the mixture. 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 later.

[0526] [ka]

[0527] Under 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-necked flask. The mixture was heated and stirred until 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 sodium hydroxide aqueous solution. The organic layer was then 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). 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 melting temperature of the obtained compound 77 was 175°C.

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

[0530] [ka]

[0531] Under 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. The mixture was heated and stirred until the internal temperature reached 220 °C, and 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 dried to obtain 9.6 g of compound 78.

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

[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-necked flask, and the mixture was stirred for 6 hours until the internal temperature reached 100 °C. After cooling to room temperature, 12 mol / L concentrated hydrochloric acid was added at a temperature below 50 °C to neutralize the mixture. 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 later.

[0536] [ka]

[0537] Under 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-necked flask. The mixture was heated and stirred until 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 sodium hydroxide aqueous solution. The organic layer was then 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). 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 melting temperature of the obtained compound 80 was 184°C.

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

[0540] [ka]

[0541] Under 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. The mixture was heated and stirred until the internal temperature reached 220 °C, and 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 dried to obtain 11.3 g of compound 81.

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

[0543] [ka]

[0544] 11.3 g of compound 81, 12.0 g of sodium hydroxide, and 30 mL of pure water were added to a 50 mL three-necked flask. The mixture was heated and stirred until 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 a temperature below 50 °C to neutralize the mixture. 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 later.

[0546] [ka]

[0547] Under 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-necked flask. The mixture was heated and stirred until 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 sodium hydroxide aqueous solution. The organic layer was then 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). 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 melting temperature of the obtained compound 83 was 176°C.

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

[0550] [ka]

[0551] Under 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. The mixture was heated and stirred until the internal temperature reached 220 °C, and 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 dried to obtain 9.7 g of compound 84.

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

[0553] [ka]

[0554] 9.7 g of compound 84, 12.0 g of sodium hydroxide, and 30 mL of pure water were added to a 50 mL three-necked flask. The mixture was heated and stirred until 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 a temperature below 50 °C to neutralize the mixture. 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 later.

[0556] [ka]

[0557] Under 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-necked flask. The mixture was heated and stirred until the internal temperature reached 60°C, and stirring was continued for 6 hours. After removing the pyridine by distillation, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L sodium hydroxide aqueous solution. The organic layer was then 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). 1 The H-NMR data is shown below.

[0558] 1 ¹H 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 melting temperature of the obtained compound 86 was 227°C.

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

[0560] [ka]

[0561] Under 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-necked flask. The mixture was heated and stirred until the internal temperature reached 60°C, and stirring was continued for 6 hours. After removing the pyridine by distillation, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L sodium hydroxide aqueous solution. The organic layer was then 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). 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 melting temperature of the obtained compound 87 was 220°C.

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

[0564] [ka]

[0565] Under 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-necked flask. The mixture was heated and stirred until the internal temperature reached 60°C, and stirring was continued for 6 hours. After removing the pyridine by distillation, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L sodium hydroxide aqueous solution. The organic layer was then 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). 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 melting temperature of the obtained compound 88 was 158°C.

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

[0568] [ka]

[0569] Under a nitrogen atmosphere, 15 g of compound 85 (50.3 mmol) and 117 mL of anhydrous pyridine were added to a 200 mL three-necked flask and cooled in an ice bath. 18.0 g (105.5 mmol) of 4-methoxybenzoyl chloride was added dropwise over approximately 5 minutes, and the mixture was heated and stirred in an oil bath warmed to 100°C for 20 hours. After the reaction was complete, the mixture was allowed to cool, and 10 mL of anhydrous methanol was added to quench at room temperature. After stirring at room temperature for about 30 minutes, the reaction solution was added dropwise to 600 mL of a hexane-water mixture (hexane:water = 5:1) to obtain fine crystals. The obtained crystals were collected by filtration, the aggregate was 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 wash each with 100 mL each of saturated sodium bicarbonate aqueous solution and saturated brine, and the resulting 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 obtained 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 melting temperature of the obtained compound 89 was 221°C.

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

[0572] [ka]

[0573] Under a nitrogen atmosphere, 5.0 g of compound 85 (16.8 mmol) and 13 mL of anhydrous pyridine were added to a 100 mL three-necked 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 complete, 26 mL of methanol was added, and the precipitated solid was collected by filtration. The obtained solid was washed with 13 mL of 2 N hydrochloric acid, then suspended in 20 mL of methanol and stirred at 60 °C for approximately 1 hour. After cooling, the white solid was collected by filtration to obtain 10.2 g of compound 90 (yield 98%, white solid). 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 melting temperature of the obtained compound 90 was 178°C.

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

[0576] [ka]

[0577] A 300 mL three-necked flask, thoroughly heated and dried, was fitted with a stopper, thermometer, and three-way stopcock, along with a stirring bar. Under a nitrogen atmosphere, 3.08 g of 3-isopropylbenzoic acid (18.8 mmol), 60 mL of dichloromethane, and 2 drops of DMF were added. After cooling the reaction solution to 0°C, 2.57 mL of oxalyl chloride (30 mmol) was slowly added dropwise. After the addition was complete, the temperature was raised to room temperature and the mixture was stirred for 3 hours. Volatile compounds in the reaction system were removed by reducing the pressure to obtain compound 91. No further purification was performed, and it was used in the synthesis of compound 92.

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

[0579] [ka]

[0580] A 100 mL three-necked flask containing a stirring bar, thoroughly heated and dried, was fitted with a stopper, thermometer, and three-way stopcock. Under a nitrogen atmosphere, 1.6 g of compound 5 and 10 mL of anhydrous pyridine were added. After cooling the reaction solution to 0°C, 20 mL of a dichloromethane solution of compound 91 synthesized in <Synthesis of Compound 91> was slowly added to the pyridine solution of compound 5, and the mixture was stirred overnight. After the reaction was complete, the solution was cooled to 0°C, 20 mL of methanol was added, and the mixture was stirred for 1 hour. After adding 20 mL of water and 30 mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with saturated ammonium chloride aqueous 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 (eluent: hexane:ethyl acetate = 10:1) and recrystallization using hexane, yielding 1.54 g of compound 92 (yield 34%, white solid). 1 The H-NMR data is shown below.

[0581] 1¹H 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 (overlap with CHCl3 signal, m, 4H), 7.33-7.36 (m, 4H), 7.76-7.79 (m, 4H). The melting temperature of the obtained compound 92 was 93°C.

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

[0583] [ka]

[0584] Compound 93 was synthesized according to the procedures and stoichiometric relationships described in the 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 the synthesis of compound 91. The obtained compound 93 was used directly in the synthesis of compound 94.

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

[0586] [ka]

[0587] A 100 mL three-necked flask, thoroughly heated and dried, was fitted with a stopper, thermometer, and three-way stopcock. Under a nitrogen atmosphere, 2.13 g of compound 5 (12.1 mmol) and 10 mL of anhydrous pyridine were added. After cooling the reaction solution to 0°C, 20 mL of a dichloromethane solution of compound 93, synthesized in <Synthesis of Compound 93>, was slowly added to the pyridine solution of compound 5, and the mixture was stirred overnight. After the reaction was complete, the solution was cooled to 0°C, 20 mL of methanol was added, and the mixture was stirred for 1 hour. After adding 20 mL of water and 30 mL of dichloromethane, the mixture was extracted three times with dichloromethane, and the collected organic layer was washed twice with saturated ammonium chloride aqueous 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 (eluent: hexane:ethyl acetate = 10:1), yielding 2.64 g of compound 94 (6.0 mmol, yield 50%, pale yellow solid). 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 melting temperature of the obtained compound 94 was 158°C.

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

[0590] [ka]

[0591] Under a nitrogen atmosphere, 200 mL of anhydrous acetonitrile, 6.36 g of 1-phenylpyrrole, and 6.74 g of cesium fluoride were added to a 1 L three-necked flask and stirred at room temperature. Subsequently, 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 (eluent: ethyl acetate) and concentrated using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 5:1) to obtain 2.31 g (10.5 mmol, yield 71%) of compound 95.

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

[0593] [ka]

[0594] A 500 mL three-necked flask with a stirring bar was equipped with a dropping funnel, thermometer, and three-way stopcock. Under a nitrogen atmosphere, 60 mL of a mixed solution of tert-butyl alcohol and acetone, 20 mL of water, and 2.51 g (11.4 mmol) of compound 95 were added, and the reaction solution was cooled to 0°C. 0.57 g (14.3 mmol) of sodium hydroxide and 2.70 g (17.1 mmol) of potassium permanganate were dissolved in 60 mL of water and slowly added dropwise to the previously prepared reaction solution. After the addition was complete, the mixture was stirred for a further 1 hour at 0°C, and then the unreacted potassium permanganate was quenched with 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 approximately 7-8, and the resulting white precipitate was filtered off. 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 crude product obtained was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 1:1), yielding 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 later.

[0596] [ka]

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

[0598] 1 ¹H 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 (overlap with CHCl3 signal, m, 6H), 7.41–7.51 (m, 4H), 7.90–7.94 (m, 4H). The melting temperature of the obtained compound 97 was 158°C.

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

[0600] [ka]

[0601] Under 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-necked flask, followed by 700 mL of water, and the mixture was stirred at room temperature. 420 mL of acetone was slowly added dropwise, and stirring continued overnight at room temperature. After adding 700 mL of ethyl acetate and stirring, the organic layer and aqueous layer were separated. The organic layer was washed with saturated brine and dried over magnesium sulfate. The mixture was concentrated using a rotary evaporator to obtain the crude product. The obtained crude product was combined with the crude product obtained by a similar procedure using 5.0 g of p-benzoquinone and by equivalence (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 equation below and the method described later.

[0603] [ka]

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

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

[0606] [ka]

[0607] Under a nitrogen atmosphere, 21.3 g (85.8 mmol) of compound 99 was added to a 100 mL three-necked flask, followed by 25.7 g of sodium iodide (171.5 mmol) and 326 mL of acetonitrile. The mixture was stirred at room temperature for a while. 21.7 mL of chlorotrimethylsilane (171.0 mmol) was then added dropwise, and the mixture was stirred at room temperature after the addition was complete. The mixture was quenched with sodium thiosulfate solution, and the resulting solution was extracted with chloroform. The organic layer was washed with water and saturated brine, and then dried over magnesium sulfate. After filtering off the magnesium sulfate, the mixture was concentrated using a rotary evaporator. The crude products from a separate lot were purified by silica gel column chromatography (eluent: hexane) to obtain 9.13 g of compound 100, which contained a small amount of impurities. No further purification was performed, and the compound 100 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 later.

[0609] [ka]

[0610] Under a nitrogen atmosphere, 9.13 g obtained in <Synthesis of Compound 100> was added to a 1 L three-necked flask, then 167 mL of tert-butyl alcohol and 42 mL of water were added, and the mixture was cooled to 0°C in an ice bath. In another flask, an aqueous solution was prepared 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, and this was slowly added dropwise to the previously prepared reaction solution. After the addition was complete, stirring was continued for 20 minutes while keeping the mixture cool in an ice bath. While cooling in an ice bath, sodium pyrosulfite was slowly added until the potassium permanganate color of the reaction solution disappeared. Ethyl acetate was added to the reaction solution, and the procedure of separating only the supernatant organic layer was repeated four times. The collected organic layer was dried over magnesium sulfate and then concentrated using a rotary evaporator. The crude product obtained was purified by silica gel column chromatography (hexane:ethyl acetate = 100:0 → 60:40) to obtain 1.74 g (16% yield) and 1.77 g (17% yield) of compounds 101-1 and 101-2, respectively.

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

[0612] [ka]

[0613] Under a nitrogen atmosphere, 1.74 g of compound 101-1 (7.06 mmol) was added to a 200 mL three-necked flask and dissolved in 7 mL of anhydrous pyridine. While cooling in an ice bath, 1.72 mL of benzoyl chloride (14.8 mmol) was slowly added dropwise, ensuring that the internal temperature did not exceed 5°C. After addition, the temperature was raised to room temperature and the mixture was stirred for a while. After cooling the reaction solution with ice, methanol was slowly added to quench it. Water and dichloromethane were then added, and the organic layer was washed three times with 1 N hydrochloric acid, once with saturated sodium bicarbonate aqueous solution, and once with saturated brine. The organic layer after washing was dried over magnesium sulfate, filtered, and concentrated using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography to obtain 1.10 g of compound 102 (yield 35%, white solid). 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 considered 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 later.

[0616] [ka]

[0617] In the synthesis of compound 102, 1.77 g of compound 102-2 (7.18 mmol) was used instead of 1.74 g of compound 101-1. Except for this, the procedure and stoichiometric relationships described in the synthesis of compound 102 were followed to obtain 2.36 g of compound 103 (73% yield, white solid). The obtained compound 103... 1 The H-NMR data is shown below. 1 ¹H 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 (overlaps with CHCl3 signal, m, 10H). The melting temperature of the obtained compound 103 was 149°C.

[0618] [Example A50] <Synthesis of Compound 104> Compound 104, shown below, was synthesized according to the reaction equation below and the method described later.

[0619] [ka]

[0620] Under a nitrogen atmosphere, 70 g (0.85 mol) of 2-cyclopenten-1-one and 900 mL of anhydrous diethyl ether were added to a 2 L four-necked flask, and the mixture was stirred while cooling the internal temperature to 0°C. Next, 94 g (1.42 mol) of cyclopentadiene was added. The cyclopentadiene used in the reaction was obtained by thermally decomposing dicyclopentadiene in tetradecane at over 160°C and was used immediately. 48.4 g (0.34 mol) of boron trifluoride ethyl ether complex was added dropwise over 10 minutes while the internal temperature remained at 0-5°C. After the addition was complete, the temperature was raised to room temperature and stirring was continued for 17 hours. After the reaction was complete, 900 mL of pure water was added and the mixture was stirred for 30 minutes. The mixture was separated into an organic layer and an aqueous layer, and the recovered aqueous layer was extracted three times with 500 mL of diethyl ether. After collecting all of the organic layer, it was separated and washed with 1 L of saturated brine. The resulting organic layer was dried over magnesium sulfate and filtered, 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 equation below and the method described later.

[0622] [ka]

[0623] Under 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-necked flask and stirred. After adding 124 mg (0.5 mmol) of osmium oxide, the mixture was stirred at room temperature for 2 days. After the reaction was complete, 2 g of sodium hydrosulfite, 24 g of Florizil, and 160 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 with 1 N sulfuric acid. The organic solvent was removed from the filtrate under reduced pressure at an ambient temperature of 40°C, and the remaining aqueous solution was adjusted again with 1 N sulfuric acid to a pH of 3. Excess sodium chloride and 500 mL of ethyl acetate were added and stirred, and the undissolved sodium chloride was filtered off by vacuum filtration. The mixture was separated into an organic layer and an aqueous layer by liquid-liquid separatory. The recovered aqueous layer was extracted three times with 400 mL of ethyl acetate. The organic layer was 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 (45% yield).

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

[0625] [ka]

[0626] Under a nitrogen atmosphere, 3.33 g of compound 105 (18.3 mmol) was added to a three-necked flask, followed by 10 mL of anhydrous pyridine, and the mixture was stirred. 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 heated 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 mixture. Then, water and dichloromethane were added, and the mixture was transferred to a separatory funnel. The mixture was washed with water and saturated ammonium chloride aqueous solution, the organic layer was dried over magnesium sulfate, and the mixture was concentrated using a rotary evaporator. The resulting 8.29 g of crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 85:15 → 65:35) and recrystallization in acetone solvent to obtain 3.16 g of compound 106 (yield 44%, pale yellow solid). 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 melting temperature of the obtained compound 106 was 127°C.

[0628] [Example A51] <Synthesis of Compound 107> Compound 107, shown below, was synthesized according to the reaction equation below and the method described later.

[0629] [ka]

[0630] Under a nitrogen atmosphere, 1.5 L of anhydrous diethyl ether was added to a 5 L four-necked flask and cooled to 0°C. Next, 22.2 g (585 mmol) of lithium aluminum hydride was added. 51 g of compound 104 (344 mmol) was dissolved in 500 mL of anhydrous diethyl ether and added dropwise to the previously prepared solution over 30 minutes. During this time, the solution temperature was kept between 0 and 5°C. After the addition was complete, the temperature was raised to room temperature and stirring was continued for 1 hour. After the reaction was complete, the solution temperature was cooled again to 0°C, and 200 mL of methanol was added dropwise over 1 hour, taking care to avoid hydrogen generation. Next, 2 L of saturated potassium sodium tartrate aqueous solution was slowly added and stirred at room temperature for 2 hours. The mixture was separated into an organic layer and an aqueous layer, and the recovered aqueous layer was extracted three times with 500 mL of diethyl ether. The organic layer was collected and washed with 1 L of saturated brine. The organic layer was dried with sodium sulfate and filtered, then concentrated using a rotary evaporator and vacuum-dried at an ambient temperature of 40°C for 2 hours, yielding 48.0 g of compound 107 (93% yield).

[0631] <Synthesis of Compound 108> Compound 108, shown below, was synthesized according to the reaction equation below and the method described later.

[0632] [ka]

[0633] Under 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-necked flask, and the mixture was cooled to 0°C. Next, 40.2 g of methanesulfonyl chloride (351 mmol) was added dropwise over 30 minutes, taking care to maintain the internal temperature between 0 and 5°C. After the addition was complete, the mixture was stirred for 30 minutes at a temperature of 5°C. After the reaction was complete, 500 mL of pure water was added and the mixture was stirred for 30 minutes. The organic layer was separated and added to 500 mL of 10% hydrochloric acid cooled in an ice bath, and the mixture was stirred. The organic layer was then separated again and added to 500 mL of saturated sodium bicarbonate aqueous solution, and the mixture was stirred. The organic layer was separated again and washed with 500 mL of saturated brine. The organic layer was dried with sodium sulfate and filtered, then concentrated using a rotary evaporator and vacuum-dried at an ambient temperature of 40°C for 2 hours, yielding 70.4 g of compound 108 (97% yield).

[0634] <Synthesis of Compound 109> Compound 109, shown below, was synthesized according to the reaction equation below and the method described later.

[0635] [ka]

[0636] Under a nitrogen atmosphere, 1 L of anhydrous diethyl ether was added to a 5 L four-necked flask, and the internal temperature was brought to 0°C. Next, 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 anhydrous diethyl ether, and this solution was added dropwise to the previously prepared solution over 30 minutes. During this time, the internal temperature was kept within the range of 0-5°C. After the dropwise addition was complete, the mixture was stirred at room temperature for 3 hours. After the reaction was complete, the internal temperature was cooled again to 0°C, and 2 L of saturated potassium sodium tartrate aqueous solution was added dropwise over 2 hours, taking care to avoid hydrogen generation, and then the mixture was stirred at room temperature for another 2 hours. The mixture was separated into an organic layer and an aqueous layer, and the recovered aqueous layer was extracted four times with 400 mL of diethyl ether. The collected organic layer was separated and washed with 1 L of saturated saline solution. The organic layer was dried with sodium sulfate and filtered, and then concentrated at atmospheric pressure at an external temperature of 50°C. After concentration, the mixture was distilled under reduced pressure at an ambient temperature of 60°C and 10 mmHg. The components distilled at 40°C were collected, yielding 37 g of compound 109 (90% yield, colorless, transparent liquid).

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

[0638] [ka]

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

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

[0641] [ka]

[0642] Under a nitrogen atmosphere, 3.0 g of compound 110 (17.8 mmol) was added to a three-necked flask, followed by 10 mL of anhydrous pyridine, and the mixture was stirred. 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 heated to room temperature and stirred overnight. The mixture was cooled again in an ice bath, and 3 mL of methanol was added to quench it. Then, water and ethyl acetate were added, and the mixture was transferred to a separatory funnel. The mixture was washed in the order of water, saturated ammonium chloride aqueous solution, and saturated saline solution, and the organic layer was dried over magnesium sulfate and concentrated using a rotary evaporator. The resulting 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). 1 The H-NMR data is shown below.

[0643] 1 ¹H 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 (overlaps with CHCl3 signal, m, 4H), 7.46 (t, J = 7.6 Hz, 2H), 7.84–7.87 (m, 4H). The melting temperature of the obtained compound 111 was 97°C.

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

[0645] [ka]

[0646] Under a nitrogen atmosphere, 33.3 g (0.25 mol) of aluminum chloride and 1.5 L of anhydrous toluene were added to a 5 L four-necked flask and stirred at room temperature. 41 g (0.50 mol) of 2-cyclopenten-1-one was dissolved in 1 L of anhydrous toluene, then added to the previously prepared reaction mixture and stirred at room temperature for 40 minutes. Next, 240.4 g (3.0 mol) 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 complete, the mixture was cooled using an ice bath, 2 L of 1 N hydrochloric acid was added, and the mixture was stirred at room temperature for 30 minutes. The mixture was separated into an organic layer and an aqueous layer, and the recovered aqueous layer was extracted twice with 500 mL of toluene. The collected organic layer was separated and washed once with 1 L of saturated brine and once with 1 L of saturated sodium bicarbonate aqueous solution. The organic layer was dried with sodium sulfate, filtered, and then concentrated using a rotary evaporator. The crude product obtained was purified by silica gel column chromatography (hexane:ethyl acetate = 20:1) to obtain 36 g of compound 112, an isomer mixture (yield 44%).

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

[0648] [ka]

[0649] Under 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-necked flask and stirred. Next, 170 mg (0.66 mmol) of osmium oxide was added and the mixture was heated and stirred at an internal temperature of 40 °C for 40 hours. After the reaction was complete, 2.7 g of sodium hydrosulfite, 33 g of Florizil, 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 with 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 with 1 N sulfuric acid to a pH of 3. The excess sodium chloride and 600 mL of ethyl acetate were added and stirred, and the undissolved sodium chloride was filtered off by vacuum filtration. The mixture was separated into an organic layer and an aqueous layer by liquid-liquid extraction. The recovered aqueous layer was extracted three times with 600 mL of ethyl acetate. The organic layer was collected, dried with 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 washing 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 later.

[0651] [ka]

[0652] Under a nitrogen atmosphere, 4.0 g of compound 113 (20.4 mmol) was added to a 100 mL three-necked flask, followed by the addition of 10 mL of anhydrous pyridine, and the mixture was stirred. 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 heated 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 mixture. Then, water and ethyl acetate were added to separate the aqueous and organic layers, and the organic layer was washed once each with saturated ammonium chloride aqueous solution, saturated sodium bicarbonate aqueous solution, and saturated brine. The organic layer was dried over magnesium sulfate and filtered off, and the organic layer was 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). 1 The H-NMR data is shown below.

[0653] 1 ¹H NMR (270 MHz, CDCl3, TMS as internal standard): δ 1.48–1.55 (overlaps with H2O signal, 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 (overlaps with CHCl3 signal, m, 4H), 7.41–7.52 (m, 2H), 7.79–7.92 (m, 4H). The melting temperature of the obtained compound 114 was 122°C.

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

[0655] [ka]

[0656] Under 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-necked 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 previously prepared reaction solution. After the addition was complete, the mixture was stirred at the same temperature for 1 hour, and then saturated sodium pyrosulfite aqueous solution 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 approximately 7-8, and the resulting white precipitate was filtered off. 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 crude product (2.51 g) containing compound 115 was used in the following step, <synthesis of compound 116>, without further purification.

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

[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-necked flask, followed by the addition of 10 mL of anhydrous 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 heated 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 and organic layers, and the organic layer was washed twice with saturated ammonium chloride aqueous solution. The organic layer was dried over sodium sulfate and filtered off, and then concentrated using a rotary evaporator. The crude product was purified by two silica gel column chromatography cycles (1st cycle: hexane:ethyl acetate = 10:1, 2nd cycle: hexane:ethyl acetate = 20:1) to obtain 3.03 g of compound 116 (colorless transparent liquid). 1 The H-NMR data is shown below.

[0660] 1 ¹H NMR (270 MHz, CDCl3, TMS as internal standard): δ 1.50–1.61 (overlaps with H₂O signal, 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 purging a 1L glass container with nitrogen, 85.8g of anhydrous magnesium chloride, 321g of decane, and 352g of 2-ethylhexyl alcohol were added and heated at 130°C for 3 hours to obtain a homogeneous solution. 241g of this solution and 6.43g of ethyl benzoate were added to the glass container and stirred at 50°C for 1 hour. After the homogeneous solution thus obtained was cooled to room temperature, 38.3mL of this homogeneous solution was added dropwise to 100mL of titanium tetrachloride, which was kept at -20°C, over 45 minutes with stirring at 350rpm. After the addition was complete, the temperature of this mixture was raised to 80°C over 3.8 hours, and at 80°C, 0.97g of compound 6 was added to the mixture. The temperature was then raised again to 120°C over 40 minutes and held at the same temperature with stirring for 35 minutes. After the reaction was complete, the solid portion was collected by thermal filtration, resuspended in 100 mL of titanium tetrachloride, and then heated again at 120°C for 35 minutes. After the reaction was complete, the solid portion was again collected by thermal filtration and thoroughly washed with decane at 100°C and decane at 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, and a portion of it was dried to investigate 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] <This polymerization> In a 2 L polymerizer, 500 g of propylene and 1 NL of hydrogen were added at room temperature. Then, a mixture of 7 mL of heptane, 0.5 mmol of triethylaluminum, 0.08 mmol of cyclohexylmethyldimethoxysilane, and 0.004 mmol (in terms of titanium atoms) of solid titanium catalyst component [α1] was added and mixed at 25°C for 10 minutes. The temperature inside the polymerizer was then rapidly raised to 70°C. Polymerization was carried out at 70°C for 1.5 hours, after which the reaction was stopped with a small amount of methanol and the propylene was purged. The resulting polymer particles were then dried under reduced pressure at 80°C overnight. The polymerization results are as follows.

[0662] Activity: 48.6kg-PP / g-catalyst Bulk density: 490 kg / m³ 3 MFR (ASTM 1238E standard, 230°C, 2.16 kg load): 0.57 g / 10 min Decane-insoluble component content: 1.87 wt% Tm: 163.92℃ Tmf: 172.08℃ Mw / Mn: 10.64 Mz / Mw: 4.85 The method for measuring the above physical properties is as follows.

[0663] (1) Bulk density: Measurements were taken in accordance with JIS K-6721. (2) Melt Flow Rate (MFR): In accordance with ASTM D1238E, the measurement temperature was set to 230°C for propylene polymers.

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

[0665] Decane soluble component content = 100 × (500 × a) / (100 × b) Decane-insoluble component content = 100 - 100 × (500 × a) / (100 × b) (4)Molecular weight distribution: Gel Chromatograph: Tosoh Corporation HLC-8321 GPC / HT type Detector: Differential refractometer Column: Two TSKgel GMH6-HT 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℃ Calibration curve preparation method: Using standard polystyrene samples Sample concentration: 0.1% (w / w) Sample solution volume: 0.4 mL Measurements were taken under the specified conditions, and the resulting chromatograms were analyzed using known methods to calculate the weight-average molecular weight (Mw), number-average molecular weight (Mn), Z-average molecular weight (Mz), and Mw / Mn and Mz / Mw values, which are indicators of molecular weight distribution (MWD). The measurement time per sample was 60 minutes.

[0667] (5) Melting point (Tm) of the polymer: The melting point (Tm), crystallization temperature (Tc), and heat of fusion (ΔH) of the polymer in this invention were measured using a differential scanning calorimeter (DSC) with a Seiko Instruments DSC220C instrument. 3-10 mg of the 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, then cooled to 30°C at 10°C / min. The peak temperature in this cooling test was defined 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 defined as the melting point (Tm), and the amount of heat released was defined as the heat of fusion (ΔH).

[0668] The final melting point (Tmf) of the polymer in this invention was measured using a differential scanning calorimeter (DSC) with a Seiko Instruments DSC220C instrument. 3-10 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, 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 to 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 a parameter for evaluating the ease of crystallization and crystal structure of polymers in the ultra-high molecular weight region, which are generally considered difficult to crystallize. More specifically, the higher the value of Tmf, the more likely the ultra-high molecular weight polymer component is to form strong, heat-resistant crystals.

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

[0671] [ka]

[0672] [In (Compound 201), the thick line represents the near side of the page, and the dotted line represents the far side of the page. Compound 201 corresponds to the diol compound derived from the endo form shown in formula (34) above.]

[0673] [ka]

[0674] [In compound 202, the thick line represents the near side of the page, and compound 202 corresponds to the diol compound derived from the exo form shown in formula (34) above.] A mechanical stirrer was attached to a 2-liter flask, and the inside was purged with nitrogen. In the flask, olefin ((Equation (33), R 4 , R 9 , R 31 ~R 34 25.4 grams of a compound (where 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. In another 1 L beaker, 30 grams of potassium permanganate, 600 ml of water, and 6.60 grams of sodium hydroxide were added to prepare an alkaline potassium permanganate solution. A dropping funnel was fitted to the 2 L flask, and the prepared alkaline potassium permanganate solution was poured into the dropping funnel. The alkaline potassium permanganate solution was slowly added dropwise so that the internal temperature did not exceed 5°C. After the addition was complete, the mixture was stirred at 0°C for 1 hour. A saturated sodium pyrosulfite solution was prepared in another flask and slowly added dropwise to the reaction mixture until a white precipitate was formed. After addition, the temperature was raised to room temperature to precipitate the white solid. After collecting the supernatant organic layer, the aqueous layer was extracted twice with ethyl acetate. The organic layers were added together, washed with water and saturated brine, and dried over magnesium sulfate. The organic layers were then concentrated to obtain 27.41 grams of crude product. The crude product was purified by silica gel column chromatography to obtain 22.71 grams of the target product (isomer mixture). The isomers were separated by further purification of the product by silica gel column chromatography, isolating 10.9 grams of compound 201 and 2.9 grams of compound 202. 1 The H-NMR data is shown below.

[0675] (Compound 201) 1¹H 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, 3 H), 3.21–3.32 (m, 1 H), 3.58–3.76 (m, 2 H), 7.06–7.36 (m, 4 H). (Compound 202) 1 ¹H 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, 1 H), 3.06 (d, J = 7.9, 1 H), 3.28 (dd, J = 17.4, 10.5 Hz, 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 using the method described later.

[0676] [ka]

[0677] The inside of a 200 ml flask was purged with nitrogen, 5 g of compound 201 was added, followed by 30 ml of anhydrous pyridine. 5.69 ml of benzoyl chloride was slowly added dropwise while cooling in an ice bath. After addition, the temperature was raised to room temperature and stirred overnight. The mixture was cooled again in an ice bath and quenched with methanol. Chloroform and water were added and stirred, after which the organic layer was separated. The organic layer was washed with saturated ammonium chloride aqueous solution and saturated brine, and then dried over magnesium sulfate. The organic layer was then concentrated to obtain 10.61 g of crude product. Purification by silica gel column chromatography yielded 6.83 g of compound 203. 1 The H-NMR data is shown below.

[0678] (Compound 203) 1 ¹H 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, 1 H), 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 temperature of compound 203 was 108.7°C.

[0679] <Synthesis of Compound 204> Compound 204, shown below, was synthesized using the method described later.

[0680] [ka]

[0681] In the synthesis of compound 203, 3.85 grams of compound 204 (yield 89%) was obtained by following the procedures and stoichiometric relationships described in the synthesis of compound 203, except that 2.2 grams of compound 202 were used instead of compound 201. 1 The H-NMR data is shown below.

[0682] (Compound 204) 1 ¹H 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 temperature of compound 204 was 168.2°C.

[0683] [Example B2] <Preparation of solid titanium catalyst component [α1]> After thoroughly purging a 1L glass container with nitrogen, 85.8g of anhydrous magnesium chloride, 321g of decane, and 352g of 2-ethylhexyl alcohol were added and heated at 130°C for 3 hours to obtain a homogeneous solution. 241g of this solution and 6.43g of ethyl benzoate were added to the glass container and stirred at 50°C for 1 hour. After the homogeneous solution thus obtained was cooled to room temperature, 38.3ml of this homogeneous solution was added dropwise to 100ml of titanium tetrachloride, which was kept at -20°C, over 45 minutes with stirring at 350rpm. After the addition was complete, the temperature of this mixture was raised to 80°C over 3.8 hours, and at 80°C, 0.91g of compound 203 was added to the mixture. The temperature was raised again to 120°C over 40 minutes and held at the same temperature with stirring for 35 minutes. After the reaction was complete, the solid portion was collected by thermal filtration, and this solid portion was resuspended in 100 ml of titanium tetrachloride. The reaction was then carried out again at 120°C for 35 minutes. After the reaction was complete, the solid portion was again collected by thermal filtration and thoroughly washed with decane at 100°C and decane at 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] <This polymerization> In a 2-liter pressure polymerizer, 500 g of propylene and 1 NL of hydrogen were added at room temperature. Then, a mixture of 7 ml of heptane, 0.5 mmol of triethylaluminum, 0.08 mmol of cyclohexylmethyldimethoxysilane, and 0.004 mmol (in terms of titanium atoms) of solid titanium catalyst component [α1] was added and mixed at 25°C for 10 minutes. The polymerizer was then rapidly heated to 70°C. Polymerization was carried out at 70°C for 1.5 hours, after which the reaction was stopped with a small amount of methanol and the propylene was purged. The resulting polymer particles were then dried under reduced pressure at 80°C overnight. The polymerization results are as follows.

[0685] Activity: 72.7kg-PP / g-catalyst Bulk density: 490 kg / m³ 3 MFR (ASTM 1238e standard, 230°C, 2.16 kg load): 0.45 g / 10 min Decane-insoluble component content: 0.49 wt% Tm: 165.39℃ Tmf: 172.33℃ Mw / Mn: 11.25 Mz / Mw: 4.41 The method for measuring the above physical properties is as described in Example A54.

[0686] [Example B3] <Synthesis of Compound 205> Compound 205, shown below, was synthesized using the method described later.

[0687] [ka]

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

[0689] (Compound 205) 1¹H NMR (270 MHz, CDCl3, TMS as internal standard): endo isomer: 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 isomer: 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 temperature of compound 205 was 116.0°C.

[0690] [Example B4] <Synthesis of Compound 206> Compound 206, shown below, was synthesized using the method described later.

[0691] [ka]

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

[0693] (Compound 206) 1 ¹H NMR (270 MHz, CDCl3, TMS as internal standard): endo isomer: 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 isomer: 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 considered to be the melting points 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 using the method described later.

[0695] [ka]

[0696] In the synthesis of compound 205, 3.80 grams (2.1 equivalents) of 2-floyl chloride were used instead of 3-methylbenzoyl chloride, but the procedure and equivalent relationships described in the synthesis of compound 205 were followed to obtain 5.40 grams (yield 94%) of compound 207 (endo:exo = 86:14), which is a mixture of endo and exo isomers.1 The H-NMR data is shown below.

[0697] (Compound 207) 1 ¹H NMR (270 MHz, CDCl3, TMS as internal standard): endo isomer: 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 isomer: 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 considered 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 using the method described later.

[0699] [ka]

[0700] In the synthesis of compound 205, except that 4.27 grams (2.1 equivalents) of 2-tenoyl chloride were used instead of 3-methylbenzoyl chloride, the procedure and equivalent relationships described in the synthesis of compound 205 were followed to obtain 5.72 grams (94% yield) of compound 208 (endo:exo = 86:14), which is a mixture of endo and exo isomers. 1 The H-NMR data is shown below.

[0701] (Compound 208) 1 ¹H NMR (270 MHz, CDCl3, TMS as internal standard): endo isomer: 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 isomer: 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 considered to be the melting points 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 using the method described later.

[0703] [ka]

[0704] In the synthesis of compound 205, 5.77 grams (88% yield) of compound 209 (endo:exo = 88:12), a mixture of endo and exo isomers, was obtained, except that 5.0 grams (2.1 equivalents) of 1-naphthoyl chloride were used instead of 3-methylbenzoyl chloride in the synthesis of compound 205, following the same procedures and equivalent relationships as described in the synthesis of compound 205. The obtained compound 209 was... 1 The H-NMR data is shown below.

[0705] (Compound 209) 1 ¹H NMR (270 MHz, CDCl3, TMS as internal standard): endo isomer: 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 isomer: 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 temperature of compound 209 was 149.8°C.

[0706] [Example B8] <Synthesis of Compound 210> Compound 210, shown below, was synthesized using the method described later.

[0707] [ka]

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

[0709] (Compound 210) 1 1H 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 temperature of compound 210 was 173.8°C.

[0710] [Example B9] <Synthesis of Compound 211> Compound 211, shown below, was synthesized using the method described later.

[0711] [ka]

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

[0713] (Compound 211) 1 ¹H NMR (270 MHz, CDCl3, TMS as internal standard): endo isomer: 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 isomer: 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 temperature of compound 211 was 124.3°C.

[0714] [Example B10] <Synthesis of Compound 212> Compound 212, shown below, was synthesized using the method described later.

[0715] [ka]

[0716] In the synthesis of compound 205, except that 5.75 grams (2.7 equivalents) of phenylacetyl chloride were used instead of 3-methylbenzoyl chloride, the procedure and equivalent relationships described in the synthesis of compound 205 were followed to obtain compound 212 (endo:exo = 78:22), a mixture of endo and exo isomers, as a colorless, transparent liquid of 1.32 grams (21% yield). 1 The H-NMR data is shown below.

[0717] (Compound 212) 1 ¹H NMR (270 MHz, CDCl3, TMS as internal standard): endo isomer: 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 isomer: 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 using the method described later.

[0718] [ka]

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

[0720] (Compound 213) 1 ¹H NMR (270 MHz, CDCl3, TMS as internal standard): endo isomer: 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 isomer: 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 temperature of compound 213 was 127.7°C.

[0721] [Example B12] <Synthesis of Compound 214> Compound 214, shown below, was synthesized using the method described later.

[0722] [ka]

[0723] The inside of a 100 ml flask was purged with nitrogen, and 5.95 grams (1 equivalent) of 3-phenylbenzoic acid was added, followed by 60 ml of dichloromethane and 2 drops of dimethylformamide. While cooling in an ice bath, 3.09 ml (1.2 equivalents) of oxalyl chloride was slowly added dropwise. After addition, the temperature was raised to room temperature and the mixture was stirred for 2 hours. Volatile compounds in the reaction system were removed by reducing the pressure to obtain compound 214. No further purification was performed, and it was used in the synthesis of compound 215.

[0724] <Synthesis of Compound 215> Compound 215, shown below, was synthesized using the method described later.

[0725] [ka]

[0726] <Synthesis of Compound 214> To a 100 ml flask containing the entire amount (2.2 equivalents) of compound 214 synthesized in <Synthesis of Compound 214>, 3 ml of anhydrous pyridine was added under a nitrogen atmosphere. While cooling in an ice bath, 2.92 grams (1 equivalent) of a mixture of compounds 201 and 202 in 10 ml of dichloromethane solution was slowly added. After dropwise addition, the temperature was raised 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 saturated ammonium chloride aqueous solution and saturated brine, and then dried over magnesium sulfate. The organic layer was then concentrated to obtain 9.87 grams of crude product. Purification by silica gel column chromatography yielded 6.82 grams (yield 88%) of compound 215 (endo:exo = 88:12), which is a mixture of endo and exo isomers. 1 The H-NMR data is shown below.

[0727] (Compound 215) 1¹H NMR (270 MHz, CDCl3, TMS as internal standard): endo isomer: 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 isomer: 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 starting from 62.5°C.

[0728] [Example B13] <Synthesis of Compound 216> Compound 216, shown below, was synthesized using the method described later.

[0729] [ka]

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

[0731] (Compound 216) 1 ¹H NMR (270 MHz, CDCl3, TMS as internal standard): endo isomer: 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 isomer: 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 temperature of compound 216 was 139.4°C.

[0732] [Example B14] <Synthesis of Compound 217> Compound 217, shown below, was synthesized using the method described later.

[0733] [ka]

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

[0735] (Compound 217) 1 1H 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 temperature of compound 217 was 208.2°C.

[0736] [Example B15] <Synthesis of Compound 218> Compound 218, shown below, was synthesized using the method described later.

[0737] [ka]

[0738] Compound 218 was synthesized following the procedures and equivalent relationships described in the synthesis of Compound 214, except that 4.63 grams (1 equivalent) of 3,4-dimethylbenzoic acid was used instead of 3-phenylbenzoic acid in the synthesis of Compound 214. The obtained Compound 218 was then used directly in the synthesis of Compound 219.

[0739] <Synthesis of Compound 219> Compound 219, shown below, was synthesized using the method described later.

[0740] [ka]

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

[0742] (Compound 219) 1¹H NMR (270 MHz, CDCl3, TMS as internal standard): endo form: 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 temperature of compound 219 was 131.1°C.

[0743] [Example B16] <Synthesis of Compound 220> Compound 220, shown below, was synthesized using the method described later.

[0744] [ka]

[0745] Compound 220 was synthesized following the procedures and equivalent relationships described in the synthesis of Compound 214, except that 4.85 grams (1 equivalent) of 5,6,7,8-tetrahydro-2-naphthoic acid was used instead of 3-phenylbenzoic acid in the synthesis of Compound 214. The obtained Compound 220 was used directly in the synthesis of Compound 221.

[0746] <Synthesis of Compound 221> Compound 221, shown below, was synthesized using the method described later.

[0747] [ka]

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

[0749] (Compound 221) 1 ¹H NMR (270 MHz, CDCl3, TMS as internal standard): endo isomer: 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 isomer: 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 temperature of compound 221 was 151.2°C.

[0750] [Example B17] <Synthesis of Compound 222> Compound 222, shown below, was synthesized using the method described later.

[0751] [ka]

[0752] Compound 222 was synthesized following the procedures and equivalent relationships described in the synthesis of compound 214, except that 5.0 grams (1 equivalent) of 4-methoxy-3-methylbenzoic acid was used instead of 3-phenylbenzoic acid in the synthesis of compound 214. The obtained compound 222 was used directly in the synthesis of compound 223.

[0753] <Synthesis of Compound 223> Compound 223, shown below, was synthesized using the method described later.

[0754] [ka]

[0755] In the synthesis of compound 219, compound 222 (2.2 equivalents) was used instead of compound 218, but the procedure and equivalent relationships described in the synthesis of compound 219 were followed, and 2.10 grams (33% yield) of compound 223, consisting only of the endo isomer, were obtained. 1 The H-NMR data is shown below.

[0756] (Compound 223) 1¹H 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 temperature of compound 223 was 187.1°C. [Industrial applicability]

[0757] The novel ester compounds according to the present invention are useful for resin additives, cosmetics and topical skin preparations, antibacterial compositions, antioxidants, chelating agents, and the production of Ziegler-Natta catalysts. In particular, they can be used as catalytic components for Ziegler-Natta catalysts, enabling the production of catalysts that provide excellent stereoregularity and productivity when polypropylene is polymerized, making them extremely valuable industrially.

Claims

1. An ester compound represented by the following general formula (1). 【Chemistry 1】 〔In formula (1), R 1 ~R 24 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group or a heteroatom-containing hydrocarbon group. R 1 ~R 10 , R 23 and R 24 may be bonded to each other to form a ring, or may form a multiple bond in which adjacent substituents are directly bonded. R 11 ~R 24 may be bonded to each other to form a ring, or may form a multiple bond in which adjacent substituents are bonded to each other. R 1 ~R 24 at least one pair of which are bonded to each other to form a ring structure. n2 to n5 each independently represent an integer between 0 and 2. n1 and n6 each independently represent an integer of 0 or 1. 1 and L 2 These are, independently, hydrocarbon groups or heteroatom-containing hydrocarbon groups.

2. L 1 and L 2 The ester compound according to claim 1, wherein each is independently a hydrocarbon group having 1 to 20 carbon atoms or a heteroatom-containing hydrocarbon group.

3. L 1 and L 2 The ester compound according to claim 1, wherein each of them is independently 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 of the following general formulas (2) to (4). 【Chemistry 2】 [In formulas (2) to (4), R 1 ~R 24 Each of these 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 These substituents may bond to each other to form a ring, or adjacent substituents may form a multiple bond through direct bonding. 11 ~R 24 The substituents may bond to each other to form a ring, or adjacent substituents may bond 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. n2 to n5 each independently represent an integer from 0 to 2. n1 and n6 each independently represent an integer of 0 or 1. L 1 and L 2 Each of these is independently a hydrocarbon group having four 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). 【Transformation 3】 [In formula (5), R 1 and R 2 Each is independently a hydrogen atom or a hydrocarbon group, and R 4 and R 9 Each of these is independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group, and R 11 , R 15 , R 17 and R 21 Each of these 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 They may bond to each other to form a ring. X is a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. L 1 and L 2 Each of these is independently a hydrocarbon group having four or more carbon atoms or a heteroatom-containing hydrocarbon group. 【Chemistry 4】 [In formula (6), R 1 and R 2 Each is independently a hydrogen atom or a hydrocarbon group, and R 4 , R 9 , R 11 , R 12 , R 15 ~R 18 , R 21 and R 22 Each of these 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 The substituents may bond to each other to form a ring, or adjacent substituents may bond to each other to form a multiple bond. X is a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. L 1 and L 2 Each of these is independently a hydrocarbon group having four 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). 【Transformation 5】 [In formula (7), R 4 , R 9 , R 12 , R 15 ~R 18 and R 21 Each of these is independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 15 ~R 18 The substituents may bond to each other to form a ring, or adjacent substituents may bond to each other to form a multiple bond. Y is a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. L 1 and L 2 Each of these is independently a hydrocarbon group having four or more carbon atoms or a heteroatom-containing hydrocarbon group. 【Transformation 6】 [In formula (8), R 1 and R 2 Each is independently a hydrogen atom or a hydrocarbon group, and R 3 , R 4 , R 9 , R 10 , R 12 , R 15 ~R 18 and R 21 Each of these is independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 15 ~R 18 The substituents may bond to each other to form a ring, or adjacent substituents may bond to each other to form a multiple bond. Y is a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group. L 1 and L 2 Each of these is independently a hydrocarbon group having four 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). 【Transformation 7】 〔In formula (9), R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group, and R 4 , R 9 , R 12 , R 15 to R 18 and R 21 are each independently a hydrogen atom, a hydrocarbon group or a heteroatom-containing hydrocarbon group. R 15 to 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. L 1 and L 2 are each independently a hydrocarbon group or a heteroatom-containing hydrocarbon group having 4 or more carbon atoms.〕

9. The ester compound according to claim 1, represented by the following general formula (31). 【Transformation 8】 [In formula (31), R 31 ~R 34 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or a heteroatom-containing hydrocarbon group, and R 4 , R 9 , R 21 and R 22 are each independently a hydrogen atom, a hydrocarbon group or a heteroatom-containing hydrocarbon group, and R 4 , R 9 , R 21 , R 22 , and R 31 ~R 34 may be bonded to each other to form a ring. L 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 selected divalent groups from the following general formula group (10). 【Chemistry 9】 [In group (10), R 1' ~R 7' Each of these is independently a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group, and R 2' ~R 7' These substituents may bond to each other to form a ring, or adjacent substituents may directly bond 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 the groups shown in the following general formula group (11). 【Chemistry 10】 [In group (11), R 1' ~R 5' Each of these is 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, and R 2' ~R 5' These substituents may bond to each other to form a ring, or adjacent substituents may directly bond to each other to form a multiple bond.

12. The ester compound according to claim 9, wherein X is a divalent group shown in the following general formula (13). 【Chemistry 11】 [In formula (13), R 2' and R 3' Each of these is 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, and R 2' and R 3' They may be joined to each other to form a ring.

13. R 1' ~R 7' The ester compound according to claim 10, wherein each is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

14. R 1' ~R 5' The ester compound according to claim 11, wherein each is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

15. R 2' and R 3' The ester compound according to claim 12, wherein each is independently 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 atoms are hydrogen atoms.

17. R 1 ~R 24 The ester compound according to any one of claims 1 to 16, wherein each is 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 The ester compound according to any one of claims 1 to 16, wherein each is 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 The ester compound according to claim 9, wherein each is independently 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 The ester compound according to claim 9, wherein each is 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 All are hydrogen atoms, R 4 , R 9 , R 21 and R 22 However, each is independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a hydrocarbon group containing a heteroatom having 1 to 6 carbon atoms, L 1 and L 2 The ester compound according to claim 9, wherein each is 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 All are hydrogen atoms, R 4 and R 9 However, each is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, L 1 and L 2 The ester compound according to claim 9, wherein each is 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 All are hydrogen atoms, R 3 ~R 22 The ester compound according to any one of claims 1 to 8, wherein each is independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.

25. L 1 and L 2 The ester compound according to any one of claims 1 to 8, wherein each is independently a hydrocarbon group having 4 to 20 carbon atoms or a heteroatom-containing hydrocarbon group.

26. L 1 and L 2 The ester compound according to any one of claims 1 to 8, wherein each is independently a hydrocarbon group having 4 to 10 carbon atoms or a heteroatom-containing hydrocarbon group.

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

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

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