Diamondoid compound and method for producing same

Abstract

This diamondoid compound is a new compound represented by general formula (1) [in the formula, ring A1 represents an aliphatic ring having two or more rings, R1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group, and n represents an integer of 0-3].

Description

Diamondoid compounds and methods for producing the same

[0001] The present invention relates to diamondoid compounds and methods for producing the same.

[0002] Adamantane is a cage-shaped compound in which 10 carbon atoms are arranged in the same manner as the diamond structure, and is therefore called the smallest diamondoid compound. In this way, diamondoid compounds in which carbon atoms are arranged in the same manner as the diamond structure include not only adamantane, but also higher diamondoid compounds such as diamantane, triamantane, and tetraamantane, which are formed by extending the carbon skeleton of adamantane, and it is known that very small amounts are isolated from crude oil (see, for example, Non-Patent Document 1).

[0003] These higher diamondoid compounds are diamonds that are even smaller than nanodiamonds, and are known to have high melting points, negative electron affinities, and different band gaps and reactivities depending on their structure.

[0004] Although intensive research has been conducted over the past 20 years and various functionalizations have been achieved, the precise synthesis of novel high-order diamond compounds has not been reported.

[0005] Science 2003, 299, 96.

[0006] The main method for obtaining diamondoid compounds is isolation from crude oil. Although diamondoid compounds such as adamantane and diamantane are commercially available, it has been difficult to obtain higher diamondoid compounds such as triamantane and tetramantane. Furthermore, there has been no method for synthesizing diamondoid compounds with structures other than those already isolated, which has hindered the development of the chemistry and applications of diamondoid compounds.

[0007] The present invention has been made in view of the above-mentioned problems, and has as its object to synthesize a novel diamondoid compound.

[0008] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that various diamondoid compounds can be synthesized by condensing an adamantane compound with an aromatic compound and then hydrogenating the condensed product in the presence of a specific catalyst. Based on this finding, the present inventors have further intensively researched and completed the present invention. The present invention includes the following features.

[0009] Item 1. General formula (1):

[0010]

[0011] [In the formula, ring A １ represents an aliphatic ring having two or more rings. １ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group, and n represents an integer of 0 to 3.

[0012] Item 2. General formula (1A):

[0013]

[0014] [In the formula, ring A ２ and Ring A ３ are the same or different and represent an aliphatic ring. １ａ , R １ｂ and R １ｃ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group. ２ａ and R ３ａ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ２ａ and R ３ａ may be taken together to form an aliphatic ring.], or general formula (1B):

[0015]

[0016] [In the formula, ring A ４ and Ring A ５ are the same or different and represent an aliphatic ring. １ａ , R １ｂ and R １ｃ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group.４ａ and R ５ａ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ４ａ and R ５ａ may be taken together to form an aliphatic ring.] The diamondoid compound according to Item 1,

[0017] Item 3. General formula (1A1):

[0018]

[0019] [In the formula, R ２ａ , R ２ｂ , R ２ｃ , R ２ｄ , R ３ａ , R ３ｂ , R ３ｃ and R ３ｄ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ２ａ and R ２ｂ , R ２ｂ and R ２ｃ , R ２ｃ and R ２ｄ , R ３ａ and R ３ｂ , R ３ｂ and R ３ｃ , R ３ｃ and R ３ｄ , and R ２ａ and R ３ａ may be joined together at least at one position to form an aliphatic ring.], or a group represented by general formula (1B1):

[0020]

[0021] [In the formula, R １ and n are the same as above. ４ａ , R ４ｂ , R ４ｃ , R ５ａ , R ５ｂ and R ５ｃ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ４ａ and R ４ｂ, R ４ｂ and R ４ｃ , R ５ａ and R ５ｂ , R ５ｂ and R ５ｃ , and R ４ａ and R ５ａ may be joined together at least one position to form an aliphatic ring.]. The diamondoid compound according to Item 1 or 2,

[0022] Item 4. General formula (1A'):

[0023]

[0024] [In the formula, ring A ２ and Ring A ３ are the same or different and represent an aliphatic ring. １ａ , R １ｂ , R １ｃ , R １ｄ , R １ｅ and R １ｆ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group.], or a group represented by general formula (1B'):

[0025]

[0026] [In the formula, ring A ４ and Ring A ５ are the same or different and represent an aliphatic ring. １ａ , R １ｂ , R １ｃ , R １ｄ , R １ｅ and R １ｆ and are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group.

[0027] Item 5. General formula (1A'1):

[0028]

[0029] [In the formula, R ２ｂ , R ２ｃ , R ２ｄ , R ３ｂ , R ３ｃ and R ３ｄare the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ２ｂ and R ２ｃ , R ２ｃ and R ２ｄ , R ３ｂ and R ３ｃ , and R ３ｃ and R ３ｄ may be joined together at least at one position to form an aliphatic ring.], or a group represented by general formula (1B'1):

[0030]

[0031] [In the formula, R ４ｂ , R ４ｃ , R ５ｂ and R ５ｃ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ４ｂ and R ４ｃ , and R ５ｂ and R ５ｃ may be joined together at least at one position to form an aliphatic ring.]. The diamondoid compound according to any one of Items 1 to 4,

[0032] Item 6. A method for producing the diamondoid compound according to any one of Items 1 to 5, comprising: (II) a compound of general formula (2):

[0033]

[0034] [In the formula, R １ and n is the same as above. １ ' is the ring A １ and hydrogenating an adamantane-fused aromatic compound represented by the following formula (1): in the presence of a catalyst, wherein the catalyst contains a catalyst containing rhodium and platinum, and a catalyst containing scandium.

[0035] Item 7. The production method according to Item 6, wherein the Lewis acid catalyst is a Lewis acid catalyst having an element of Group 3, Group 13, or Group 14 of the periodic table as an active center.

[0036] Item 8. The production method according to Item 6 or 7, wherein step (II) is carried out in the presence of an organic solvent.

[0037] Item 9. The production method according to Item 8, wherein the organic solvent is an alkane.

[0038] Item 10. The adamantane-fused aromatic compound is represented by (IA) general formula (4):

[0039]

[0040] [In the formula, ring A １ ' is the ring A １ and Ring A １ ' indicates the aromatic ring corresponding to X. １ represents a halogen atom.] is reacted with a nucleophilic agent, and then a compound represented by the general formula (5A) or (5B):

[0041]

[0042] [In the formula, R １ and n is the same as above.] to react with an adamantanone compound represented by the general formula (6):

[0043]

[0044] [In the formula, A １ ", R １ and n is as defined above.] and (IB) a step of reacting the adamantane-containing arene compound obtained in step (IA) with a Brønsted acid and / or a Lewis acid.

[0045] Item 11. The production method according to Item 10, wherein the nucleophilic agent is an organolithium compound and / or an organomagnesium compound.

[0046] Item 12. The aromatic compound represented by the general formula (4) is represented by the general formula (4A):

[0047]

[0048] [In the formula, X １ is the same as above. ２’ and Ring A３’ are the same or different and each represents an aromatic ring. ２ａ and R ３ａ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ２ａ and R ３ａ may be taken together to form an aromatic ring.], or a compound represented by general formula (4B):

[0049]

[0050] [In the formula, ring A ４ and Ring A ５ are the same or different and each represents an aromatic ring. ２ represents a halogen atom. ４ａ and R ５ａ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ４ａ and R ５ａ may be taken together to form an aromatic ring.

[0051] According to the present invention, a variety of novel diamondoid compounds can be precisely synthesized.

[0052] In this specification, the term "containing" is a concept that encompasses all of "comprise," "consist essentially of," and "consist only of."

[0053] In addition, in this specification, when a numerical range is expressed as "A to B," it means A or more and B or less.

[0054] 1. Diamondoid Compound The diamondoid compound of the present invention has the general formula (1):

[0055]

[0056] [In the formula, ring A １ represents an aliphatic ring having two or more rings. １represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group, and n represents an integer of 0 to 3.

[0057] R １ The alkyl group represented by the formula (I) is not particularly limited, and either a linear alkyl group or a branched alkyl group can be employed. Examples of the alkyl group include alkyl groups having 1 to 6 carbon atoms (particularly 1 to 4 carbon atoms), such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

[0058] These alkyl groups may also have a substituent. Examples of the substituent that the alkyl group may have include a hydroxyl group, an alkoxy group described below, a cycloalkyl group described below, an amino group described below, and an adamantyl group. When the alkyl group has a substituent, the number of the substituents can be, for example, 1 to 6, and particularly 1 to 3.

[0059] R １ The cycloalkyl group represented by the formula (I) is not particularly limited, and examples thereof include cycloalkyl groups having 3 to 10 carbon atoms (particularly 4 to 8 carbon atoms), such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group.

[0060] These cycloalkyl groups may have a substituent. Examples of the substituent that the cycloalkyl group may have include a hydroxyl group, the alkyl groups described above, the alkoxy groups described below, the amino groups described below, and an adamantyl group. When the cycloalkyl group has a substituent, the number of the substituents may be, for example, 1 to 6, and particularly 1 to 3.

[0061] R １ The adamantyl group represented by the following formula is not particularly limited, and examples thereof include a 1-adamantyl group and a 2-adamantyl group.

[0062] These adamantyl groups may have a substituent. Examples of the substituent that the adamantyl group may have include a hydroxyl group, the alkyl group described above, the alkoxy group described below, the cycloalkyl group described above, the amino group described below, and the adamantyl group described above. When the adamantyl group has a substituent, the number of the substituents can be, for example, 1 to 6, and particularly 1 to 3.

[0063] In addition, R １ The number of R is not particularly limited and can be, for example, an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1. １ When R １ When there are three, the adamantane ring moiety is represented by the general formula (7):

[0064]

[0065] [In the formula, R １ａ , R １ｂ and R １ｃ and may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group.]

[0066] In general formula (7), R １ａ , R １ｂ and R １ｃ The alkyl group, cycloalkyl group and adamantyl group represented by the formula (I) can be those mentioned above. The same applies to the type and number of the substituents.

[0067] Also, ring A １ is not particularly limited as long as it is an aliphatic ring having two or more rings, and various aliphatic rings can be used. As the aliphatic ring, either an aliphatic hydrocarbon ring or a heteroaliphatic ring can be used, and it can be a ring formed by combining two or more (for example, 2 to 1000 rings, particularly 2 to 100 rings) of cycloalkane rings (cyclohexane rings), adamantane rings, heteroaliphatic rings (piperidine rings, tetrahydropyran rings, pyrrolidine rings, tetrahydrofuran rings, tetrahydrothiophene rings, etc.), etc., such as

[0068]

[0069]

[0070] etc.

[0071] The above-mentioned ring A １ may have a substituent. １ Examples of the substituent that may be possessed by Ring A include a hydroxyl group, the alkyl group described above, the alkoxy group described below, the cycloalkyl group described above, the amino group described below, and an adamantyl group. １ When has a substituent, the number of the substituents can be, for example, 1 to 6, particularly 1 to 3.

[0072] From the above, the diamondoid compound of the present invention is １ The general formula (1A):

[0073]

[0074] [In the formula, ring A ２ and Ring A ３ are the same or different and represent an aliphatic ring. １ａ , R １ｂ and R １ｃ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group. ２ａ and R ３ａ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ２ａ and R ３ａ may be taken together to form an aliphatic ring.], or general formula (1B):

[0075]

[0076] [In the formula, ring A ４ and Ring A ５ are the same or different and represent an aliphatic ring. １ａ , R １ｂ and R １ｃ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group. ４ａ and R ５ａare the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ４ａ and R ５ａ may be taken together to form an aliphatic ring.

[0077] In general formulas (1A) and (1B), R １ａ , R １ｂ and R １ｃ The alkyl group, cycloalkyl group and adamantyl group represented by the formula (I) can be those mentioned above. The same applies to the type and number of the substituents.

[0078] In general formula (1A), R ２ａ and R ３ａ The alkyl group, cycloalkyl group and adamantyl group represented by the formula (I) can be those mentioned above. The same applies to the type and number of the substituents.

[0079] In general formula (1A), R ２ａ and R ３ａ The alkoxy group represented by the formula (I) is not particularly limited, and examples thereof include alkoxy groups having 1 to 6 carbon atoms (particularly 1 to 4 carbon atoms), such as a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy group.

[0080] These alkyl groups may have a substituent. Examples of the substituent that the alkoxy group may have include a hydroxyl group, the above-mentioned alkyl groups, the above-mentioned alkoxy groups, the above-mentioned cycloalkyl groups, the amino group described below, and an adamantyl group. When the alkoxy group has a substituent, the number of the substituents may be, for example, 1 to 6, and particularly 1 to 3.

[0081] In general formula (1A), R ２ａ and R ３ａThe amino group represented by the formula (I) may have a substituent. Examples of the substituent that the amino group may have include a hydroxyl group, the alkyl group described above, the alkoxy group described above, the cycloalkyl group described above, and an adamantyl group. When the amino group has a substituent, the number of the substituents can be, for example, 1 to 6, and particularly 1 to 3.

[0082] In general formula (1B), R ４ａ and R ５ａ The alkyl group, alkoxy group, cycloalkyl group, amino group and adamantyl group represented by the formula (I) can be those mentioned above. The same applies to the type and number of the substituents.

[0083] In general formula (1A), ring A ２ and Ring A ３ The aliphatic ring represented by the formula (I) is not particularly limited, and any of an aliphatic hydrocarbon ring and a heteroaliphatic ring can be used. The aliphatic ring can be a ring using a single ring or two or more rings (for example, 1 to 1000 rings, particularly 1 to 100 rings) of a cycloalkane ring (cyclohexane ring), an adamantane ring, a heteroaliphatic ring (piperidine ring, tetrahydropyran ring, pyrrolidine ring, tetrahydrofuran ring, etc.), etc., and examples thereof include

[0084]

[0085]

[0086] etc.

[0087] The above-mentioned ring A ２ and Ring A ３ The aliphatic ring represented by the formula (I) may have a substituent. ２ and Ring A ３ Examples of the substituent that the aliphatic ring represented by the following formula may have include a hydroxyl group, a halogen atom as described below, the alkyl group as described above, the alkoxy group as described above, the cycloalkyl group as described above, the amino group as described above, and the adamantyl group as described above. １ When has a substituent, the number of the substituents can be, for example, 1 to 6, particularly 1 to 3.

[0088] In general formula (1B), ring A ４ and Ring A５ The aliphatic ring represented by the formula: ２ and Ring A ３ The same applies to the type and number of substituents.

[0089] In general formula (1A), R ２ａ and R ３ａ can be joined together to form an aliphatic ring. In this case, the aliphatic ring formed is ２ and Ring A ３ The same applies to the type and number of substituents.

[0090] In addition, in the general formula (1B), R ４ａ and R ５ａ can be joined together to form an aliphatic ring. In this case, the aliphatic ring formed is ２ and Ring A ３ The same applies to the type and number of substituents.

[0091] From the above, the diamondoid compound of the present invention is a compound represented by the general formula (1A) ２ and Ring A ３ and ring A in general formula (1B) ４ and Ring A ５ are both cyclohexane rings, the general formula (1A1):

[0092]

[0093] [In the formula, R ２ａ , R ２ｂ , R ２ｃ , R ２ｄ , R ３ａ , R ３ｂ , R ３ｃ and R ３ｄ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ２ａ and R ２ｂ , R ２ｂ and R ２ｃ , R ２ｃ and R ２ｄ , R ３ａand R ３ｂ , R ３ｂ and R ３ｃ , R ３ｃ and R ３ｄ , and R ２ａ and R ３ａ may be joined together at least at one position to form an aliphatic ring.], or a group represented by general formula (1B1):

[0094]

[0095] [In the formula, R ４ａ , R ４ｂ , R ４ｃ , R ５ａ , R ５ｂ and R ５ｃ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ４ａ and R ４ｂ , R ４ｂ and R ４ｃ , R ５ａ and R ５ｂ , R ５ｂ and R ５ｃ , and R ４ａ and R ５ａ may be joined together at least at one position to form an aliphatic ring.

[0096] In general formula (1A1), R ２ａ , R ２ｂ , R ２ｃ , R ２ｄ , R ３ａ , R ３ｂ , R ３ｃ and R ３ｄ The alkyl group, alkoxy group, cycloalkyl group, amino group and adamantyl group represented by the formula (I) can be those mentioned above. The same applies to the type and number of the substituents.

[0097] In general formula (1B1), R ４ａ , R ４ｂ , R ４ｃ , R ５ａ , R ５ｂ and R ５ｃThe alkyl group, alkoxy group, cycloalkyl group, amino group and adamantyl group represented by the formula (I) can be those mentioned above. The same applies to the type and number of the substituents.

[0098] In general formula (1A1), R ２ａ and R ２ｂ , R ２ｂ and R ２ｃ , R ２ｃ and R ２ｄ , R ３ａ and R ３ｂ , R ３ｂ and R ３ｃ , R ３ｃ and R ３ｄ , and R ２ａ and R ３ａ may be joined together at least at one position to form an aliphatic ring. ２ and Ring A ３ The same applies to the type and number of substituents.

[0099] In addition, in the general formula (1B1), R ４ａ and R ４ｂ , R ４ｂ and R ４ｃ , R ５ａ and R ５ｂ , R ５ｂ and R ５ｃ , and R ４ａ and R ５ａ may be joined together at least at one position to form an aliphatic ring. ２ and Ring A ３ The same applies to the type and number of substituents.

[0100] Also, ring A １ In the case where the adamantane ring is condensed into an aliphatic ring, the diamondoid compound of the present invention can be said to be a compound having two or more adamantane rings. In this case, the diamondoid compound of the present invention can be, for example, a compound represented by the general formula (1A'):

[0101]

[0102] [In the formula, ring A ２ and Ring A ３ are the same or different and represent an aliphatic ring. １ａ , R １ｂ , R １ｃ , R １ｄ , R １ｅ and R １ｆ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group.], or a group represented by general formula (1B'):

[0103]

[0104] [In the formula, ring A ４ and Ring A ５ are the same or different and represent an aliphatic ring. １ａ , R １ｂ , R １ｃ , R １ｄ , R １ｅ and R １ｆ and may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group.

[0105] In general formula (1A'), R １ａ , R １ｂ , R １ｃ , R １ｄ , R １ｅ and R １ｆ The alkyl group, cycloalkyl group and adamantyl group represented by the formula (I) can be those mentioned above. The same applies to the type and number of the substituents.

[0106] In general formula (1B'), R １ａ , R １ｂ , R １ｃ , R １ｄ , R １ｅ and R １ｆ The alkyl group, cycloalkyl group and adamantyl group represented by the formula (I) can be those mentioned above. The same applies to the type and number of the substituents.

[0107] In the general formula (1A'), ring A ２ and Ring A ３The aliphatic ring represented by the formula (1A) includes ring A ２ and Ring A ３ The same applies to the type and number of substituents.

[0108] In the general formula (1B'), ring A ４ and Ring A ５ The aliphatic ring represented by the formula (1A) includes ring A ２ and Ring A ３ The same applies to the type and number of substituents.

[0109] Also, ring A １ is an aliphatic ring to which an adamantane ring is fused, and ２ and Ring A ３ and ring A in general formula (1B) ４ and Ring A ５ are all cyclohexane rings, the diamondoid compound of the present invention can be said to be a compound in which two or more adamantane rings are condensed to a structure in which at least four aliphatic rings are condensed. In this case, the diamondoid compound of the present invention has a general formula (1A'1):

[0110]

[0111] [In the formula, R ２ｂ , R ２ｃ , R ２ｄ , R ３ｂ , R ３ｃ and R ３ｄ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ２ｂ and R ２ｃ , R ２ｃ and R ２ｄ , R ３ｂ and R ３ｃ , and R ３ｃ and R ３ｄ may be joined together at least at one position to form an aliphatic ring.], or a group represented by general formula (1B'1):

[0112]

[0113] [In the formula, R ４ｂ , R ４ｃ , R ５ｂ and R ５ｃ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ４ｂ and R ４ｃ , and R ５ｂ and R ５ｃ may be joined together at least at one position to form an aliphatic ring.

[0114] In general formula (1A'1), R ２ｂ , R ２ｃ , R ２ｄ , R ３ｂ , R ３ｃ and R ３ｄ The alkyl group, alkoxy group, cycloalkyl group, amino group and adamantyl group represented by the formula (I) can be those mentioned above. The same applies to the type and number of the substituents.

[0115] In general formula (1B'1), R ４ｂ , R ４ｃ , R ５ｂ and R ５ｃ The alkyl group, alkoxy group, cycloalkyl group, amino group and adamantyl group represented by the formula (I) can be those mentioned above. The same applies to the type and number of the substituents.

[0116] In general formula (1A'1), R ２ｂ and R ２ｃ , R ２ｃ and R ２ｄ , R ３ｂ and R ３ｃ , and R ３ｃ and R ３ｄ may be joined together at least at one position to form an aliphatic ring. ２ and Ring A ３ The same applies to the type and number of substituents.

[0117] In addition, in the general formula (1B'1), R ４ｂ and R ４ｃ , and R ５ｂ and R ５ｃ may be joined together at least at one position to form an aliphatic ring. ２ and Ring A ３ The same applies to the type and number of substituents.

[0118] Specifically, the diamondoid compound of the present invention that satisfies the above conditions is

[0119]

[0120]

[0121]

[0122] etc.

[0123] These diamondoid compounds of the present invention can be used in applications generally used for nanodiamonds and known diamondoid compounds, such as electron emission materials, power semiconductors, organic electronics, and biologically active substances that take advantage of their low toxicity and novel structure.Specifically, they can be used for applications such as photoresist materials for fine semiconductors, thermally conductive materials (thermally conductive nanowires, etc.), thermally conductive films, power semiconductor devices, diamond synthesis seed materials, diamond semiconductors, industrial diamonds, physiologically active substances, drug discovery, and highly flexible materials.

[0124] 2. Method for Producing Diamondoid Compound The diamondoid compound of the present invention can be produced, for example, by the method represented by the following general formula (II):

[0125]

[0126] [In the formula, R １ and n is the same as above. １ ' is the ring A １and (b) hydrogenating an adamantane-fused aromatic compound represented by the formula (I) in the presence of a catalyst. The catalyst used in this process contains a catalyst containing rhodium and platinum, and a catalyst containing scandium.

[0127] (2-1) Adamantane-fused aromatic compound In the general formula (1), R １ and n can be as explained above. In other words, the structure of the adamantane ring moiety in the adamantane-fused aromatic compound can be the same as the structure of the adamantane ring moiety in the diamondoid compound of the present invention.

[0128] In addition, in the general formula (1), ring A １ ' is the ring A １ The aromatic ring corresponding to

[0129] That is, ring A １’ is not particularly limited as long as it is an aromatic ring having two or more rings, and various aromatic rings can be used. The aromatic ring can be a ring formed by combining two or more (for example, 2 to 1000, particularly 2 to 100) aromatic hydrocarbon rings (such as a benzene ring) and heteroaromatic rings (such as a pyridine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, etc.). １’ may be a structure consisting of only the aromatic rings described above, or may be a ring formed by combining a total of two or more (e.g., 2 to 1000, particularly 2 to 100) of the aromatic rings and the aliphatic rings described above.

[0130] That is, ring A １’ For example,

[0131]

[0132]

[0133] etc.

[0134] The above-mentioned ring A １’ may have a substituent. １’Examples of the substituent that may be possessed by Ring A include the above-mentioned halogen atoms, the above-mentioned alkyl groups, the above-mentioned cycloalkyl groups, and the above-mentioned adamantyl groups. １’ When has a substituent, the number of the substituents can be, for example, 1 to 6, particularly 1 to 3.

[0135] Therefore, the adamantane-fused aromatic compound has ring A １’ The general formula (2A):

[0136]

[0137] [In the formula, R １ａ , R １ｂ and R １ｃ is the same as above. ２’ and Ring A ３’ are each the ring A ２ and Ring A ３ or general formula (2B):

[0138]

[0139] [In the formula, R １ａ , R １ｂ and R １ｃ is the same as above. ４’ and Ring A ５’ are each the ring A ４ and Ring A ５ The aromatic ring represented by the formula (I) is a ring having a structure represented by the formula (I).

[0140] In general formula (2A), ring A ２’ and Ring A ３’ The aromatic ring represented by the formula (I) is not particularly limited, and may be a ring using one or more (for example, 1 to 1000, particularly 1 to 100) aromatic hydrocarbon rings (such as a benzene ring) and heteroaromatic rings (such as a pyridine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, etc.). ２’ and Ring A ３’may be a structure consisting of only the aromatic rings described above, or may be a ring formed by combining a total of two or more (e.g., 2 to 1000, particularly 2 to 100) of the aromatic rings and the aliphatic rings described above.

[0141] Ring A ２’ and Ring A ３’ Examples of the aromatic ring represented by the formula:

[0142]

[0143]

[0144] etc.

[0145] The above-mentioned ring A ２’ and Ring A ３’ The aromatic ring represented by the formula may have a substituent. ２’ and Ring A ３’ Examples of the substituent that the aromatic ring represented by the following formula may have include the above-mentioned halogen atoms, the above-mentioned alkyl groups, the above-mentioned cycloalkyl groups, and the above-mentioned adamantyl groups. ２’ and Ring A ３’ When has a substituent, the number of the substituents can be, for example, 1 to 6, particularly 1 to 3.

[0146] In general formula (2B), ring A ４’ and Ring A ５’ The aromatic ring represented by the formula: ２’ and Ring A ３’ The same applies to the type and number of substituents.

[0147] The adamantane-fused aromatic compound is also a compound represented by the general formula (2A), ２’ and Ring A ３’ and ring A in general formula (2B). ４’ and Ring A ５’ are both benzene rings, the general formula (2A1):

[0148]

[0149] [In the formula, R ２ａ , R ２ｂ , R ２ｃ , R２ｄ , R ３ａ , R ３ｂ , R ３ｃ and R ３ｄ is the same as above.], or a compound represented by general formula (2B1):

[0150]

[0151] [In the formula, R ４ａ , R ４ｂ , R ４ｃ , R ５ａ , R ５ｂ and R ５ｃ is the same as above.]

[0152] Also, ring A １’ In the case where the adamantane ring is fused to an aromatic ring, the adamantane ring-fused aromatic compound can be said to be a compound having two or more adamantane rings. In this case, the adamantane ring-fused aromatic compound can be, for example, a compound represented by the general formula (2A'):

[0153]

[0154] [In the formula, ring A ２’ , ring A ３’ , R １ａ , R １ｂ , R １ｃ , R １ｄ , R １ｅ and R １ｆ is the same as above.], or a compound represented by general formula (2B'):

[0155]

[0156] [In the formula, ring A ４’ , ring A ５’ , R １ａ , R １ｂ , R １ｃ , R １ｄ , R １ｅ and R １ｆ is the same as above.]

[0157] Also, ring A １’ is an aromatic ring to which an adamantane ring is condensed, and ring A in general formula (2A) ２’ and Ring A ３’and ring A in general formula (2B). ４’ and Ring A ５’ are all benzene rings, the adamantane-fused aromatic compound can be said to be a compound in which two or more adamantane rings are fused to a structure in which at least four rings are fused. In this case, the adamantane-fused aromatic compound is represented by the general formula (2A'1):

[0158]

[0159] [In the formula, R ２ｂ , R ２ｃ , R ２ｄ , R ３ｂ , R ３ｃ and R ３ｄ is the same as above.], or a compound represented by general formula (2B'1):

[0160]

[0161] [In the formula, R ４ｂ , R ４ｃ , R ５ｂ and R ５ｃ is the same as above.]

[0162] Specific examples of adamantane-fused aromatic compounds that satisfy the above conditions include:

[0163]

[0164]

[0165]

[0166] etc.

[0167] The method for producing such an adamantane-fused aromatic compound will be described in detail later.

[0168] (2-2) Catalyst In the present invention, the catalyst used in step (II) contains a catalyst containing rhodium and platinum, and a Lewis acid catalyst.

[0169] Catalyst containing rhodium and platinum In the catalyst containing rhodium and platinum, the molar ratio of rhodium to platinum is not particularly limited, but from the viewpoints of reaction conversion, yield, selectivity, etc., the platinum content is preferably 0.10 to 2.00 mol, more preferably 0.15 to 1.00 mol, and even more preferably 0.20 to 0.50 mol per mol of rhodium.

[0170] The catalyst containing rhodium and platinum is not particularly limited as long as it contains rhodium and platinum, but it is preferable that the rhodium and platinum are supported on a carrier.

[0171] Such a carrier is not particularly limited, but is preferably a carrier containing polysilane and alumina (composite carrier) from the viewpoint of reaction conversion rate, yield, selectivity, etc.

[0172] The polysilane is not particularly limited, and examples thereof include polydialkylsilanes such as polydimethylsilane and polydiethylsilane; and polyalkylarylsilanes such as polymethylphenylsilane and polyethylphenylsilane, and known or commercially available products can be used.

[0173] There are no particular limitations on the alumina, and known or commercially available products can be used.

[0174] When rhodium and platinum are supported on a carrier, the supported amounts are not particularly limited, and for example, the supported amount of rhodium is preferably 0.04 to 5.00 mmol / g (particularly 0.05 to 2.00 mmol / g) and the supported amount of platinum is preferably 0.005 to 0.05 mmol / g (particularly 0.01 to 0.04 mmol / g).

[0175] Such a catalyst containing rhodium and platinum can be a known or commercially available product, or can be synthesized by the method described in J. Am. Chem. Soc. 2018, 140, 11325-11334.

[0176] The amount of the catalyst containing rhodium and platinum used is not particularly limited, but from the viewpoints of the conversion rate, yield, selectivity, and the like of the reaction, the amount is preferably 0.05 to 1 mol, more preferably 0.06 to 0.5 mol, even more preferably 0.07 to 0.3 mol, and particularly preferably 0.08 to 2 mol, relative to 1 mol of the adamantane-fused aromatic compound as the raw material.

[0177] Lewis Acid Catalyst In the present invention, the use of both a catalyst containing rhodium and platinum and a Lewis acid catalyst can synergistically improve catalytic activity.

[0178] The Lewis acid catalyst used in the present invention is not particularly limited, but from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, it is preferable that the Lewis acid catalyst has an element of Group 3, 13, or 14 of the periodic table as its active center.

[0179] Examples of elements of Group 3, 13 or 14 of the periodic table include scandium (Sc), zinc (Zn), yttrium (Y), indium (In), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), etc. Among these, rare earth elements (elements of Group 3 of the periodic table) are preferred, and scandium is more preferred.

[0180] Furthermore, the catalytic activity of the Lewis acid can be enhanced by employing a strong electron-withdrawing group. Examples of the electron-withdrawing group used for this purpose include a trifluoromethanesulfonyl group (hereinafter sometimes referred to as an "OTf group"), a methanesulfonyl group, various substituted benzenesulfonyl groups, and a trifluoroacetyl group.

[0181] Specific examples of Lewis acid catalysts that can be used in the present invention include scandium(III) trifluoromethanesulfonate, zinc(II) trifluoromethanesulfonate, indium(III) trifluoromethanesulfonate, and ytterbium(III) trifluoromethanesulfonate, with scandium(III) trifluoromethanesulfonate, indium(III) trifluoromethanesulfonate, and ytterbium(III) trifluoromethanesulfonate being preferred, scandium(III) trifluoromethanesulfonate and ytterbium(III) trifluoromethanesulfonate being more preferred, and scandium(III) trifluoromethanesulfonate being even more preferred. These Lewis acid catalysts can be used alone or in combination of two or more.

[0182] The amount of the Lewis acid catalyst used is not particularly limited, but from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, it is preferably 0.05 to 1 mol, more preferably 0.06 to 0.5 mol, still more preferably 0.07 to 0.3 mol, and particularly preferably 0.08 to 2 mol, relative to 1 mol of the adamantane-fused aromatic compound as the raw material.

[0183] (2-3) Solvent In the present invention, step (II) can usually be carried out in an organic solvent.

[0184] The organic solvent that can be used is not particularly limited, but from the viewpoint of the conversion rate, yield, selectivity, etc. of the reaction, alkanes are preferred, and specific examples include hexane, heptane, octane, etc. These organic solvents can be used alone or in combination of two or more kinds.

[0185] The amount of these organic solvents used is not particularly limited, and can be the amount of the solvent.

[0186] (2-4) Hydrogenation In the present invention, in the step (II), the adamantane-fused aromatic compound can usually be hydrogenated by bringing a hydrogen-containing gas such as hydrogen gas into contact with the adamantane-fused aromatic compound.

[0187] Specifically, the atmosphere in the system can be a hydrogen-containing gas atmosphere such as hydrogen gas. In this case, the pressure of the hydrogen-containing gas atmosphere such as hydrogen gas is not particularly limited, but is preferably 0.1 to 10 MPa, more preferably 0.2 to 5 MPa, and even more preferably 0.3 to 2 MPa, from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction.

[0188] (2-5) Other Conditions This reaction can be carried out usually at 80 to 200° C., preferably 100 to 150° C. This reaction can be carried out usually for 1 to 200 hours, preferably 10 to 150 hours, more preferably 50 to 100 hours.

[0189] After the completion of this reaction, if necessary, the diamondoid compound of the present invention can be obtained by purifying it by a conventional method.Specifically, for example, an organic solvent (ethyl acetate or the like) is added to the reaction mixture to dissolve the organic substance in the organic layer, and then the metal catalyst is adsorbed by silica gel and purified by gel filtration chromatography.

[0190] 3. Method for Producing Adamantane-Fused Aromatic Compound The adamantane-fused aromatic compound used as a raw material in the above step (II) is, for example, a compound represented by the following formula: (IA) General Formula (4):

[0191]

[0192] [In the formula, ring A １” is the ring A １ and Ring A １ ' indicates the aromatic ring corresponding to X. １ represents a halogen atom.] is reacted with a nucleophilic agent, and then a compound represented by the general formula (5A) or (5B):

[0193]

[0194] [In the formula, R １ and n is the same as above.] to react with an adamantanone compound represented by the general formula (6):

[0195]

[0196] [In the formula, A １ ", R １and n is as defined above.], and (IB) a step of reacting the adamantane-containing arene compound obtained in step (IA) with a Bronsted acid and / or a Lewis acid.

[0197] (3-1) Step (IA) Aromatic Compound (General Formula (4)) In the general formula (4), X １ Examples of the halogen atom represented by the formula (I) include a chlorine atom, a bromine atom, and an iodine atom.

[0198] In addition, in the general formula (4), ring A １” is the ring A １ and Ring A １ ' indicates the aromatic ring corresponding to

[0199] That is, ring A １” is not particularly limited as long as it is an aromatic ring having two or more rings, and various aromatic rings can be used. The aromatic ring can be a ring formed by combining two or more (for example, 2 to 1000, particularly 2 to 100) aromatic hydrocarbon rings (such as a benzene ring) and heteroaromatic rings (such as a pyridine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, etc.). １” may be a structure consisting of only the aromatic rings described above, or may be a ring formed by combining a total of two or more (e.g., 2 to 1000, particularly 2 to 100) of the aromatic rings and the aliphatic rings described above.

[0200] That is, ring A １” For example,

[0201]

[0202]

[0203]

[0204]

[0205] etc.

[0206] The above-mentioned ring A １”may have a substituent. １” Examples of the substituent that may be possessed by Ring A include the above-mentioned halogen atoms, the above-mentioned alkyl groups, the above-mentioned cycloalkyl groups, the above-mentioned adamantyl groups, and adamantanonyl groups. １” When has a substituent, the number of the substituents can be, for example, 1 to 6, particularly 1 to 3.

[0207] From the above, the aromatic compounds used as raw materials are specifically as follows:

[0208]

[0209]

[0210]

[0211]

[0212] etc.

[0213] As the aromatic compounds used as raw materials, known or commercially available products can be used.

[0214] The nucleophilic agent is not particularly limited, and any nucleophilic agent that can induce the Friedel-Crafts reaction can be used. Among them, organolithium compounds, organomagnesium compounds, etc. are preferred from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction.

[0215] The organolithium compound is not particularly limited, and known compounds can be used, including alkyllithiums such as methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, and n-hexyllithium; cycloalkyllithiums such as cyclohexyllithium; and aryllithiums such as phenyllithium. These organolithium compounds can be used alone or in combination of two or more. Of these, in this step, alkyllithiums are preferred, and n-butyllithium is more preferred, from the viewpoints of reaction conversion, yield, selectivity, and the like.

[0216] Examples of the organic magnesium compound include alkyl magnesium halides such as methyl magnesium chloride, methyl magnesium bromide, n-butyl magnesium chloride, n-butyl magnesium bromide, n-hexyl magnesium chloride, and n-hexyl magnesium bromide; phenyl magnesium chloride, phenyl magnesium bromide, 4-n-butylphenyl magnesium chloride, and 4-n-butylphenyl magnesium bromide.

[0217] These nucleophiles can be used alone or in combination of two or more.

[0218] The amount of the nucleophilic agent used is not particularly limited, but is preferably 0.2 to 5.0 mol, more preferably 0.3 to 3.0 mol, and even more preferably 0.5 to 2.0 mol per mol of the aromatic compound as the raw material, from the viewpoints of the reaction conversion rate, yield, selectivity, etc. When multiple nucleophilic agents are used, it is preferable to adjust the total amount thereof to be within the above range.

[0219] Adamantanone Compound (General Formula (5A) or (5B)) Specific examples of the usable adamantanone compound include:

[0220]

[0221] etc.

[0222] The amount of the adamantanone compound used is not particularly limited, but from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, it is preferably 0.2 to 5.0 mol, more preferably 0.3 to 3.0 mol, and even more preferably 0.5 to 2.0 mol relative to 1 mol of the aromatic compound as a raw material.

[0223] Solvent In the present invention, step (IA) can usually be carried out in an organic solvent.

[0224] The organic solvent that can be used is not particularly limited, but from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, hydrocarbons, ethers, etc. are preferred. Examples of hydrocarbons include aliphatic saturated hydrocarbons such as pentane, hexane, heptane, etc.; and aromatic hydrocarbons such as benzene, etc. Examples of ethers include 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, etc. Among these, from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, ethers are preferred, and tetrahydrofuran is more preferred. These organic solvents can be used alone or in combination of two or more.

[0225] The amount of these organic solvents used is not particularly limited, and can be the amount of the solvent.

[0226] Other Conditions In this step, the reaction between the aromatic compound as a raw material and the nucleophile can be carried out usually at −120 to −30° C., preferably −100 to −50° C., and the subsequent reaction with the adamantanone compound can be carried out usually at 0 to 70° C., preferably 10 to 50° C. Furthermore, in this step, the reaction between the aromatic compound as a raw material and the nucleophile can be carried out usually for 1 minute to 10 hours, preferably 5 minutes to 5 hours, and more preferably 10 minutes to 3 hours, and the subsequent reaction with the adamantanone compound can be carried out usually for 1 to 100 hours, preferably 2 to 50 hours, and more preferably 5 to 30 hours.

[0227] After completion of this step, the adamantane-containing arene compound can be obtained by purification by a conventional method, if necessary. Specifically, for example, an organic solvent (e.g., ethyl acetate) is added to the reaction mixture to dissolve the organic compound in the organic layer, and then the metal compound is adsorbed onto silica gel and purified by gel filtration chromatography.

[0228] (3-2) Step (IB) Adamantane-containing arene compound (general formula (6)) The adamantane-containing arene compound is a compound obtained by the above-mentioned general formula (IA), specifically,

[0229]

[0230]

[0231]

[0232]

[0233] etc.

[0234] Brønsted Acid and / or Lewis Acid The Brønsted acid and / or Lewis acid is not particularly limited, and various acids can be used, for example, inorganic acids such as sulfuric acid, nitric acid, phosphoric acid, polyphosphoric acid, hydrogen fluoride (HF), hydrofluoric acid, hydrochloric acid, hydrogen bromide, hydrogen iodide, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, perbromic acid, and periodic acid; sulfonic acids such as fluorosulfonic acid, chlorosulfonic acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, difluoromethanesulfonic acid, trichloromethanesulfonic acid, perfluorobutanesulfonic acid, perfluorooctane sulfonic acid, benzenesulfonic acid, toluenesulfonic acid, and nitrobenzenesulfonic acid; mono- or polycarboxylic acids such as formic acid, acetic acid, propionic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, glycolic acid, lactic acid, benzoic acid, oxalic acid, and succinic acid; ３ , B.F. ３ , BCl ３ , B(OCH ３ ) ３ , AlCl ３ , AlBr ３ , SbF ３ , SbCl ３ , SbF ５ , P.F. ３ , P.F. ５ , AsF ３ , AsCl ３ , AsF ５ , TiCl ４ , NbF ５ , TaF ５ Lewis acids such as HBF ４ , HPF ６ , HAsF ６ , HSbF ６ , HSbCl ６and acids composed of Lewis acids such as Brønsted acids and hydrogen halides. These acids can be used alone or in combination of two or more. Among them, from the viewpoint of reaction conversion, yield, selectivity, etc., Bronsted acids are preferred, mono- or polycarboxylic acids are more preferred, mono- or polyfluoroacetic acids are even more preferred, and trifluoroacetic acid is particularly preferred. In this specification, the term "acid" refers to a compound that is not an acid according to the Bronsted definition but is an acid according to the Lewis definition.

[0235] The amount of Bronsted acid and / or Lewis acid used is not particularly limited, but from the viewpoints of reaction conversion, yield, selectivity, etc., it is preferably 0.2 to 5.0 mol, more preferably 0.3 to 3.0 mol, and even more preferably 0.5 to 2.0 mol per mol of the starting adamantane-containing arene compound. When the Bronsted acid and / or Lewis acid is liquid, the amount used can be the amount of the solvent. When multiple Bronsted acids and / or Lewis acids are used, it is preferable to adjust their total amount to be within the above range.

[0236] Solvent In the present invention, step (IB) can usually be carried out in an organic solvent.

[0237] The organic solvent that can be used is not particularly limited, but from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, hydrocarbons, halogenated hydrocarbons, ethers, etc. are preferred. Examples of hydrocarbons include aliphatic hydrocarbons such as pentane, hexane, and heptane, and aromatic hydrocarbons such as benzene, toluene, and xylene. Examples of halogenated hydrocarbons include chloroform, dichloroethane, trichloroethane, chlorobenzene, and dichlorobenzene. Examples of ethers include 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether. Among these, from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, halogenated hydrocarbons are preferred, and dichloroethane is more preferred. These organic solvents can be used alone or in combination of two or more.

[0238] The amount of these organic solvents used is not particularly limited, and can be the amount of the solvent.

[0239] Other Conditions This step can be carried out usually at 40 to 100° C., preferably 50 to 90° C. This step can be carried out usually for 5 minutes to 10 hours, preferably 10 minutes to 8 hours, more preferably 30 minutes to 5 hours.

[0240] After completion of this step, the adamantane-fused aromatic compound can be obtained by purification by a conventional method as necessary. Specifically, for example, an organic solvent (e.g., ethyl acetate) is added to the reaction mixture to dissolve the organic substance in the organic layer, and then impurities are adsorbed onto silica gel and purified by gel filtration chromatography.

[0241] The present invention will be specifically explained below by way of examples, but the present invention is not limited thereto.

[0242] Unless otherwise noted, all reagents, including dehydrated solvents, were commercially available and used without purification. Azulene, quinoline-8-boronic acid, 2-bromobiphenyl, 1-iodo-2-bromobenzene, 4-bromo-9,9-dimethyl-9H-fluorene, 4-bromo-9,9-diphenyl-9H-fluorene, 4-bromo-9,9'-spirobifluorene, 4-bromo-9-phenyl-9H-carbazole, 1-bromonaphthalene, 1-bromopyrene, 3-bromofluoranthene, 1,4-dibromonaphthalene, and 2-adamantanone were purchased from Tokyo Chemical Industry Co., Ltd. [IrCl(cod)]2, [Ir(OMe)(cod)]2, Pd(OAc)2, pyrene-1-boronic acid, B2pin2, PtBu3, Cs2CO3, K3PO4, and NOSbF6 were purchased from Sigma-Aldrich Co. LLC. 1,1,2,2-Tetrachloroethane, cyclohexane, and hexane were purchased from Fujifilm Wako Pure Chemical Industries, Ltd. 2,2'-Dibromobiphenyl, 2-bromo-2'-chloro-1,1'-biphenyl, 2-bromo-1,1'-binaphthalene, 3-bromo-4-phenylthiophene, and 3-bromo-2,2'-bithiophene were synthesized according to procedures reported in the literature. All reactions were carried out under N ２Reactions were carried out under a gas atmosphere using flame-dried glassware and dehydrated solvents using standard vacuum line techniques. Toluene, tetrahydrofuran (THF), and diethyl ether (EtO) were purified by passing through a solvent purification system (Glass Contour). All steps and purification procedures were carried out under ambient conditions using reagent-grade solvents. "RT" (room temperature) refers to 25°C. Analytical thin-layer chromatography (TLC) was performed using E. Merck silica gel 60 F254 precoated plates (0.25 mm). Chromatograms were analyzed using a UV lamp (254 nm or 365 nm). Flash column chromatography was performed on a Biotage Isolera equipped with a Kanto Silica Gel 60N (spherical, neutral, 40-100 μm) or a Biotage SNAP Cartridge KP-Sil column. Preparative recycling gel permeation chromatography (GPC) was performed on a JAI LC-9260 II NEXT instrument equipped with a JAIGEL-2HR column using chloroform as the eluent. High-resolution mass spectrometry (HRMS) was acquired on a JEOL JMS-T100TD (Direct Analysis in Real Time, DART), a JEOL JMS-T100GCV (Direct EI), and a Bruker Daltonics compact (ESI). Electron paramagnetic resonance (EPR) spectra were recorded on a JEOL ESR JES TE-200 instrument using an argon-filled quartz Schlenk tube. Nuclear magnetic resonance (NMR) spectra were recorded on a JEOL ECS-600 ( 1 H 600MHz, 13 C 150MHz) spectrometer or JEOL ECS-500 ( 1 H 500MHz, 13 The measurements were recorded using a C 125 MHz spectrometer. 1 H NMR chemical shifts are expressed in parts per million (ppm) relative to CDCl3 (7.26 ppm), CD2Cl2 (5.34 ppm), or tetrachloroethane (TCE)-d2 (5.94 ppm). 13C NMR chemical shifts are expressed in ppm relative to CDCl3 (77.16 ppm), Cl2CDCl2 (73.78 ppm), or CD2Cl2 (53.84 ppm). Data are reported as chemical shift, multiplicity (s = singlet, d = doublet, dd = doublet of doublets, t = triplet, td = triplet of doublets, q = quartet, dq = doublet of quartet, m = multiplet, brs = broad singlet, brd = broad doublet), coupling constant (Hz), and integration.

[0243] Synthesis Example 1

[0244]

[0245] Synthesis of 2-(2-azulenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Compound S1). Azulene (7.8 mmol, 1.00 g), cyclooctadiene iridium chloride dimer ([IrCl(cod)]2) (0.19 mmol, 131 mg, 3 mol%), 2,2'-bipyridyl (0.39 mmol, 60.4 mg, 6 mol%), and bis(pinacolato)diboron (B2pin2) (4.3 mmol, 1.09 g, 0.55 equiv.) were placed in a dry 100 mL two-neck flask. The flask was degassed, and then cyclohexane (50 mL) was added. The reaction mixture was stirred at 80 °C for 29 h. After cooling to room temperature, the reaction mixture was quenched by adding water, and the organic layer was extracted three times with ethyl acetate. The combined organic layers were dried over Na2SO4 and concentrated under vacuum. The crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 100:0 to 80:20) to give 2-(2-azulenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (compound S1) as a blue solid (971 mg, 57%). 1 The 1 H NMR spectrum was consistent with reported data.

[0246] Synthesis of 2-(2-bromophenyl)-azulene (Compound S2) Compound S1 (2.68 mmol, 680 mg), 1-iodo-2-bromobenzene (5.35 mmol, 1.51 g, 2.0 equivalents), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (Pd2(dba)3·CHCl3) (0.26 mmol, 282 mg, 10 mol%), and Cs2CO3 (8.04 mmol, 2.62 g, 3.0 equivalents) were added to a dry 100 mL three-neck flask under open air. The flask was filled with argon, sealed, and placed in a glove box. Tri-tert-butylphosphine (P t To the mixture was added 2-(2-bromophenyl)azulene (compound S2) (0.26 mmol, 54.1 mg, 10 mol%), followed by toluene (15 mL), 1,4-dioxane (5 mL), and HO (5 mL). The reaction mixture was stirred at 100 °C for 19 hours. After cooling to room temperature, the reaction mixture was quenched by adding water, and the organic layer was extracted three times with ethyl acetate. The combined organic layers were dried over NaSO and concentrated in vacuo. The crude product was purified by silica gel column chromatography (eluent: hexane) to obtain 2-(2-bromophenyl)azulene (compound S2) as a blue solid (462 mg, 62%). 1 H NMR (600 MHz, CDCl3) δ8.38 (d, J = 9.6 Hz, 2H), 7.74 (dd, J = 8.4, 1.2 Hz, 1H), 7.65 (s, 2H), 7.57-7.62 (m, 2H), 7.41 (td, J = 6.0, 1.2 Hz, 1H), 7.19-7.23 (m, 3H) 13 HRMS (DART, positive) m / z calcd for C 16 H 12 Br [M+H] +: m / z 283.01169. Found: m / z 283.01170.

[0247] Synthesis Example 2

[0248]

[0249] Synthesis of 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrene (Compound S3). Pyrene (1.0 mmol, 202 mg, 1.0 equiv.), cyclooctadienemethoxyiridium(I) dimer ([Ir(OMe)(cod)]2) (50 μmol, 33.1 mg, 5 mol%), 4,4′-di-tert-butyl-2,2′-bipyridyl (dtbpy, 100 μmol, 26.8 mg, 10 mol%), and bis(pinacolato)diboron (B2pin2) (1.1 mmol, 279 mg, 1.1 equiv.) were added to a dry 100 mL two-neck flask. The flask was degassed, and then cyclohexane (20 mL) was added. The reaction mixture was stirred at 80°C for 16 h. After cooling to room temperature, water was added to the reaction mixture to quench the reaction, and the organic layer was extracted three times with ethyl acetate. The combined organic layers were dried over Na2SO4 and concentrated in vacuo. The crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 100:0 to 80:20) to obtain 4,4,5,5-tetramethyl-2-(2-pyrenyl)-1,3,2-dioxaborolane (compound S3) as a white solid (236 mg, 72%). 1 The 1 H NMR spectrum was consistent with reported data.

[0250] Synthesis of 2-(2-bromophenyl)pyrene (Compound S4) 1-bromo-2-iodobenzene (1.00 mmol, 282 mg, 1.0 equiv.), 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrene (1.0 mmol, 328 mg, 1.0 equiv.), palladium acetate (30 μmol, 8.98 mg, 3 mol%), triphenylphosphine (90 μmol, 31.5 mg, 9 mol%), and K2CO3 (3.00 mmol, 414 mg, 3.0 equiv.) were added to a dry 100 mL three-neck flask. The flask was degassed, followed by the addition of toluene (4.0 mL), ethanol (1.0 mL), and HO (1.0 mL). The reaction mixture was stirred at 80 °C for 15 h. After cooling to room temperature, the reaction mixture was quenched by adding water, and the organic layer was extracted three times with ethyl acetate. The combined organic layers were dried over Na2SO4 and concentrated in vacuo. The crude product was purified by silica gel column chromatography (eluent: hexane / CHCl3 = 100:0 to 90:10) and recrystallized from hot ethanol to give 2-(2-bromophenyl)pyrene (compound S4) as a white solid (279 mg, 78%). 1 H NMR (600 MHz, CDCl3) δ8.20-8.23 (m, 4H), 8.11 (d, J = 1.2 Hz, 4H), 8.03 (t, J = 7.8 Hz, 1H), 7.78 (dd, J = 7.8, 1.2 Hz, 1H), 7.56 (dd, J = 7.2, 1.2 Hz, 1H), 7.46 (td, J = 7.8, 1.2 Hz, 1H), 7.30 (td, J = 7.8, 1.8 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ143.04, 138.93, 133.34, 132.18, 131.39, 131.02, 129.08, 127.96, 127.60, 126.19, 126.02, 125.30, 124.73, 124.09, 123.25. HRMS (DART, positive) m / z calcd for C 22 H 14[M+H] + : m / z 357.02734. Found: m / z 357.02735.

[0251] Synthesis Example 3

[0252]

[0253] Synthesis of 1-(2-bromophenyl)pyrene (Compound S5) 1-Bromo-2-iodobenzene (800 μmol, 226 mg, 1.0 equiv.), pyrene-1-boronic acid (880 μmol, 216 mg, 1.1 equiv.), palladium acetate (Pd(OAc)2) (40 μmol, 8.98 mg, 5 mol%), triphenylphosphine (PPh3) (120 μmol, 31.5 mg, 15 mol%), and Na2CO3 (2.40 mmol, 254 mg, 3.0 equiv.) were added to a 100 mL two-neck flask. After degassing the flask, toluene (8.0 mL) and HO (4.0 mL) were added. The reaction mixture was stirred at 80 °C for 18 h. After cooling to room temperature, the reaction mixture was quenched by adding water, and the organic layer was extracted three times with ethyl acetate. The combined organic layers were dried over NaSO and concentrated in vacuo. The crude product was purified by silica gel column chromatography (eluent: hexane) to give 1-(2-bromophenyl)pyrene (compound S5) as a white solid (228 mg, 80%). 1 The 1 H NMR spectrum was consistent with reported data.

[0254] Synthesis Example 4

[0255]

[0256] Synthesis of 8-(2-bromophenyl)quinoline (Compound S6) To a dry 100 mL two-neck flask were added quinoline-8-boronic acid (960 μmol, 167.1 mg, 1.2 equiv.), 1-bromo-2-iodobenzene (800 μmol, 226.3 mg, 1.0 equiv.), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane adduct (PdCl(dppf)·CHCl) (40 μmol, 32.4 mg, 5 mol%), and NaCO (2.40 mmol, 253.1 mg, 3.0 equiv.). The flask was degassed, followed by the addition of toluene (3.0 mL), ethanol (0.5 mL), and HO (0.5 mL). The reaction mixture was stirred at 80 °C for 18 h. After cooling to room temperature, the reaction mixture was quenched by adding water, and the organic layer was extracted three times with ethyl acetate. The combined organic layers were dried over NaSO and concentrated in vacuo. The crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 100:0 to 95:5) to give 8-(2-bromophenyl)quinoline (compound S6) as a white solid (182 mg, 80%). 1 H NMR (600 MHz, CDCl3) δ8.92 (dd, J = 4.2, 1.8 Hz, 1H), 8.21 (dd, J = 8.4, 1.8 Hz, 1H), 7.90 (dd, J = 7.8, 1.8 Hz, 1H), 7.73 (dd, J = 7.2, 1.2 Hz, 1H), 7.60-7.65 (m, 2H), 7.39-7.44 (m, 3H), 7.28-7.31 (m, 1H). 13 C NMR (150 MHz, CDCl3) δ150.62, 146.43, 141.13, 140.69, 136.25, 132.80, 132.06, 130.80, 129.18, 128.56, 128.36, 127.09, 126.03, 124.47, 121.22. HRMS (DART, positive) m / z calcd for C 15 H 11 BrN [M+H] +: m / z 284.00694. Found: m / z 284.00708.

[0257] Synthesis Example 5

[0258]

[0259] Synthesis of 4-protoadamantanone. A dry 500 mL three-neck flask equipped with a magnetic stir bar was charged with lead(IV) acetate (Pb(OAc)) (60.0 g, 115 mmol, 1.8 equiv.), 1-adamantanol (10.0 g, 65.7 mmol, 1.0 equiv.), iodine (29.2 g, 115 mmol, 1.8 equiv.), and anhydrous benzene (300 mL). The reaction mixture was stirred at 73 °C for 4 h. After cooling to room temperature, the mixture was neutralized with aqueous NaHCO. The organic layer was washed with aqueous NaSO, dried over NaSO, and concentrated in vacuo. The crude product was used without further purification.

[0260] The crude product, methanol (300 mL), and potassium hydroxide (22.1 g, 394 mmol, 6.0 equiv.) were added to a 300 mL round-bottom flask equipped with a magnetic stir bar. The reaction mixture was stirred at 85 °C for 16 h. After cooling to room temperature, the organic layer was extracted five times with diethyl ether, dried over Na2SO4, and concentrated in vacuo. The crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 90:10 to 80:20) to give compound 1 (5.63 g, 57%). 1 The 1 H NMR spectrum was consistent with reported data. 1H NMR (600 MHz, CDCl3) δ2.72-2.76 (m, 1H), 2.61 (q, J = 6.0 Hz, 2H), 2.54 (dd, J = 18.0, 3.0 Hz, 1H), 2.41 (t, J = 3.6 Hz, 1H), 2.23-2.31 (m, 2H), 1.92-1.99 (m, 2H), 1.80 (dd, J =12.0, 2.4 Hz, 1H), 1.67-1.71 (m, 3H), 1.63 (dd, J = 11.4, 2.4 Hz, 1H), 1.53 (dq, J = 13.1, 2.4 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ216.73, 51.25, 45.15, 41.50, 38.26, 37.50, 37.38, 37.28, 49.96 39.26.

[0261] Synthesis Examples 6-1 to 6-17, 6-30, 6-31, 6-34, and 6-36

[0262]

[0263] ｎ BuLi represents n-butyllithium, and THF represents tetrahydrofuran.

[0264] (Step IA) At room temperature (25°C), an aromatic compound (0.3 mmol, 1.0 equivalent) was placed in a dry 50 mL two-neck flask, and after nitrogen substitution, dehydrated tetrahydrofuran (THF; 3 mL) was added. The solution was cooled to -78°C, and then normal butyllithium ( ｎ To the reaction solution, solid 4-protoadamantanone (Compound 1; 0.33 mmol, 1.1 equivalents) was added dropwise at −78° C. in normal hexane, followed by stirring for 1 hour. ２ ​The mixture was added under airflow, warmed to room temperature (25°C), and stirred for 12 hours. The reaction solution was then cooled to 0°C, and methanol was added to terminate the reaction. The resulting reaction solution was then extracted three times with ethyl acetate, and the resulting organic layer was dried over magnesium sulfate, after which the solvent was distilled off under reduced pressure. The resulting crude product was used in the next step without further purification.

[0265] (Step IB) The obtained compound was placed in a dried Schlenk tube at room temperature (25°C), and after nitrogen substitution, 1,2-dichloroethane (1.5 mL) and trifluoroacetic acid (1.5 mL) were added. The mixture was heated to 75°C and stirred for 3 hours, and then saturated aqueous sodium bicarbonate solution was added dropwise at room temperature (25°C) to terminate the reaction. An extraction operation using ethyl acetate was performed three times, and the obtained organic layer was dried over sodium sulfate, followed by distillation of the solvent under reduced pressure. The crude product was purified by silica gel column chromatography (developing solvent: hexane). Subsequently, purification was performed using gel filtration chromatography to obtain the target compound.

[0266] Synthesis Examples 6-18 to 6-29, 6-32, 6-33, and 6-35

[0267]

[0268] (Step IA) At room temperature (25°C), an aromatic compound (0.3 mmol, 1.0 equivalent) was placed in a dry 50 mL two-neck flask, and after nitrogen substitution, dehydrated tetrahydrofuran (THF; 3 mL) was added. The solution was cooled to -78°C, and then normal butyllithium ( ｎ To the reaction solution, solid 4-protoadamantanone (Compound 1; 0.33 mmol, 1.1 equivalents) was added dropwise at −78° C. and stirred for 1 hour. ２The mixture was added under an air stream, and the temperature was raised to room temperature (25°C), followed by stirring for 12 hours. The reaction solution was then cooled to 0°C, and methanol was added to terminate the reaction. The resulting reaction solution was then extracted three times with ethyl acetate, and the resulting organic layer was dried over magnesium sulfate, after which the solvent was distilled off under reduced pressure. The resulting mixture was then subjected to the next step without further purification.

[0269] (Step IB) The obtained crude product was placed in a dried Schlenk tube at room temperature (25°C), and after nitrogen substitution, 1,1,2,2-tetrachloroethane (1.5 mL) and trifluoroacetic acid (1.5 mL) were added. The mixture was heated to 75°C and stirred for 3 hours, and then saturated aqueous sodium bicarbonate solution was added dropwise at room temperature (25°C) to terminate the reaction. An extraction operation using ethyl acetate was performed three times, and the obtained organic layer was dried over sodium sulfate, and the solvent was then distilled off under reduced pressure. The crude product was purified by silica gel column chromatography (developing solvent: hexane). Subsequently, purification was performed using gel filtration chromatography (developing solvent: CHCl ３ ), the target compound was obtained.

[0270] Examples The raw material compounds used in Synthesis Examples 6-1 to 6-36 are as follows.

[0271]

[0272]

[0273] The intermediate (adamantane-containing arene compound) obtained by carrying out step IA using the above-mentioned compound as a raw material compound is as follows.

[0274]

[0275]

[0276] The intermediates (adamantane-fused arene compounds) obtained by similarly carrying out Steps IA and IB using the above-described compounds as raw materials are as follows. The yields shown below for each compound are the total yields for Steps IA and IB.

[0277]

[0278]

[0279]

[0280] Synthesis Example 6-1: 10,11,12,13,14,14a-hexahydro-9H-8b,12:10,14-dimethanocycloocta[l]phenanthrene. Synthesis method: Synthesis method A. 2-Bromobiphenyl was used. Yield 49.1 mg, yield 57%, white solid. 1 H NMR (600 MHz, CD2Cl2) δ 7.83-7.81 (m, 1H), 7.78-7.80 (m, 1H), 7.44-7.40 (m, 2H), 7.34-7.27 (m, 4H), 2.96 (s, 1H), 2.77 (q, J = 3.0 Hz, 1H), 2.58 (dt, J = 12.0, 2.4 Hz, 1H), 2.25 (t, J = 3.0 Hz, 1H), 2.07-2.11 (m, 1H), 1.86-1.96 (m, 3H), 1.76-1.85 (m, 3H), 1.68 (dq, J = 12.6, 3.0 Hz, 1H), 1.58 (dt, J = 12.6, 1.2 Hz, 1H), 1.27-1.30 (m, 1H). 13 C NMR (150 MHz, CDCl3) δ 145.02, 137.94, 134.16, 133.00, 128.06, 127.74, 126.64, 126.37, 125.77, 124.22, 123.92, 123.87, 45.76, 41.42, 38.68, 37.90, 37.63, 35.77, 30.68, 28.90, 28.51, 28.41. HRMS (DART, positive) m / z calcd for C 22 H 21 [MH] + : m / z 285.16378. Found: m / z 285.16426.

[0281] Synthesis Example 6-2: 4-Bromo-10,11,12,13,14,14a-hexahydro-9H-8b,12:10,14-dimethanocycloocta[l]phenanthrene. Synthesis method: Synthesis method A. 2,2'-Dibromo-1,1'-biphenyl was used. Yield 64.7 mg, yield 59%, white solid. 1 H NMR (600 MHz, CD2Cl2) δ 8.26 (dd, J = 6.6, 1.2 Hz, 1H), 7.59 (td, J = 7.8, 1.2 Hz, 1H), 7.42 (dd, J = 6.6, 1.2Hz, 1H), 7.38 (d, J = 7.8 Hz, 1H), 7.33 (td, J = 7.2, 1.8 Hz, 1H), 7.26, (td, J = 7.2, 1.2 Hz, 1H), 7.15 (t, J = 8.4 Hz, 1H), 2.78 (s, 1H), 2.69 (d, J = 2.4 Hz, 1H), 2.55 (dt, J = 12.0, 2.4 Hz, 1H), 2.24 (t, J = 3.0 Hz, 1H), 2.07 (dq, J = 9.6, 2.4 Hz, 1H), 1.91-1.93 (m, 1H), 1.68-1.83 (m, 6H), 1.52 (d, J = 12.0 Hz, 1H), 1.38 (dd, J = 7.8, 2.4 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 146.13, 142.26, 134.71, 132.97, 131.77, 129.04, 128.40, 128.05, 125.20, 125.03, 123.54, 120.23, 46.43, 41.96, 37.77, 37.59, 37.57, 35.54, 30.67, 30.47, 29.54, 28.70, 28.09. HRMS (DART, positive) m / z calcd for C 22 H 20 Br [MH] + : m / z 363.07429. Found: m / z 363.07532.

[0282] Synthesis Example 6-3: 4-chloro-10,11,12,13,14,14a-hexahydro-9H-8b,12:10,14-dimethanocycloocta[l]phenanthrene. Synthesis method: Synthesis method A. 2-Bromo-2'-chloro-1,1'-biphenyl was used. Yield 24.8 mg, yield 31%, white solid. 1 H NMR (600 MHz, CDCl3) δ 8.28 (dd, J = 7.8, 1.2 Hz, 1H), 7.42 (dd, J = 7.8, 1.2 Hz, 1H), 7.37 (d, J = 7.8 Hz, 1H), 7.34-7.31 (m, 2H), 7.28 (td, J = 7.8, 1.2 Hz, 1H), 7.21 (t, J = 7.8 Hz, 1H), 2.80 (s, 1H), 2.70 (d, J = 3,0 Hz, 1H), 2.54 (dt, J = 12.0, 2.4 Hz, 1H), 2.25 (s, 1H), 2.07 (dq, J = 12.6, 3.0 Hz, 1H), 1.92 (d, J = 12.6 Hz, 1H), 1.73-1.84 (m, 6H), 1.51 (d, J = 12.6 Hz, 1H), 1.37 (d, J = 13.2, 1H). 13 C NMR (150 MHz, CDCl3) δ 146.21, 142.08, 132.93, 131.10, 130.86, 129.46, 128.91, 128.36, 127.73, 125.25, 124.62, 123.64, 46.25, 42.00, 37.78, 37.66, 37.61, 35.58, 30.62, 29.49, 28.73, 28.14. HRMS (DART, positive) m / z calcd for C 22 H 20 Cl [MH] + : m / z 319.12480. Found: m / z 319.12505.

[0283] Synthesis Example 6-4: 2,7-Dichloro-10,11,12,13,14,14a-hexahydro-9H-8b,12:10,14-dimethanocycloocta[l]phenanthrene. Synthesis method: Synthesis method A. 2-Bromo-2,2'-dichloro-1,1'-biphenyl was used. Yield 33.0 mg, yield 31%, white solid. 1 H NMR (600 MHz, CD2Cl2) δ 7.71 (d, J = 9.0 Hz, 1H), 7.67 (d, J = 8.4 Hz, 1H), 7.39 (d, J = 2.4 Hz, 1H), 7.37 (s, 1H), 7.25-7.29 (m, 2H), 2.93 (s, 1H), 2.69 (d, J = 3.0 Hz, 1H), 2.49 (dt, J = 10.2 Hz, 1H), 2.26 (t, J = 2.4 Hz, 1H), 2.07-2.10 (m, 1H), 1.74-1.93 (m, 6H), 1.65 (dq, J = 12.6, 3.0 Hz, 1H), 1.58-1.61 (m, 2H), 1.27 (dq, J = 12.6, 1.8 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 146.60, 139.74, 134.20, 134.08, 131.82, 130.62, 126.84, 126.69, 126.24, 125.51, 125.11, 124.58, 45.64, 42.22, 38.45, 37.59, 37.34, 36.04, 30.48, 28.65, 28.44, 28.16 (one sp3 carbon atom was overlapping with others.) HRMS (DART, positive) m / z calcd for C 22 H 20 Cl2[M] + : m / z 354.09421. Found: m / z 354.09401.

[0284] Synthesis example 6-5: 6, 7, 8, 9, 10, 10a-ヘキサヒドロ-5H-4b, 8: 6,10 - Synthetic method of ジメタノシクロオクタ[3,4]ナフト[2.1-a]アズレン: Synthesis method A. Compound S2 was used, and 75 μmol of Sulfonate was used. The yield is 5.8 mg, yield 23%, cyan solid. 1 H NMR (600 MHz, CDCl3) δ 8.53 (d, J = 10.2 Hz, 1H), 8.20 (d, J = 9.0 Hz, 1H), 7.91 (dd, J = 5.4, 1.8 Hz, 1H), 7.69 (s, 1H), 7.46 (dd, J = 6.0, 1.2 Hz, 1H), 7.41 (t, J = 3.6 Hz, 1H), 7.30-7.39 (m, 2H), 7.00-7.06 (m, 2H), 3.63 (s, 1H), 3.45 (q, J = 3.0 Hz, 1H), 2.61 (dt, J = 12.0, 1.8 Hz, 1H), 2.29 (t, J = 6.0 Hz, 1H), 2.02-2.10 (m, 4H), 1.82-1.87 (m, 4H), 1.69 (d, J = 12.0 Hz, 1H), 1.31 (d, J = 10.8 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 146.58, 146.42, 142.48, 136.05, 135.13, 134.02, 131.61, 129.09, 127.18, 126.64, 126.15, 125.78, HRMS (DART, positive) m / z calcd for C 26 H 25 [M+H] + : m / z 337.19508. Found: m / z 337.19458.

[0285] Synthesis Example 6-6: 12c,13,15,16,17,18-hexahydro-14H-13,17:15,18a-dimethanobenzo[g]cycloocta[p]chrysene Synthesis method: Synthesis method A. 9-(2-bromophenyl)phenanthrene was used. Yield 60.3 mg, yield 52%, white solid. 1 H NMR (600 MHz, CD2Cl2) δ 8.69 (d, J = 8.4 Hz, 1H), 8.65 (d, J = 7.2 Hz, 1H), 8.46 (d, J = 7.2 Hz, 1H), 7.91 (d, J = 8.4 Hz, 1H), 7.63-7.66 (m, 1H), 7.57-7.61 (m, 3H), 7.50 (td, J = 7.2, 1.8 Hz, 1H), 7.45 (d, J = 7.8 Hz, 1H), 7.33 (td, J = 7.8, 1.2 Hz, 1H), 7.22-7.27 (m, 1H), 3.41 (s, 1H), 3.17 (d, J = 3.0 Hz, 1H), 2.61 (dt, J = 12.0, 2.4 Hz, 1H), 2.32 (d, J = 3.0 Hz, 1H), 2.18 (d, J = 12.0 Hz, 2H), 2.10 (dq, J = 13.2, 2.4 Hz, 1H), 2.02 (dd, J = 12.0, 2.4 Hz, 1H), 1.76 (s, 2H), 1.59 (t, J = 1.8 Hz, 1H), 1.45 (d, J = 13.2, 1.8 Hz, 1H), 1.27 (dd, J = 12.6, 3.0 Hz, 1H), 0.90 (d, J = 13.8 Hz, 1H). 13C NMR (150 MHz, CDCl3) δ 145.12, 135.07, 133.59, 133.54, 130.95, 130.80, 130.39, 129.38, 128.86, 127.17, 126.66, 126.40, 125.98, 125.71, 125.59, 125.47, 125.33, 123.67, 123.32, 122.55, 47.16, 41.25, 40.59, 38.60, 37.42, 36.49, 32.88, 30.98, 29.03, 27.04. HRMS (EI, positive) m / z calcd for C 30 H 24 [M] + : m / z 386.20345. Found: m / z 386.20250.

[0286] Synthesis Example 6-7: 1,3,4,5,6,18b-hexahydro-2H-1,5:3,6a-dimethanodibenzo[c,g]cycloocta[l]phenanthrene. Synthesis method: Synthesis method A. 2-Bromo-1,1'-binaphthalene was used, and the scale was 0.8 mmol. Yield: 133.0 mg, yield 43%, white solid. 1 H NMR (600 MHz, CD2Cl2) δ 7.89-7.92 (m, 4H), 7.70-7.72 (m, 2H), 7.36-7.42 (m, 2H), 7.14-7.18 (m, 2H), 3.03 (s, 1H), 2.89 (d, J = 3.0 Hz, 1H), 2.68 (dt, J = 12.0, 3.0 Hz 1H), 2.28 (t, J = 3.0 Hz, 1H), 2.10 (dq, J = 12.0, 2.4 Hz, 1H), 1.98 (d, J = 13.2 Hz, 1H), 1.83-1.87 (m, 3H), 1.71-1.74 (m, 2H), 1.65 (d, J = 13.2 Hz, 1H), 1.54-1.55 (m, 1H), 1.50 (d, J = 13.2 Hz, 1H). 13C NMR (150 MHz, CDCl3) δ 145.01, 138.50, 132.54, 130.94, 130.65, 130.48, 129.74, 128.05, 127.96, 127.90, 127.81, 127.51, 124.96, 124.92, 124.72, 124.60, 124.03, 122.26, 46,66, 42.43, 37.98, 37.80, 37.05, 36.49, 31.17, 29.56, 29.06, 27.98. HRMS (DART, positive) m / z calcd for C 30 H 27 [M+H] + : m / z 387.21073. Found: m / z 387.21131.

[0287] Synthesis example 6-8: 6b, 7, 9, 10, 11, 12-ヘキサヒドロ-8H-7, 11: 9, 12ｽジメタノジベンゾ[m,ppｽｽr]シクロオクタ[k]テトラフェン Synthesis method: Synthesis method A. Compound S5 was used. The yield was 45.2 mg, yield 37%, white solid. 1 H NMR (600 MHz, CDCl3) δ 8.72 (d, J = 9.6 Hz, 1H), 8.21 (s, 1H), 8.13-8.15 (m, 2H), 8.06 (s, 1H), 8.04 (d, J = 3.0 Hz, 2H), 7.96-7.98 (m, 2H), 7.57 (dd, J = 7.2, 1.8 Hz, 1H), 7.39-7.43 (m, 2H), 3.22 (s, 1H), 3.09 (d, J = 2.4 Hz, 1H), 2.64 (dt, J = 7.2, 2.4 Hz, 1H), 2.33 (t, J = 3.0 Hz, 1H), 2.17-2.20 (m, 1H), 2.06-2.08 (m, 1H), 2.00-2.02 (m, 1H), 1.78-1.84 (m, 3H), 1.69-1.72 (m, 2H), 1.53-1.57 (m, 1H), 1.44 (d, J = 6.6 Hz, 1H). 13C NMR (150 MHz, CDCl3) δ 146.93, 137.48, 133.10, 131.50, 130.98, 130.83, 130.73, 130.63, 127.79, 127.71, 127.25, 127.01, 126.97, 126.35, 125.84, 125.72, 125.22, 125.02, 124.66, 124.45, 124.08, 122.36, 46.67, 41.96, 38.00, 37.74, 35.55, 30.84, 29.85, 28.89, 28.13. HRMS (DART, positive) m / z calcd for C 32 H 27 [M+H] + : m / z 411.21073. Found: m / z 411.21043.

[0288] Synthesis Example 6-9: 12,13,14,15,16,16a-hexahydro-11H-10b,14:12,16-dimethanobenzo[pqr]cycloocta[f]picene Synthesis method: Synthesis method A. Compound S4 was used. Yield 60.4 mg, yield 49%, white solid. 1H NMR (600 MHz, CDCl3) δ 8.58 (s, 1H), 8.19 (d, J = 9.6 Hz, 1H), 8.10-8.14 (m, 3H), 8.02 (d, J = 9.0 Hz, 1H), 7.93-7.96 (m, 2H), 7.68-7.70 (m, 1H), 7.46-7.47 (m, 1H), 7.36-7.38 (m, 2H), 3.86 (s, 1H), 3.56 (d, J = 3.0 Hz, 1H), 2.64 (dt, J = 12.0, 2.4 Hz, 1H), 2.35 (t, J = 3.0 Hz, 1H), 2.22-2.26 (m, 2H), 2.10 (d, J = 2.4 Hz, 1H), 2.00 (d, J = 13.2 Hz, 1H), 1.75 (s, 2H), 1.59 (s, 1H), 1.39 (d, J = 13.2 Hz, 1H), 1.27 (dd, J = 10.2, 2.4 Hz, 1H), 0.91 (d, J = 12.6 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 144.83, 134.64, 134.17, 133.78, 131.46, 130.70, 130.18, 128.41, 127.81, 127.72, 127.12, 127.04, 126.90, 125.79, 125.54, 125.33, 125.20, 125.15, 125.10, 124.85, 122.53, 119.95, 47.43, 41.88, 41.06, 38.72, 37.22, 36.57, 33.27, 30.93, 28.78, 27.27. HRMS (DART, positive) m / z calcd for C 32 H 27 [M+H] + : m / z 411.21073. Found: m / z 411.21062。

[0289] Synthesis Example 6-10: 7b,8,10,11,12,13-Hexahydro-9H-8,12:10,13a-dimethanocycloocta[3,4]naphtho[1,2-c]thiophene. Synthesis method: Synthesis method A (the reaction solvent in Step I was changed to dehydrated diethyl ether). 3-Bromo-4-phenylthiophene was used. Yield 49.1 mg, 57%, white solid. 1 H NMR (600 MHz, CD2Cl2) δ 7.68 (dd, J = 6.0, 1.8 Hz, 1H), 7.51 (d, J = 3.0 Hz, 1H), 7.37 (d, J = 7.2 Hz, 1H), 7.24-7.30 (m, 2H), 7.03 (d, J = 3.0 Hz, 1H), 2.91 (s, 1H), 2.72 (d, J = 3.0 Hz, 1H), 2.40-2.43 (dt, J = 12.0, 3.0 Hz 1H), 2.19 (d, J = 3.0 Hz, 1H), 2.06-2.09 (m, 1H), 1.98 (dq, J = 6.0, 1.8 Hz, 1H), 1.91-1.97 (m, 2H), 1.78-1.84 (m, 3H), 1.66 (dq, J = 12.0, 3.0 Hz, 1H), 1.60 (d, J = 12.0 Hz 1H), 1.30 (dq, J = 12.0, 1.8 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 148.13, 137.10, 136.48, 132.06, 127.35, 126.25, 126.13, 124.02, 118.24, 117.45, 47.18, 42.06, 39.81, 38.14, 37.34, 36.08, 30.69, 28.59, 28.38. HRMS (DART, positive) m / z calcd for C 28 H 26 N [M+H] + : m / z 293.13585. Found: m / z 293.13595.

[0290] Synthesis example 6-11: 2, 3, 4, 5, 6, 6a-ヘキサヒドロ-1H-2, 6: 4, 16b -Synthetic method of ジメタノシクロオクタ[3,4]ナフト[2,1-h]キノリン: Synthesis method A. Compound S6 was not used. The yield was 37.9 mg, yield 37%, white solid. 1 H NMR (600 MHz, CDCl3) δ 8.97 (dd, J = 6.0, 1.8 Hz, 1H), 8.70 (dd, J = 7.8, 1.8 Hz, 1H), 8.16 (dd, J = 4.8, 1.8 Hz, 1H), 7.76 (d, J = 8.4 Hz, 1H), 7.69 (d, J = 8.4 Hz, 1H), 7.44 (d, J = 8.4 Hz, 1H), 7.35-7.40 (m, 3H), 3.06 (s, 1H), 2.88 (d, J = 2.4 Hz, 1H), 2.60 (dt, J = 6.0, 2.4 Hz, 1H), 2.29 (t, J = 3.0 Hz, 1H), 2.11 (dq, J = 7.2, 3.0 Hz, 1H), 1.98-2.01 (m, 1H), 1.94 (dq, J = 10.4, 1.8Hz, 1H), 1.68-1.87 (m, 5H), 1.55 (s, 1H), 1.35 (d, J = 12.0 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 149.45, 145.91, 145.63, 140.48, 136.21, 131,96, 131.65, 127.95, 127.68, 126.89, 125.55, 124.67, 123.13, 120.41, 46.55, 41.85, 37.92, 37.69, 37.61, 35.15, 31.15, 29.45, 28.84, 28.03. HRMS (DART, positive) m / z calcd for C 25 H 24 N [M+H] + : m / z 338.19032. Found: m / z 354.19078.

[0291] Synthesis Example 6-12: 5,6,7,8,9,9a-hexahydro-4H-3b,7:5,9-dimethanocycloocta[5,6]benzo[2,1-b:3,4-b']dithiophene. Synthesis method: Synthesis method A (the reaction solvent in step I was changed to dehydrated diethyl ether). 3-Bromo-2,2'-bithiophene was used. Yield 35.8 mg, yield 40%, brown solid. 1 H NMR (600 MHz, CDCl3) δ 7.11 (d, J = 5.4 Hz, 1H), 7.07 (d, J = 4.8 Hz, 1H), 6.97 (d, J = 4.8 Hz, 1H), 6.96 (d, J = 4.8 Hz, 1H), 2.99 (s, 1H), 2.55 (q, J = 3.0 Hz, 1H), 2.33 (dt, J = 12.0, 2.4 Hz, 1H), 2.20 (t, J = 3.0 Hz, 1H), 1.98-2.03 (m, 2H), 1.91 (dd, J = 12.0, 2.4 Hz, 2H), 1.76-1.83 (m, 4H), 1.64-1.67 (m, 1H), 1.30 (d, J = 12.6 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 145.15, 138.39, 130.67, 129.97, 125.59, 124.26, 121.77, 121.50, 47.58, 41.49, 38.07, 37.81, 37.29, 36.89, 31.62, 30.24, 29.04, 27.67. HRMS (DART, positive) m / z calcd for C 18 H 19 S2 [M+H] + : m / z 299.09220. Found: m / z 299.09219.

[0292] Synthesis Example 6-13: 10,11,12,13,14,14a-hexahydro-9H-8b,12:10,14-dimethanocycloocta[5,6]benzo[1,2,3,4-ghi]perylene. Synthesis method: Synthesis method A. 2-Bromo-1,1'-binaphthalene was used, on a 0.8 mmol scale. Yield: 21.2 mg, 7%, yellow solid.1 H NMR (600 MHz, CDCl3) δ 8.16-8.18 (m, 2H), 7.67 (t, J = 7.8 Hz, 2H), 7.74 (t, J = 7.8 Hz, 2H), 7.52 (t, J = 8.4 Hz, 2H), 7.43 (td, J = 7.8, 1.2 Hz, 2H), 3.24 (s, 1H), 2.84 (d, J = 3.0 Hz, 1H), 2.63 (d, J = 12.0 Hz, 1H), 2,32 (d, J = 3.0 Hz, 1H), 2.05-2.10 (m, 3H), 1.92-1.97 (m, 2H), 1.84-1.86 (m, 2H), 1.78-1.82 (m, 1H), 1.69 (d, J = 13.2 Hz, 1H), 1.26 (d, J = 12.6 Hz, 1H). 13 C NMR (150 MHz, CD2Cl2) δ 141.24, 134.29, 133.40, 133.32, 131.58, 131.33, 128.49, 128.35, 128.25, 127.74, 127.71, 127.55, 126.33, 126.28, 126.10, 124.79, 123.13, 120.44, 120.28, 46.85, 41.05, 38.26, 38.01, 37.63, 36.28, 31.51, 29.44, 28.58, 28.28. HRMS (EI, positive) m / z calcd for C 30 H 24 [M] + : m / z 384.18780. Found: m / z 384.18730.

[0293] Synthesis example 6-14: 5-フェニル-10, 11, 12, 13, 14, 14a-ヘキサヒドロ-9H -8b,12:10,14-Synthetic method of ジメタノシクロオクタ[l]フェナントレン: Synthesis method A. 1-ブロモ-2, 3-ジフェニルベンゼンをした. The yield was 33.2 mg, yield 31%, white solid. 1H NMR (600 MHz, CDCl2CDCl2) δ 7.38-7.48 (m, 2H), 7.17-7.32 (m, 7H), 7.06 (td, J = 6.6, 1.8 Hz, 1H), 6.79 (dd, J = 6.6, 1.8 Hz, 1H), 6.69 (t, J = 7.8 Hz, 1H), 2.98 (s, 1H), 2.69 (d, J = 2.4 Hz, 1H), 2.52 (dt, J = 12.0, 2.4 Hz, 1H), 2.21 (bs, 1H), 2.02 (dd, J = 10.8, 1.8 Hz, 1H), 1.72-1.92 (m, 6H), 1.48 (d, J = 12.6 Hz, 2H), 1.27 (d, J = 12.0 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 147.31, 144.17, 139.94, 138.96, 133.00, 132.10, 130.73, 130.16, 127.49, 126.60, 126.56, 125.40, HRMS (DART, positive) m / z calcd for C 28 H 25 [MH] + : m / z 361.19556. Found: m / z 361.19483.

[0294] Synthesis example 6-15: 12, 13, 14, 15, 16, 16a-ヘキサヒドロ-11H-10b, 14:12,16-ジメタノベンゾ[e]シクロオクタ[l]ピレン Synthesis method: Synthesis method A. 1-ブロモ-2, 3-ジフェニルベンゼンをした. The yield was 16.1 mg, yield 15%, white solid. 1H NMR (600 MHz, CDCl3) δ 8.64-8.67 (m, 2H), 8.51-8.53 (m, 2H), 7.62-7.68 (m, 6H), 3.34 (s, 1H), 2.93 (d, J = 3.0 Hz, 1H), 2.73 (dt, J = 12.0, 2.4 Hz, 1H), 2.35 (d, J = 2.4 Hz, 1H), 2.12-2.20 (m, 3H), 2.03 (dt, J = 12.0, 3.0 Hz, 1H), 1.80-1.90 (m, 4H), 1.69 (d, J = 12.6 Hz, 1H), 1.28 (dd, J = 12.0, 1.8 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 144.75, 137.34, 130.15, 129.20, 129.01, 127.46, 127.18, 127.14, 127.11, 127.05, 125.82, 124.05, 123.59, 123.57, 121.93, 120.87, 120.68, 46.49, 41.18, 40.09, 37.93, 37.58, 36.39, 31.14, 28.99, 28.67, 28.45 HRMS (DART, positive) m / z calcd for C 28 H 25 [M+H] + : m / z 361.19508. Found: m / z 361.19483.

[0295] Synthesis Example 6-16: 5-(phenanthrene-9-yl)-10,11,12,13,14,14a-hexahydro-9H-8b,12:10,14-dimethanocycloocta[l]phenanthrene. Synthesis method: Synthesis method A. 1-Bromo-3-(9-phenanthrene)-2-phenylbenzene was used. Yield: 26.4 mg, 19%, white solid. The product was obtained as a 1:1 mixture with rotamers. 1H NMR (600 MHz, CDCl2CDCl2) δ 8.78 (d, J = 7.8 Hz, 1H), 8.66-8.69 (m, 2H), 8.56 (d, J = 8.4 Hz, 1H), 8.14 (d, J = 8.4 Hz, 1H), 7.99 (s, 1H), 7.96 (d, J = 7.2 Hz, 1H), 7.71 (t, J = 7.2 Hz, 1H), 7.58-7.65 (m, 5H), 7.17-7.53 (m, 14H), 7.31-7.40 (m, 4H), 7.06 (m, 2H), 6.94 (t, J = 7.2 Hz, 1H), 6.84 (t, J = 7.8 Hz, 1H), 6.77 (d, J = 7.8 Hz, 1H), 6.43 (t, J = 7.8 Hz, 1H), 6.31 (t, J = 7.8 Hz, 1H), 2.91 (s, 1H), 2.87 (s, 1H), 2.80 (d, J = 11.4 Hz, 2H), 2.51 (d, J = 9.0 Hz, 2H), 2.24 (brs, 2H), 1.78-2.10 (m, 16H), 1.55-1.59 (m, 2H), 1.48 (t, J = 11.4 Hz, 2H). 13C NMR (150 MHz, CDCl3) δ 145.96, 145.33, 141.75, 140.65, 140.22, 139.58, 137.79, 137.55, 134.96, 132.87, 132.47, 132.33, 131.87, 131.44, 131.13, 130.28, 130.16, 129.78, 129.59, 128.89, 128.73, 128.22, 127.90, 127.74, 127.70, 127.34, 127.08, 126.99, 126.90, 126.70, 126.65, 126.52, 126.42, 126.34, 126.28, 126.03, 125.80, 125.27, 125.21, 125.04, 123.28, 123.23, 122.80, 122.58, 122.54, 46.46, 46.16, 42.23, 42.04, 38.16, 38.01, 37.87, 37.78, 37.53, 35.63, 35.50, 30.95, 30.81, 29.51, 29.36, 28.97, 28.94, 28.57, 28.48 (seven sp2 carbon atoms and one sp3 carbon atom were overlapping with others.). HRMS (DART, positive) m / z calcd for C 36 H 30 [M] + : m / z 462.23475. Found: m / z 462.23445.

[0296] Synthesis Example 6-17: 13,14,15,16,17,17a-hexahydro-12H-11b,15:13,17-dimethanotribenzo[f,ij,no]cycloocta[l]tetraphene. Synthesis method: Synthesis method A. 1-Bromo-3-(9-phenanthrene)-2-phenylbenzene was used. Yield 8.3 mg, 6%, white solid. 1H NMR (600 MHz, CDCl3) δ 8.77 (dd, J = 8.4, 1.2 Hz, 1H), 8.70-8.73 (m, 3H), 8.55-8.57 (m, 2H), 7.61-7.69 (m, 8H), 3.36 (s, 1H), 2.99 (d, J = 2.4 Hz, 1H), 2.79 (dt, J = 12.0, 2.4 Hz, 1H), 2.40 (t, J = 1.8 Hz, 1H), 2.17-2.27 (m, 3H), 2.08 (d, J = 12.6 Hz, 1H), 1.98 (dd, J = 12.6, 2.4 Hz, 1H), 1.87-1.93 (m, 3H), 1.74 (d, J = 13.2 Hz, 1H), 1.34 (dd, J = 12.6, 1.2 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 144.31, 137.11, 130.98, 129.58, 129.24, 129.09, 128.49, 128.36, 127.78, 127.66, 127.60, 127.05, 126.68, 126.57, 126.38, 123.68, 123.31, 121.23, 46.45, 41.59, 39.39, 38.04, 37.71, 36.22, 31.35, 29.10, 28.74, 28.66 (eight sp2 carbon atoms were overlapping with others.). HRMS (DART, positive) m / z calcd for C 36 H 28 [M] + : m / z 460.21910. Found: m / z 460.22123.

[0297] Synthesis example 6-18: 8, 9, 10, 11, 12, 12a-ヘキサヒドロ-7H-6b, 10: 8, 12-ジメタノシクロオクタ[a]アセナフチレン Synthesis method: Synthesis method B. 1-ブロモナフタレンをした. The yield is 18.7 mg, yield 24%, colorless oil. 1H NMR (600 MHz, CDCl3) δ 7.59 (dd, J = 7.8, 1.8 Hz, 2H), 7.41-7.45 (m, 2H), 7.23 (dd, J = 6.6, 1.2 Hz, 1H), 7.17 (d, J = 6.0 Hz, 1H), 3.51 (s, 1H), 2.77 (d, J = 2.4 Hz, 1H), 2.47 (dt, J = 12.0, 1.8 Hz, 1H), 2.21-2.27 (m, 2H), 2.03 (dq, J = 12.6, 2.4 Hz, 1H), 1.80-1.93 (m, 6H), 1.66 (dt, J = 12.0, 1.2 Hz, 1H), 1.32 (dt, J = 13.2, 2.4 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 152.71, 145.26, 137.11, 132.12, 127.48, 127.46, 123.06, 122.87, 117.54, 116.58, 57.65, 47.08, 44.71, 39.40, 39.04, 37.29, 31.90, 29.37, 28.93, 28.04. HRMS (DART, positive) m / z calcd for C 20 H 19 [MH] + : m / z 259.14813. Found: m / z 259.14792.

[0298] Synthesis Example 6-19: 4-Bromo-8,9,10,11,12,12a-hexahydro-7H-6b,10:8,12-dimethanocycloocta[a]acenaphthylene. Synthesis method: Synthesis method B. 1,4-Dibromonaphthalene was used. Yield 55.2 mg, 55%, white solid. 1H NMR (600 MHz, CD2Cl2) δ 7.74 (dt, J = 7.2, 1.2 Hz, 1H), 7.64 (s, J = 7.2 Hz, 1H), 7.54-7.56 (m, 1H), 7.29 (dd, J = 6.0, 1.2 Hz, 1H), 7.05 (d, J = 7.2 Hz, 1H), 3.50 (s, 1H), 2.75 (d, J = 2.4 Hz, 1H), 2.45 (dt, J = 12.0, 2.4 Hz, 1H), 2.24 (t, J = 3.0 Hz, 1H), 2.18-2.21 (m, 1H), 2.02-2.05 (m, 1H), 1.80-1.92 (m, 6H), 1.65-1.68 (m, 1H), 1.24 (dq, J = 10.4, 2.4 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 152.68, 145.52, 138.27, 131.58, 130.60, 128.76, 122.34, 118.56, 117.67, 117.48, 57.698, 46.87, 44.78, 39.24, 38.88, 37.19, 31.81, 29.29, 28.92, 28.01. HRMS (DART, positive) m / z calcd for C 20 H 18 Br [MH] + : m / z 337.05864. Found: m / z 337.06045.

[0299] Synthesis Example 6-20: 6b,7,9,10,11,12-hexahydro-8H-7,11:9,12a-dimethanocycloocta[4,5]cyclopenta[1,2,3-cd]pyrene. Synthesis method: Synthesis method B. 1-Bromopyrene was used. Yield 52.1 mg, 52%, white solid. 1H NMR (600 MHz, CDCl3) δ 8.10-8.12 (m, 2H), 8.03-8.05 (m, 2H), 7.92-7.97 (m, 2H), 7.84 (dd, J = 7.2, 1.2 Hz, 1H), 7.68 (s, 1H), 3.82 (s, 1H), 2.92 (d, J = 3.0 Hz, 1H), 2.64 (dt, J = 12.0, 2.4 Hz, 1H), 2.40 (dq, J = 12.0, 2.4 Hz, 1H), 2.34 (t, J = 3.0 Hz, 1H), 2.09 (qdJ = 12.6, 3.0 Hz 1H), 1.97-2.01 (m, 2H), 1.88-1.92 (m, 4H), 1.79 (d, J = 12.6 Hz, 1H), 1.53-1.55 (m, 1H). 13 C NMR (150 MHz, CDCl3) δ 151.52, 141.80, 134.71, 133.33, 131.32, 128.86, 126.79, 126.53, 126.23, 124.83, 124.51, 124.25, 123.29, 120.02, 116.33, 58.80, 48.05, 44.50, 39.43, 39.04, 37.44, 32.08, 29.44, 29.38, 28.33. calcd for C 26 H 23 [M+H] + : 335.17943, found: 335.17893.

[0300] Synthesis Example 6-21: 8,9,10,11,12,12a-hexahydro-7H-6b,10:8,12-dimethanocycloocta[4,5]cyclopenta[1,2,3-cd]fluoranthene Synthesis method: Synthesis method B. 3-Bromofluoranthene was used. Yield 47.2 mg, 47%, white solid. 1H NMR (600 MHz, CD2Cl2) δ 7.86-7.93 (m, 4H), 7.34-7.39 (m, 3H), 7.32 (d, J = 7.0 Hz, 1H), 3.74 (s, 1H), 2.86 (d, J = 2.4 Hz, 1H), 2.57 (dt, J = 12.0, 2.4 Hz, 1H), 2.29 (dq, J = 12.0, 3.0 Hz 1H), 2.26 (t, J = 2.4 Hz, 1H), 2.05 (dq, J = 12.0, 2.4 Hz, 1H), 1.96 (d, J = 12.6 Hz, 1H), 1.80-1.87 (m, 6H), 1.28 (d, J = 13.2 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 152.90, 145.70, 140.73, 134.57, 133.56, 133.45, 132.20, 126.97, 122.21, 121.57, 119.50, 118.50, 60.10, 50.22, 45.76, 39.44, 39.29, 37.17, 32.26, 29.98, 29.15, 28.60 (four sp2 carbon atoms were overlapping with others). HRMS (DART, positive) m / z calcd for C 26 H 23 [M+H] + : m / z 335.17943. Found: m / z 335.17893.

[0301] Synthesis Example 6-22: 4-(naphthalen-1-yl)-8,9,10,11,12,12a-hexahydro-7H-6b,10:8,12-dimethanocycloocta[a]acenaphthylene. Synthesis method: Synthesis method B. 4-Bromo-1,1'-binaphthalene was used. Yield: 48.7 mg, 42%, white solid. The product was obtained as a 1:1 mixture with rotamers. 1H NMR (600 MHz, CD2Cl2) δ 7.93-7.96 (m, 2×2H), 7.57-7.61 (m, 2×1H), 7.53-7.55 (m, 2×1H), 7.45-7.50 (m, 2×2H), 7.43 (d, J = 6.6 Hz, 2×1H), 7.23-7.33 (m, 2×4H), 7.06-7.08 (m, 2×1H), 3.62 (s, 1H), 3.57 (s, 1H), 2.80 (d, J = 2.4 Hz, 2×1H), 2.55-2.57 (m, 2×1H), 2.27-2.31 (m, 2×2H), 2.08 (dt, J = 12.6, 3.0 Hz, 2×1H), 1.84-1.99 (m, 2×6H), 1.80 (t, J = 13.2 Hz, 1H), 1.76 (d, J = 13.2 Hz, 1H), 1.47 (d, J = 12.6 Hz, 1H), 1.37 (d, J = 12.6 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 152.45, 145.32, 138.49, 138.41, 137.15, 137.07, 134.68, 134.60, 133.75, 132.94, 131.74, 129.23, 129.18, 128.25, 128.23, 128.07, 127.99, 127.76, 127.53, 127.46, 126.86, 125.90, 125.85, 125.81, 125.52, 122.08, 117.73, 117.61, 116.48, 116.35, 57.82, 46.91, 44.91, 44.86, 39.45, 39.13, 37.35, 37.33, 31.91, 29.44, 29.01, 28.98, 28.10 (ten sp2 carbon signals and seven sp3 carbon signals were overlapping with others). HRMS (DART, positive) m / z calcd for C 30 H 27 [M+H] +: m / z 387.21073. Found: m / z 387.21074.

[0302] Synthesis example 6-23: 7, 8, 9, 10, 11, 11a-ヘキサヒドロ-6H-5b, 9: 7,11-ジSynthesis method of メタノシクロオクタ[4,5]シクロペンタ[1.2.3-cd]ペリレン:Synthesis method B. 4-ブロモ-1,1'-ビナフタレンを Use した. The yield was 23.2 mg, yield 20%, yellow solid. 1 H NMR (600 MHz, CDCl3) δ 8.10 (t, J = 7.8 Hz, 2H), 8.04-8.07 (m, 2H), 7.61 (d, J = 8.4 Hz, 2H), 7.43 (td, J = 12.6, 2.4 Hz, 2H), 7.25 (dd, J = 5.4, ​​1.8 Hz, 1H), 7.19 (d, J = 7.2 Hz, 1H), 3.48 (s, 1H), 2.76 (d, J = 2.4 Hz, 1H), 2.46 (d, J = 12.0 Hz, 1H), 2.22-2.27 (m, 2H), 2.03 (dq, J = 8.4, 1.2 Hz, 1H), 1.80-1.93 (m, 6H), 1.70 (d, J = 13.2 Hz, 1H), 1.39 (dd, J = 13.2, 1.2 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 152.38, 144.99, 137.99, 135.50, 131.66, 129.56, 128.72, 128.60, 127.55, 127.52, 126.48, 120.76, HRMS (DART, positive) m / z calcd for C 30 H 25 [M+H] +: m / z 385.19508. Found: m / z 385.19567。

[0303] Synthesis Example 6-24: 10,11,12,13,14,14a-Hexahydro-9H-8b,12:10,14-dimethanocyclooct[a]pyrene Synthesis method: Synthesis method B. 4-Bromophenanthrene was used. Yield 23.1 mg, yield 24%, white solid. 1 H NMR (600 MHz, CDCl3) δ 7.74-7.76 (m, 4H), 7.57-7.62 (m, 4H), 3.38 (s, 1H), 2.94 (d, J = 3.0 Hz, 1H), 2.74 (dt, J = 12.0, 3.0 Hz, 1H), 2.36 (t, J = 3.0 Hz, 1H), 2.14-2.18 (m, 3H), 2.01-2.04 (m, 1H), 1.82-1.92 (m, 4H), 1.70 (d, J = 13.2 Hz, 1H), 1.26 (dq, J = 12.0, 3.0 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 144.32, 136.89, 131.37, 131.12, 127.47, 126.97, 126.89, 126.70, 126.26, 125.87, 125.60, 123.02, 120.92, 46.88, 41.11, 40.55, 38.03, 37.56, 36.79, 31.44, 29.01, 28.75, 28.28 (one sp2 carbon atom was overlapping with others). HRMS (DART, positive) m / z calcd for C 24 H 23 [M+H] + : m / z 311.17943. Found: m / z 311.18003。

[0304] Synthesis Example 6-25: 4,4-dimethyl-4,8,9,10,11,12,13,13a-octahydro-7b,11:9,13-dimethanocycloocta[l]cyclopenta[def]phenanthrene. Synthesis method: Synthesis method B. 4-Bromo-9,9-dimethyl-9H-fluorene was used. Yield 42.1 mg, yield 43%, white solid. 1 H NMR (600 MHz, CD2Cl2) δ 7.22-7.27 (m, 4H), 7.16-7.19 (m, 2H), 3.26 (s, 1H), 2.78 (d, J = 3.0 Hz, 1H), 2.57 (dt, J = 12.0, 2.4 Hz, 1H), 2.25 (d, J = 2.4 Hz, 1H), 2.04-2.09 (m, 2H), 1.92-1.99 (m, 2H), 1.80-1.87 (m, 3H), 1.70-1.75 (m, 2H), 1.50 (s, 3H), 1.50 (s, 3H), 1.32 (d, J = 12.0 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 151.21, 150.76, 140.69, 136.88, 135.49, 133.67, 128.05, 127.87, 122.48, 120.85, 120.16, 119.90, 50.19, 48.83, 41.27, 39.51, 38.74, 38.28, 37.23, 31.58, 28.80, 28.36, 28.30, 26.73, 26.54. HRMS (DART, positive) m / z calculation for C 25 H 27 [MH] + : m / z 327.19508. Found: m / z 327.19515.

[0305] Synthesis Example 6-26: 4,4-Diphenyl-4,8,9,10,11,12,13,13a-octahydro-7b,11:9,13-dimethanocycloocta[l]cyclopenta[def]phenanthrene. Synthesis method: Synthesis method B. 4-Bromo-9,9-diphenyl-9H-fluorene was used. Yield 41.7 mg, yield 35%, white solid. 1H NMR (600 MHz, CD2Cl2) δ 7.19-7.28 (m, 16H), 3.31 (s, 1H), 2.80 (d, J = 3.0 Hz, 1H), 2.58 (dt, J = 12.0, 3.0 Hz, 1H), 2.26 (t, J = 3.0 Hz, 1H), 2.07-2.10 (m, 2H), 1.93-2.01 (m, 2H), 1.77-1.86 (m, 3H), 1.71-1.76 (m, 2H), 1.34 (d, J = 11.4 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 148.59, 148.19, 146.04, 145.73, 141.18, 137.79, 136.45, 134.03, 128.50, 128.34, 128.31, 128.28, 128.15, 128.11, 126.66, 123.57, 123.30, 123.02, 121.39, 68.32, 48.70, 41.40, 39.50, 38.74, 38.24, 37.24, 31.48, 28.80, 28.38, 28.34 (five sp2 carbon atoms were overlapping with others.). HRMS (DART, positive) m / z calcd for C 35 H 31 [M+H] + : m / z 451.24203. Found: m / z 451.23986.

[0306] Synthesis Example 6-27: 9',10',11',12',13',13a'-Hexahydro-8'H-spiro[fluorene-9,4'-[7b,11:9,13]dimethanocycloocta[l]cyclopenta[def]phenanthrene. Synthesis method: Synthesis method B. 4-Bromo-9,9'-spirobifluorene was used. Yield 47.1 mg, 35%, white solid. 1H NMR (600 MHz, CDCl3) δ 7.84 (dt, J = 7.8, 1.2 Hz, 2H), 7.35-7.38 (m, 2H), 7.21 (t, J = 7.8 Hz, 2H), 7.06-7.13 (m, 4H), 6.80 (d, J = 7.8 Hz, 1H), 6.72 (d, J = 7.8 Hz, 1H), 6.59-6.62 (m, 2H), 3.45 (s, 1H), 2.85 (d, J = 2.4 Hz, 1H), 2.62 (dt, J = 12.0, 2.4 Hz, 1H), 2.33 (t, J = 1.8 Hz, 1H), 2.08-2.17 (m, 3H), 1.93-2.02 (m, 3H), 1.85-1.92 (m, 2H), 1.75 (d, J = 12.6 Hz, 1H), 1.46 (d, J = 12.0 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 148.28, 148.06, 146.83, 146.38, 141.91, 141.76, 140.78, 139.53, 138.21, 133.71, 128.73, 128.52, 127.81, 127.73, 124.37, 124.23, 123.31, 121.66, 121.35, 121.12, 120.07, 49.03, 41.47, 39.52, 39.02, 38.30, 37.28, 31.58, 28.83, 28.50, 28.40 (one sp3 carbon atom and three sp2 carbon atom were overlapping with others.). HRMS (DART, positive) m / z calcd for C 35 H 27 [M-H] + : m / z 447.21073. Found: m / z 447.20926。

[0307] Synthesis Example 6-28: 4-Phenyl-4,8,9,10,11,12,13,13a-octahydro-7b,11:9,13-dimethanocycloocta[5,6]benzo[1,2,3,4-def]carbazole. Synthesis method: Synthesis method B. 4-Bromo-9-phenyl-9H-carbazole was used. Yield 63.2 mg, 55%, white solid. 1 H NMR (600 MHz, CDCl3) δ 7.69 (dd, J = 8.4, 1.2 Hz, 2H), 7.57 (t, J = 7.8 Hz, 2H), 7.35-7.42 (m, 5H), 7.14 (d, J = 6.6 Hz, 1H), 7.11 (d, J = 6.6 Hz, 1H), 3.55 (d, J = 3.0 Hz, 1H), 2.92 (d, J = 3.0 Hz, 1H), 2.67 (td, J = 12.0, 3.0 Hz, 1H), 2.32 (s, 1H), 2.20 (dd, J = 12.6, 1.8 Hz, 1H), 2.10-2.13 (m, 2H), 2.01 (d, J = 12.6 Hz, 1H), 1.87-1.90 (m, 4H), 1.78 (d, J = 11.4 Hz, 1H), 1.45 (d, J = 12.6 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 140.93, 139.53, 138.33, 138.02, 134.01, 129.86, 127.32, 127.12, 126.03, 124.518, 123.02, 122.01, 115.75, 113.95, 108.07, 108.00, 50.09, 41.40, 40.06, 39.66, 38.42, 37.24, 32.34, 28.90, 28.82, 28.33 (two sp2 carbon atoms were overlapping with others.). HRMS (DART, positive) m / z calcd for C 28 H 26 N [M+H] + : m / z 376.20597. Found: m / z 376.20772.

[0308] Synthesis Example 6-29: 10,11,12,13,14,14a-hexahydro-9H-8b,12:10,14-dimethanocycloocta[e]acephenanthrene. Synthesis method: Synthesis method B. 9-Bromophenanthrene was used. Yield: 38.2 mg, 41%, white solid. The product was obtained as a 1:1 mixture with structural isomers. 1 H NMR (600 MHz, CDCl3) δ 8.57-8.61 (m, 2×1H), 8.26-8.33 (m, 2×1H), 7.87-7.89 (m, 2×1H), 7.52-7.65 (m, 2×3H), 7.45 (d, J = 14.4 Hz, 1H), 7.38-7.40 (m, 2×1H), 7.30-7.34 (d, J = 6.6 Hz, 1H), 3.55 (s, 1H), 3.52 (s, 1H), 2.83 (d, J = 2.4 Hz, 1H), 2.79 (d, J = 2.4 Hz, 1H), 2.51-2.57 (m, 2×1H), 2.24-2.31 (m, 2×2H), 2.07-2.09 (m, 2×1H), 1.83-2.00 (m, 2×6H), 1.70 (dt, J = 13.2, 2.4 Hz, 2×1H), 1.46-1.49 (m, 1H), 1.33 (dt, J = 13.2, 2.4 Hz, 1H). 13C NMR (150 MHz, CDCl3) δ 152.44, 150.51, 144.99, 143.14, 136.11, 135.95, 134.25, 134.21, 129.38, 129.33, 128.91, 128.73, 127.82, 127.78, 126.53, 126.48, 125.29, 122.98, 119.39, 119.35, 119.23, 118.26, 117.71, 116.59, 57.46, 57.09, 50.97, 46.88, 46.47, HRMS (DART, positive) m / z calcd for C 30 H 25 [M+H] + : m / z 311.17943. Found: m / z 311.17946.

[0309] Other compounds, 1 Identification was carried out by 1 H NMR etc.

[0310] Example 1

[0311]

[0312] DMPSi represents polydimethylsilane. Sc(OTf) ３ indicates scandium(III) trifluoromethanesulfonate.

[0313] Adamantane-fused arene compound 6 (0.1 mmol, 1 equivalent) obtained in Synthesis Example 6-1, polydimethylsilane, and alumina-supported rhodium and platinum composite catalyst (Rh / Pt(DMPSi / Al ２ O ３ 10 mol%), scandium(III) trifluoromethanesulfonate (Sc(OTf) ３10 mol%) was added, followed by the addition of dehydrated heptane (1.5 mL). The test tube was placed in a stainless steel pressure vessel, and the inside of the vessel was thoroughly purged with hydrogen gas (10 atmospheres (1 MPa)). The reaction solution was heated to 125°C and then stirred for 72 hours. Thereafter, the reaction solution was cooled to room temperature, filtered using Celite, and washed with ethyl acetate. The obtained organic layer was distilled off the solvent under reduced pressure. The crude product was purified by silica gel column chromatography (developing solvent: hexane only). Subsequently, purification was carried out using gel filtration chromatography to obtain diamondoid compound 7 (2.7 mg, 12%). 1 H NMR (600 MHz, C6D6) δ 1.62-2.06 (m, 18H), 1.40 (d, J = 12 Hz 1H), 1.08-1.34 (m, 8H), 1.01 (d, J = 10.2 Hz 1H),0.85-0.95 (m, 2H), 0.58-0.79 (m, 4H). GC-MS(EI) 298.30 (m / z).

[0314] Examples 2 to 10 Reactions were carried out in the same manner as in Example 1, except that appropriate compounds were used as raw materials.

[0315]

[0316] Example 3: (6br,8R,10S,12s)-hexadecahydro-1H-6b,10:8,12-dimethanocycloocta[a]acenaphthylene 1 H NMR (600 MHz, C6D6) δ 2.26-2.21 (m, 1H), 1.94 (t, J = 2.7 Hz, 1H), 1.87 (d, J = 2.4 Hz, 1H), 1.82-1.39 (m, 21H), 1.35-1.31 (m, 1H), 1.21 (d, J = 11.3 Hz, 1H), 1.15-1.04 (m, 3H), 0.77-0.73 (m, 1H). 13C NMR (600 MHz, CDCl3) δ 55.2, 48.2, 41.6, 39.8, 39.4, 39.3, 38.3, 37.2, 36.2, 33.1, 31.7, 31.4, 29.5, 29.5, 28.8, 27.3, 26.1, 25.2, 25.1, 17.9.Isomer 1 H NMR (600 MHz, C6D6) δ 2.32-2.27 (m, 1H), 2.00 (t, J = 3.1 Hz, 1H), 1.93 (d, J = 2.7 Hz, 1H), 1.88-1.37 (m, 22H), 1.27 (d, J = 12.4 Hz, 1H), 1.21-1.09 (m, 3H), 0.80 (dd, J = 12.7, 3.4 Hz, 1H). 13 C NMR (600 MHz, CDCl3) δ 56.9, 49.4, 45.5, 43.4, 42.3, 40.8, 40.4, 39.8, 39.2, 38.4, 37.9, 34.0, 33.5, 31.8, 31.3, 30.1, 29.8, 29.6, 29.3, 28.7, 28.1, 27.3, 26.8, 25.9, 25.4, 22.6, 22.0, 18.5. HRMS (ESI) m / z: [M+H]+ Calcd for C 20 H 30 270.2348; Found 270.2339.

[0317]

[0318] Example 4: (8br, 10R, 12S, 14s)-2-メトキシオクタデカヒドロ-1H-8b,12:10,14-ジメタノシクロオクタ[l]フェナントレン 1 H NMR (600 MHz, C6D6) δ 3.54 (q, 1H), 3.13 (m, 3H), 2.06-1.43 (m, 22H), 1.42-1.35 (m, 6H), 1.31-1.24 (m, 3H), 1.06 (dd, J = 11.9, 2.6 Hz, 1H). 13C NMR (600 MHz, CDCl3) δ 131.5, 126.2, 76.8, 55.7, 52.9, 43.0, 42.4, 40.3, 38.6, 37.5, 36.8, 35.6, 32.6, 32.4, 28.9, 28.8, 27.9, 26.9, 26.7, 26.2, 24.6, 23.4. HRMS (ESI) m / z: [M+H] + Calcd for C 22 H 48 O 328.3705; Found 328.3714.

[0319] Example 5: (8br,10R,12S,14s)-N,N-dimethyloctadecahydro-1H-8b,12:10,14-dimethanocycloocta[l]phenanthren-2-amine 1 H NMR (600 MHz, C6D6) δ 3.91-3.99 (1H), 3.15-3.22 (1H), 2.19-2.26 (2H), 1.95-2.04 (2H), 1.80-1.88 (1H), 0.98-1.81 (32H). 13 C NMR (600 MHz, CDCl3) δ 64.3, 52.9, 42.7, 42.1, 39.6, 38.3, 37.2, 36.7, 35.6, 32.5, 28.8, 28.7, 28.6, 28.2, 27.7, 27.1, 26.7, 26.6, 26.0, 25.5, 24.5, 24.3, 23.7, 23.2. HRMS (ESI) m / z: [M+H] + Calcd for C 24 H 38 N 341.3083; Found 341.3081.

[0320] Example 6: (6br,8R,10S,12s)-hexadecahydro-1H-6b,10:8,12-dimethanocycloocta[a]acenaphthylene-1-ol 1 H NMR (600 MHz, C6D6) δ 1.99-1.85 (m, 7H), 1.80-0.71 (m, 23H). 13C NMR (600 MHz, CDCl3) δ 86.2, 77.0, 76.8, 53.6, 42.4, 41.5, 38.9, 37.6, 36.6, 31.7, 31.2, 30.4, 30.3, 29.3, 29.0, 28.1, 26.8, 26.8, 22.1, 20.5. HRMS (ESI) m / z: [M+H] + Calcd for C 20 H 30 O 286.2296; Found 286.2297.

[0321] Example 7: (4br,6R,8S,10s)-Octadecahydro-1H-4b,8:6,10-dimethanocycloocta[a]cyclopenta[fg]acenaphthylene 1 H NMR (600 MHz, C6D6) δ 2.53 (td, J = 11.9, 8.5 Hz, 1H), 2.42-2.36 (m, 1H), 2.30-2.25 (m, 1H), 2.10-1.95 (m, 3H), 1.89-1.78 (m, 5H), 1.76-1.68 (m, 3H), 1.65-1.33 (m, 14H), 1.29-1.21 (m, 2H), 1.10-1.01 (m, 2H). 13 C NMR (600 MHz, CDCl3) δ 52.8, 48.4, 39.9, 39.4, 39.3, 38.7, 38.5, 38.1, 37.6, 37.3, 34.9, 34.2, 32.5, 31.5, 30.9, 29.6, 29.2, 29.0, 29.0, 27.1, 25.6, 20.5. HRMS (ESI) m / z: [M+H]+ Calcd for C 22 H 32 296.2504; Found 296.2510.

[0322] Example 8: (8bS,14R)-2-((8bS,10S,14R,14aR)-octadecahydro-1H-8b,12:10,14-dimethanocycloocta[l]phenanthren-7-yl)octadecahydro-1H-8b,12:10,14-dimethanocycloocta[l]phenanthrene 1H NMR (600 MHz, C6D6) δ 1.93-2.05 (5H), 1.84-1.89 (1H), 1.55-1.80 (20H), 0.97-1.55 (38H). HRMS (ESI) m / z: [M+H] + Calcd for C 44 H 46 594.5164; Found 594.5120.

[0323] Example 9: (9s,11R,13S,14ar)-icosahydro-1H-9,13:11,14a-dimethanocycloocta[e]acephenanthrene. Isolation of 3 isomers was difficult. The ratio of isomers was 1:1.4:0.5. (from GC) HRMS (ESI) m / z: [M+H] + Calcd for C 24 H 36 324.2817; Found 324.2833.

[0324] Example 10: 1-((8br,10R,12S,14s)-octadecahydro-1H-8b,12:10,14-dimethanocycloocta[l]phenanthren-2-yl)ethan-1-ol. Isolation of two isomers was difficult. The ratio of isomers was 1:1.5 (from GC) HRMS (ESI) m / z: [M-H] + Calcd for C 24 H 37 O 341.2844; Found 341.2849.

Claims

1. (delete)

2. General formula (1A): 【Chemical 1】 [In the formula, ring A ２ and Ring A ３ are the same or different and represent an aliphatic ring. １ａ , R １ｂ and R １ｃ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group. ２ａ and R ３ａ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ２ａ and R ３ａ may be joined together to form an aliphatic ring. Or general formula (1B): 【Chemistry 2】 [In the formula, ring A ４ and Ring A ５ are the same or different and represent an aliphatic ring. １ａ , R １ｂ and R １ｃ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group. ４ａ and R ５ａ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ４ａ and R ５ａ may be joined together to form an aliphatic ring. A diamondoid compound is a compound represented by the formula:

3. General formula (1A1): 【Chemistry 3】 [In the formula, R ２ａ , R ２ｂ , R ２ｃ , R ２ｄ , R ３ａ , R ３ｂ , R ３ｃ and R ３ｄ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ２ａ and R ２ｂ , R ２ｂ and R ２ｃ , R ２ｃ and R ２ｄ , R ３ａ and R ３ｂ , R ３ｂ and R ３ｃ , R ３ｃ and R ３ｄ , and R ２ａ and R ３ａ may be joined together at least at one position to form an aliphatic ring. Or general formula (1B1): 【Chemistry 4】 [In the formula, R １ and n are the same as above. ４ａ , R ４ｂ , R ４ｃ , R ５ａ , R ５ｂ and R ５ｃ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ４ａ and R ４ｂ , R ４ｂ and R ４ｃ , R ５ａ and R ５ｂ , R ５ｂ and R ５ｃ , and R ４ａ and R ５ａ may be joined together at least at one position to form an aliphatic ring. The diamondoid compound according to claim 2, which is a compound represented by the formula:

4. General formula (1A'): 【Chemistry 5】 [In the formula, ring A ２ and Ring A ３ are the same or different and represent an aliphatic ring. １ａ , R １ｂ , R １ｃ , R １ｄ , R １ｅ and R １ｆ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group. or general formula (1B'): 【Chemistry 6】 [In the formula, ring A ４ and Ring A ５ are the same or different and represent an aliphatic ring. １ａ , R １ｂ , R １ｃ , R １ｄ , R １ｅ and R １ｆ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group. The diamondoid compound according to claim 2, which is a compound represented by the formula:

5. General formula (1A'1): 【Chemistry 7】 [In the formula, R ２ｂ , R ２ｃ , R ２ｄ , R ３ｂ , R ３ｃ and R ３ｄ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ２ｂ and R ２ｃ , R ２ｃ and R ２ｄ , R ３ｂ and R ３ｃ , and R ３ｃ and R ３ｄ may be joined together at least at one position to form an aliphatic ring. or general formula (1B'1): 【Chemistry 8】 [In the formula, R ４ｂ , R ４ｃ , R ５ｂ and R ５ｃ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ４ｂ and R ４ｃ , and R ５ｂ and R ５ｃ may be joined together at least at one position to form an aliphatic ring.

5. The diamondoid compound according to claim 4, which is a compound represented by the formula:

6. A method for producing the diamondoid compound according to any one of claims 2 to 5, comprising: (II) General formula (2): 【Chemistry 9】 [In the formula, R １ and n is the same as above. １ ' is the ring A １ The aromatic ring corresponding to the formula is shown below. a step of hydrogenating an adamantane-fused aromatic compound represented by the formula: Equipped with The production method, wherein the catalyst comprises a catalyst containing rhodium and platinum and a Lewis acid catalyst.

7. 7. The method according to claim 6, wherein the Lewis acid catalyst has an element of Group 3, Group 13 or Group 14 of the periodic table as the active center.

8. The method according to claim 6, wherein the step (II) is carried out in the presence of an organic solvent.

9. The method according to claim 8 , wherein the organic solvent is an alkane.

10. The adamantane-fused aromatic compound is (IA) General formula (4): 【Chemistry 10】 [In the formula, ring A １ ' is the ring A １ and Ring A １ ' indicates the aromatic ring corresponding to X. １ represents a halogen atom.] and a nucleophilic agent, and then reacting an aromatic compound represented by the general formula (5A) or (5B): 【Chemistry 11】 [In the formula, R １ and n is the same as above.] and reacting the compound with an adamantanone compound represented by the formula: General formula (6): 【Chemistry 12】 [In the formula, A １” , R １ and n is the same as above.] A step of obtaining an adamantane-containing arene compound represented by the formula: (IB) A step of reacting the adamantane-containing arene compound obtained in the step (IA) with a Bronsted acid and / or a Lewis acid. and The aromatic compound represented by the general formula (4) General formula (4A): 【Chemistry 13】 [In the formula, X １ is the same as above. ２’ and Ring A ３’ are the same or different and represent an aromatic ring. ２ａ and R ３ａ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ２ａ and R ３ａ may be joined together to form an aromatic ring. Or general formula (4B): 【Chemistry 14】 [In the formula, ring A ４ and Ring A ５ are the same or different and each represents an aromatic ring. ２ represents a halogen atom. ４ａ and R ５ａ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ４ａ and R ５ａ may be joined together to form an aromatic ring. The method according to claim 6, wherein the compound is represented by the formula:

11. The method according to claim 10, wherein the nucleophilic agent is an organolithium compound and / or an organomagnesium compound.

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