Method for producing fused polycyclic compounds having fused five-membered rings, indacene derivatives, and p-phenylenevinylene derivatives and methods for producing the same

Abstract

To provide a method for producing a fused polycyclic compound having a fused five-membered ring that can yield an intermediate with many substituents useful as a scaffold for chemical reactions, and new p-phenylenevinylene derivatives prepared by such a production method.SOLUTION: A method for producing a fused polycyclic compound having a fused five-membered ring comprises converting a compound having a substructure represented by a general formula (1) in the figure into a compound having a substructure represented by a general formula (2) in the figure by action of an acid. In the general formula (1), R1 and R2 are each independently an alkyl group or the like, each X is independently a halogen atom, and the ring structure designated as Ar is an aromatic ring that may have substituents. In the general formula (2), R1 and R2 are each independently an alkyl group or the like, each X is independently a halogen atom, and the ring structure designated as Ar is an aromatic ring that may have substituents.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a fused polycyclic compound having fused five-membered rings, an indacene derivative, and a carbon-bridged p-phenylenevinylene derivative and a method for producing the same. [Background technology]

[0002] Indacene, a three-ring aromatic compound in which one six-membered ring and two five-membered rings are fused, is useful as an intermediate for preparing various chemical products such as pharmaceuticals, and electronic materials such as light-emitting materials, electron transport materials, and hole transport materials, which are made of compounds with large π-electron systems. While the synthesis of fused polycyclic aromatic compounds is generally not easy, the present inventors have proposed synthesizing such indacene derivatives using a relatively simple procedure and further developing them to produce p-phenylenevinylene derivatives with large π-electron systems (see, for example, Patent Document 1).

[0003] The p-phenylene vinylene derivatives described in Cited Document 1 are compounds with a ladder-like structure bridged by carbon atoms, which exhibit good luminescence efficiency and are said to be useful as molecular wires. Such p-phenylene vinylene derivatives are said to be synthesized from indacene derivatives in which aryl groups such as phenyl groups are bonded to carbon atoms constituting a five-membered ring, and Cited Document 1 introduces a procedure for synthesizing indacene derivatives in which the five-membered ring moiety is substituted with many phenyl groups.

[0004] On the other hand, when fused polycyclic compounds such as indacene derivatives are viewed as intermediates for synthesizing various chemical products, it is desirable that they have many substituents that serve as footholds for chemical reactions, such as leaving groups, etc. However, while the synthetic procedure shown in Cited Document 1 is convenient for obtaining indacene derivatives that have many aryl groups, such as phenyl groups, on the five-membered ring moiety, it is difficult to obtain indacene derivatives that have many alkyl groups or substituents that serve as footholds for chemical reactions on the five-membered ring moiety. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-32197 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a fused polycyclic compound having fused five-membered rings, which can provide an intermediate having many substituents useful as a scaffold for chemical reactions, and a novel p-phenylenevinylene derivative prepared by such a production method. [Means for solving the problem]

[0007] As a result of extensive research aimed at solving the above-mentioned problems, the present inventors have discovered that by treating a compound having a partial structure represented by the following general formula (1) with an acid such as a Lewis acid, a new five-membered ring is formed, converting it into a compound having a partial structure represented by the following general formula (2). The reaction mechanism is assumed to be as follows. In the following chemical reaction scheme, a compound (BF3·OEt2) in which diethyl ether is coordinated to boron trifluoride, a Lewis acid, is shown as the acid; however, the present invention is not limited to this. In addition, the following reaction scheme shows an example in which only one five-membered ring is formed. However, if the aromatic ring represented by Ar has two substituents for forming a five-membered ring, two five-membered rings will be formed, and if the aromatic ring represented by Ar has three substituents for forming a five-membered ring, three five-membered rings will be formed. Since the new five-membered ring formed in this way has multiple halogen atoms (X), compounds containing this five-membered ring are useful intermediates in the synthesis of various chemical products.

[0008] [ka]

[0009] Specifically, the present invention provides the following:

[0010] The present invention provides a method for producing a fused polycyclic compound having fused five-membered rings, characterized by reacting a compound having a partial structure represented by the following general formula (1) with an acid to convert it into a compound having a partial structure represented by the following general formula (2): [ka] (The double bond marked with * in the above general formula (1) may be cis or trans, and in general formula (1), R 1 and R 2 are each independently a hydrogen atom, -CQ3, or an aryl group which may have a substituent, or R 1 and R 2 and combine to form a ring structure, and each Q independently represents a hydrogen atom. an alkyl group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle, an alkoxy group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle, an alkylsulfanyl group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle, an alkylamino group or alkylaryl group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle In the above general formula (2), each X is independently a halogen atom, and the ring structure marked with the symbol Ar is an aromatic ring which may have a substituent. 1 and R 2 are each independently a hydrogen atom, -CQ3, or an aryl group which may have a substituent, or R 1 and R 2 and combine to form a ring structure, and each Q independently represents a hydrogen atom. an alkyl group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle, an alkoxy group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle, an alkylsulfanyl group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle, an alkylamino group or alkylaryl group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle wherein each X is independently a halogen atom, and the ring structure marked with Ar is an aromatic ring which may have a substituent.

[0011] The acid is preferably a Lewis acid.

[0012] The Lewis acid is preferably boron trifluoride or a compound in which a Lewis base is bound to boron trifluoride to form a complex.

[0013] The present invention also relates to an indacene derivative represented by any one of the following general formulas (3A) to (3F). [ka] (In the above general formulas (3A) to (3F), each R is independently a hydrogen atom, -CQ3, or an aryl group which may have a substituent, or two Rs bonded to the same carbon atom combine with each other to form a ring structure, and each Q is independently a hydrogen atom. an alkyl group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle, an alkoxy group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle, an alkylsulfanyl group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle, an alkylamino group or alkylaryl group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle and each X is independently a halogen atom.

[0014] The present invention also relates to a carbon-bridged p-phenylene vinylene derivative represented by the following general formula (4). [ka] (In the above general formula (4), each R is -CQ3, and each Q is independently a hydrogen atom. an alkyl group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle, an alkoxy group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle, an alkylsulfanyl group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle, an alkylamino group or alkylaryl group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle )

[0015] Each R in the above general formula (4) is preferably an n-butyl group.

[0016] The present invention also provides a method for producing a carbon-bridged p-phenylene vinylene derivative, comprising: step i) reacting a compound represented by general formula (11) below with a first acid to obtain a compound represented by general formula (12); step ii) reacting an alkyllithium compound with the compound represented by general formula (12) below, and then reacting the compound represented by general formula (13) below to obtain a compound represented by general formula (14); step iii) coupling the compound represented by general formula (14) below with a 1,4-phenylenediboronic acid compound to obtain a compound represented by general formula (15) below; and step iv) reacting the compound represented by general formula (15) below with a second acid to obtain a compound represented by general formula (16) below. [ka] (In the above chemical reaction formula, each X is independently a halogen atom, and each R 1 and R 2are each independently a hydrogen atom, -CQ3, or an aryl group which may have a substituent, or R 1 and R 2 and combine to form a ring structure, and each R 3 and R 4 are each independently a hydrogen atom, -CQ3, or an aryl group which may have a substituent, or R 3 and R 4 and combine to form a ring structure, and each Q independently represents a hydrogen atom. an alkyl group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle, an alkoxy group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle, an alkylsulfanyl group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle, an alkylamino group or alkylaryl group having 1 to 12 carbon atoms which may have a heteroatom or branch in the middle )

[0017] The first acid and the second acid are preferably both Lewis acids.

[0018] The Lewis acid is preferably boron trifluoride or a compound in which a Lewis base is bound to boron trifluoride to form a complex.

[0019] Above R 1 , R 2 , R 3 and R 4 It is preferred that all of the groups are n-butyl groups. [Effects of the Invention]

[0020] According to the present invention, there are provided a method for producing a fused polycyclic compound having fused five-membered rings, which can give an intermediate having many substituents useful as a scaffold for chemical reactions, and a novel p-phenylenevinylene derivative prepared by such a production method. DETAILED DESCRIPTION OF THE INVENTION

[0021] Hereinafter, one embodiment of the method for producing a fused polycyclic compound having linked five-membered rings of the present invention, one embodiment of the indacene derivative of the present invention, one embodiment of the carbon-bridged p-phenylene vinylene derivative of the present invention, and one embodiment of the method for producing a carbon-bridged p-phenylene vinylene of the present invention will be described. Note that the present invention is not limited to the following embodiments and examples, and can be practiced with appropriate modifications within the scope of the present invention.

[0022] <Method for producing fused polycyclic compounds containing five-membered rings> First, one embodiment of the method for producing a fused polycyclic compound having five-membered rings linked together according to the present invention will be described. The method for producing a fused polycyclic compound having five-membered rings linked together according to the present invention is characterized in that a compound having a partial structure represented by the following general formula (1) is converted into a compound having a partial structure represented by the following general formula (2) by reacting it with an acid. By carrying out this production method, a five-membered ring fused to the aromatic ring represented by Ar in the following general formula (1) is added. This reaction can be carried out at room temperature and with a good yield. Furthermore, since a halogen atom represented by X in the following general formula (2) is introduced into the fused ring, the compound represented by general formula (2) obtained by this reaction is useful as an intermediate for synthesizing various chemical products. Thus, according to the production method of the present invention, intermediates useful for synthesizing various chemical products can be prepared with good yield through simple experimental procedures.

[0023] [ka]

[0024] In the above general formula (1), for convenience, the double bond portion is expressed as a trans form, but this double bond portion, i.e., the double bond marked with *, may be in either a cis form or a trans form. As already explained, the compound represented by general formula (1) takes on a cationic intermediate structure when the hydroxyl group contained in general formula (1) is abstracted by an acid, and at that time, it enters an equilibrium state where it alternates between the cis form and the trans form. When it takes on the cis form, R 1 and R 2 The carbon atom to which the bond is attached attacks the aromatic ring, forming a five-membered ring. According to this reaction mechanism, the bond marked with an * in general formula (1) can be either cis or trans. In the chemical reaction formula below, BF3·OEt2 is used as an example of the acid, but of course other acids can also be used.

[0025] [ka]

[0026] R in the above general formula (1) 1 and R 2 are each independently (a) a hydrogen atom, -CQ3, or an aryl group which may have a substituent, or (b) R 1 and R 2 In the case of (a), each Q is independently a hydrogen atom or a monovalent organic group. 1 or R 2becomes -CQ3, these have the structure -CH3, -CH2Q, CHQ2, or -CQ3, and therefore have a carbon atom at the alkyl terminal, and the latter three have a hydrogen atom or a monovalent organic group at the end. Examples of such monovalent organic groups include alkyl groups having 1 to 12 carbon atoms, which may have a heteroatom or branching along the chain, alkoxy groups having 1 to 12 carbon atoms, which may have a heteroatom or branching along the chain, alkylsulfanyl groups having 1 to 12 carbon atoms, which may have a heteroatom or branching along the chain, alkylamino groups having 1 to 12 carbon atoms, which may have a heteroatom or branching along the chain, and alkylaryl groups. Examples of alkyl groups having 1 to 12 carbon atoms, which may have a branching along the chain, include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and 2-ethylhexyl. These alkyl groups may have an aryl group, which may have a substituent, in the chain or at the terminal. Although alkyl groups having heteroatoms or aryl groups in the chain cannot strictly be called alkyl groups, in the present invention, such groups are also referred to as alkyl groups. In this case, the number of carbon atoms contained in the aryl group is not included in the number of carbon atoms of the alkyl group. Furthermore, these alkyl groups may have various substituents. Examples of such substituents include a hydroxyl group, a nitro group, an amino group, a sulfo group, an aryl group, and an alkoxy group. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom. Among these, Q is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Examples of the aryl group that may have the substituent include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a thienyl group, a furyl group, a pyridyl group, and a pyrimidyl group. In the case of (b), R 1 and R 2 Examples of the ring structure formed by combining these include an optionally substituted aliphatic ring and aromatic ring, such as a cyclopentane ring, a fluorene ring, a cyclohexane ring, an indene ring, a tetrahydrofuran ring, a pyran ring, a pyrrolidine ring, and a piperidine ring.

[0027] In the general formula (1), each X is independently a halogen atom. Examples of such a halogen atom include a chlorine atom, a bromine atom, and an iodine atom, with a bromine atom being preferred.

[0028] In the above general formula (1), the ring structure marked with the symbol Ar is an aromatic ring which may have a substituent. Examples of such aromatic rings include a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, a thiophene ring, a furan ring, a pyridine ring, and a pyrimidine ring. Among these, a benzene ring and a naphthalene ring are preferred. Note that the above general formula (1) is a partial structure of a compound, and this Ar may have any substituent, or may be a fused ring. For example, if this Ar has one more chain group shown in general formula (1), a compound having two fused five-membered rings is obtained, and if it has two more chain groups, a compound having three fused five-membered rings is obtained.

[0029] An example of a compound having the partial structure represented by the general formula (1) is as follows: In the following chemical formula, Me represents a methyl group, Bu represents an n-butyl group, Hex represents an n-hexyl group, and Ph represents a phenyl group. [ka]

[0030] By reacting an acid with a compound having the partial structure represented by the above general formula (1), a five-membered ring is formed, and a compound having the partial structure represented by the above general formula (2) is obtained. The acid may be a Bronsted acid or a Lewis acid. For example, if the acid is a Bronsted acid, a proton is added to the hydroxyl group to form -OH2 + If the acid is a Lewis acid, the Lewis acid coordinates with the oxygen atom of the hydroxyl group and then the coordinated molecule is eliminated. Thus, any acid may be used, but among these, Lewis acids are preferred.

[0031] Examples of Lewis acids include boron trifluoride, boron trichloride, aluminum chloride, and titanium(IV) chloride. Among these Lewis acids, boron trifluoride is a preferred example, and from the viewpoint of ease of handling, boron trifluoride bonded to a Lewis base is more preferred. Examples of such Lewis bases include, but are not limited to, diethyl ether.

[0032] When an acid is allowed to act on a compound having a partial structure represented by the general formula (1) to obtain a compound having a partial structure represented by the general formula (2), the compound having the partial structure represented by the general formula (1) is dissolved in a solvent and then the acid is allowed to act on the compound. The amount of acid added in this case can be, for example, about 2 to 10 times the molar amount of the compound having the partial structure represented by the general formula (1). After the acid is added, the reaction is carried out at room temperature for about 10 to 30 minutes to obtain a compound having a partial structure represented by the general formula (2).

[0033] R in the above general formula (2) 1 and R 2 are each independently (a) a hydrogen atom, -CQ3, or an aryl group which may have a substituent, or (b) R 1 and R 2 In the case of (a), each Q is independently a hydrogen atom or a monovalent organic group. 1 or R 2When the alkyl group is -CQ3, it has a carbon atom at the alkyl terminal and a hydrogen atom or a monovalent organic group at the end. Examples of such monovalent organic groups include alkyl groups having 1 to 12 carbon atoms, which may have a heteroatom or branch, alkoxy groups having 1 to 12 carbon atoms, which may have a heteroatom or branch, alkylsulfanyl groups having 1 to 12 carbon atoms, which may have a heteroatom or branch, alkylamino groups having 1 to 12 carbon atoms, which may have a heteroatom or branch, and alkylaryl groups. Examples of alkyl groups having 1 to 12 carbon atoms, which may have a branch, include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and 2-ethylhexyl. These alkyl groups may have an aryl group, which may have a substituent, in the chain or at the terminal. These alkyl groups may also have various substituents. Examples of such a substituent include a hydroxyl group, a nitro group, an amino group, a sulfo group, an aryl group, an alkoxy group, etc. Examples of the heteroatom include an oxygen atom, a sulfur atom, a nitrogen atom, etc. Among these, Q is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an alkyl group having 3 to 12 carbon atoms. Examples of the aryl group that may have the substituent include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a thienyl group, a furyl group, a pyridyl group, a pyrimidyl group, etc. In the case of (b), R 1 and R 2 Examples of the ring structure formed by combining these include an optionally substituted aliphatic ring and aromatic ring, such as a cyclopentane ring, a fluorene ring, a cyclohexane ring, an indene ring, a tetrahydrofuran ring, a pyran ring, a pyrrolidine ring, and a piperidine ring.

[0034] In the general formula (2), each X is independently a halogen atom. Examples of such a halogen atom include a chlorine atom, a bromine atom, and an iodine atom, with a bromine atom being preferred.

[0035] In the above general formula (2), the ring structure marked with the symbol Ar is an aromatic ring which may have a substituent. Examples of such aromatic rings include a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, a thiophene ring, a furan ring, a pyridine ring, and a pyrimidine ring. Among these, a benzene ring and a naphthalene ring are preferred. Note that the above general formula (2) is a partial structure of a compound, and this Ar may have any substituent, or this Ar may be fused with a ring other than the newly formed five-membered ring.

[0036] Examples of compounds having the partial structure represented by general formula (2) above include the following. In the chemical formulas below, Me represents a methyl group, Bu represents an n-butyl group, Hex represents an n-hexyl group, and Ph represents a phenyl group. In the chemical formulas below, compounds 2a to 2p correspond to compounds synthesized by the production method of the present invention using compounds 1a to 1p shown in Compound Example 1 above as starting materials, as examples of compounds having the partial structure represented by general formula (1). For example, compound 2a below corresponds to a compound obtained by the production method of the present invention using compound 1a as a starting material.

[0037] [ka]

[0038] <Indacene derivatives> The indacene derivatives represented by the following general formulas (3A) to (3F) also constitute the present invention. The indacene derivatives of the present invention are compounds having a three-ring structure and a skeleton in which five-membered rings are fused to both sides of a central benzene ring. The indacene derivatives of the present invention are preferably prepared by the method of the present invention for producing a fused polycyclic compound in which five-membered rings are fused, and contain many halogen atoms in the molecule, which serve as scaffolds for chemical reactions, and are therefore useful as synthetic intermediates for chemical products.

[0039] [ka]

[0040] In the general formulas (3A) to (3F), each R is independently (a) a hydrogen atom, -CQ3, or an aryl group which may have a substituent, or (b) two Rs bonded to the same carbon atom combine to form a ring structure. In the case of (a), each Q is independently a hydrogen atom or a monovalent organic group. That is, when R is -CQ3, it has a carbon atom at the alkyl terminal, and a hydrogen atom or a monovalent organic group at the end of the carbon atom. Examples of such monovalent organic groups include alkyl groups having 1 to 12 carbon atoms which may have a heteroatom or branching, alkoxy groups having 1 to 12 carbon atoms which may have a heteroatom or branching, alkylsulfanyl groups having 1 to 12 carbon atoms which may have a heteroatom or branching, alkylamino groups having 1 to 12 carbon atoms which may have a heteroatom or branching, and alkylaryl groups. Examples of alkyl groups having 1 to 12 carbon atoms, which may have a branch, include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and 2-ethylhexyl. These alkyl groups may have an aryl group, which may have a substituent, in the chain or at the terminal. These alkyl groups may also have various substituents. Examples of such substituents include a hydroxyl group, a nitro group, an amino group, a sulfo group, an aryl group, and an alkoxy group. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom. Among these, Q is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 3 to 12 carbon atoms. Examples of the aryl group, which may have a substituent, include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a thienyl group, a furyl group, a pyridyl group, and a pyrimidyl group. In the case of (b), examples of the ring structure formed by combining two Rs bonded to the same carbon atom include an optionally substituted aliphatic ring or aromatic ring, such as a cyclopentane ring, a fluorene ring, a cyclohexane ring, an indene ring, a tetrahydrofuran ring, a pyran ring, a pyrrolidine ring, and a piperidine ring.

[0041] In the above general formulas (3A) to (3F), each X is independently a halogen atom. Examples of such a halogen atom include a chlorine atom, a bromine atom, and an iodine atom, with a bromine atom being preferred.

[0042] The compound represented by general formula (3A) and the compound represented by general formula (3B) are related in that one compound becomes the other compound by flipping one five-membered ring upside down. These general formulas correspond to the above-mentioned compounds 2o and 2p, respectively, and these compounds are synthesized from the above-mentioned compounds 1o and 1p, respectively. In this way, in the method of producing a fused polycyclic compound having fused five-membered rings of the present invention, the compounds of the above-mentioned general formulas (3A) to (3F) can be produced separately by adjusting the position and number of the substituents of the substituted benzene starting material.

[0043] <Carbon-bridged p-phenylene vinylene derivative> The present invention also includes a carbon-bridged p-phenylenevinylene derivative represented by the following general formula (4): The carbon-bridged p-phenylenevinylene derivative of the present invention is preferably prepared by the above-mentioned method for producing a fused polycyclic compound having fused five-membered rings of the present invention.

[0044] [ka]

[0045] In the general formula (4), each R is -CQ3, and each Q is independently a hydrogen atom or a monovalent organic group. That is, each R has a carbon atom as an alkyl terminal, and a hydrogen atom or a monovalent organic group at the end of the carbon atom. Examples of such monovalent organic groups include alkyl groups having 1 to 12 carbon atoms, which may have a heteroatom or branch, alkoxy groups having 1 to 12 carbon atoms, which may have a heteroatom or branch, alkylsulfanyl groups having 1 to 12 carbon atoms, which may have a heteroatom or branch, alkylamino groups having 1 to 12 carbon atoms, which may have a heteroatom or branch, and alkylaryl groups. Examples of alkyl groups having 1 to 12 carbon atoms, which may have a branch, include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and 2-ethylhexyl. These alkyl groups may have an aryl group, which may have a substituent, in the chain or at the end. These alkyl groups may also have various substituents. Examples of such substituents include a hydroxyl group, a nitro group, an amino group, a sulfo group, an aryl group, and an alkoxy group. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom. Among these, R is preferably an n-butyl group, and it is more preferable that all R are n-butyl groups.

[0046] In the above general formula (4), the key point of the present invention is that each R is bonded to the p-phenylenevinylene skeleton via a carbon atom that becomes an alkyl terminal, thereby forming a substituted or unsubstituted alkyl group that may have a branch. In the above general formula (4), those in which each R is an aryl group are already known, and it has been reported that they all have good luminous efficiency and molecular wire functions (for example, see J. Am. Chem. Soc. 2012, 134, 19254 and JP-A-2011-32197). However, according to the studies of the present inventors, it has been found that in the case of a carbon-bridged p-phenylenevinylene derivative in which each R is an alkyl group having 1 or more carbon atoms, the molar absorption coefficient and the radiative decay constant in fluorescence emission become larger. A large molar absorption coefficient means that the excitation light can be efficiently absorbed, and a large radiative decay constant in fluorescence emission means that the time from excitation to fluorescence radiative decay is short, which means that stronger fluorescence can be emitted. For reference, Table 1 shows the molar absorption coefficient and the radiative decay constant when each R is an Ar(p-octylphenyl group) and an n-butyl group (the present invention) in the above general formula (4).

[0047]

Table 1

[0048] The carbon-bridged p-phenylenevinylene derivative of the present invention is also prepared by the method for producing a carbon-bridged p-phenylenevinylene derivative which is one of the present inventions. Next, the method for producing the carbon-bridged p-phenylenevinylene derivative of the present invention will be described.

[0049] <Method for Producing p-Phenylenevinylene Derivative> The method for producing a p-phenylene vinylene derivative of the present invention is an application of the method for producing a fused polycyclic compound having fused five-membered rings of the present invention, and is characterized by comprising: step [i] of reacting a compound represented by general formula (11) with a first acid to obtain a compound represented by general formula (12): step [ii] of reacting the compound represented by general formula (12) with an alkyllithium compound and then with a compound represented by general formula (13) to obtain a compound represented by general formula (14): step [iii] of coupling the compound represented by general formula (14) with a 1,4-phenylenediboronic acid compound to obtain a compound represented by general formula (15): and step [iv] of reacting the compound represented by general formula (15) with a second acid to obtain a compound represented by general formula (16). Each step is described below.

[0050] [ka] (In the above chemical reaction formula, each X is independently a halogen atom, and each R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a heteroatom or a branch, or an aryl group which may have a substituent, or R 1 and R 2 and combine to form a ring structure, and each R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a heteroatom or a branch, or an aryl group which may have a substituent, or R 3 and R 4 and combine to form a ring structure.)

[0051] [Process i] Step i is a step of reacting a compound represented by the general formula (11) with a first acid to obtain a compound represented by the general formula (12). This chemical reaction is the same as the chemical reaction in the method of producing the fused polycyclic compound having fused five-membered rings of the present invention.

[0052] In the general formulas (11) and (12), R 1 and R 2 are each independently (a) a hydrogen atom, -CQ3, or an aryl group which may have a substituent, or (b) R 1 and R 2 In the case of (a), each Q is independently a hydrogen atom or a monovalent organic group. 1 or R 2 When the alkyl group is -CQ3, it has a carbon atom at the alkyl terminal and a hydrogen atom or a monovalent organic group at the end. Examples of such monovalent organic groups include alkyl groups having 1 to 12 carbon atoms, which may have a heteroatom or branch, alkoxy groups having 1 to 12 carbon atoms, which may have a heteroatom or branch, alkylsulfanyl groups having 1 to 12 carbon atoms, which may have a heteroatom or branch, alkylamino groups having 1 to 12 carbon atoms, which may have a heteroatom or branch, and alkylaryl groups. Examples of alkyl groups having 1 to 12 carbon atoms, which may have a branch, include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and 2-ethylhexyl. These alkyl groups may have an aryl group, which may have a substituent, in the chain or at the terminal. These alkyl groups may also have various substituents. Examples of such a substituent include a hydroxyl group, a nitro group, an amino group, a sulfo group, an aryl group, an alkoxy group, etc. Examples of the heteroatom include an oxygen atom, a sulfur atom, a nitrogen atom, etc. Among these, Q is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an alkyl group having 3 to 12 carbon atoms. Examples of the aryl group that may have the substituent include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a thienyl group, a furyl group, a pyridyl group, a pyrimidyl group, etc. In the case of (b), R 1 and R 2Examples of the ring structure formed by combining R include an optionally substituted aliphatic ring and aromatic ring, such as a cyclopentane ring, a fluorene ring, a cyclohexane ring, an indene ring, a tetrahydrofuran ring, a pyran ring, a pyrrolidine ring, and a piperidine ring. 1 and R 2 In general formula (11), R is preferably an n-butyl group. 1 and R 2 is R in general formula (12) 1 and R 2 are the same as

[0053] In the general formulas (11) and (12), each X is independently a halogen atom. Examples of such a halogen atom include a chlorine atom, a bromine atom, and an iodine atom. Among these, a bromine atom is preferred. Note that each X in the general formula (11) is the same as the corresponding X in the general formula (12).

[0054] By allowing the compound represented by the general formula (11) to react with a first acid, a five-membered ring is formed, and a compound represented by the general formula (12) is obtained. The first acid may be a Bronsted acid or a Lewis acid. This is as already explained in the method for producing a fused polycyclic compound of the present invention in which five-membered rings are fused. Among these acids, Lewis acids are preferred as the first acid.

[0055] Examples of Lewis acids include boron trifluoride, boron trichloride, aluminum chloride, and titanium(IV) chloride. Among these Lewis acids, boron trifluoride is a preferred example, and from the viewpoint of ease of handling, boron trifluoride bonded to a Lewis base is more preferred. Examples of such Lewis bases include, but are not limited to, diethyl ether.

[0056] When the compound represented by the general formula (11) is reacted with the first acid to obtain the compound represented by the general formula (12), the compound represented by the general formula (11) is dissolved in a solvent and then reacted with the first acid. In this case, the amount of the first acid added can be, for example, about 2 to 10 times the number of moles of the compound represented by the general formula (11). After adding the acid, the reaction is carried out at room temperature for about 10 to 30 minutes to obtain the compound represented by the general formula (12).

[0057] The compound represented by general formula (12) obtained in step i is subjected to appropriate purification and then to step ii.

[0058] [Step ii] Step ii is a step of reacting an alkyllithium compound with a compound represented by the general formula (12) and then reacting with a compound represented by the general formula (13) to obtain a compound represented by the general formula (14). That is, one X in the compound represented by the general formula (12) is lithiated to impart nucleophilicity, and then this is allowed to attack the carbonyl group of the compound represented by the general formula (13) to obtain a compound represented by the general formula (14).

[0059] R in general formulas (12) and (14) 1 , R 2 and X are the same as those in the general formula (11). 1 and R 2 is R in general formula (12) 1 and R 2 and X in general formula (14) is the same as the corresponding X in general formula (12).

[0060] The alkyllithium compound is a reagent for lithiating X in the compound represented by general formula (12), and n-butyllithium is preferably used. The conditions for lithiation include, but are not limited to, dissolving the compound represented by general formula (12) in a solvent to form a solution, cooling the solution to −78°C, and adding the alkyllithium compound dropwise over about 1 hour with stirring. A preferred solvent is dehydrated tetrahydrofuran. The amount of alkyllithium compound added is preferably about equimolar to the compound represented by general formula (12). After the dropwise addition of the alkyllithium compound is complete, the mixture is stirred for about 1 hour while maintaining the temperature, thereby completing the lithiation.

[0061] Next, the compound represented by general formula (13) is added dropwise to the solution after the lithiation is completed. After the addition is complete, stirring is continued for about 30 minutes, and then the solution temperature is gradually returned to room temperature to quench the reaction. For example, an aqueous ammonium chloride solution can be added to the reaction solution to quench the reaction. This reaction yields the compound represented by general formula (14).

[0062] R in general formulas (13) and (14) 3 and R 4 are each independently (a) a hydrogen atom, -CQ3, or an aryl group which may have a substituent, or (b) R 3 and R 4 In the case of (a), each Q is independently a hydrogen atom or a monovalent organic group. 3 or R 4When the alkyl group is -CQ3, it has a carbon atom at the alkyl terminal and a hydrogen atom or a monovalent organic group at the end. Examples of such monovalent organic groups include alkyl groups having 1 to 12 carbon atoms, which may have a heteroatom or branch, alkoxy groups having 1 to 12 carbon atoms, which may have a heteroatom or branch, alkylsulfanyl groups having 1 to 12 carbon atoms, which may have a heteroatom or branch, alkylamino groups having 1 to 12 carbon atoms, which may have a heteroatom or branch, and alkylaryl groups. Examples of alkyl groups having 1 to 12 carbon atoms, which may have a branch, include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and 2-ethylhexyl. These alkyl groups may have an aryl group, which may have a substituent, in the chain or at the terminal. These alkyl groups may also have various substituents. Examples of such a substituent include a hydroxyl group, a nitro group, an amino group, a sulfo group, an aryl group, an alkoxy group, etc. Examples of the heteroatom include an oxygen atom, a sulfur atom, a nitrogen atom, etc. Among these, Q is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an alkyl group having 3 to 12 carbon atoms. Examples of the aryl group that may have the substituent include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a thienyl group, a furyl group, a pyridyl group, a pyrimidyl group, etc. In the case of (b), R 3 and R 4 Examples of the ring structure formed by combining R include an optionally substituted aliphatic ring and aromatic ring, such as a cyclopentane ring, a fluorene ring, a cyclohexane ring, an indene ring, a tetrahydrofuran ring, a pyran ring, a pyrrolidine ring, and a piperidine ring. 3 and R 4 In general formula (13), R is preferably an n-butyl group. 3 and R 4 is R in general formula (14) 3 and R 4 are the same as

[0063] The compound represented by the general formula (14) obtained in step ii is subjected to appropriate purification and then to step iii.

[0064] [Step iii] Step iii is a step in which the compound represented by the general formula (14) is coupled with a 1,4-phenylenediboronic acid compound to obtain the compound represented by the general formula (15). Through this reaction, two molecules of the compound represented by the general formula (14) are bonded via a p-phenylene group to form the compound represented by the general formula (15). The coupling reaction here is known as the Suzuki-Miyaura cross-coupling reaction.

[0065] R in general formula (15) 1 , R 2 , R 3 and R 4 is R in general formula (14) 1 , R 2 , R 3 and R 4 Since it is the same as the above, the explanation will be omitted here.

[0066] The 1,4-phenylenediboronic acid compound corresponds to the boronic acid compound used in the Suzuki-Miyaura cross-coupling reaction. It can be 1,4-phenylenediboronic acid itself, or a compound in which both boronic acid moieties are protected. When using a compound with a protected boronic acid moiety, the protecting group can be a pinacol ester of boronic acid, a biscyclohexyldiol ester of boronic acid, a diaminonaphthalenamide of boronic acid, or a trifluoroborate salt.

[0067] The coupling reaction conditions for the compound represented by general formula (14) with a 1,4-phenylenediboronic acid compound can be the same as those typically used in the Suzuki-Miyaura cross-coupling reaction. One example of such conditions involves adding 0.5 equivalents of 1,4-phenylenediboronic acid to 1 equivalent of the compound represented by general formula (14), adding a palladium(0) catalyst and triphenylphosphine to a solvent containing aqueous potassium carbonate, and reacting at approximately 100°C for approximately 24 hours. The palladium(0) catalyst is preferably, but is not limited to, tris(dibenzylideneacetone)dipalladium(0), also known as Pd2(dba)3. The solvent is preferably, but is not limited to, dioxane.

[0068] The compound represented by the general formula (15) obtained in step iii is subjected to step iv either directly or after suitable purification.

[0069] [Process iv] Step iv is a step of reacting a compound represented by the above general formula (15) with a second acid to obtain a compound represented by the above general formula (16).

[0070] R in general formulas (15) and (16) 1 , R 2 , R 3 and R 4 is R in general formula (14) 1 , R 2 , R 3 and R 4 Since it is the same as the above, the explanation will be omitted here.

[0071] The second acid may be a Bronsted acid or a Lewis acid, and among these acids, Lewis acids are preferred as the second acid.

[0072] Examples of Lewis acids include boron trifluoride, boron trichloride, aluminum chloride, and titanium(IV) chloride. Among these Lewis acids, boron trifluoride is a preferred example, and from the viewpoint of ease of handling, boron trifluoride bonded to a Lewis base is more preferred. Examples of such Lewis bases include, but are not limited to, diethyl ether.

[0073] When the compound represented by the general formula (15) is reacted with the second acid to obtain the compound represented by the general formula (16), the compound represented by the general formula (15) is dissolved in a solvent and then reacted with the second acid. In this case, the amount of the second acid added can be, for example, about 2 to 10 times the number of moles of the compound represented by the general formula (15). After adding the acid, the reaction is carried out at room temperature for about 10 to 30 minutes to obtain the compound represented by the general formula (16). [Example]

[0074] The present invention will be explained in more detail below by showing examples, but the present invention is not limited to the following examples in any way.

[0075] First, as a general procedure for synthesizing starting compounds 0a to 0p for synthesizing compounds 1a to 1p represented in Compound Example 1 above, some of the compounds 0a to 0p are selected and the procedure is described below. Compounds 0a to 0p for which no synthesis procedure is described below can be synthesized by a procedure similar to the synthesis procedure below or are commercially available. Compounds 0a to 0p correspond to the starting compounds for synthesizing compounds 1a to 1p in Compound Example 1 above, respectively. Similarly, compounds 1a to 1p correspond to the starting compounds for synthesizing compounds 2a to 2p in Compound Example 2 above, respectively.

[0076] Synthesis of 5-(p-tolylethynyl)nonan-5-ol (compound 0h) [ka]

[0077] 1-Ethynyl-4-methylbenzene (290 mg, 2.50 mmol) was dissolved in 10 mL of dry tetrahydrofuran (THF) and the solution was cooled to 0 °C. To this solution, n-butyllithium (1.57 mL, 2.50 mmol as a 1.59 M hexane solution) was added dropwise, and the mixture was stirred for 0.5 hours while maintaining the temperature. 5-Nonanone (349 mg, 2.45 mmol) was then added dropwise, and the mixture was stirred at 0 °C for 3 hours. After completion of the reaction, the reaction solution was quenched by adding water (10 mL) and extracted three times with 10 mL of methylene chloride. The combined organic phase was dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane:methylene chloride = 1:1) to give compound 0h as a pale yellow oil (yield: 416 mg, 64%). 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.32-7.31(m,2H),7.12-7.09(m,2H),7.23-7.18(m,2H),2.34(s,3H),1.96(s,1) H),1.78-1.66(m,4H),1.58-1.51(m,4H),1.42-1.34(m,4H),0.96-0.92(m,6H). 13 C{ 1 H}-NMR(150MHz,CDCl3):δ(ppm) 138.1,131.5,128.9,119.8,91.5,84.3,71.6,41.8,26.5,22.9,21.4,14.0. HRMS(APCI+) m / z calculation for C 18 H 27 O([M+H] + ):259.2062,found:259.2056.

[0078] 5-(o-Tolylethynyl)nonan-5-ol (Compound 0i) [ka]

[0079] Compound 0i was obtained as a colorless oil (yield 81%) by the same procedure as above, except that different starting materials were used. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.39(d,J=7.8Hz,1H),7.23-7.18(m,2H),7.15-7.11(m,1H),2.43(s,3H),1.98(s ,1H),1.80-1.69(m,4H),1.61-1.53(m,5H),1.44-1.34(m,4H),0.91-0.96(m,7H). 13 C{ 1 H}-NMR(150MHz,CDCl3):δ(ppm) 139.9,131.9,129.2,128.0,125.4,122.6,96.3,83.0,71.7,41.9,26.5,22.8,20.6,14.0. HRMS (APCI+) m / z calculation for C 18 H 25 O([MH] + ):257.1905,found:257.1895.

[0080] Synthesis of 5-[(4-methoxyphenyl)ethynyl]nonan-5-ol (compound 0j) [ka]

[0081] 1-Bromo-4-methoxybenzene (486.2 mg, 2.60 mmol), 5-ethynyl-5-nonanol (451.6 mg, 2.68 mmol), PdCl(PPh) (78.9 mg, 0.11 mmol), and CuI (67.4 mg, 0.11 mmol) were dissolved in piperidine (2.7 mL). The solution was stirred at 80 °C for 3 days, filtered, and the filtrate was concentrated. This was purified by silica gel column chromatography (hexane:methylene chloride = 1:4) to give compound 0j as a brown oil (yield 273.8 mg, 38%). 1H-NMR(400MHz, CDCl3):δ(ppm) 7.37-7.34(m,2H),6.85-6.81(m,2H),3.81(s,2H),1.95(s,1H),1.78-1 .68(m,4H),1.58-1.51(m,6H),1.42-1.34(m,4H),0.95(t,J=7.3Hz,6H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 159.5,133.1,115.0,113.8,90.8,84.1,71.6,55.3,41.9,26.5,22.9,14.1 HRMS (APCI+) m / z calculation for C 18 H 27 O2([M+H] + ):275.2011,found:257.2000.

[0082] 5-[(4-bromophenyl)ethynyl]nonan-5-ol (compound 0k) [ka]

[0083] Compound 0k was obtained as a yellow oil (yield 27%) by the same procedure as above, except that different starting materials were used. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.45-7.42(m,2H),7.29-7.26(m,2H),1.95(s,1H),1.78-1.66(m,4H),1.57-1.49(m,4H),1.42-1.33(m,4H),0.93(t,J=7.2Hz,6H). 13 C{ 1 H}-NMR(150MHz,CDCl3):δ(ppm) 133.0,131.4,122.3,121.8,93.5,83.1,71.5,41.7,26.4,22.8,14.0. HRMS (APCI+) m / z calculation for C 17 H 24 BrO([M+H]+ ):323.1011,found:323.1002.

[0084] 5-{[4-(trifluoromethyl)phenyl]ethynylnonan-5-ol (compound 01) [ka]

[0085] Compound 01 was obtained as a pale yellow oil (yield 64%) by the same procedure as above, except that different starting materials were used. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.56(d,J=8.2Hz,2H),7.52(d,J=8.2Hz,2H),1.99(s,1H),1.80-1.67(m,4H),1.58-1.50(m,9H),1.39(m,4H),0.95(t,J=7.3Hz,6H). 13 C{ 1 H}-NMR(150MHz,CDCl3):δ(ppm) 131.9,129.9(q, 2 J C-F =33Hz), 126.7, 125.2, 123.9(q, 1 J C-F =271Hz),94.8,83.0,71.7,41.7,26.5,22.9,14.1. HRMS (APCI+) m / z calculation for C 18 H 23 F3O([M] + ):317.1701,found: 312.1691.

[0086] 5-[(1,1'-biphenyl)-4-ylethynyl]nonan-5-ol (compound 0m) [ka]

[0087] Compound 0m was obtained as a pale yellow solid (yield 65%) by the same procedure as above, except that different starting materials were used. Mp:52-53℃. 1 H-NMR (400MHz, CDCl3): δ(ppm)7.59(dt,J=7.0,1.4Hz,2H),7.55(dd,J=6.4,1.8Hz,2H),7.51-7.48(m,2H),7.47-7. 43(m,2H),7.38-7.34(m,1H),1.99(s,1H),1.79-1.68(m,4H),1.64-1.52(m,4H),1.40(m,4H),0.96(t,J=7.1Hz,6H). 13 C{ 1 H}-NMR(150MHz,CDCl3):δ(ppm) 140.9,140.3,132.1,128.8,127.6,127.0,126.9,121.8,92.9,84.1,71.7,41.9,26.5,22.9,14.1. HRMS (APCI+) m / z calculation for C 23 H 28 O([M] + ):320.2140,found:320.2123.

[0088] 2-(3-butyl-3-hydroxynon-1-ynyl)naphthalene (compound 0n) [ka]

[0089] Compound 0n was obtained as a yellow oil (yield 71%) by the same procedure as above, except that different starting materials were used. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.94(s,1H),7.82-7.76(m,3H),7.49-7.45(m,3H),2.01(s,1H),1,79-1 .74(m,4H),1.61-1.56(m,4H),1.46-1.38(m,4H),0.97(t,J=7.2Hz,3H). 13 C{ 1H}-NMR(150MHz,CDCl3):δ(ppm) 132.8,132.6,131.3,128.4,127.8,127.62,127.56,126.5,126.4,120.1,92.6,84.5,71.6,41.8,26.5,22.9,14.0. HRMS (APCI+) m / z calculation for C 21 H 26 O([M] + ):294.1984,found:294.1984.

[0090] 1,3-bis(3-butyl-3-hydroxynon-1-ynyl)benzene (compound 0p) [ka]

[0091] Compound 0p was obtained as a white solid (yield 56%) by the same procedure as above, except that different starting materials were used. Mp:115-117℃. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.47(brs,1H),7.35(dd,J=8.4,1.2Hz,2H),7.25(t,J=8.4Hz,1H),1.96(s,2H),1 .78-1.67(m,8H),1.58-1.50(m,16H),1.43-1.34(m,8H),0.95(t,J=7.6Hz,12H). 13 C{ 1 H}-NMR(150MHz,CDCl3):δ(ppm) 134.7,131.3,128.3,123.1,92.9,83.4,71.6,41.8,26.5,22.9,14.1. HRMS (APCI+) m / z calculation for C 12 H 13 Br2([M] + ):410.3185,found:410.3175.

[0092] Next, some of the compounds 1a-1p are selected from the compounds 1a-1p and the procedures are described below as general procedures for synthesizing the starting compounds 1a-1p for synthesizing the compounds 2a-2p shown in the above Compound Example 2. Compounds 1a-1p for which no synthesis procedures are described below can be synthesized by a procedure similar to the synthesis procedure below. Furthermore, as described above, compounds 1a-1p correspond to the starting compounds for synthesizing the compounds 2a-2p in the above Compound Example 2, respectively.

[0093] Synthesis of (E)-3,4-dibromo-2-methyl-4-phenylbut-3-en-2-ol (compound 1a) [ka]

[0094] N-Bromosuccinimide (NBS; 698 mg, 3.92 mmol) and tetrabutylammonium bromide (TBAB; 1.27 g, 3.93 mmol) were added to a methylene chloride solution (0.25 mL) of 2-methyl-4-phenylbut-3-yn-2-ol (209 mg, 1.30 mmol) and stirred at room temperature for 72 hours. Saturated aqueous sodium thiosulfate was added to the reaction solution, which was then extracted three times with 10 mL of methylene chloride. The combined organic phases were dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane:methylene chloride = 1:1) to give compound 1a as a white solid (yield 205 mg, 49%). Mp:174-175℃. 1 H-NMR (400MHz, CDCl3): δ(ppm) 7.41-7.36(m,2H),7.33-7.27(m,3H),1.74(s,6H). 13 C{ 1 H}-NMR(100 MHz, CDCl3):δ(ppm) 143.6,130.7,128.6,128.6,128.5,113.9,76.0,30.0. HRMS (APCI+) m / z calculation for C 11 H 11Br2([M-OH] + ):300.9228,found:300.9220.

[0095] (E)-1,2-Dibromo-3-methyl-1-phenylpent-1-en-3-ol (compound 1b) [ka]

[0096] Compound 1b was obtained as a white solid (yield 82%) by the same procedure as above, except that compound 0b was used as the starting material. Mp:54.5-56℃. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.40-7.37(m,2H),7.33-7.29(m,1H),7.26(dd,J=4.7,2.7Hz,2H),2.98(s,1 H),2.28-2.19(m,1H),2.00-1.91(m,1H),1.71(s,3H),1.07(t,J=7.3Hz,3H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 143.8,130.3,128.5,128.4,128.2,113.9,78.4,34.2,28.0,8.3 HRMS(APCI+) m / z calculation for C 12 H 13 Br2([M-OH] + ):314.9384,found:314.9374.

[0097] (E)-1,2-Dibromo-2-phenylhept-1-en-3-ol (compound 1c) [ka]

[0098] Compound 1c was obtained as a white solid (yield 42%) by the same procedure as above, except that compound 0c was used as the starting material. 1H-NMR(400MHz, CDCl3):δ(ppm) 7.40-7.36(m,2H),7.32-7.28(m,1H),7.25-7.22(m,2H),2.85(s,1H),2.31 -2.23(m,2H),1.80-1.71(m,2H),1.60-1.34(m,10H),0.95(q,J=6.9Hz,6H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 144.2,129.9,128.5,128.3,128.1,114.0,80.6,40.2,25.5,23.0,14.1 HRMS (APCI+) m / z calculation for C 17 H 24 BrO([MH] + ):401.0116,found: 401.0101.

[0099] (E)-1,2-Dibromo-1-phenylnon-1-en-3-ol (compound 1d) [ka]

[0100] Compound 1d was obtained as a colorless oil (yield 42%) by the same procedure as above, except that compound 0d was used as the starting material. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.41-7.32(m,5H),4.97(q,J=7.2Hz,1H),2.00-1.99(m,1H),1.79-1.69(m,2H),1.53-1.31(m,8H),0.91(t,J=7.1Hz,3H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 140.4,129.0,128.5,128.1,117.0,74.0,36.1,31.8,29.2,25.1,22.7,14.2. HRMS(APCI+) m / z calculation for C 15 H 19Br2([M-OH] + ):356.9854,found:356.9838.

[0101] (E)-2,3-Dibromo-1,1,3-triphenylprop-2-en-1-ol (Compound 1e) [ka]

[0102] Compound 1e was obtained as a white solid (yield 76%) by the same procedure as above, except that compound 0e was used as the starting material. Mp:103℃(decomposition). 1 H-NMR (400MHz, CDCl3): δ(ppm) 7.52-7.48(m,4H),7.42-7.31(m,11H),4.20(s,1H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 144.4,143.4,130.4,129.1,128.8,128.7,128.4,128.2,128.1,119.1,84.5 HRMS(APCI+) m / z calculation for C 21 H 15 Br2([M-OH] + ):424.9541,found:424.9532.

[0103] (E)-9-(1,2-dibromo-2-phenylvinyl)-9H-fluoren-9-ol (Compound 1g) [ka]

[0104] Compound 1g was obtained as a white solid (yield 76%) by the same procedure as above, except that compound 0g was used as the starting material. Mp:141-143℃(sublimation). 1H-NMR (400MHz, CDCl3): δ(ppm) 7.67-7.65(m,4H),7.45-7.41(m,2H),7.38-7.34(m,4H),7.26-7.31(m,3H),3.24(s,1H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 147.3,143.1,140.7,129.7,128.6,128.5,128.4,123.6,120.3,116.3. HRMS(APCI+) m / z calculation for C 21 H 15 BrO([M+H] + ):440.9484,found:440.9472.

[0105] (E)-1,2-Dibromo-3-butyl-1-(p-tolyl)hept-1-en-3-ol (Compound 1h) [ka]

[0106] Compound 1h was obtained as a white solid (yield 92%) by the same procedure as above, except that compound 0h was used as the starting material. Mp:41-42℃. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.20-7.18(m,2H),7.15-7.13(m,2H),2.88(s,1H),2.37(s,3H),2.30-2 .22(m,2H),1.79-1.71(m,2H),1.60-1.34(m,8H),0.96(t,J=7.1Hz,6H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 141.6,138.4,129.8,129.3,128.2,114.4,80.7,40.4,25.7,23.1,21.5,14.2. HRMS(APCI+) m / z calculation for C 18 H 25Br2([M-OH] + ):399.0323,found:399.0309.

[0107] (E)-1,2-Dibromo-3-butyl-1-(o-tolyl)hept-1-en-3-ol (compound 1i) [ka]

[0108] Compound 1i was obtained as a colorless oil (yield 90%) by the same procedure as above, except that compound 0i was used as the starting material. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.25-7.20(m,3H),7.10-7.07(m,1H),2.87(s,1H),2.37-2.23(m,5H),1.79-1.72(m,2H),1.62-1.33(m,8H),0.96(t,J=7.1Hz,6H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 143.4,134.4,130.7,130.4,128.6,127.9,126.3,114.0,80.7,40.4,25.7,25.6,23.0,19.1,14.1. HRMS(APCI+) m / z calculation for C 18 H 25 Br2([M-OH] + ):399.0323,found:399.0303.

[0109] (E)-1,2-Dibromo-3-butyl-1-(p-methoxyphenyl)hept-1-en-3-ol (Compound 1j) [ka]

[0110] Compound 1j was obtained as a colorless oil (yield 39%) by the same procedure as above, except that compound 0j was used as the starting material. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.24-7.18(m,2H),6.91-6.88(m,2H),3.83(s,3H),2.90(s,1H),2.29-2 .22(m,2H),1.79-1.71(m,2H),1.53-1.34(m,8H),0.96(t,J=7.3Hz,6H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 159.3,136.7,129.8,129.7,114.3,113.8,80.6,55.3,40.2,25.6,23.0,14.1. HRMS(APCI+) m / z calculation for C 18 H 27 Br2O2([M+H] + ):433.0372,found:433.0370.

[0111] (E)-1,2-Dibromo-3-butyl-1-(p-bromophenyl)hept-1-en-3-ol (Compound 1k) [ka]

[0112] Compound 1k was obtained as a white solid (yield 94%) by the same procedure as above, except that compound 0k was used as the starting material. Mp:47-48℃. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.53-7.49(m,2H),7.13-7.09(m,2H),2.78(s,1H),2.28-2.20(m,2H),1. 79-1.71(m,2H),1.58-1.49(m,2H),1.46-1.34(m,6H),0.98-0.94(m,6H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 143.0,131.8,130.7,129.9,122.4,112.7,80.7,40.2,25.5,23.0,14.0. HRMS(APCI+) m / z calculation for C 17 H 22 BrO([M-OH] + ):462.9272,found:462.9250.

[0113] (E)-1,2-Dibromo-3-butyl-1-(p-trifluoromethylphenyl)hept-1-en-3-ol (Compound 1l) [ka]

[0114] Compound 1l was obtained as a colorless oil (yield 94%) by the same procedure as above, except that compound 0l was used as the raw material. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.65(d,J=7.6Hz,2H),7.36(d,J=7.6Hz,2H),2.75(s,1H),2.29-2.22(m,2H),1 .81-1.73(m,2H),1.60-1.51(m,2H),1.48-1.35(m,6H),0.97(t,J=7.3Hz,6H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 147.5,131.2,130.3(q, 2 J C-F =32Hz), 128.8, 125.8, 123.8(q, 1 J C-F =271Hz),112.2,80.9,40.3,25.6,23.0,14.1 HRMS(APCI+) m / z calculation for C 18 H 22 Br2F3([M-OH] + ):470.0040,found:470.0027.

[0115] 4-[(E)-1,2-Dibromo-3-butyl-3-hydroxyhept-1-enyl][1,1'-biphenyl] (Compound 1m) [ka]

[0116] Compound 1m was obtained as a white solid (yield 66%) by the same procedure as above, except that compound 0m was used as the raw material. Mp:46-47℃. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.62-7.60(m,4H),7.47-7.43(m,2H),7.38-7.32(m,3H),2.87(s,1H),2.32 -2.24(m,2H),1.81-1.74(m,2H),1.62-1.36(m,8H),0.98(t,J=7.1Hz,6H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 143.0,141.1,140.3,130.1,128.8,128.7,127.6,127.2,127.1,113.8,80.7,40.2,25.6,23.0,14.1. HRMS(APCI+) m / z calculation for C 23 H 29 BrO([M+H] + ):479.0580,found:479.0561.

[0117] 2-[(E)-1,2-Dibromo-3-butyl-3-hydroxyhept-1-enyl]naphthalene (Compound 1n) [ka]

[0118] Compound 1n was obtained as a pale yellow oil (yield 87%) by the same procedure as above, except that compound 0n was used as the starting material. 1H-NMR(400MHz, CDCl3):δ(ppm) 7.87-7.84(m,3H),7.72(s,1H),7.53-7.49(m,2H),7.35(dd,J=8.7,1.8Hz,1H),2.89( s,1H),2.34-2.26(m,2H),1.83-1.76(m,2H),1.64-1.37(m,8H),0.99(t,J=7.1Hz,6H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 141.4,133.0,132.8,130.3,128.4,128.3,127.7,127.4,126.7,126.4,125.9,114.1,80.7,40.3,25.6,23.0,14.2. HRMS(APCI+) m / z calculation for C 21 H 26 BrO([M] + ):452.0350,found:452.0350.

[0119] 1,4-bis[(E)-1,2-dibromo-3-butyl-3-hydroxyhept-1-enyl]benzene (compound 1o) [ka]

[0120] Compound 1o was obtained as a yellow viscous oil (yield 90%) by the same procedure as above, except that compound 0o was used as the starting material. 1 H-NMR (400MHz, CDCl3): δ(ppm) 7.26(s,4H),2.83(s,1H),2.29-2.23(m,4H),1.80-1.72(m,4H),1.60-1.34(m,24H),0.96(t,J=7.1Hz,12H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 143.8,130.4,128.5,113.2,80.7,40.2,25.6,23.0,14.1. HRMS(APCI+) m / z calculation for C 28 H 41 BrO([MH] + ):725.9891,found:708.9877.

[0121] 1,3-Bis[(E)-1,2-dibromo-3-butyl-3-hydroxyhept-1-enyl]benzene (Compound 1p) [ka]

[0122] Compound 1p was obtained as a colorless oil (yield 71%) by the same procedure as above, except that compound 0p was used as the starting material. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.41(t,J=7.6Hz,1H),7.19(dd,J=7.6,1.6Hz,2H),7.10(t,J=1.6Hz,1H),2.83(s, 2H), 2.29-2.18(m, 4H), 1.81-1.74(m, 4H), 1.60-1.35(m, 16H), 0.99-0.91(m, 12H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 144.3,130.6,128.8,128.5,128.1,113.1,80.7,40.2,25.5,23.0,14.1. HRMS(APCI+) m / z calculation for C 28 H 42 Br4O2([M-OH] + ):705.9891,found:708.9862.

[0123] Next, as a general procedure for synthesizing compounds 2a to 2p shown in Compound Example 2 above using starting compounds 1a to 1p, some of the compounds 2a to 2p are selected and the procedure is described. Compounds 2a to 2p for which no synthesis procedure is described below can be synthesized by a procedure similar to the synthesis procedure below. Furthermore, as described above, compounds 1a to 1p correspond to the starting compounds for synthesizing compounds 2a to 2p in Compound Example 2 above, respectively.

[0124] Synthesis of 2,3-dibromo-1,1-dimethyl-1H-indene (compound 2a) [ka]

[0125] To a chloroform solution (5.7 mL) of compound 1a (183 mg, 0.57 mmol), BF3·OEt2 (245 mg, 1.72 mmol) was added and stirred at room temperature for 15 minutes. The reaction mixture was quenched by adding an excess of methanol, and the resulting product was purified by silica gel column chromatography (hexane:methylene chloride = 1:1) to obtain compound 2a as a colorless oil (yield 164 mg, 95%). The spectral data for compound 2a were in good agreement with those reported previously (Knorr, R. et al., J. Org. Chem. 2016, 12, 1178-1184).

[0126] 2,3-Dibromo-1-ethyl-1-methyl-1H-indene (compound 2b) [ka]

[0127] Compound 2b was obtained as a colorless oil (yield 92%) by the same procedure as above, except that compound 1b was used as the starting material. 1H-NMR (400MHz, CDCl3): δ(ppm) 7.37-7.34(m,1H),7.33-7.28(m,1H),7.27-7.25(m,2H),1.94-1.81(m,2H),1.30(s,3H),0.36(t,J=7.6Hz,3H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 148.0,141.1,137.1,127.2,126.3,121.4,120.6,120.1,56.9,30.6,23.8,8.0. HRMS(APCI+) m / z calculation for C 12 H 12 Br2([M] + ):313.9306,found: 313.9300.

[0128] 2,3-Dibromo-1,1-dibutyl-1H-indene (compound 2c) [ka]

[0129] Compound 2c was obtained as a colorless oil (yield 82%) by the same procedure as above, except that compound 1c was used as the starting material. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.35-7.33(m,1H),7.30(td,J=7.0,1.5Hz,1H),7.28-7.24(m,1H),7.23-7.21(m, 1H),1.86-1.75(m,4H),1.19-1.04(m,4H),0.83-0.71(m,8H),0.51-0.39(m,2H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 146.9,142.0,136.2,127.0,126.2,121.3,120.7,119.9,60.5,37.5,25.1,22.7,13.8. HRMS (APCI+) m / z calculation for C 17 H 22Br2([M] + ):384.0088,found:384.0076.

[0130] 2,3-Dibromo-1-hexyl-1H-indene (compound 2d) [ka]

[0131] Compound 2d was obtained as a colorless oil (yield 90%) by the same procedure as above, except that compound 1d was used as the starting material. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.39-7.31(m,3H),7.27(td,J=7.2,1.5Hz,1H),3.66-3.60(m,1H),2.12 -2.03(m,1H),1.96-1.88(m,1H),1.29-1.04(m,7H),0.97-0.84(m,4H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 144.4,142.2,131.1,127.3,126.2,122.7,122.0,120.2,54.0,31.6,30.2,29.8,29.5,24.0,22.7,14.1. HRMS(APCI+) m / z calculation for C 15 H 18 Br2([M] + ):355.9770,found:355.9764.

[0132] 2',3'-Dibromospiro[fluorene-9,1'-indene] (Compound 2g) [ka]

[0133] Compound 2g was obtained as a white solid (yield 98%) by the same procedure as above, except that compound 1g was used as the raw material. Mp:155-156℃. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.80(d,J=7.2Hz,2H),7.48(d,J=7.7Hz,1H),7.40(dd,J=7.9,7.0Hz,2H),7.35-7.31(m,1H), 7.19(dd,J=7.9,7.0Hz,2H),7.09-7.05(m,1H),6.86(d,J=7.2Hz,2H),6.64(d,J=7.7Hz,1H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 145.9,143.4,142.3,142.0,131.9,128.6,128.0,127.9,127.3,124.1,123.6,122.7,120.3,77.2,70.6. HRMS(APCI+) m / z calculation for C 21 H 12 Br2([M] + ):421.9300,found:421.9294.

[0134] 2,3-Dibromo-1,1-dibutyl-6-methyl-1H-indene (compound 2h) [ka]

[0135] Compound 2h was obtained as a white solid (yield 99%) by the same procedure as above, except that compound 1h was used as the starting material. Mp:35.5-36.5℃. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.21(d,J=7.8Hz,1H),7.10(d,J=7.8Hz,1H),7.02(s,1H),2.40(s,3H),1. 81-1.74(m,4H),1.18-1.06(m,4H),0.84-0.71(m,8H),0.41-0.52(m,2H). 13 C{ 1H}-NMR(100MHz,CDCl3):δ(ppm) 147.0,139.5,136.2,134.8,127.7,122.2,120.6,119.6,60.3,37.6,25.1,22.8,21.7,13.8. HRMS(APCI+) m / z calculation for C 18 H 24 Br2([M] + ):398.0239,found:398.0229.

[0136] 2,3-Dibromo-1,1-dibutyl-5-methyl-1H-indene (compound 2i) [ka]

[0137] Compound 2i was obtained as a white solid (yield 72%) by the same procedure as above, except that compound 1i was used as the starting material. Mp:44.5-46℃. 1 H-NMR(400MHz,CDCl3):δ(ppm) 7.13 (dd,J=7.0,7.0Hz,1H),7.07(d,J=7.0Hz,1H),7.01(d,J=7.0Hz,1H),2.72(s,3 H),1.83-1.71(m,4H),1.19-1.05(m,4H),0.81-0.70(m,8H),0.50-0.39(m,2H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 147.8,138.3,137.5,131.0,130.1,125.9,119.9,119.4,59.6,37.9,25.0,22.7,19.9,13.8. HRMS(APCI+) m / z calculation for C 18 H 24 Br2([M] + ):398.0239,found:398.0238.

[0138] 2,3-Dibromo-1,1-dibutyl-6-methoxy-1H-indene (compound 2j) [ka]

[0139] Compound 2j was obtained as a colorless oil (yield 95%) by the same procedure as above, except that compound 1j was used as the starting material. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.23(d,J=8.2Hz,1H),6.83(dd,J=8.2,2.3Hz,1H),6.80(d,J=2.3Hz,1H),3.85(s ,3H),1.83-1.70(m,4H),1.20-1.04(m,4H),0.86-0.69(m,8H),0.54-0.40(m,2H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 159.0,148.6,135.2,133.0,120.5,120.1,111.4,108.7,60.4,55.6,37.7,25.1,22.7,13.8. HRMS(APCI+) m / z calculation for C 18 H 24 Br2O2([M] + ):414.0194,found:414.0191.

[0140] 2,3,6-tribromo-1,1-dibutyl-1H-indene (compound 2k) [ka]

[0141] Compound 2k was obtained as a white solid (yield 68%) by the same procedure as above, except that compound 1k was used as the starting material. Mp:43-44℃. 1H-NMR(400MHz, CDCl3):δ(ppm) 7.45(dd,J=7.8,1.6Hz,1H),7.36(d,J=1.6Hz,1H),7.19(d,J=7.8Hz,1H),1 .83-1.72(m,4H),1.21-1.05(m,4H),0.83-0.66(m,8H),0.51-0.38(m,2H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 149.0,141.1,136.7,130.4,124.7,121.4,120.9,120.1,61.0,37.5,25.1,22.8,13.9. HRMS(APCI+) m / z calculation for C 17 H 21 Br3([M] + ):461.9188,found: 461.9197.

[0142] 2,3-Dibromo-1,1-dibutyl-6-(trifluoromethyl)-1H-indene (Compound 2l) [ka]

[0143] Compound 2l was obtained as a white solid (yield 30%) by the same procedure as above, except that compound 1l was used as the starting material. Mp:66.5-68℃. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.59(d,J=8.0Hz,1H),7.45(s,1H),7.44(d,J=8.0Hz,1H),1.90-1.79(m,4H),1.20-1.09(m,4H),0.81-0.69(m,8H),0.47-0.36(m,2H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 147.4,145.3,139.6,128.3(q, 2 J C-F =32Hz), 124.7, 124.4(q, 1J C-F =276Hz),120.2,120.0,118.0,61.1,37.3,25.0,22.6,13.7. HRMS(APCI+) m / z calculation for C 18 H 21 Br2F3([M]+):451.9962,found:451.9942.

[0144] 2,3-Dibromo-1,1-dibutyl-6-phenyl-1H-indene (Compound 2m) [ka]

[0145] Compound 2m was obtained as a colorless viscous liquid (yield 63%) by the same procedure as above, except that compound 1m was used as the starting material. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.65-7.63(m,2H),7.55(dd,J=4.0,1.6Hz,1H),7.49-46(m,3H),7.41-7.34(m,2 H),1.91-1.79(m,4H),1.23-1.07(m,4H),0.90-0.73(m,8H),0.61-0.48(m,2H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 147.5,141.3,141.1,139.4,136.3,128.8,127.3,127.2,126.1,120.5,120.2,120.1,60.7,37.6,25.1,22.7,13.8. HRMS(APCI+) m / z calculation for C 23 H 26 Br2([M] + ):460.0396,found:460.0384.

[0146] 2,3-Dibromo-1,1-dibutyl-1H-cyclopenta[a]naphthalene (compound 2n) [ka]

[0147] Compound 2n was obtained as a white solid (yield 92%) by the same procedure as above, except that compound 1n was used as the starting material. Mp:72-73.5℃. 1 H-NMR(400MHz, CDCl3):δ(ppm) 8.07(d,J=8.4Hz,1H),7.95(d,J=8.8Hz,1H),7.86(d,J=8.4Hz,1H),7.61-7.47(m,3H),2.2 9-2.22(m,2H),2.09-2.02(m,2H),1.14-0.97(m,4H),0.70-0.59(m,8H),0.30-0.19(m,2H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 141.4,139.9,136.7,132.5,129.7,128.7,128.5,126.6,125.0,122.7,120.7,118.7,62.5,37.8,25.0,22.6,13.7. HRMS(APCI+) m / z calculation for C 21 H 24 Br2([M] + ):434.0239,found:434.0230.

[0148] 2,3,6,7-tetrabromo-1,1,5,5-tetrabutyl-1,5-dihydro-s-indacene (compound 2o) [ka]

[0149] Compound 2o was obtained as a white solid (yield 85%) by the same procedure as above, except that compound 1o was used as the starting material. Mp:130.5-131℃. 1H-NMR (400MHz, CDCl3): δ(ppm) 7.17(s,2H),1.88-1.81(m,8H),1.21-1.04(m,8H),0.83-0.71(m,16H),0.48-0.37(m,4H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 146.5,140.6,136.0,120.7,113.2,60.5,37.7,25.1,22.7,13.8. HRMS(APCI+) m / z calculation for C 28 H 38 Br4([M] + ):689.9702,found:689.9692.

[0150] 2,3,5,6-tetrabromo-1,1,7,7-tetrabutyl-1,7-dihydro-s-indacene (compound 2p) [ka]

[0151] Compound 2p was obtained as a white solid (yield 56%) by the same procedure as above, except that compound 1p was used as the starting material. Mp:173-174℃. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.34(s,1H),7.09(s,1H),1.89-1.78(m,8H),1.20-0.99(m,8H),0.86-0.75(m,4H),0.69(t,J=7.3Hz,12H),0.39(m,4H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 145.9,141.4,135.7,120.7,114.8,112.1,60.4,37.5,25.2,22.7,13.7. HRMS(APCI+) m / z C 28 H 38 Br4([M] +):689.9702,found:689.9705.

[0152] Synthesis of 5-(2-dibromo-1,1-dibutyl-1H-inden-3-yl)nonan-5-ol (compound 3) [ka]

[0153] To a solution (1 mL) of compound 2c (334 mg, 0.86 mmol) in anhydrous THF, n-butyllithium (0.54 mL of a 1.59 M hexane solution) was added at −78°C and stirred at that temperature for 1 h. Freshly distilled 5-nonanone (122 mg, 0.85 mmol) was added dropwise and stirred for 30 min. The solution was then gradually warmed to room temperature, and aqueous ammonium chloride (5 mL) was added to quench the reaction. The reaction mixture was added to 10 mL of water and extracted with 20 mL of methylene chloride. The organic phase was separated and dried over magnesium sulfate, then filtered, and the filtrate was concentrated under reduced pressure. This was purified by silica gel column chromatography (methylene chloride:hexane = 4:1) to give compound 3 as a colorless oil (yield 206 mg, 45%). Note that compound 3 is distinct from the compounds represented by general formulas (3A) to (3F) above. 1 H-NMR(400MHz, CDCl3):δ(ppm) 7.72-7.69(m,1H),7.21-7.15(m,3H),2.55(s,1H),2.28-2.21(m,2H),1.84-1.76(m,2H),1.74-1.6 7(m,4H),1.48-1.38(m,2H),1.34-1.02(m,11H),0.89-0.77(m,7H),0.71(m,6H),0.44-0.33(m,2H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 148.8,143.5,142.7,131.6,126.3,124.9,122.2,121.2,79.1,59.7,41.1,38.0,26.0,25.4,23.1,22.9,14.1,13.9. HRMS(APCI+) m / z C 26 H 41 BrO calcd for ([M] + ):448.2341,found:448.2329.

[0154] Synthesis of 5,5'-[1,4-phenylenebis(1,1-dibutyl-1H-indene-2,3-diyl)]bis(nonan-5-ol) (Compound 4) [ka]

[0155] A microwave reactor containing compound 3 (206 mg, 0.45 mmol), 1,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene (69.1 mg, 0.21 mmol), Pd(dba) (19 mg, 0.021 mmol), triphenylphosphine (16 mg, 0.061 mmol), 1,4-dioxane (0.5 mL), and 2 M aqueous potassium carbonate (0.3 mL) was charged and argon gas was applied. The reaction mixture was stirred at 100 °C for 2 h, cooled to room temperature, diluted with chloroform, and passed through a short plug of silica gel. The resulting solution was extracted three times with 10 mL of chloroform. The combined organic phase was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The solvent was removed in vacuo, and the resulting compound 4 was used in the next reaction without further purification. It should be noted that this compound 4 is different from the compound represented by the above general formula (4).

[0156] 5,5,7,7,12,12,14,14-octabutyl-5,7,12,14-tetrahydrodiindeno[2,1-a:2',1'-g]-s-indacene (COPV2(Bu)) [ka]

[0157] Compound 4 (49mg, 6.0×10 -2BF3·OEt2 (51 mg, 0.36 mmol) was added to a chloroform solution (1 mL) of COPV2 (2 mmol) at room temperature and stirred for 15 minutes. Methanol was then added to the reaction solution to quench the reaction. The resulting solution was concentrated and passed through a short-path silica gel column using hexane as a developing solvent to obtain COPV2(Bu) as a yellow solid (yield: 31 mg, 67%). COPV2(Bu) is the carbon-bridged p-phenylene vinylene derivative of the present invention. Mp:205-207℃. 1 H-NMR0(400MHz,THF-d8):δ(ppm) 7.36(s,2H),7.32(d,J=7.7Hz,4H),7.21-7.17(m,2H),7.13-7.09(m,2H),2. 25-2.03(m,16H),1.16-1.01(m,16H),0.98-0.80(m,8H),0.77-0.63(m,32H). 13 C{ 1 H}-NMR(100MHz,CDCl3):δ(ppm) 156.1,155.7,154.8,140.9,137.6,126.3,123.8,121.8,118.6,113.1,53.8,53.5,38.3,26.9,26.7,23.1,13.8. HRMS(APCI+) m / z C 58 H 82 ([M] + ):778.6417,found:778.6418.

[0158] In COPV2(Bu), a carbon-bridged p-phenylene vinylene derivative of the present invention, all bridging carbons are substituted with two butyl groups. As shown in Table 1 of the present specification, this compound has a larger molar absorption coefficient and a larger radiative deactivation constant in fluorescence emission than COPV2(Ar), in which the bridging carbons are substituted with aryl groups (p-octylphenyl groups). Furthermore, a larger radiative deactivation constant in fluorescence emission means that the time from excitation to fluorescence deactivation is shorter, meaning that more intense fluorescence can be emitted. Therefore, the carbon-bridged p-phenylene vinylene derivative of the present invention can be said to have superior properties as a fluorescent dye compared to previously known carbon-bridged p-phenylene vinylene derivatives.

Claims

1. A method for producing a fused polycyclic compound having fused five-membered rings, characterized by reacting a compound having a partial structure represented by the following general formula (1) with an acid to convert it into a compound having a partial structure represented by the following general formula (2): 【Chemistry 1】 (The double bond marked with * in the above general formula (1) may be cis or trans, and in general formula (1), R １ and R ２ are each independently a hydrogen atom, -CQ ３ or an aryl group which may have a substituent, or R １ and R ２ and combine to form a ring structure, each Q is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a heteroatom or branching therein, an alkoxy group having 1 to 12 carbon atoms which may have a heteroatom or branching therein, an alkylsulfanyl group having 1 to 12 carbon atoms which may have a heteroatom or branching therein, or an alkylamino group or alkylaryl group having 1 to 12 carbon atoms which may have a heteroatom or branching therein, each X is independently a halogen atom, and the ring structure marked with the symbol Ar is an aromatic ring which may have a substituent. １ and R ２ are each independently a hydrogen atom, -CQ ３ or an aryl group which may have a substituent, or R １ and R ２ and combine to form a ring structure, each Q is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a heteroatom or a branch along the way, an alkoxy group having 1 to 12 carbon atoms which may have a heteroatom or a branch along the way, an alkylsulfanyl group having 1 to 12 carbon atoms which may have a heteroatom or a branch along the way, or an alkylamino group or alkylaryl group having 1 to 12 carbon atoms which may have a heteroatom or a branch along the way, each X is independently a halogen atom, and the ring structure marked with the symbol Ar is an aromatic ring which may have a substituent.

2. 2. The process according to claim 1, wherein the acid is a Lewis acid.

3. 3. The method according to claim 2, wherein the Lewis acid is boron trifluoride or a compound formed by binding a Lewis base to boron trifluoride to form a complex.

4. An indacene derivative represented by any one of the following general formulas (3A) to (3F): 【Chemistry 2】 (In the above general formulas (3A) to (3F), each R is independently a hydrogen atom, —CQ ３ or an aryl group which may have a substituent, or two R's bonded to the same carbon atom combine to form a ring structure, each Q is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a heteroatom or a branch, an alkoxy group having 1 to 12 carbon atoms which may have a heteroatom or a branch, an alkylsulfanyl group having 1 to 12 carbon atoms which may have a heteroatom or a branch, or an alkylamino or alkylaryl group having 1 to 12 carbon atoms which may have a heteroatom or a branch, and each X is independently a halogen atom.

5. A carbon-bridged p-phenylene vinylene derivative represented by the following general formula (4): 【Transformation 3】 (In the above general formula (4), each R is -CQ ３ and each Q is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a heteroatom or a branch in the middle, an alkoxy group having 1 to 12 carbon atoms which may have a heteroatom or a branch in the middle, an alkylsulfanyl group having 1 to 12 carbon atoms which may have a heteroatom or a branch in the middle, or an alkylamino group or alkylaryl group having 1 to 12 carbon atoms which may have a heteroatom or a branch in the middle.

6. 6. The carbon-bridged p-phenylene vinylene derivative according to claim 5, wherein each R in said general formula (4) is an n-butyl group.

7. A step i of reacting a compound represented by the following general formula (11) with a first acid to obtain a compound represented by the following general formula (12); A step ii of reacting a compound represented by the following general formula (12) with an alkyl lithium compound, and then reacting the compound represented by the following general formula (13) to obtain a compound represented by the following general formula (14); Step iii: subjecting a compound represented by the following general formula (14) to a coupling reaction with a 1,4-phenylenediboronic acid compound to obtain a compound represented by the following general formula (15); and step iv of reacting a compound represented by the following general formula (15) with a second acid to obtain a compound represented by the following general formula (16): 【Chemistry 4】 (In the above chemical reaction formula, each X is independently a halogen atom, and each R １ and R ２ are each independently a hydrogen atom, -CQ ３ or an aryl group which may have a substituent, or R １ and R ２ and combine to form a ring structure, and each R ３ and R ４ are each independently a hydrogen atom, -CQ ３ or an aryl group which may have a substituent, or R ３ and R ４ and combine to form a ring structure, and each Q is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a heteroatom or a branch in the middle, an alkoxy group having 1 to 12 carbon atoms which may have a heteroatom or a branch in the middle, an alkylsulfanyl group having 1 to 12 carbon atoms which may have a heteroatom or a branch in the middle, or an alkylamino group or alkylaryl group having 1 to 12 carbon atoms which may have a heteroatom or a branch in the middle.

8. 8. The method according to claim 7, wherein the first acid and the second acid are both Lewis acids.

9. 9. The method according to claim 8, wherein the Lewis acid is boron trifluoride or a compound formed by binding a Lewis base to boron trifluoride to form a complex.

10. The R １ , R ２ , R ３ and R ４ The method according to claim 7, wherein all of are n-butyl groups.

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