JP2010138089A - Method for producing tricyclic compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To synthesize a fluorene derivative by a new method. <P>SOLUTION: The method for producing a tricyclic compound such as a fluorene derivative comprises reacting an organic aluminum compound with a specific dicyclic fluorine-containing compound. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a tricyclic compound.

  Tricyclic compounds such as fluorene derivatives (hereinafter also referred to as “compounds having a fluorene skeleton” and “fluorene compounds”) are known to be highly useful as organic semiconductors, and many compounds can be synthesized. It is being considered. For example, a fluorene derivative is required to have a high Tg in order to ensure the stability of the material. Moreover, in order to use a fluorene derivative as a light emitting material, a high molecular weight derivative (polyfluorene derivative) is required for the purpose of making the emission wavelength visible. Many fluorene derivatives satisfying such requirements are known in which an alkyl group or an aryl group is introduced at the 9-position of the fluorene skeleton.

  In particular, from the viewpoint of function when used as a material for electronic devices, those in which an aryl group is introduced at the 9-position are promising. In the conventional synthesis method, the aryl group at the 9-position is a phenyl group or 2, Most of them are 2-biphenyl groups.

  For example, in Non-Patent Document 1, a fluorene derivative having an aryl group introduced at the 9-position is obtained by the following synthesis route.

  In Non-Patent Document 2, a fluorene derivative having an aryl group introduced at the 9-position is obtained by the following synthesis route.

  Furthermore, in Non-Patent Document 3, a fluorene derivative having an aryl group introduced at the 9-position is obtained by the following synthesis route.

  However, a practical method for synthesizing a fluorene compound (monomer unit) that is a raw material for synthesizing a fluorene derivative obtained by the methods disclosed in Non-Patent Documents 1 to 3 is not known.

  Furthermore, purity is an important point in actual use of the fluorene derivative. In order to increase the purity of the fluorene derivative, it is very important to establish the substitution position selectivity in the molecule of the fluorene compound that is a monomer unit. Specifically, it is desirable that a substituent can be introduced at a desired position of the fluorene mother nucleus and the 9-position aryl group.

  So far, a method has been reported in which bromine is selectively introduced only into the phenyl group of fluorene after construction of the 9-phenylfluorene skeleton. However, in order to obtain the target product with practically sufficient purity, it is necessary to extend the carbon chain length after selectively introducing a halogen element such as bromine into each phenyl group as shown below. is there. The method disclosed in Non-Patent Document 4 for introducing bromine into the 4,4'-position of fluorene is as follows.

  As described above, in Non-Patent Document 4, bromine is introduced into fluorene, followed by synthesis of fluorenone by oxidation, followed by arylation with a phenylmagnesium reagent and arylation by Friedel-Crafts reaction. However, in this method, the aryl group that can be introduced at the 9-position in the second step can only be introduced from an aromatic compound used as a solvent, and the aromatic compound is added as a reaction solvent, so an excessive amount is required. .

  On the other hand, Patent Document 1 discloses a method in which two aryl groups can be introduced without using an excessive amount as described below, but this method has many steps and the yield of the final product is satisfactory. Not.

  Non-Patent Document 5 discloses a method for introducing bromine into the 9-position aryl group of fluorenone. As shown in the following formula, after arylation of fluorenone using an excess amount of aniline in the presence of an acid, amino A method using a bromination reaction by diazotization of a group and a Sandmeyer reaction is employed. However, this method has many problems such as the need to use an equivalent amount of copper, which is a heavy metal.

  On the other hand, in order to synthesize a wide variety of fluorene derivatives, a synthesis method capable of introducing a substituent at a desired position in the fluorene skeleton is desired. For this purpose, a method of constructing a fluorene skeleton from a reaction represented by the following formula in Patent Document 2 after synthesizing a biaryl compound by coupling between aryl groups having a substituent is superior. However, this method requires a cyclization reaction by heating in a large amount of polyphosphoric acid, and is not a good synthesis method.

  On the other hand, Non-Patent Document 6 discloses a method for obtaining a compound having a fluorene skeleton by the following reaction.

However, in this method, not only an excessive amount of art complex but also an equivalent amount of niobium, which is a heavy metal, must be used, and the halogen substituent necessary for synthesizing a material incorporating a fluorene skeleton is resistant to reduction. There is a problem that it is not possible. Furthermore, the introduction of a substituent at the 9-position of the fluorene skeleton is greatly limited in that only a compound used as a solvent is allowed.
JP 2007-119785 A JP 2006-069999 A KT. Wong et al. J. Am. Chem. Soc. 2002, 124, 11576 O. Nuyken et al. Macromol. Chem. Phys. 2000, 201, 2257 MSWong et al. Organic Letters, 2006, 8, 1499 Organic Letters 2001, 3rd volume, 2285 pages Macromol. Chem. Phys. 2000, 201, 2257 T. Akiyama et al., Chem. Asian J., 2008, 3, 261

  The main object of the present invention is to synthesize a tricyclic compound by a novel method.

As a result of intensive studies to achieve the above-mentioned problems, the present inventor has made tricyclic compounds such as fluorene derivatives simple and high by reacting an organoaluminum compound with a specific bicyclic fluorine-containing compound. It was found that it can be produced in a yield. As a result of further research based on this finding, the present invention has been completed. That is, the present invention provides the following inventions.
Item 1. A method for producing a tricyclic compound, which is represented by the following general formula (1):
Al (R ¹ ) ₃ (1)
[Wherein, R ¹ are the same or different and each may be an alkyl group which may be substituted, an alkoxy group which may be substituted, an aryl group which may be substituted, a heteroaryl group which may be substituted, An aralkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted; two R ¹ out of three R ¹ are bonded to each other to form a ring; Also good. ]
An organoaluminum compound represented by the following general formula (2):

[Wherein, Ar ¹ and Ar ² are the same or different and each represents an optionally substituted aryl group or an optionally substituted heteroaryl group;
The CF ₂ R ² group and the H group are bonded to the 2-position from the bonding position of Ar ¹ and Ar ² , respectively.
R ² represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, a substituted An aralkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted; ]
A method for producing a tricyclic compound by reacting with a compound represented by the formula:
Item 2. R ^{2 in the} general formula (2) is a fluorine atom, and the resulting tricyclic compound is represented by the following general formula (3):

[Wherein, Ar ¹ , Ar ² and R ¹ are the same as described above, and two R ¹ may be bonded to each other to form a ring. ]
Item 2. The production method according to Item 1, which is a tricyclic compound represented by the formula:
Item 3. R ^{2 in the} general formula (2) is a hydrogen atom, a halogen atom excluding a fluorine atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, or a substituted atom. A heteroaryl group which may be substituted, an aralkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted, and the resulting tricyclic compound represented by the following general formula (3c) :

[Wherein, Ar ¹ , Ar ² , R ¹ and R ² are the same as defined above. However, R ² is not a fluorine atom. ]
Item 2. The production method according to Item 1, which is a tricyclic compound represented by the formula:
Item 4. A method for producing a tricyclic compound, comprising:
Step 1: the following general formula (4):
R ¹ -X ¹ (4)
[Wherein, R ¹ is an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, and optionally substituted. An aralkyl group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group; X ¹ represents a halogen atom; ]
A halogen-containing compound represented by the following general formula (5):
R ³ -M (5)
[Wherein, R ³ represents an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, or optionally substituted. An aralkyl group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group;
M represents a metal selected from the group consisting of lithium, boron, magnesium, zinc and copper. A step of mixing with an organometallic compound represented by
Step 2: The solution obtained in Step 1 and the following general formula (6):
Al (R ⁴ ) ₃ (6)
[Wherein, R ⁴ are the same or different and each represents an alkyl group or a halogen atom. ]
A step of mixing an aluminum compound represented by:
Step 3: The solution obtained in Step 2 and the following general formula (2):

[Wherein, Ar ¹ and Ar ² are the same or different and each represents an optionally substituted aryl group or an optionally substituted heteroaryl group;
The CF ₂ R ² group and the H group are bonded to the 2-position from the bonding position of Ar ¹ and Ar ² , respectively.
R ² is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, a substituted An aralkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted; ]
A method for producing a tricyclic compound comprising a step of mixing with a compound represented by the formula:
Item 5. R ^{2 in the} general formula (2) is a fluorine atom, and the resulting tricyclic compound is represented by the following general formula (3):

[Wherein Ar ¹ , Ar ² and R ¹ are the same as defined above. ]
Item 5. The method according to Item 4, which is a tricyclic compound represented by:
Item 6. R ^{2 in the} general formula (2) is a hydrogen atom, a halogen atom excluding a fluorine atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, or a substituted atom. A heteroaryl group which may be substituted, an aralkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted, and the resulting tricyclic compound represented by the following general formula (3c) :

[Wherein, Ar ¹ , Ar ² , R ¹ and R ² are the same as defined above. ]
Item 5. The method according to Item 4, which is a tricyclic compound represented by:
Item 7. A method for producing a tricyclic compound, comprising:
Step 1: the following general formula (4b):

[Wherein, X ² and X ³ are the same or different and each represents a halogen atom,
R ^1a and R ^1b are the same or different and each is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, or optionally substituted. A heteroaryl group, an optionally substituted aralkyl group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group;
m and n are the same or different and are an integer of 0-4. ]
A halogen-containing compound represented by the following general formula (5):
R ³ -M (5)
[Wherein, R ³ represents an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, or optionally substituted. An aralkyl group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group;
M represents a metal selected from the group consisting of lithium, boron, magnesium, zinc and copper. A step of mixing with an organometallic compound represented by
Step 2: The solution obtained in Step 1 and the following general formula (6):
Al (R ⁴ ) ₃ (6)
[Wherein, R ⁴ are the same or different and each represents an alkyl group or a halogen atom. ]
A step of mixing an aluminum compound represented by:
Step 3: The solution obtained in Step 2 and the following general formula (2):

[Wherein, Ar ¹ and Ar ² are the same or different and each represents an optionally substituted aryl group or an optionally substituted heteroaryl group;
The CF ₂ R ² group and the H group are bonded to the 2-position from the bonding position of Ar ¹ and Ar ² , respectively.
R ² is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, a substituted An aralkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted; ]
A method for producing a tricyclic compound comprising a step of mixing with a compound represented by the formula:
Item 8. R ^{2 in the} general formula (2) is a fluorine atom, and the resulting tricyclic compound is represented by the following general formula (3a):

[Wherein, Ar ¹ , Ar ² , R ^1a , R ^1b , m and n are the same as defined above. ]
Item 8. The production method according to Item 7, which is a tricyclic compound represented by:

  According to the present invention, a tricyclic compound having a fluorene skeleton or the like, which has been complicated in the conventional synthesis process or has a low yield, can be easily produced in a high yield. In particular, in the present invention, since the fluorine selectivity of aluminum is high, a reactive substituent can be introduced in advance at a desired position on the organic group of the raw material fluorine compound or aluminum reagent. By further polymerizing the tricyclic compound introduced with the reactive substituent, a polymer of a tricyclic compound such as a polyfluorene derivative having high usefulness as an organic semiconductor is synthesized in a simple and high yield. can do.

The present invention is a method for producing a tricyclic compound such as a compound having a fluorene skeleton, which is represented by the following general formula (1):
Al (R ¹ ) ₃ (1)
An organoaluminum compound represented by the following general formula (2):

It reacts with the compound represented by these, It is characterized by the above-mentioned. Details will be described below.

I. Organoaluminum compound In the present invention, as an organoaluminum compound, the following general formula (1):
Al (R ¹ ) ₃ (1)
Use the one represented by.

In the general formula (1), R ^{1 s} are the same or different and may be an alkyl group which may be substituted, an alkoxy group which may be substituted, an aryl group which may be substituted, or a heteroaryl which may be substituted. A group, an aralkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted; Further, two R ¹ out of the three R ¹ may be bonded to each other to form a ring.

Examples of the alkyl group of the “optionally substituted alkyl group” represented by R ¹ in the general formula (1) include C1-20 linear, branched or cyclic alkyl groups. Examples thereof include C1-12 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, and cyclodecyl. More preferably, it is a C1-8 alkyl group. The substituent is not particularly limited as long as it does not adversely affect the method of the present invention. As what has a substituent, the perfluoroalkyl group by which all the H atoms in the alkyl group illustrated here were substituted by the F atom is mentioned, for example.

Examples of the alkoxy group of the “optionally substituted alkoxy group” represented by R ¹ include C1-20 linear, branched or cyclic alkoxy groups. Examples thereof include C1-12 alkoxy groups such as methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, octyloxy and the like. More preferably, it is a C1-8 alkoxy group. The substituent is not particularly limited as long as it does not adversely affect the method of the present invention.

Examples of the aryl group of the “optionally substituted aryl group” represented by R ¹ include a 1-4 cyclic aryl group, specifically, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl. Group, fluorenyl group, benzofuryl group, benzothienyl group and the like are exemplified.

The aryl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the method of the present invention. For example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (for example, a C1-20 alkyl group), an aralkyl group (for example, a benzyl group), an aryl group (for example, a phenyl group, Biphenyl group), heteroaryl group (for example, pyridyl group, etc.), alkenyl group (for example, C2-20 alkenyl group such as vinyl group), alkoxy group (for example, C1-20 alkoxy group), aralkyloxy group (for example, Benzyloxy group etc.), alkenyloxy group (eg C2-20 alkenyloxy group), alkylthio group (eg C1-20 alkylthio group), alkoxyalkyl group, alkylthioalkyl group, ester group (eg -COO-tert-Bu) Etc.), a hydroxyl group which may be protected (for example, —OH, —O—Sitert-Bu) e _2, etc.), optionally protected amino group _{(-NH 2, -NHCH 3, -NCH} 3 Ph , etc.), carbonyl group, nitrile group, azido group, a boronic ester group, a protected or unprotected carboxyl Group, an optionally protected thiol group, an optionally protected silyl group, and the like. 1 to 3 of the aryl groups may be substituted with at least one selected from the group consisting of these.

Examples of the heteroaryl group of the “optionally substituted heteroaryl group” represented by R ¹ include an aryl having at least one heteroatom selected from 1 to 4 cyclic oxygen, nitrogen and sulfur in the ring. Specific examples include thienyl group, furyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolyl group, quinolyl group, isoquinolyl group and the like.

The heteroaryl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the method of the present invention. For example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (for example, a C1-20 alkyl group), an aralkyl group (for example, a benzyl group), an aryl group (for example, a phenyl group, Biphenyl group), heteroaryl group (for example, pyridyl group, etc.), alkenyl group (for example, C2-20 alkenyl group such as vinyl group), alkoxy group (for example, C1-20 alkoxy group), aralkyloxy group (for example, Benzyloxy group etc.), alkenyloxy group (eg C2-20 alkenyloxy group), alkylthio group (eg C1-20 alkylthio group), alkoxyalkyl group, alkylthioalkyl group, ester group (eg -COO-tert-Bu) Etc.), a hydroxyl group which may be protected (for example, —OH, —O—Sitert-Bu) e _2, etc.), optionally protected amino group _{(-NH 2, -NHCH 3, -NCH} 3 Ph , etc.), carbonyl group, nitrile group, azido group, a boronic ester group, a protected or unprotected carboxyl Group, an optionally protected thiol group, an optionally protected silyl group, and the like. 1 to 3 of the heteroaryl groups may be substituted with at least one selected from the group consisting of these.

Examples of the aralkyl group of the “optionally substituted aralkyl group” represented by R ¹ include C7-C20 aralkyl such as 2-phenylethyl, benzyl, 1-phenylethyl, 3-phenylpropyl, 4-phenylbutyl and the like. Groups and the like. The aralkyl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the method of the present invention.

As the alkenyl group of the “optionally substituted alkenyl group” represented by R ¹ , for example, a linear or branched C2-C20 alkenyl group such as vinyl, allyl, 1-butenyl, isobutenyl, preferably C2 -C12 alkenyl group is mentioned. The alkenyl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the method of the present invention. Examples of the substituted alkenyl group include α or β-styryl, 2,2-diphenylvinyl group, and the like.

Examples of the alkynyl group of the “optionally substituted alkynyl group” represented by R ¹ include a linear or branched C 2 to C 20 alkynyl group such as ethynyl, 1-propynyl, 1-butynyl, 1-octynyl and the like. , Preferably a C2-C12 alkynyl group is mentioned. The alkynyl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the method of the present invention. Examples of the substituted alkynyl group include a 2-phenylethynyl group.

In addition, when two R ^1s out of three R ¹ are bonded to each other to form a ring, the bond is any of a single bond, an alkylene bond, and a bond via a hetero atom (O, N, S, etc.). There may be.

In the aluminum compound represented by the general formula (1), specific examples of the case where two of R ¹ of the three R ¹ are combined to form a ring with each other, the compound represented by the following general formula (1a) Can be mentioned.

In the general formula (1a), R ¹ is the same as that in the general formula (1).

In the general formula (1a), R ^1a and R ^1b are the same or different and are each a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (eg, a C1-20 alkyl group) An aralkyl group (for example, a benzyl group), an aryl group (for example, a phenyl group, a biphenyl group, etc.), a heteroaryl group (for example, a pyridyl group, etc.), an alkenyl group (for example, a C2-20 alkenyl group such as a vinyl group), An alkoxy group (for example, C1-20 alkoxy group), an aralkyloxy group (for example, benzyloxy group, etc.), an alkenyloxy group (for example, C2-20 alkenyloxy group), an alkylthio group (for example, C1-20 alkylthio group), An alkoxyalkyl group, an alkylthioalkyl group, an ester group (for example, —COO-tert-Bu, etc.), Protection which may be a hydroxyl group (e.g., -OH, -O-Sitert-BuMe 2 , etc.), optionally protected amino group _{(-NH 2, -NHCH 3, -NCH} 3 Ph , etc.), carbonyl group, A nitrile group, an azide group, a boronic ester group, an optionally protected carboxyl group, an optionally protected thiol group, and an optionally protected silyl group are shown.

When the tricyclic compound obtained by the production method of the present invention is further subjected to a reaction such as polymerization, among these R ^1a and R ^1b , a halogen atom, a boronic ester group, a protected amino group, a protected Particularly preferred are a carboxyl group, a protected hydroxyl group, a protected silyl group, an azide group and the like. Further, among these, a halogen atom is particularly preferable.

In the general formula (1a), m and n indicating the number of substituents on the aromatic ring represented by R ^1a and R ^1b are the same or different and are usually an integer of 0 to 4, preferably an integer of 0 to 2. , More preferably 1. For example, the tricyclic compound (fluorene compound) obtained in the present invention has one substituent on each of the aromatic rings represented by R ^1a and R ^1b , and these substituents are reactive or polymerized. In the case of having a property, a polyfluorene derivative can be easily produced by polymerizing the fluorene compound obtained by the present invention.

In addition, even when the substituents on the aromatic ring represented by R ^1a and R ^1b are not reactive or polymerizable, these substituents are converted into polymerizable substituents (for example, deprotection reaction), then reacted or A polyfluorene derivative can also be obtained by polymerization.

Preparation of Organoaluminum Compound In the present invention, the organoaluminum compound is, for example, the following general formula (4):
R ¹ -X ¹ (4)
A halogen-containing compound represented by the following general formula (5):
R ³ -M (5)
An organometallic compound represented by
The following general formula (6):
Al (R ⁴ ) ₃ (6)
It can prepare by mixing with the aluminum compound represented by these.

The mixing order of the halogen-containing compound represented by the general formula (4), the organometallic compound represented by the general formula (5), and the aluminum compound represented by the general formula (6) is not particularly limited. The halogen-containing compound represented by 4) and the organometallic compound represented by the general formula (5) are mixed, and the substituent X ¹ in the halogen-containing compound represented by the general formula (4) is substituted with the metal M After that, it is more preferable to prepare the organoaluminum compound represented by the general formula (1) by adding the aluminum compound represented by the general formula (6) thereto.

In the halogen-containing compound represented by the general formula (4), X ¹ represents a halogen atom. The halogen atom is F, Cl, Br or I, preferably Br or I. R ¹ is the same as that in the general formula (1).

In the general formula (5), R ³ is an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, a substituted An aralkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted is shown, and specific examples thereof include the same as R ^{1 in the} general formula (1). In particular, R ³ is preferably a C1-C12 alkyl group, a phenyl group, a C2-C12 alkenyl group, or a C2-C12 alkynyl group. M represents a metal selected from the group consisting of lithium, boron, magnesium, zinc and copper.

Moreover, as a suitable specific example among the organometallic compounds represented by the general formula (5), when M is lithium, the general formula (5a):
R ³ -Li (5a)
(In the formula, R ³ is the same as that of the general formula (5).)
The compound represented by these is mentioned.

When M is boron, the general formula (5b):
(R ³ ) ₃ B (5b)
(In the formula, R ³ is the same as that of the general formula (5).)
The compound represented by these is mentioned.

When M is magnesium, the general formula (5c):
R ³ —MgY ¹ (5c)
(In the formula, Y ¹ represents a halogen atom, and R ³ is the same as that in the general formula (5).)
The compound represented by these is mentioned. Examples of the halogen atom represented by Y ¹ include Cl, Br, and I, preferably Cl or Br.

When M is zinc, the general formula (5d):
(R ³ ) ₂ Zn (5d)
(In the formula, R ³ is the same as that of the general formula (5).)
The compound represented by these is mentioned.

When M is copper, the general formula (5e):
(R ³ ) ₂ CuLi, (R ³ ) ₂ CuMgY ² , (R ³ ) ₂ CuMgLiY ² , or R ³ Cu · BF ₃ (5e)
(In the formula, Y ² represents a halogen atom, and R ³ is the same as that of the general formula (5).)
The compound represented by these is mentioned. Examples of the halogen atom represented by Y ² include Cl, Br, and I, preferably Cl or Br.

  Of the organometallic compounds containing the above organic group, compounds represented by general formulas (5a) to (5d) are preferred, and compounds represented by general formula (5a) or (5c) are more preferred. .

  The organometallic compound containing the organic group is usually prepared in an appropriate solution because it is difficult to isolate. Any known method can be adopted as this preparation method.

In the aluminum compound represented by the general formula (6), R ⁴ is the same or different and represents an alkyl group or a halogen atom.

Examples of the alkyl group represented by R ⁴ include a C1-C20 alkyl group. The alkyl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the method of the present invention. As the halogen atom represented by ^{R 4,} F, Cl, Br or I and the like, preferably Cl or Br.

  The mixing ratio of the halogen-containing compound represented by the general formula (4), the organometallic compound represented by the general formula (5) and the aluminum compound represented by the general formula (6) is represented by the general formula (6). The halogen-containing compound represented by the general formula (4) is usually about 1 to 2 mol, preferably about 1 to 1.5 mol, the organic compound represented by the general formula (5) per 1 mol of the aluminum compound. What is necessary is just to prepare a metal compound as about 3-6 mol normally, Preferably it is the range of about 3-4.5 mol.

  In addition, an aprotic solvent is used as the solvent used in this preparation. For example, chlorinated solvents such as dichloromethane, dichloroethane, tetrachloroethane, carbon tetrachloride; hydrocarbon solvents such as hexane, heptane, cyclohexane, petroleum ether, benzene, toluene, xylene; diethyl ether, diisopropyl ether, THF, DME, dioxane And ether solvents such as Among these, low-polarity solvents such as dichloromethane, dichloroethane, tetrachloroethane, carbon tetrachloride, hexane, heptane, benzene, toluene, xylene, and the like, and chlorine-based solvents such as dichloromethane, dichloroethane, tetrachloroethane, and carbon tetrachloride are preferred. And aromatic solvents such as benzene, toluene and xylene are most preferably used.

  The preparation is preferably performed under anhydrous conditions in an atmosphere of an inert gas (for example, nitrogen, argon, etc.).

  The preparation temperature can be appropriately selected according to the activity of the aluminum used and the activity of the organometallic compound. Usually, it is in the range of, for example, about -78 ° C to 200 ° C, preferably about -30 ° C to 100 ° C, and the boiling point of the solvent used from room temperature is used.

  The preparation is completed in several minutes to several days at the above reaction temperature. The progress of the preparation can be evaluated by various analytical methods, and analytical means such as GLC, HPLC, TLC, NMR, and IR are effective.

In addition, in the organoaluminum compound represented by the general formula (1), an organoaluminum compound represented by the general formula (1a) in which two R ¹ out of three R ¹ are bonded to each other to form a ring is prepared. In this case, instead of the halogen-containing compound represented by the general formula (4), the following general formula corresponding to the compound dimerized by bonding of the R ¹ group of the halogen-containing compound represented by the general formula (4) (4a):
^{X 2 -R 1c -R 1c -X 3} (4a)
A compound represented by the following may be used.

In the halogen-containing compound represented by the general formula (4a), the halogen atoms represented by X ² and X ³ are the same or different and the same as X ^{1 in the} general formula (4) can be mentioned. The group represented by R ^1c is a divalent group corresponding to the group represented by R ¹ in the general formulas (1) and (4). That is, the groups represented by R ^1c are the same or different and may be an alkylene group which may be substituted, an alkoxylene group which may be substituted, an arylene group which may be substituted, or a heteroarylene which may be substituted. A group, an optionally substituted aralkylene group, an optionally substituted alkenylene group, or an optionally substituted alkynylene group; Specific examples of these divalent groups include divalent groups corresponding to the group represented by R ¹ in the general formula (1).

  Specific examples of the halogen-containing compound represented by the general formula (4a) include, for example, the following general formula (4b):

The compound represented by these is mentioned.

In the general formula (4b), X ² and X ³ are the same as those in the general formula (4a).

In the general formula ^(4b), m and n represents the number of substituents on the aromatic ring represented by ^{R 1a} and ^{R 1b} and ^{R 1a} and ^{R 1b} are the same or different, in the general formula (1a) It is the same as that of the organoaluminum compound shown.

  The organoaluminum compound represented by the general formula (1a) can be prepared by using the halogen-containing compound represented by the general formula (4b) as a raw material.

  In the preparation of the organoaluminum compound, the halogen-containing compound represented by the general formula (4a) or the general formula (4b) is used instead of the halogen-containing compound represented by the general formula (4). An organoaluminum compound can be prepared under the same preparation conditions as when the halogen-containing compound represented by (4) is used.

II. Fluorine compound In the production method of the present invention, the fluorine compound used as a raw material is represented by the following general formula (2):

It is represented by

In the general formula (2), the rings represented by Ar ¹ and Ar ² are the same or different and each represents an optionally substituted aryl group or an optionally substituted heteroaryl group.

The aryl group of the “optionally substituted aryl group” represented by Ar ¹ and Ar ² includes, for example, a 1-4 cyclic aryl group, and specifically includes a phenyl group, a naphthyl group, an anthryl. Group, phenanthryl group, fluorenyl group, benzofuryl group, benzothienyl group and the like are exemplified.

The aryl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the method of the present invention. For example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (for example, a C1-20 alkyl group), an aralkyl group (for example, a benzyl group), an aryl group (for example, a phenyl group, Biphenyl group), heteroaryl group (for example, pyridyl group, etc.), alkenyl group (for example, C2-20 alkenyl group such as vinyl group), alkoxy group (for example, C1-20 alkoxy group), aralkyloxy group (for example, Benzyloxy group etc.), alkenyloxy group (eg C2-20 alkenyloxy group), alkylthio group (eg C1-20 alkylthio group), alkoxyalkyl group, alkylthioalkyl group, ester group (eg -COO-tert-Bu) Etc.), a hydroxyl group which may be protected (for example, —OH, —O—Sitert-Bu) e _2, etc.), optionally protected amino group _{(-NH 2, -NHCH 3, -NCH} 3 Ph , etc.), carbonyl group, nitrile group, azido group, a boronic ester group, a protected or unprotected carboxyl Group, an optionally protected thiol group, an optionally protected silyl group, and the like. 1 to 3 of the aryl groups may be substituted with at least one selected from the group consisting of these.

Examples of the heteroaryl group of the “optionally substituted heteroaryl group” represented by Ar ¹ and Ar ² include, for example, at least one heteroatom selected from 1 to 4 cyclic oxygen, nitrogen and sulfur. Specific examples include thienyl group, furyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolyl group, quinolyl group, isoquinolyl group and the like. .

The heteroaryl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the method of the present invention. For example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (for example, a C1-20 alkyl group), an aralkyl group (for example, a benzyl group), an aryl group (for example, a phenyl group, Biphenyl group), heteroaryl group (for example, pyridyl group, etc.), alkenyl group (for example, C2-20 alkenyl group such as vinyl group), alkoxy group (for example, C1-20 alkoxy group), aralkyloxy group (for example, Benzyloxy group etc.), alkenyloxy group (eg C2-20 alkenyloxy group), alkylthio group (eg C1-20 alkylthio group), alkoxyalkyl group, alkylthioalkyl group, ester group (eg -COO-tert-Bu) Etc.), a hydroxyl group which may be protected (for example, —OH, —O—Sitert-Bu) e _2, etc.), optionally protected amino group _{(-NH 2, -NHCH 3, -NCH} 3 Ph , etc.), carbonyl group, nitrile group, azido group, a boronic ester group, a protected or unprotected carboxyl Group, an optionally protected thiol group, an optionally protected silyl group, and the like. 1 to 3 of the heteroaryl groups may be substituted with at least one selected from the group consisting of these.

In the general formula (2), the group represented by the formula: CF ₂ R ² and the H group are bonded to the 2-position from the bonding position of Ar ¹ and Ar ² , respectively.

In the general formula (2), R ² represents a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkoxy group which may be substituted, an aryl group which may be substituted, or a hetero which may be substituted. An aryl group, an optionally substituted aralkyl group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group is shown.

Examples of the halogen atom represented by R ² include F, Cl, Br, and I, and preferably F, Cl, or Br.

Examples of the alkyl group of the “optionally substituted alkyl group” represented by R ² include C1-20 linear, branched or cyclic alkyl groups. Examples thereof include C1-12 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, and cyclodecyl. More preferably, it is a C1-8 alkyl group. The substituent is not particularly limited as long as it does not adversely affect the method of the present invention.

Examples of the alkoxy group of the “optionally substituted alkoxy group” represented by R ² include C1-20 linear, branched or cyclic alkoxy groups. Examples thereof include C1-12 alkoxy groups such as methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, octyloxy and the like. More preferably, it is a C1-8 alkoxy group. The substituent is not particularly limited as long as it does not adversely affect the method of the present invention.

Examples of the aryl group of the “optionally substituted aryl group” represented by R ² include a 1-4 cyclic aryl group, and specifically include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl. Group, fluorenyl group, benzofuryl group, benzothienyl group and the like are exemplified.

The aryl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the method of the present invention. For example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (for example, a C1-20 alkyl group), an aralkyl group (for example, a benzyl group), an aryl group (for example, a phenyl group, Biphenyl group), heteroaryl group (for example, pyridyl group, etc.), alkenyl group (for example, C2-20 alkenyl group such as vinyl group), alkoxy group (for example, C1-20 alkoxy group), aralkyloxy group (for example, Benzyloxy group etc.), alkenyloxy group (eg C2-20 alkenyloxy group), alkylthio group (eg C1-20 alkylthio group), alkoxyalkyl group, alkylthioalkyl group, ester group (eg -COO-tert-Bu) Etc.), a hydroxyl group which may be protected (for example, —OH, —O—Sitert-Bu) e _2, etc.), optionally protected amino group _{(-NH 2, -NHCH 3, -NCH} 3 Ph , etc.), carbonyl group, nitrile group, azido group, a boronic ester group, a protected or unprotected carboxyl Group, an optionally protected thiol group, an optionally protected silyl group, and the like. 1 to 3 of the aryl groups may be substituted with at least one selected from the group consisting of these.

Examples of the heteroaryl group of the “optionally substituted heteroaryl group” represented by R ² include an aryl having at least one heteroatom selected from 1 to 4 cyclic oxygen, nitrogen and sulfur in the ring. Specific examples include thienyl group, furyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolyl group, quinolyl group, isoquinolyl group and the like.

The heteroaryl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the method of the present invention. For example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (for example, a C1-20 alkyl group), an aralkyl group (for example, a benzyl group), an aryl group (for example, a phenyl group, Biphenyl group), heteroaryl group (for example, pyridyl group, etc.), alkenyl group (for example, C2-20 alkenyl group such as vinyl group), alkoxy group (for example, C1-20 alkoxy group), aralkyloxy group (for example, Benzyloxy group etc.), alkenyloxy group (eg C2-20 alkenyloxy group), alkylthio group (eg C1-20 alkylthio group), alkoxyalkyl group, alkylthioalkyl group, ester group (eg -COO-tert-Bu) Etc.), a hydroxyl group which may be protected (for example, —OH, —O—Sitert-Bu) e _2, etc.), optionally protected amino group _{(-NH 2, -NHCH 3, -NCH} 3 Ph , etc.), carbonyl group, nitrile group, azido group, a boronic ester group, a protected or unprotected carboxyl Group, an optionally protected thiol group, an optionally protected silyl group, and the like. 1 to 3 of the heteroaryl groups may be substituted with at least one selected from the group consisting of these.

Examples of the aralkyl group of the “optionally substituted aralkyl group” represented by R ² include C7-C20 aralkyl such as 2-phenylethyl, benzyl, 1-phenylethyl, 3-phenylpropyl, 4-phenylbutyl and the like. Groups and the like. The aralkyl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the method of the present invention.

As the alkenyl group of the “optionally substituted alkenyl group” represented by R ² , for example, a linear or branched C2-C20 alkenyl group such as vinyl, allyl, 1-butenyl, isobutenyl, etc., preferably C2 -C12 alkenyl group is mentioned. The alkenyl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the method of the present invention. Examples of the substituted alkenyl group include α or β-styryl, 2,2-diphenylvinyl group, and the like.

The alkynyl group of the “optionally substituted alkynyl group” represented by R ² includes, for example, a C2-C20 alkynyl group having a straight chain or branched chain such as ethynyl, 1-propynyl, 1-butynyl, 1-octynyl and the like. , Preferably a C2-C12 alkynyl group is mentioned. The alkynyl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the method of the present invention. Examples of the substituted alkynyl group include a 2-phenylethynyl group.

  In addition, the fluorine-containing compound represented by the general formula (2) is commercially available or can be easily produced by those skilled in the art according to a known method.

  Specific examples of the fluorine-containing compound represented by the general formula (2) include the following general formula (2a):

The compound represented by these is mentioned.

In the general formula, R ² is the same as that in the general formula (2).

In the general formula, R ^2a and R ^2b are the same or different, and are a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (for example, a C1-20 alkyl group), an aralkyl group ( For example, benzyl group etc.) aryl group (eg phenyl group, biphenyl group etc.), heteroaryl group (eg pyridyl group etc.), alkenyl group (eg C 2-20 alkenyl group such as vinyl group), alkoxy group (eg C1-20 alkoxy group), aralkyloxy group (for example, benzyloxy group, etc.), alkenyloxy group (for example, C2-20 alkenyloxy group), alkylthio group (for example, C1-20 alkylthio group), alkoxyalkyl group, Alkylthioalkyl group, ester group (for example, —COO-tert-Bu etc.), protected Which may hydroxyl (e.g., -OH, -O-Sitert-BuMe 2 , etc.), optionally protected amino group _{(-NH 2, -NHCH 3, -NCH} 3 Ph , etc.), carbonyl group, nitrile group, azido A group, a boronic acid ester group, an optionally protected carboxyl group, an optionally protected thiol group, and an optionally protected silyl group.

When the tricyclic compound obtained by the production method of the present invention is further subjected to a reaction such as polymerization, among these R ^2a and R ^2b, a halogen atom, a boronic acid ester group, a protected amino group, a protected carboxyl Particularly preferred are groups, protected hydroxyl groups, protected silyl groups, azide groups and the like.

  In the production method of the present invention, when the fluorine-containing compound represented by the general formula (2a) is used as a raw material, a compound having a fluorene skeleton is obtained.

In the general formula (2a), m and n indicating the number of substituents on the aromatic ring represented by R ^2a and R ^2b are the same or different and are usually an integer of 0 to 4, preferably an integer of 0 to 2. , More preferably 1. For example, in the general formula (2a), when each of the substituents on the aromatic ring represented by R ^2a and R ^2b has one and each of these substituents has reactivity or polymerizability, A polyfluorene derivative can be easily produced by polymerizing the obtained bicyclic compound.

In addition, even when the substituents on the aromatic ring represented by R ^2a and R ^2b are not reactive or polymerizable, these substituents are converted into polymerizable substituents (for example, deprotection reaction), then reacted or A polyfluorene derivative can also be obtained by polymerization.

III. Tricyclic compounds wherein as, in the manufacturing method of the present invention, the bonding position of Ar ¹ and Ar ² of the fluorine-containing compound represented by the general formula (2) as a position 1, Ar ¹ and Ar ^There are at least one CF ₂ R ² group (on Ar ¹ ) and H group (on Ar ² ) at each 2-position of ² . Although the reaction mechanism is not clear, by reacting the fluorine-containing compound with the organoaluminum compound, the F atom of the CF ₂ R ² group bonded to the 2-position of Ar ^{1 and} the 2-position H atom on Ar ² are generally Apart from the compound represented by the formula (2), the C atom of the CF ₂ R ² group and the C atom at the 2-position of Ar ² form a ring to obtain a tricyclic compound having a 5-membered ring. It is thought that

In the fluorine-containing compound represented by the general formula (2), when R ² is a fluorine atom, that is, when the CF ₂ R ² group at the 2-position of Ar ¹ is a CF ₃ group, the following general formula ( 3):

The tricyclic compound represented by these is obtained.

In General Formula (3), Ar ¹ , Ar ² , and R ¹ are the same as those in General Formula (1) and General Formula (2).

Moreover, two R < ¹ > may couple | bond together and may form the ring. For example, when the organoaluminum compound represented by the general formula (1a) is reacted with the compound represented by the general formula (2), the following general formula (3a):

The tricyclic compound (fluorene compound) represented by these is obtained.

In the general formula (3a), Ar ¹ , Ar ² , R ^1a , R ^1b , m and n are the same as those in the general formula (1a) and the general formula (2).

Further, for example, in the fluorine-containing compound represented by the general formula (2a), when R ² is a fluorine atom, the organic aluminum compound represented by the general formula (1a) and the general formula (2a) When the fluorine-containing compound to be reacted is reacted, the following general formula (3b):

The tricyclic compound (fluorene compound) represented by these is obtained.

In general formula (3b), R ^1a , R ^1b , R ^2a , R ^2b , m and n are the same as those in general formula (1a) and general formula (2a).

In the fluorine-containing compound represented by the general formula (2), R ² is a hydrogen atom, a halogen atom excluding a fluorine atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, or a substituted group. In the case of an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted aralkyl group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group, General formula (3c):

The tricyclic compound represented by these is obtained.

In the general formula (3c), Ar ¹ , Ar ² , R ¹ and R ² are the same as those in the general formula (1) and the general formula (2). In general formula (3c), R ² is not a fluorine atom.

  Here, when the fluorine-containing compound represented by the general formula (2a) is reacted with the organoaluminum compound represented by the general formula (1), the following general formula (3d):

The tricyclic compound (fluorene compound) represented by these is obtained.

In the general formula (3d), R ^2a , R ^2b , R ¹ , R ² , m and n are the same as those in the general formula (1) and the general formula (2a).

  According to the present invention, by using a fluorine compound having a substituent on the aromatic ring as a raw material, the compound represented by the general formula (3) or the like in which the substituent is introduced at a desired position on the aromatic ring is represented by 3 A cyclic compound is obtained. Such a compound is extremely useful as a monomer and can be led to a polyfluorene derivative or the like by polymerization.

IV. Production Method The present invention comprises an organoaluminum compound represented by the general formula (1) and the general formula (2).
It is carried out by reacting with a fluorine-containing compound represented by

  As the reaction solvent used in this reaction, an aprotic solvent is used. For example, chlorinated solvents such as dichloromethane, dichloroethane, tetrachloroethane, carbon tetrachloride; hydrocarbon solvents such as hexane, heptane, cyclohexane, petroleum ether, benzene, toluene, xylene; diethyl ether, diisopropyl ether, THF, DME, dioxane And ether solvents such as Of these, low-polarity solvents such as dichloromethane, dichloroethane, tetrachloroethane, carbon tetrachloride, hexane, heptane, benzene, toluene, and xylene are preferable, and chlorine-based solvents such as dichloromethane, dichloroethane, tetrachloroethane, and carbon tetrachloride are preferred. And aromatic solvents such as benzene, toluene and xylene are most preferably used.

  The amount of the organoaluminum compound used is usually in the range of about 0.1 to 20 mol, preferably about 1 to 10 mol, and more preferably about 2 to 5 mol with respect to 1 mol of the raw material fluorine-containing compound.

  The concentration of the raw material fluorine-containing compound in the reaction is usually about 0.01 to 10 mol / L, preferably about 0.1 to 5 mol / L.

  The mixing order of the raw material fluorine-containing compound, the organoaluminum compound and the solvent is not particularly limited. Preferably, a method of adding a raw material fluorine-containing compound to a mixture of a solvent and an organic aluminum compound, and a method of adding an organic aluminum compound to a solution of the solvent and the raw material fluorine-containing compound can be mentioned.

  The reaction is preferably performed under anhydrous conditions in an inert gas (eg, nitrogen, argon, etc.) atmosphere.

  The reaction temperature can be appropriately selected according to the activity of aluminum functioning as the Lewis acid used. Usually, it is in the range of, for example, about −78 ° C. to 200 ° C., preferably in the range of −30 ° C. to 100 ° C., and about the boiling point of the solvent used from room temperature is used.

  The reaction of the present invention is completed in several minutes to several days at the above reaction temperature. The progress of the reaction can be evaluated by various analytical methods, and analytical means such as GLC, HPLC, TLC, NMR, and IR are effective.

  After completion of the reaction, the tricyclic compound is obtained through a normal purification step. A known method can be employed for the purification step of the compound. For example, the reaction solution can be extracted by adding an organic solvent as necessary, and further purified by a known method such as silica gel column chromatography or recrystallization.

  In the present invention, the raw material fluorine-containing compound includes the halogen-containing compound represented by the general formula (4), the organometallic compound represented by the general formula (5), and the aluminum represented by the general formula (6). A tricyclic compound can also be obtained by mixing the compound.

The order of mixing the reagents in this case is not particularly limited, but preferably, the halogen-containing compound represented by the general formula (4) or the like and the organometallic compound represented by the general formula (5) or the like are mixed. Step 1 to
Step 2 for mixing the solution obtained in Step 1 with the aluminum compound represented by the general formula (6), and the fluorine-containing compound represented by the solution obtained in Step 2 and the general formula (2) Step 3 of mixing
The target tricyclic compound can be produced in a series of steps (in situ).

  In this case, an organoaluminum compound represented by the general formula (1) or the like is once produced in the reaction system, and this reacts with a fluorine compound represented by the general formula (2) or the like to produce a tricyclic compound. And when the organoaluminum compound represented by the general formula (1) or the like is not clearly formed and the tricyclic compound represented by the general formula (3) or the like is generated. Though conceivable, the reaction may proceed in any reaction form as long as the tricyclic compound represented by the general formula (3) or the like is obtained.

As described above, in the production method of the present invention, Ar ¹ and Ar ² in the fluorine-containing compound represented by the general formula (2) or the like are each positioned at the 1st position, and each of Ar ¹ and Ar ² At least one CF ₂ R ² group (on Ar ¹ ) and H group (on Ar ² ) are present at the ^2-position . Although the reaction mechanism is not clear, by reacting the fluorine-containing compound with the organoaluminum compound (or reacting in situ as described above), F ^{2 of} the CF ₂ R ² group bonded to the 2-position of Ar ¹ The H atom at the 2-position on the atom and Ar ² is separated from the compound represented by the general formula (2) etc., and the C atom of the CF ₂ R ² group and the C atom at the 2-position of Ar ² are bonded to form a ring. It is believed that a tricyclic compound that forms and has a five-membered ring is obtained.

In the fluorine-containing compound represented by the general formula (2), when R ² is a fluorine atom, that is, when the CF ₂ R ² group at the 2-position of Ar ¹ is a CF ₃ group, as described above, The following general formula (3):

The tricyclic compound represented by these is obtained.

In General Formula (3), Ar ¹ , Ar ² , and R ¹ are the same as those in General Formula (1) and General Formula (2). Moreover, two R < ¹ > may couple | bond together and may form the ring.

  In this case, in addition to the compound represented by the general formula (3), the following general formula (3f) generated when the ring formation reaction does not proceed:

May be obtained.

In General Formula (3f), Ar ¹ , Ar ² , and R ¹ are the same as those in General Formula (1) and General Formula (2). Moreover, as described above, two R ¹ out of the three R ¹ may be bonded to each other to form a ring.

In the fluorine-containing compound represented by the general formula (2), R ² is a hydrogen atom, a halogen atom excluding a fluorine atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, or a substituted group. An aryl group that may be substituted, a heteroaryl group that may be substituted, an aralkyl group that may be substituted, an alkenyl group that may be substituted, or an alkynyl group that may be substituted, As shown below, the following general formula (3c):

The tricyclic compound represented by these is obtained.

In the general formula (3c), Ar ¹ , Ar ² , R ¹ and R ² are the same as those in the general formula (1) and the general formula (2). In the general formula (3c), the R ² group is not an F atom.

  In this case, in addition to the compound represented by the above general formula (3c), the ring formation reaction did not proceed and the following general formula (3g):

May be obtained.

In the general formula (3g), Ar ¹ , Ar ² , R ¹ and R ² are the same as those in the general formula (1) and the general formula (2). In the general formula (3g), the R ² group is not an F atom. Two R ^{1 's} may be bonded to each other to form a ring.

  According to the present invention, by using a fluorine compound having a substituent on the aromatic ring as a raw material, the compound represented by the general formula (3) or the like in which the substituent is introduced at a desired position on the aromatic ring is represented by 3 A cyclic compound is obtained. Such a compound is extremely useful as a monomer, and can be led to a polymer of a tricyclic compound such as a polyfluorene derivative by polymerization.

  Although the reaction mechanism in the production method of the present invention is not clear, after the defluorination substitution reaction with an organoaluminum compound, a cation intermediate generated in the defluorination process causes a Friedel-Crafts reaction to an aryl group in the molecule to cyclize Presumed to be. As shown in a reference example to be described later, the formation process of a new carbon-carbon bond by the first defluorination substitution cannot be progressed well with an art complex. In the present invention, it is essential to use a neutral trivalent aluminum reagent, and the reaction described in Non-Patent Document 6 is clearly different in this respect. In the reaction described in Non-Patent Document 6, it is presumed that a heavy metal such as niobium must be used in combination in order to use an art complex.

The raw material fluorine compound (for example, 2-fluoroalkylbiphenyl derivative), which is a substrate used in the present invention, can be synthesized by various methods as shown below, and thus is easily available. A variety of tricyclic compounds can be easily synthesized.
1) Introduction of fluoroalkyl group into 2-halogenated biaryl (or heterobiaryl) 2) Difluoromethylation reaction of biaryl derivative (or heterobiaryl derivative) having a carbonyl group or an acetal group at the 2-position with a fluorinating agent 3) Biarylation reaction by coupling reaction of an aryl compound (or heteroaryl compound) having a fluoroalkyl group at the 2-position Among these, if synthesized from the method of 3), a very diverse substitution in the biaryl (or heterobiaryl) skeleton Since introduction of a group becomes possible, many substituents can be introduced at desired positions in the tricyclic compound obtained by the production method of the present invention. Thus, it can be expected to produce a tricyclic compound (fluorene derivative or the like) that has not been obtained by an existing method and a new organic semiconductor material or the like using the compound.

V. Method of Use As described above, in the tricyclic compound obtained by the production method of the present invention, a substituent can be introduced at a desired position on the organic group of the raw material fluorine-containing compound and / or the organoaluminum compound. Therefore, when the tricyclic compound obtained by the production method of the present invention has a polymerizable substituent (for example, a halogen group, a boronic acid, a boronic acid ester, etc.), or a substituent (protecting group, etc.) of the compound Is converted into a polymerizable substituent, by polymerizing these compounds, a polymer of a tricyclic compound such as a polyfluorene derivative having high usefulness as an organic semiconductor can be synthesized easily and in high yield. it can.

  As a method for obtaining a tricyclic compound polymer by polymerizing the tricyclic compound obtained by the production method of the present invention, a known method can be adopted, for example, Suzuki polymerization disclosed in WO00 / 53656. Yamamoto polymerization disclosed in Macromolecules, 31, 1099-1103 (1988). Suzuki polymerisation involves the coupling of halogen groups and boron-derived coordination groups. Yamamoto polymerization involves the coupling of halogen groups. Therefore, for example, when Yamamoto polymerization is assumed, the polymerizable substituent introduced into the fluorene compound in advance includes at least one selected from the group consisting of a halogen group, a boronic acid group, a boronic ester group, and a borane group. It is done.

  As described above, when the tricyclic compound obtained by the production method of the present invention is polymerized by these methods, a halogen group or boronic acid is formed on the organic group of the organoaluminum compound and / or on the aromatic ring of the starting fluorine-containing compound. It is sufficient to introduce at least one polymerizable substituent selected from the group consisting of a group, a boronic acid ester group and a borane group.

  When the tricyclic compound represented by the general formula (3) obtained by the production method of the present invention is polymerized to obtain a polymer of the tricyclic compound, the tricyclic compound is polymerized alone. Alternatively, two or more kinds may be mixed and polymerized.

  When a tricyclic compound is polymerized to obtain a polyfluorene derivative, the average molecular weight of the polyfluorene derivative is appropriately selected according to the purpose of use, but gel permeation chromatography can be obtained because good mechanical properties can be obtained. It is preferable that the polystyrene conversion weight average molecular weight by a graph method is 2000-1 million, and it is preferable that it is 5000-500000 at the point from which especially favorable solubility and a process characteristic are acquired.

  Examples are given below to clarify the features of the present invention. The present invention is not limited to these examples.

Example 1 (Synthesis of 9,9-dimethylfluorene from 2-phenylbenzotrifluoride)
Under a nitrogen atmosphere, 2N trimethylaluminum-hexane solution (1 mmol) was added dropwise at room temperature to a solution of 2-phenylbenzotrifluoride (0.2 mmol) in dichloroethane (1 mL). After stirring at that temperature for 30 minutes, the reaction was quenched with 1N aqueous hydrochloric acid and the product was extracted with ether. Yields were integrated by GLC using decane as an internal standard (48% yield). The structure was determined by GC-MS.

MS m / z 194 (M +), 179 (M-CH3), 89 (C7H5).
1H-NMR (CDCl3): δ 1.48 (s, 6H), 7.25-7.34 (m, 4H), 7.40-7.45 (m, 2H), 7.70-7.73 (m, 2H).

Example 2 (Preparation of triphenylaluminum hexane solution and synthesis of 9,9-diphenylfluorene from 2-phenylbenzotrifluoride)
In a nitrogen atmosphere, iodobenzene (612 mg, 3 mmol) was added dropwise at −78 ° C. to 3 mL (3 mmol) of n-BuLi (1M hexane solution) placed in a double flask. The solution was stirred at room temperature for 1 hour. The obtained phenyllithium solution was cooled to −78 ° C., and 267 mg (1 mmol) of aluminum bromide was added and stirred under a nitrogen stream. Further, 3 mL of methylene chloride was added to this solution and stirred at -78 ° C for 24 hours.

  2-Phenylbenzotrifluoride (0.2 mmol) was added to the triphenylaluminum solution obtained here at room temperature with stirring. The reaction was stirred at this temperature for 1 hour, then quenched with 1N hydrochloric acid and extracted with ether. From the GLC analysis of the reaction solution, it was found that 9,9-diphenylfluorene was obtained in a yield of 12%. The structure of the product obtained here was determined from the molecular ion peak and the fragment peak in the analysis by GC-MS.

MS m / z 318 (M +), 241 (MC ₆ H ₅ ).
1H-NMR (CDCl3): δ 7.10-7.60 (m, 16H), 7.76 (d, J = 7.6Hz, 2H).
13C-NMR (CDCl3): δ 65.48, 120.13, 126.20, 126.60, 127.44, 127.69, 128.13, 128.18, 140.14, 145.93, 151.14.

Example 3 (Preparation of 2,2-biphenylaluminum and synthesis of spirobifluorene from 2-phenylbenzotrifluoride)
2,2-Diiodobiphenyl (0.6 mmol) and n-bryllithium (1.8 mmol) were stirred in hexane-toluene (1: 1, 2 mL) at room temperature for 1 hour to prepare 2,2-dilithiobiphenyl. did. Aluminum bromide (0.55 mmol) was added thereto, and the mixture was stirred at room temperature for 30 minutes to prepare a hexane solution of 2,2-biphenylaluminum. To this solution was added dropwise a toluene solution (5 mL) of 2-phenylbenzotrifluoride (0.5 mmol), and the mixture was stirred at room temperature for 1 hour. After the reaction solution was post-treated in the same manner as before, it was confirmed from the GC-MS and GLC analysis of the reaction solution that spirobifluorene was obtained in a yield of 27%.

MS m / z 316 (M +).
1H-NMR (CDCl3): δ 6.72 (d, J = 7.6Hz, 4H), 7.06-7.11 (m, 4H), 7.30-7.37 (m, 4H), 7.83 (d, J = 7.6Hz, 4H).
13C-NMR (CDCl3): δ 65.92, 119.95, 124,01, 127.67, 127.78, 141.73, 148.74.

Example 4 (Synthesis of 2,7-dibromospirobifluorene)
4,4'-Dibromo-2-trifluoromethylbiphenyl was synthesized from 4,4'-dibromobiphenyl-2-carboxylic acid (synthesized according to J. Am. Chem. Soc., 1956, 78, 3196). ₄ was synthesized. Next, to a biphenylaluminum reagent prepared in the same manner as in Example 3 (0.55 mmol, hexane-toluene solution (1: 1, 2 mL)), 4,4′-dibromo-2-trifluoromethylbiphenyl (0.5 mmol) in toluene (5 mL) was added dropwise and stirred at this temperature for 30 min. After the post-treatment, GC-MS and GLC analysis of the reaction solution revealed that 2,7-dibromospirobifluorene was obtained in 45% yield.

MS m / z 477 (M + 5), 475 (M + 3), 473 (M + 1), 396 (M + 3-Br), 394 (M + 1-Br), 334, 314
1H-NMR (CDCl3): δ6.72 (d, J = 7.5Hz, 2H), 6.85 (s, 2H), 7.06-7.11 (m, 2H), 7.33-7.37 (m, 2H), 7.50 (d, J = 8.0Hz, 2H), 7.65 (d, J = 8.0Hz, 2H), 7.83 (d, J = 7.5Hz, 2H).

Example 5 (Synthesis of 2-bromospirobifluorene)
4-Bromo-2-phenylbenzotrifluoride was synthesized according to Chemistry & Biology, 2006, 13, pp. 1227. Next, a xylene solution (5 mL) of 4-bromo-2-phenylbenzotrifluoride (0.4 mmol) was added dropwise to 2,2-biphenylaluminum reagent (0.44 mmol) prepared in the same manner as in Example 3 at room temperature. The mixture was stirred at this temperature for 30 minutes. After the post-treatment, it was confirmed from GC-MS and GLC analysis of the reaction solution that 2-bromospirobifluorene was obtained in 50% yield.

MS m / z 396 (M + 2), 394 (M +), 315 (M-Br).
1H-NMR (CDCl3): δ 6.70-6.88 (m, 2H), 6.75 (d, J = 7.5Hz, 2H), 7.15-7.20 (m, 3H), 7.33-7.43 (m, 2H), 7.35- 7.56 (m, 2H), 7.74-7.87 (m, 2H), 7.75 (d, J = 7.5Hz, 2H).

Example 6 (Synthesis of spiroindenothiophene fluorene)
3-Phenyl-2-trifluoromethylthiophene was purchased from ApoLLo and used as it was. To a 2,2-biphenylaluminum reagent (0.44 mmol) prepared in the same manner as in Example 3, a xylene solution (5 mL) of 3-phenyl-2-trifluoromethylthiophene (0.4 mmol) was added dropwise at room temperature. Stir at temperature for 1 hour. After the post-treatment, it was confirmed from the GC-MS and GLC analysis of the reaction solution that spiroindenothiophene fluorene was obtained in 46% yield.

MS m / z 322 (M +).
1H-NMR (CDCl3): δ 6.60 (d, J = 7.6Hz, 1H), 6.82 (d, J = 7.2Hz, 2H), 6.95 (t, J = 8.0Hz, 1H), 7.15 (t, J = 7.5Hz, 2H), 7.28 (t, J = 7.5Hz, 1H), 7.34-7.40 (m, 4H), 7.58 (d, J = 7.5Hz, 1H), 7.82 (d, J = 7.5Hz, 2H ).

Example 7 (Synthesis of 9-methylfluorene with 2-difluoromethylbiphenyl and trimethylaluminum)
2-difluoromethylbiphenyl was synthesized by heating 2-biphenylcarboxaldehyde (purchased by Aldrich) and 2,2-difluoro-1,3-dimethylimidazolidine (purchased by Tokyo Kasei) in acetonitrile. Under a nitrogen atmosphere, 2N trimethylaluminum-hexane solution (1 mmol) was added dropwise at room temperature to a solution of 2-difluoromethylbiphenyl (0.2 mmol) in dichloroethane (1 mL). After stirring at that temperature for 30 minutes, the reaction was quenched with 1N aqueous hydrochloric acid and the product was extracted with ether. Yields were integrated by GLC using decane as an internal standard (35% yield). The structure was determined by GC-MS.

MS m / z 180 (M +), 179 (MH), 165 (M-CH3).
1H-NMR (CDCl3): δ1.53 (t, J = 7.6H, 3H), 3.95 (q, J = 7.6H, 1H), 7.28-7.40 (m, 4H), 7.50-7.55 (m, 2H) , 7.75-7.80 (m, 2H).
13C-NMR (CDCl3): δ 18.3, 42.4, 119.8, 124.1, 126.5, 127.0, 140.6, 149.2.

Reference Example 1 (Defluorinated biphenylation reaction of 2,2-biphenylaluminum and diphenyldifluoromethane)
Addition of butyl anion to 2,2-biphenylaluminum by adding an equimolar amount of n-butyllithium in hexane to hexane solution of 2,2-biphenylaluminum (0.4 mmol) prepared in the same manner as in Example 3. An art complex was prepared. To this solution, diphenyldifluoromethane (0.2 mmol) was added dropwise and stirred at room temperature for 30 minutes. After workup with 1N hydrochloric acid, GLC analysis of the product confirmed that 9,9-diphenylfluorene was obtained only in 1% yield.

Reference example 2
To a hexane solution (1 mL) of triphenylaluminum (0.8 mmol) prepared in the same manner as in Example 2, a dichloroethane solution (1 mL) of 4-isobutyl-α, α-difluorotoluene (0.2 mmol) was stirred at room temperature for 30 minutes. . After the post-treatment, 4-isobutylphenyldiphenylmethane was obtained in 84% yield by GLC and GC-MS.

Reference example 3
Aluminum and equimolar phenyl lithium were further added dropwise to triphenylaluminum obtained by the method of Example 2 to prepare a hexane solution of a tetraphenylaluminum lithium-art complex. When this was reacted with 4-isobutyl-α, α-difluorotoluene as in Reference Example 3, the yield of the desired product was only 20%.

Claims (8)

A method for producing a tricyclic compound, which is represented by the following general formula (1):
Al (R ¹ ) ₃ (1)
[Wherein, R ¹ are the same or different and each may be an alkyl group which may be substituted, an alkoxy group which may be substituted, an aryl group which may be substituted, a heteroaryl group which may be substituted, An aralkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted; two R ¹ out of three R ¹ are bonded to each other to form a ring; Also good. ]
An organoaluminum compound represented by the following general formula (2):

[Wherein, Ar ¹ and Ar ² are the same or different and each represents an optionally substituted aryl group or an optionally substituted heteroaryl group;
The CF ₂ R ² group and the H group are bonded to the 2-position from the bonding position of Ar ¹ and Ar ² , respectively.
R ² represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, a substituted An aralkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted; ]
A method for producing a tricyclic compound by reacting with a compound represented by the formula: R ^{2 in the} general formula (2) is a fluorine atom, and the resulting tricyclic compound is represented by the following general formula (3):

[Wherein, Ar ¹ , Ar ² and R ¹ are the same as described above, and two R ¹ may be bonded to each other to form a ring. ]
The manufacturing method of Claim 1 which is a tricyclic compound represented by these. R ^{2 in the} general formula (2) is a hydrogen atom, a halogen atom excluding a fluorine atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, or a substituted atom. A heteroaryl group which may be substituted, an aralkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted, and the resulting tricyclic compound represented by the following general formula (3c) :

[Wherein, Ar ¹ , Ar ² , R ¹ and R ² are the same as defined above. However, R ² is not a fluorine atom. ]
The manufacturing method of Claim 1 which is a tricyclic compound represented by these. A method for producing a tricyclic compound, comprising:
Step 1: the following general formula (4):
R ¹ -X ¹ (4)
[Wherein, R ¹ is an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, and optionally substituted. An aralkyl group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group; X ¹ represents a halogen atom; ]
A halogen-containing compound represented by the following general formula (5):
R ³ -M (5)
[Wherein, R ³ represents an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, or optionally substituted. An aralkyl group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group;
M represents a metal selected from the group consisting of lithium, boron, magnesium, zinc and copper. A step of mixing with an organometallic compound represented by
Step 2: The solution obtained in Step 1 and the following general formula (6):
Al (R ⁴ ) ₃ (6)
[Wherein, R ⁴ are the same or different and each represents an alkyl group or a halogen atom. ]
A step of mixing an aluminum compound represented by:
Step 3: The solution obtained in Step 2 and the following general formula (2):

[Wherein, Ar ¹ and Ar ² are the same or different and each represents an optionally substituted aryl group or an optionally substituted heteroaryl group;
The CF ₂ R ² group and the H group are bonded to the 2-position from the bonding position of Ar ¹ and Ar ² , respectively.
R ² is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, a substituted An aralkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted; ]
A method for producing a tricyclic compound comprising a step of mixing with a compound represented by the formula: R ^{2 in the} general formula (2) is a fluorine atom, and the resulting tricyclic compound is represented by the following general formula (3):

[Wherein Ar ¹ , Ar ² and R ¹ are the same as defined above. ]
The manufacturing method of Claim 4 which is a tricyclic compound represented by these. R ^{2 in the} general formula (2) is a hydrogen atom, a halogen atom excluding a fluorine atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, or a substituted atom. A heteroaryl group which may be substituted, an aralkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted, and the resulting tricyclic compound represented by the following general formula (3c) :

[Wherein, Ar ¹ , Ar ² , R ¹ and R ² are the same as defined above. ]
The manufacturing method of Claim 4 which is a tricyclic compound represented by these. A method for producing a tricyclic compound, comprising:
Step 1: the following general formula (4b):

[Wherein, X ² and X ³ are the same or different and each represents a halogen atom,
R ^1a and R ^1b are the same or different and each is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, or optionally substituted. A heteroaryl group, an optionally substituted aralkyl group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group;
m and n are the same or different and are an integer of 0-4. ]
A halogen-containing compound represented by the following general formula (5):
R ³ -M (5)
[Wherein, R ³ represents an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, or optionally substituted. An aralkyl group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group;
M represents a metal selected from the group consisting of lithium, boron, magnesium, zinc and copper. A step of mixing with an organometallic compound represented by
Step 2: The solution obtained in Step 1 and the following general formula (6):
Al (R ⁴ ) ₃ (6)
[Wherein, R ⁴ are the same or different and each represents an alkyl group or a halogen atom. ]
A step of mixing an aluminum compound represented by:
Step 3: The solution obtained in Step 2 and the following general formula (2):

[Wherein, Ar ¹ and Ar ² are the same or different and each represents an optionally substituted aryl group or an optionally substituted heteroaryl group;
The CF ₂ R ² group and the H group are bonded to the 2-position from the bonding position of Ar ¹ and Ar ² , respectively.
R ² is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, a substituted An aralkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted; ]
A method for producing a tricyclic compound comprising a step of mixing with a compound represented by the formula: R ^{2 in the} general formula (2) is a fluorine atom, and the resulting tricyclic compound is represented by the following general formula (3a):

[Wherein, Ar ¹ , Ar ² , R ^1a , R ^1b , m and n are the same as defined above. ]
The manufacturing method of Claim 7 which is a tricyclic compound represented by these.