KR20170040735A - A fluorene-based compound, and a method for preparing the fluorene-based compound - Google Patents

Abstract

Provided in the present invention is a novel fluorene-based compound which has improved purity and reaction efficiency, and can be used to produce high-purity or inexpensive materials required for organic EL devices. According to the present invention, a compound having a fluorene structure represented by chemical formula (I) is obtained by reacting an OH precursor having a structure represented by chemical formula (II) in the molecule thereof in the presence of a catalyst support and an acid, and/or in the presence of a fixed bed catalyst. A^1 and A^2 are each independently an alkyl group, an aryl group, or a heteroaryl group, which may be optionally substituted, and A^1 and A^2 may bond to form a ring.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a fluorene-based compound, a fluorene-based compound, and a fluorene-based compound.

The present invention relates to a novel fluorene-based compound and a process for producing the fluorene-based compound.

Recently, a compound having a fluorene skeleton or a fluorene-based compound having an active group such as fluorine has been studied as an intermediate for producing a material having a more complicated chemical structure as a compound used in a light emitting material or the like of an organic electroluminescent device .

For example, it is known that compounds substituted with 1, 3, 4, 5, 6, and 8-positions of a fluorene ring as a strong electron withdrawing group as an organic electronic material have a high electron accepting ability Patent Publication No. 2009-249355). In this document, fluorene is used as a raw material for producing this compound, and a method for producing a fluorene skeleton is not described.

To prepare a fluorene skeleton, for example, a method in which an alcoholic form of biphenyl is used as a substrate (also referred to as an OH precursor) to make a ring with hydroxymethylene is known (Japanese Patent Application Laid-Open Publication No. 2012-211089). This publication aims at producing a monohalogen-substituted fluorene compound by a simpler method, and succeeds in obtaining a target compound by reacting an OH precursor with a distillate as described herein.

Japanese Patent Application Laid-Open No. 2009-249355 Japanese Patent Application Laid-Open No. 21-2101089

As described above, a compound having a fluorene skeleton, a fluorene-based compound having an active group such as fluorine, and a production method thereof are also known for a time. However, this production method has a problem in that the reaction efficiency is poor and the olefinic by- And it can not be used for producing a high-purity or low-cost material required for an organic EL device, for example. Therefore, a new production method is also required to increase the selection method of the production method, and further to further increase the purity and the reaction efficiency.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have succeeded in producing a fluorene compound at a very high efficiency by reacting an OH precursor together with a carrier such as a porous inorganic material as well as an acid. It has also been found by this method that a novel active-group-containing fluorene-based compound, which has not been previously known, can be produced, and the present invention has been completed.

[One]

Reacting an OH precursor having a structure represented by the following formula (II) in the molecule in the presence of a carrier and an acid and / or in the presence of a fixed-rate catalyst to obtain a fluorene structure represented by the following formula (I) ≪ / RTI >

A ¹ and A ² are each independently alkyl, aryl or heteroaryl, and these groups may be substituted, and A ¹ and A ² may combine to form a ring.

[2]

The OH precursor represented by the following general formula (2-1) or (2-2) is reacted in the presence of a carrier and an acid and / or in the presence of a high- The production method according to the above [1], wherein a cyanine compound is produced.

Of the formulas (1), (2-1) and (2-2)

A ¹ and A ² are each independently alkyl, aryl or heteroaryl which may be substituted, A ¹ and A ² may be combined to form a ring,

R ¹ to R ⁴ and R ⁵ to R ⁸ are each independently hydrogen, alkyl, aryl, heteroaryl or diaryl substituted amino, and these groups may be substituted and R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ^7, and R ⁷ and R ⁸ may be independently bonded to form a ring,

The hydrogen in the fluorene compound represented by the formula (1) may be substituted with fluorine, chlorine, bromine, iodine or alkoxy. In this case, in the formula (2-1) or The corresponding hydrogen in the OH precursor to be displayed is similarly substituted.

[3]

Wherein the carrier is an inorganic oxide or a metal sulfate,

Wherein said acid is sulfuric acid, phosphoric acid, polyphosphoric acid or sulfonic acid,

The production method according to the above [1] or [2], wherein the fixed catalyst is a sulfonated resin or a surface-treated sulfonated porous material.

[4]

The production method according to any one of [1] to [3], wherein the carrier is a porous material.

[5]

Of the formulas (1), (2-1) and (2-2)

A ¹ and A ² are each independently alkyl, aryl or heteroaryl, A ¹ and A ² may be bonded to form an aliphatic or aromatic ring,

R ¹ to R ⁴ and R ⁵ to R ⁸ are each independently hydrogen, alkyl, aryl, heteroaryl or diaryl substituted amino, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ and R ⁷ and R ⁸ may be independently bonded to form an aromatic ring,

The hydrogen in the fluorene skeleton of the fluorene compound represented by the formula (1) may be substituted with fluorine, chlorine, bromine, iodine or alkoxy. In this case, in the formula (2-1) or -2) in which the corresponding hydrogen in the OH precursor is equally substituted,

The production method according to any one of [1] to [4] above.

[6]

Of the formulas (1), (2-1) and (2-2)

A ¹ and A ² are each independently alkyl, aryl or heteroaryl,

R ¹ to R ⁴ are each independently hydrogen, alkyl, aryl, heteroaryl, diaryl substituted amino or fluorine, at least one of R ¹ to R ⁴ is fluorine,

R ⁵ to R ⁸ are each independently hydrogen, alkyl, aryl, heteroaryl, diaryl substituted amino, chlorine, bromine, iodine or alkoxy, and at least one of R ⁵ to R ⁸ is chlorine, bromine, Alkoxy,

The production method according to any one of [1] to [5] above.

[7]

A fluorene-based compound represented by the following general formula (1).

In the formula (1)

A ¹ and A ² are each independently alkyl, aryl or heteroaryl,

R ¹ to R ⁴ are each independently hydrogen, alkyl, aryl, heteroaryl, diaryl substituted amino or fluorine, at least one of R ¹ to R ⁴ is fluorine,

R ⁵ to R ⁸ are each independently hydrogen, alkyl, aryl, heteroaryl, diaryl substituted amino, chlorine, bromine, iodine or alkoxy, and at least one of R ⁵ to R ⁸ is chlorine, bromine, Lt; / RTI >

[8]

In the formula (1)

A ¹ and A ² are each independently alkyl,

R ¹ to R ⁴ are each independently hydrogen, alkyl, aryl, heteroaryl, diaryl substituted amino or fluorine, at least one of R ¹ to R ⁴ is fluorine,

R ⁵ to R ⁸ are each independently hydrogen, alkyl, aryl, heteroaryl, diaryl substituted amino, chlorine, bromine, iodine or alkoxy, and at least one of R ⁵ to R ⁸ is chlorine, bromine, Alkoxy,

The fluorene-based compound according to the above-mentioned [7].

According to a preferred embodiment of the present invention, the conversion ratio from the OH precursor to the fluorene compound can be dramatically increased by using a carrier, particularly a porous carrier together with an acid, in comparison with a conventional production method using distractions. Further, according to this preferred embodiment, it is possible to produce a novel active-group-containing fluorene-based compound which has not been known in the prior art, and thus it is possible to increase variations of materials which can be used, for example, in organic EL devices.

One. Fluorene-based  Method for producing a compound

A method for producing a fluorene compound according to the present invention comprises reacting an OH precursor having in its molecule a structure represented by the following formula (II) in the presence of a carrier and an acid and / or in the presence of a high- (I) in a molecule.

On the other hand, "having a structure in a molecule" means that a substituent, a ring, or the like is bonded to the structure or a ring is condensed to form the molecule, and the structure corresponds to a structure of a part of the molecule. In addition, the structure itself may be the corresponding molecule, which means that the structure and the molecule have the same chemical structure. For example, a compound having a fluorene structure represented by the formula (I) in a molecule is a compound formed by binding a substituent, a ring, or the like to a fluorene structure represented by the formula (I) or condensing a ring. The same applies to the OH precursor having the structure represented by the formula (II) in the molecule.

A more specific method for producing a fluorene compound according to the present invention is a method for producing an OH precursor represented by the following general formula (2-1) or (2-2) in the presence of a carrier and an acid, To produce a fluorene-based compound represented by the following general formula (1).

The formula (1) represents a fluorene compound as a target compound, the formula (I) represents a fluorene structure moiety in a fluorene compound as a target compound, and is represented by formula (2-1) (II) represents a raw material for producing the fluorene compound. This production method is characterized in that the OH group (hydroxyl group) in the compound having the structure represented by the formula (2-1) or the formula (2-2) as the raw material or the structure represented by the formula (II) (Dehydration cyclization reaction) in which an acid is reacted with an adjacent carbon (represented by the above-mentioned " * "). On the other hand, this raw material is also referred to as an OH precursor for convenience.

≪ A ^One , A ² , R ^One ~ R ⁴  And R ⁵ ~ R ⁸ About>

The formula (1) or formula (I), the formula (2-1), the formula (2-2) or the formula (II) Therefore, A ¹ , A ² , R ¹ to R ⁴ and R ⁵ to R ⁸ used in each formula means the same groups, respectively. A ¹ and A ² , R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ and R ⁷ and R ⁸ may be combined to form a ring When a ring is formed in the formula (2-1), the formula (2-2), or the formula (II), a ring is formed at the corresponding position in the formula (1) or the formula (I). When no ring is formed in the formula (2-1), the formula (2-2) or the formula (II), no ring is formed at the corresponding position in the formula (1) or the formula (I) (1) or a compound having a fluorene structure represented by the formula (I) in the molecule may be produced, followed by reaction for forming these rings.

As described above, the process for producing a fluorene-based compound according to the present invention uses a simple reaction in which an OH group in an OH precursor is reacted with an adjacent carbon to cyclize the OH group. Therefore, the formula (I) A ¹ , A ² , R ¹ to R ⁴ and R ⁵ to R ⁸ used in the formulas (II), (2-1) and (2-2) Is not particularly limited. Examples of such groups are as follows.

A ¹ and A ² are each independently alkyl, aryl or heteroaryl, and these groups may be substituted, and A ¹ and A ² may combine to form a ring. When A ¹ and A ² are alkyl or the like, it is presumed that the reaction with the reaction solvent or the like is difficult to occur due to factors such as steric hindrance or reaction activity, and the intramolecular dehydroxylation reaction of the OH precursor itself is likely to proceed. It is considered that the compound is likely to be obtained. On the other hand, if A ¹ and A ² are hydrogen, it is presumed that the reaction rate is faster for the intermolecular dehydration reaction with toluene than the intramolecular dehydration reaction of the OH precursor itself, and it is considered that the target compound of fluorene is hardly obtained.

R ¹ to R ⁴ and R ⁵ to R ⁸ are each independently hydrogen, alkyl, arylheteroaryl or diaryl substituted amino, and these groups may be substituted and R ¹ and R ² , R ² , R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ^7, and R ⁷ and R ⁸ may be independently bonded to form a ring. The reason why the intramolecular dehydroxylation reaction of the OH precursor itself is not inhibited even when it has various substituents as R ¹ to R ⁴ and R ⁵ to R ⁸ is that the steric hindrance of each substituent to the site of the cyclization reaction Or a steric hindrance such as R ¹ or R ⁸ near the site).

The hydrogen in the fluorene compound represented by the formula (1) may be substituted with fluorine, chlorine, bromine, iodine or alkoxy, and in this case, the formula (2-1) ) Is substituted for the corresponding hydrogen in the OH precursor.

Examples of the alkyl for A ¹ , A ² , R ¹ to R ⁴ and R ⁵ to R ⁸ include straight chain or branched chain, and examples thereof include straight chain alkyl having 1 to 24 carbon atoms or straight chain alkyl having 3 to 24 Lt; / RTI > Preferred alkyl is alkyl of 1 to 18 carbon atoms (branched chain alkyl of 3 to 18 carbon atoms). More preferred alkyl is alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms). More preferred alkyl is alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms). Particularly preferred alkyl is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).

Specific examples of alkyl include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, Methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl , 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, hexadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, and the like.

Examples of the aryl for A ¹ , A ² , R ¹ to R ⁴ and R ⁵ to R ⁸ include aryl having 6 to 30 carbon atoms. Preferable aryl is aryl having 6 to 16 carbon atoms, more preferably aryl having 6 to 14 carbon atoms, still more preferably aryl having 6 to 12 carbon atoms, and particularly preferably aryl having 6 to 10 carbon atoms.

Specific examples of aryl include phenyl which is monocyclic aryl, (2-, 3-, 4-) biphenyl which is a bicyclic aryl, (1-, 2-) naphthyl which is a condensed tricyclic aryl, terphenyl -Terphenyl-4'-yl, o-terphenyl-4'-yl, m-terphenyl-5'- M-terphenyl-4-yl, o-terphenyl-2-yl, o-terphenyl- P-terphenyl-3-yl, p-terphenyl-4-yl), condensed tricyclic aryl, acenaphthylene- (1-, 2-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl-3 (1-, 2-, 3-, 4-thiophen-4-yl, m- (1-, 2-, 3-), pentacene- (1-, 2-, 5-) 5-, 6-yl, and the like.

The heteroaryl in A ¹ , A ² , R ¹ to R ⁴ and R ⁵ to R ⁸ includes, for example, heteroaryl having 2 to 30 carbon atoms. Preferred heteroaryl is heteroaryl having 2 to 25 carbon atoms, more preferably heteroaryl having 2 to 20 carbon atoms, still more preferably heteroaryl having 2 to 15 carbon atoms, particularly preferably heteroaryl having 2 to 10 carbon atoms / RTI > The heteroaryl includes, for example, those having 1 to 5 hetero atoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring-constituting atom.

Specific heteroaryls include, for example, furyl, thienyl, pyrroyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furanzyl, thiadiazolyl, Thiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo [b] thienyl, indolyl, isoindolyl, , Benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, Cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl , Indolizinyl and the like.

Examples of the diaryl-substituted amino in R ¹ to R ⁴ and R ⁵ to R ⁸ include an amino group in which the aforementioned aryl is substituted.

The alkyl, aryl or heteroaryl selected as A ¹ , A ² , R ¹ to R ⁴ and R ⁵ to R ⁸ , or diaryl substituted amino selected from R ¹ to R ⁴ and R ⁵ to R ⁸ , And examples of the substituent include the same alkyl and aryl described above.

A ¹ and A ² , R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ and R ⁷ and R ⁸ are each independently a bond to form a ring , And the formed ring may be an aliphatic ring or an aromatic ring. The aliphatic ring is, for example, a cycloalkane ring, specifically, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, etc., and these rings may be substituted with the above-mentioned alkyl or aryl. Examples of the aromatic ring include rings having the same structures as those exemplified as the above aryl or heteroaryl, specifically, benzene ring, naphthalene ring, pyridine ring, etc. These rings may be substituted with the above-mentioned alkyl or aryl have. Among them, a benzene ring is more preferable as the ring formed.

In the case where these group rings are formed, in particular, in formula (1), at least one of R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ and R ⁶ and R ⁷ forms a ring it is most preferably preferably, R ² and R ³ and R ³ and R ⁴ either is more preferable to form a ring from, and R ³ and R ⁴ form a ring.

The hydrogen in the fluorene compound represented by the formula (1) thus formed may be substituted with fluorine, chlorine, bromine, iodine or alkoxy. On the other hand, the OH precursor represented by the formula (2-1) or (2-2) as the raw material is also substituted as described above.

The alkoxy group as a substituent includes, for example, alkoxy of 1 to 15 carbon atoms. Preferred alkoxy is alkoxy of 1 to 10 carbon atoms. More preferred alkoxy is alkoxy of 1 to 4 carbon atoms.

Specific examples of alkoxy include alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, cyclopentyloxy, hexyloxy, Heptyloxy, cycloheptyloxy, octyloxy, cyclooctyloxy, phenoxy, and the like.

In the case of having these substituents, there is no limitation on the substitution form (number and position) of fluorine, chlorine, bromine, iodine or alkoxy, but hydrogen in the fluorene skeleton of the fluorene compound represented by formula (1) .

Further, in the formula (1), at least one of R ¹ to R ⁴ is fluorine, and at least one of R ⁵ to R ⁸ is preferably chlorine, bromine, iodine or alkoxy.

In this case, in the formula (1)

R ¹ to R ⁴ are each independently hydrogen, alkyl, aryl, heteroaryl, diaryl substituted amino or fluorine, at least one of R ¹ to R ⁴ is fluorine,

R ⁵ to R ⁸ are each independently hydrogen, alkyl, aryl, heteroaryl, diaryl substituted amino, chlorine, bromine, iodine or alkoxy, and at least one of R ⁵ to R ⁸ is chlorine, bromine, Lt; / RTI >

< In general formula (1)  Displayed Fluorene-based  For compounds>

The fluorene compound according to the present invention is a fluorene compound represented by the following general formula (1).

In the formula (1)

A ¹ and A ² are each independently alkyl, aryl or heteroaryl,

R ¹ to R ⁴ are each independently hydrogen, alkyl, aryl, heteroaryl, diaryl substituted amino or fluorine, at least one of R ¹ to R ⁴ is fluorine,

R ⁵ to R ⁸ are each independently hydrogen, alkyl, aryl, heteroaryl, diaryl substituted amino, chlorine, bromine, iodine or alkoxy, and at least one of R ⁵ to R ⁸ is chlorine, bromine, Lt; / RTI &gt;

The details of each of A ¹ , A ² , R ¹ to R ⁴ and R ⁵ to R ⁸ are as described above.

More specific fluorene compounds include those listed below. In the structural formula, "Me" is a methyl group, "Et" is an ethyl group, "tBu" is a t-butyl group, "OMe" is a methoxy group, "OEt" is an ethoxy group, and "Ph"

&Lt; On the carrier  About>

It is considered that the carrier, in the production method according to the present invention, has a role in which the acid used at the same time acts effectively on the OH precursor. For example, it is presumed that the acid is adsorbed on the surface of the carrier present in the reaction field to form catalytic active sites, which act on the OH precursor to dramatically increase the reaction efficiency, but the present invention is not limited to this principle.

Therefore, the carrier is not particularly limited as long as it is a substance capable of exhibiting the above-mentioned action. As an example, inorganic oxides and metal sulfates may be cited, and they are preferably porous materials (porous materials). As the carrier, a single kind may be used alone, or two or more kinds may be used in combination.

Inorganic oxide include, silica (SiO _2), alumina (Al ₂ O _3), titania (TiO _2), magnesia (MgO), zirconia (ZrO _2), tin oxide (SnO ₂ or SnO), hafnium oxide (HfO ₂ ), Iron oxide (Fe ₂ O ₃ or Fe ₃ O ₄ ), and alumina and silica are particularly preferably used.

Of a metal sulphate is aluminum sulphate _{(Al 2 (SO 4) 3} ), zinc sulfate (ZnSO _4), sulfuric acid, tin (SnSO _4), iron sulfate II (FeSO _4), ferrous sulfate III (Fe ₂ (SO _{4) 3} ), and aluminum sulfate and zinc sulfate are particularly used.

If the porous material, the specific surface area is 30 ~ 1500g / m ² it is preferable, and, 50 ~ 1000g / m ² is more preferred, and, 100 ~ 800g / m ² are more preferred, and, 200 ~ 700g / m ² is particularly preferable. , And most preferably from 300 to 600 g / m ² . When the specific surface area is 30 to 1500 g / m ^2, the balance between the reaction efficiency and the purification efficiency is the most excellent.

The amount of the carrier used in the reaction may vary depending on the specific surface area. In general, the amount is preferably 0.1 to 5 moles, more preferably 0.2 to 3 moles, and still more preferably 0.3 to 2 moles per mole of the OH precursor.

Examples of the carrier include, but are not limited to, powders, spherical granules, amorphous granules, clusters and the like.

&Lt; About the acid used in the reaction >

The acid can be an acid used in a conventional reaction for producing a fluorene compound from an OH precursor. For example, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, chloric acid, bromic acid, iodic acid, periodic acid, permanganic acid, thiocyanic acid, tetrafluoroboric acid, hexafluorophosphoric acid, Sulfonic acid, para-toluenesulfonic acid, and the like. Of these acids, sulfuric acid, phosphoric acid, polyphosphoric acid or sulfonic acid is preferable, and concentrated sulfuric acid is particularly preferable.

The amount of the acid to be used in the reaction is generally 0.05 to 2 moles, preferably 0.1 to 1 mole, and more preferably 0.2 to 0.5 moles, relative to 1 mole of the OH precursor.

&Lt; Settlement  About catalyst>

It is considered that the high-fixation catalyst has a role that the acidic functional group already bonded (chemical bonding, physical adsorption, etc.) to the catalyst effectively acts on the OH precursor in the production method according to the present invention. For example, it is presumed that acidic functional groups are present on the surface of the high-purity catalyst existing in the reaction field, and that this acts on the OH precursor to dramatically increase the reaction efficiency, but the present invention is not limited to this principle.

Examples of the acidic functional group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Among these acidic functional groups, a sulfonic acid group is preferable. Examples of the substance to which the acid functional group binds include a resin, the above-mentioned carrier, and a porous carrier. Examples of the high-fixation catalyst include a sulfonated resin and a porous material having a sulfonated surface.

A high surface property (表面性狀) of settled catalyst, the specific surface area is 20 ~ 1200g / m ² is preferable, and, 30 ~ 1000g / m ² is more preferable, and, 40 ~ 800g / m ² is more preferred, and 80 to 600g / m ^2, particularly preferably, 100 ~ 500g / m ² is most preferable. When the specific surface area is 20 to 1200 g / m ^2, the balance between the reaction efficiency and the purification efficiency is the most excellent. The amount of the acidic functional group in the fixed-bed catalyst is preferably 0.05 mmol / g or more, more preferably 0.1 mmol / g or more, still more preferably 0.3 mmol / g or more, and particularly preferably 0.5 mmol / g or more. When the amount of the acidic functional group is 0.05 mmol / g or more, the reaction efficiency is excellent.

AMBERLYST 15 (H), AMBERLYST 16 (H), AMBERLYST 36 (H), AMBERLITE IR120 (H), and AMBERLITE IR120 (H) are commercially available from Sigma-Aldrich Japan, Such as Taycacure-6, Taycacure-10, and Taycacure-15, manufactured by Tayca Corporation, such as AMBERJET 1200 (H), DOWEX 15W x 2, DOWEX 15W x 4, DOWEX 15W x 8, Sulfuric acid-containing silica gel containing high sulfuric acid such as 22% sulfuric acid silica gel, 44% sulfuric acid silica gel, and 55% sulfuric acid silica gel manufactured by Wako Pure Chemical Industries, Ltd.

The amount of the high-purification catalyst to be used in the reaction is generally preferably from 0.02 to 1 mole of the acidic functional group per mole of the OH precursor, more preferably from 0.03 to 0.8 mole of the acidic functional group , And more preferably 0.05 to 0.7 mol of an acidic functional group.

On the other hand, inorganic oxides such as alumina, silica and zeolite are also sometimes referred to as solid acid catalysts because they have a small number of active sites having acidic properties on their surfaces. It does not have the desired reaction efficiency. Thus, the solid acid catalysts generally known are not simply fixed catalysts in the present invention, but are classified as carriers only.

&Lt; Temperature and time of reaction >

The reaction temperature may be a temperature which has been used in a conventional reaction for producing a fluorene compound from an OH precursor, preferably 50 to 200 ° C, more preferably 70 to 150 ° C, and even more preferably 80 to 130 ° C . The reaction time may be a time used in a conventional reaction for producing a fluorene compound from an OH precursor, preferably 0.1 to 10 hours, more preferably 0.5 to 5 hours, and even more preferably 0.8 to 3 hours .

&Lt; Regarding Reaction Solvent >

The solvent used in the reaction may be a solvent which has been used in a conventional reaction for producing a fluorene compound from an OH precursor. Examples of the solvent include dichloromethane, orthodichlorobenzene, carbon tetrachloride, toluene, xylene, , p-xylene, m-xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, acetic acid and chloroform. Particularly preferable are toluene, xylene, o-xylene, p-xylene, m-xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene and 1,3,5-trimethylbenzene Do.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

[Example 1]

Synthesis of a fluorene-based target compound from an OH precursor was attempted using activated alumina (Al ₂ O ₃ ) manufactured by Wako Pure Chemical Industries, Ltd. as a carrier and concentrated sulfuric acid as an acid. On the other hand, activated alumina (Al ₂ O ₃ ) has an average particle diameter of 45 μm and a specific surface area of 137 m ² / g.

First, 31.65 g of (3,5-difluorophenyl) boronic acid, 50 g of methyl 2-bromo-5-chlorobenzoate, tetrakis (triphenylphosphine) palladium (0) (6.95 g, "Pd (PPh ₃ ) _4" ), potassium carbonate (55.4 g) and toluene (450 ml) were placed in a flask and stirred for 5 minutes. Then, water (50 ml) was added and refluxed for 4 hours. After the completion of the heating, the reaction solution was cooled, and water (100 ml) was added. Thereafter, the reaction mixture was extracted with toluene, and the organic layer was dried over anhydrous sodium sulfate. The drying agent was removed, and the solvent was distilled off under reduced pressure. The crude product was dissolved in an appropriate amount of toluene. Column purification (solvent: Chloro-3 ', 5'-difluoro- [1,1'-biphenyl] -2-carboxylate was obtained by reducing the solvent under reduced pressure to give methyl 4-chloro-3', 5'-difluoro- [heptane / toluene = (57 g, yield 100%).

Then, methyl 4-chloro-3 ', 5'-difluoro- [1,1'-biphenyl] -2-carboxylate (22 g) and tetrahydrofuran (50 ml) were added to a flask The mixture was stirred for 5 minutes, and a tetrahydrofuran solution (250 ml) of 0.96 M methylmagnesium bromide was slowly added dropwise, and then the reaction solution was stirred at room temperature for 2 hours. Thereafter, a saturated aqueous ammonium chloride solution (150 ml) was slowly added dropwise. The reaction mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate. The drying agent was removed, and the solvent was distilled off under reduced pressure. The resulting product was dissolved in an appropriate amount of toluene and subjected to column purification using silica gel (solvent: toluene) (OH) precursor, 2- (4-chloro-3 ', 5'-difluoro- [1,1'-biphenyl] -2-yl) propan- 97.7%).

Finally, 2- (4-chloro-3 ', 5'-difluoro- [1,1'-biphenyl] -2-yl) propan-2-ol (1.13g), activated alumina (Al ₂ O ₃ ) (0.4 g) and toluene (16 ml) were placed in a flask, and concentrated sulfuric acid (0.08 g) was added with stirring. Thereafter, the mixture was refluxed at 110 DEG C for 1 hour. The reaction solution was analyzed by gas chromatography. As a result, the conversion rate from the OH precursor to the fluorene target compound was 100%. After completion of the reaction, the reaction solution was subjected to short column purification (solvent: toluene) with silica gel and the solvent was distilled off under reduced pressure to obtain 7-chloro-1,3-difluoro-9,9- -Fluorene was obtained (1.04 g, yield 98%). On the other hand, the molar ratio of the OH precursor: activated alumina: concentrated sulfuric acid in this reaction is about 1: 1: 0.2.

The structure of the fluorene-based target compound was confirmed by MS spectrum and NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 7.55 (d, 1H), 7.38 (s, 1H), 7.32 (d, 1H), 7.15 (d, 1H), 6.70 (t, 1H), 1.56 (s, 6H).

[Comparative Example 1]

Synthesis of the fluorene-based target compound from the OH precursor was attempted using concentrated sulfuric acid as an acid without using a carrier.

The OH precursor (1.13 g) and acetic acid (16 ml) were placed in a flask, and concentrated sulfuric acid (0.08 g) was added with stirring. Thereafter, the mixture was refluxed at 117 DEG C for 1 hour. The reaction solution was analyzed by gas chromatography. As a result, the conversion rate from the OH precursor to the fluorene-based target compound was 17.7%, and the conversion rate to the olefin based product was 82.3%. After completion of the reaction, water (20 ml) was added. The reaction mixture was extracted with toluene, and the organic layer was dried over anhydrous sodium sulfate. The drying agent was removed, and the solvent was distilled off under reduced pressure. The resulting product was dissolved in an appropriate amount of toluene, and the residue was purified by silica gel column chromatography (solvent: heptane) By distillation, an olefinic side product, 4-chloro-3 ', 5'-difluoro-2- (propen-2-yl) -1,1'-biphenyl was obtained (0.75 g, yield 71% . On the other hand, the molar ratio of the OH precursor: concentrated sulfuric acid in this reaction is about 1: 0.2.

MS spectrum and NMR measurements confirmed the structure of the olefinic byproducts.

_{^{1 H-NMR (CDCl 3)}} : δ = 7.29 (s, 1H), 7.28 (d, 1H), 7.16 (d, 1H), 6.90 (d, 2H), 6.75 (t, 1H), 5.13 (s, 1H), 4.99 (s, 1H), 1.68 (s, 3H).

[Comparative Example 2]

Synthesis of the fluorene-based target compound from the OH precursor was attempted using concentrated sulfuric acid as an acid without using a carrier.

The OH precursor (1.13 g) and toluene (16 ml) were placed in a flask, and concentrated sulfuric acid (0.08 g) was added with stirring. Thereafter, the mixture was refluxed at 110 DEG C for 1 hour. The reaction solution was analyzed by gas chromatography. As a result, the conversion from the OH precursor to the fluorene-based target compound was 37.7%, and the conversion to olefinic by-products was 62.3%. On the other hand, the molar ratio of the OH precursor: concentrated sulfuric acid in this reaction is about 1: 0.2.

[Comparative Example 3]

As the carrier, the same activated alumina (Al ₂ O ₃ ) as in Example 1 was used to synthesize the fluorene-based target compound from the OH precursor without using an acid.

The OH precursor (1.13 g), activated alumina (0.4 g) and toluene (16 ml) were placed in a flask and refluxed at 110 ° C for 1 hour. The reaction solution was analyzed by gas chromatography to find that the remaining OH precursor was 95%, the conversion rate from the OH precursor to the fluorene target compound was 0%, and the conversion rate to the olefinic side product was 5%. On the other hand, the molar ratio of the OH precursor: activated alumina in this reaction is about 1: 1.

[Comparative Example 4]

Synthesis of the fluorene-based target compound from the OH precursor was attempted using a trifluoroborane ethyl ether complex (Et ₂ O. BF ₃ ) as an acid without using a carrier.

The OH precursor (2.83 g) and chloroform (30 ml) were placed in a flask and cooled to 5 캜 or lower. Trifluoroboron diethyl ether complex (2.13 g) was added dropwise at a temperature range of 0 to 5 占 폚, and the mixture was stirred at room temperature for 1 hour. The reaction solution was analyzed by gas chromatography. As a result, the conversion rate from the OH precursor to the fluorene-based target compound was 30.5% and the conversion rate to the olefinic side product was 69.5%. On the other hand, the molar ratio of the OH precursor: trifluoroborane diethyl ether complex in this reaction is about 1: 1.5.

[Example 2]

Synthesis of the fluorene-based target compound from the OH precursor was attempted using the same activated alumina (Al ₂ O ₃ ) as in Example 1 as a carrier and concentrated sulfuric acid as an acid.

The OH precursor (1.13 g), activated alumina (0.14 g) and toluene (16 ml) were placed in a flask and concentrated sulfuric acid (0.08 g) was added with stirring. Thereafter, the mixture was refluxed at 110 DEG C for 2 hours. The reaction solution was analyzed by gas chromatography. As a result, the conversion rate from the OH precursor to the fluorene target compound was 100%. After completion of the reaction, the reaction solution was subjected to short column purification (solvent: toluene) with silica gel, and the solvent was distilled off under reduced pressure to obtain the desired fluorene-based compound. On the other hand, the molar ratio of the OH precursor: activated alumina: concentrated sulfuric acid in this reaction is about 1: 0.35: 0.2.

[Comparative Example 5]

Synthesis of the fluorene-based target compound from the OH precursor was attempted using concentrated sulfuric acid as an acid without using a carrier.

The OH precursor (1.13 g) and toluene (16 ml) were placed in a flask, and concentrated sulfuric acid (0.08 g) was added with stirring. Thereafter, the mixture was refluxed at 110 DEG C for 2 hours. The reaction solution was analyzed by gas chromatography. As a result, the conversion from the OH precursor to the fluorene-based target compound was 36.5%, and the conversion to olefinic by-products was 63.5%. On the other hand, the molar ratio of the OH precursor: concentrated sulfuric acid in this reaction is about 1: 0.2.

[Example 3]

Synthesis of the fluorene-based target compound from the OH precursor was attempted using spherical silica gel (SiO ₂ , product name: PSQ100) manufactured by Shin-Etsu Kasei Kogyo Co., Ltd. as carrier and concentrated sulfuric acid as acid. On the other hand, silica gel (SiO ₂ ) has an average particle size of 110 μm and a specific surface area of 490 m ² / g.

The OH precursor (1.13 g), silica gel (0.4 g) and toluene (16 ml) were placed in a flask, and concentrated sulfuric acid (0.08 g) was added with stirring. Thereafter, the mixture was refluxed at 110 DEG C for 2 hours. The reaction solution was analyzed by gas chromatography. As a result, the conversion rate from the OH precursor to the fluorene target compound was 100%. On the other hand, the molar ratio of the OH precursor: silica gel: concentrated sulfuric acid in this reaction is about 1: 1.7: 0.2.

[Comparative Example 6]

Synthesis of the fluorene-based target compound from the OH precursor was attempted using the same silica gel (SiO ₂ ) as that in Example 3 as a carrier and without using an acid.

The OH precursor (1.13 g), silica gel (0.4 g) and toluene (16 ml) were placed in a flask and refluxed at 110 ° C for 2 hours. The reaction solution was analyzed by gas chromatography to find that the remaining OH precursor was 93.2%, the conversion rate from the OH precursor to the fluorene target compound was 0%, and the conversion rate to the olefin side product was 6.8%. On the other hand, the molar ratio of the OH precursor: silica gel in this reaction is about 1: 1.7.

[Example 4]

Synthesis of the fluorene-based target compound from the OH precursor was attempted using a fine powder of aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) as a carrier and concentrated sulfuric acid as an acid.

The OH precursor (1.13 g), aluminum sulfate (0.4 g) and toluene (16 ml) were placed in a flask and concentrated sulfuric acid (0.08 g) was added with stirring. Thereafter, the mixture was refluxed at 110 DEG C for 2 hours. The reaction solution was analyzed by gas chromatography. As a result, the conversion rate from the OH precursor to the fluorene target compound was 100%. On the other hand, the molar ratio of the OH precursor: aluminum sulfate: concentrated sulfuric acid in this reaction was about 1: 0.3: 0.2.

[Comparative Example 7]

Synthesis of the fluorene-based target compound from the OH precursor was attempted using the same aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) as in Example 4 as a carrier and without using an acid.

The OH precursor (1.13 g), aluminum sulfate (0.4 g) and toluene (16 ml) were placed in a flask and refluxed at 110 ° C for 2 hours. The reaction solution was analyzed by gas chromatography to find that the residual OH precursor was 3.2%, the conversion rate from the OH precursor to the fluorene target compound was 15.5%, and the conversion rate to the olefinic side product was 81.3%. On the other hand, the molar ratio of the OH precursor: aluminum sulfate in this reaction is about 1: 0.3.

[Example 5]

The synthesis of the fluorene-based target compound from the OH precursor was attempted using Styrene-DVB strongly acidic macroreticular resin (trade name: AMBERLYST 15 (H)) as a high-fixation catalyst. Respectively. On the other hand, AMBERLYST 15 (H) is a polystyrene type strong cation exchange resin having sulfonic acid as a functional group, and has a sulfonic acid content of 4.4 mmol / g and a specific surface area of 50 m ² / g.

The OH precursor (1.13 g), AMBERLYST 15 (H) (0.4 g) and toluene (16 ml) were placed in a flask and refluxed at 110 ° C for 2 hours. The reaction solution was analyzed by gas chromatography. As a result, the conversion rate from the OH precursor to the fluorene target compound was 100%. On the other hand, the molar ratio of the acid functional group of the OH precursor to the high-settling catalyst in this reaction is about 1: 0.44.

[Example 6]

Synthesis of the fluorene-based target compound from the OH precursor was attempted using a high-concentration sulfuric acid-containing silica gel (product name: 55% sulfuric acid silica gel) manufactured by Wako Pure Chemical Industries, Ltd. as a high-settling catalyst. On the other hand, the specific surface area of the high-concentration sulfuric acid-containing silica gel is 300 to 800 m ² / g.

The OH precursor (1.13 g) and toluene (16 ml) were placed in a flask, stirred at room temperature for 1 minute, and then 55% sulfuric acid silica gel (0.4 g) was added. Thereafter, the mixture was refluxed at 110 DEG C for 2 hours. The reaction solution was analyzed by gas chromatography. As a result, the conversion rate from the OH precursor to the fluorene target compound was 100%. On the other hand, the molar ratio of the acid functional group of the OH precursor to the high-settling catalyst in this reaction is about 1: 0.56.

[Example 7]

Synthesis of the fluorene-based target compound from the OH precursor was attempted using Taycacure (product name: Taycacure SAC-10) manufactured by Tayca Corporation as a high-fixation catalyst. On the other hand, the content of the sulfonic acid in the Taycacure SAC-10 is 0.84 mmol / g and the specific surface area is 245 m ² / g.

The OH precursor (1.13 g), Taycacure SAC-10 (0.4 g) and toluene (16 ml) were placed in a flask and refluxed at 110 ° C for 2 hours. The reaction solution was analyzed by gas chromatography. As a result, the conversion rate from the OH precursor to the fluorene target compound was 100%. On the other hand, the molar ratio of the acidic functional group of the OH precursor to the high-settling catalyst in this reaction is about 1: 0.084.

[Example 8]

Synthesis of fluorene-based target compounds was attempted from a different OH precursor using Taycacure (product name: Taycacure SAC-15) manufactured by Tayca Corporation as a high-settling catalyst. On the other hand, the content of the sulfonic acid in the Taycacure SAC-15 is 0.55 mmol / g and the specific surface area is 205 m ² / g.

First, methyl 2-hydroxy-4-methoxybenzoate (50 g) and pyridine (350 ml) were placed in a flask, cooled to 0 ° C, and then trifluoromethanesulfonic anhydride (154.9 g, Tf ₂ O &quot;) was slowly added dropwise. Thereafter, the reaction solution was stirred at 0 占 폚 for 1 hour and at room temperature for 2 hours. After the reaction, 500 ml of water was added. The reaction mixture was extracted with toluene, and the organic layer was dried over anhydrous sodium sulfate, and then the drying agent was removed, and the solvent was distilled off under reduced pressure. The obtained preparation was dissolved in an appropriate amount of toluene and subjected to column purification (solvent: toluene) using silica gel. The solvent was distilled off under reduced pressure to obtain methyl 4-methoxy-2 - (((trifluoromethyl) sulfonyl) oxy) benzoate (86.3 g, 100% yield).

Subsequently, 23 g of methyl 4-methoxy-2 - (((trifluoromethyl) sulfonyl) oxybenzoate and 25.4 g of (4- (diphenylamino) phenyl) , Triphenylphosphine palladium (0) (2.54 g, "Pd (PPh ₃ ) _4" ), tripotassium phosphate (31.1 g), toluene (184 ml) and ethanol (28 ml) Lt; / RTI &gt; Water (28 ml) was then added and refluxed for 3 hours. After the completion of heating, the reaction solution was cooled, and water (150 ml) was added. Thereafter, the reaction mixture was extracted with toluene, and the organic layer was dried over anhydrous sodium sulfate, the drying agent was removed, and the solvent was distilled off under reduced pressure. The resulting preparation was dissolved in an appropriate amount of toluene and subjected to column purification using silica gel (solvent: heptane / toluene = 1/2 (volume ratio)) and the solvent was distilled off under reduced pressure to obtain methyl 4 '- (diphenylamino) - [1,1-biphenyl] -2-carboxylate (29.7 g, yield 99%).

Then, 35 g of methyl 4 '- (diphenylamino) -5-methoxy- [1,1-biphenyl] -2-carboxylate and 45 ml of tetrahydrofuran were placed in a flask under a nitrogen atmosphere The mixture was stirred for 5 minutes, and a tetrahydrofuran solution (375 ml) of 0.91 M methylmagnesium bromide was slowly added dropwise. Thereafter, the reaction solution was refluxed for 4 hours. After completion of the reaction, a saturated aqueous ammonium chloride solution (400 ml) was slowly added dropwise. The reaction mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate, and the drying agent was removed, and the solvent was distilled off under reduced pressure. The resulting preparation was dissolved in an appropriate amount of toluene and subjected to column purification (solvent: toluene) using silica gel and the solvent was distilled off under reduced pressure to obtain 2- (4'- (diphenylamino) -5-methoxy - [1,1'-biphenyl] -2-yl) propan-2-ol was obtained (25.7 g, yield 73.4%).

Finally, the obtained OH precursor (13.5 g), Taycacure SAC-15 (6.7 g) and toluene (162 ml) were placed in a flask and refluxed at 110 ° C for 2 hours. The reaction solution was analyzed by gas chromatography. As a result, the conversion rate from the OH precursor to the fluorene target compound was 100%. After completion of the reaction, the reaction solution was subjected to short column purification (solvent: toluene) with silica gel and the solvent was distilled off under reduced pressure to obtain 6-methoxy-9,9-dimethyl-N, N-diphenyl-9H -Fluorene-2-amine (12.7 g, yield 98%). On the other hand, the molar ratio of the acid functional group of the OH precursor to the high-settling catalyst in this reaction is about 1: 0.11.

The structure of the fluorene-based target compound was confirmed by MS spectrum and NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 7.52 (d, 1H), 7.27 ~ 7.23 (m, 5H), 7.17 ~ 7.12 (m, 6H), 7.03 ~ 6.99 (m, 3H), 6.81 (d, 1H ), 3.86 (s, 3H), 1.38 (s, 6H).

[Comparative Example 8]

Synthesis of the fluorene-based target compound obtained in Example 5 was attempted from the OH precursor used in Example 5 using p-toluenesulfonic acid as an acid without using a carrier.

The OH precursor (1.13 g), p-toluenesulfonic acid (0.4 g) and toluene (16 ml) used in Example 5 were placed in a flask and refluxed at 110 ° C for 2 hours. The reaction solution was analyzed by gas chromatography. As a result, the conversion rate from the OH precursor to the fluorene-based target compound was 16.7% and the conversion rate to the olefin based product was 83.3%. On the other hand, the molar ratio of the OH precursor: p-toluenesulfonic acid in this reaction is about 1: 0.58. Also, p-toluenesulfonic acid is the acid chosen for comparison with the high-settling catalyst, not the high-settling catalyst.

[Comparative Example 9]

Synthesis of a fluorene-based target compound from an OH precursor as a comparative object was attempted using Taycacure (product name: Taycacure SAC-10) manufactured by Tayca Corporation as a high-purification catalyst. On the other hand, the OH precursor as a comparison object used herein is a compound having no substituent at the alcohol moiety (i.e., A ¹ and A ² in the formula (II) are hydrogen).

2-biphenylmethanol (0.37 g), Taycacure SAC-10 (0.2 g) and toluene (8 ml) as OH precursors to be compared were put in a flask and refluxed at 110 ° C for 2 hours. The reaction solution was analyzed by gas chromatography. As a result, the fluorene-based target compound (i.e., 9H-fluorene) was not obtained from the OH precursor, and a condensate dehydrated between the OH precursor and the solvent toluene was obtained . The conversion rate was 93.3% for 2- (4-methylbenzyl) -1,1'-biphenyl and 6.7% for 2- (2-methylbenzyl) -1,1'-biphenyl. On the other hand, the molar ratio of the acidic functional group of the OH precursor to the high-settling catalyst in this reaction is about 1: 0.084.

The results are summarized in Tables 1 and 2.

[Table 1]

[Table 2]

* P-Toluenesulfonic acid is the acid selected for comparison with the high-

It is not a high-purification catalyst.

As described above, according to the production method of the present invention, all of the fluorene-based target compounds are obtained at a very high conversion rate. On the contrary, in the reaction using the conventional method (Comparative Examples 1, 2, 4, 5, 8), the conversion to the fluorene-based target compound was extremely low, and in the reaction using only the carrier, (Comparative Examples 3, 6, and 7), the conversion rate to the fluorene-based target compound was extremely low, and the OH precursor as a raw material remained unreacted. Further, in the case of using an OH precursor having no substituent in the alcohol moiety (i.e., in which A ¹ and A ² in the formula (II) are hydrogen) (Comparative Example 9), the fluorene- Only an intermolecular dehydration condensation product with toluene as a solvent was obtained. This suggests that, in the absence of a substituent at the alcohol moiety, the intermolecular dehydration reaction with toluene is much faster than the intramolecular dehydration reaction of the OH precursor itself. On the other hand, when a substituent is present in the alcohol moiety (A ¹ and A ² are alkyl or the like), the reaction with toluene as a solvent is difficult to occur due to factors such as steric hindrance or reaction activity, It is presumed that the fluorene-based target compound tends to be obtained easily.

Industrial availability

According to the present invention, it is possible to dramatically increase the conversion ratio from the OH precursor to the fluorene compound, and it is possible to produce a novel fluorene compound containing an active group which has not been known heretofore. As a result, for example, variation of materials that can be used for organic EL devices can be increased.

Claims (8)

Reacting an OH precursor having a structure represented by the following formula (II) in the molecule in the presence of a carrier and an acid and / or in the presence of a fixed-rate catalyst to obtain a fluorene structure represented by the following formula (I) &Lt; / RTI &gt;

A ¹ and A ² are each independently alkyl, aryl or heteroaryl, and these groups may be substituted, and A ¹ and A ² may combine to form a ring. The method according to claim 1,
The OH precursor represented by the following general formula (2-1) or (2-2) is reacted in the presence of a carrier and an acid and / or in the presence of a high- To produce a cyanine compound.

Of the formulas (1), (2-1) and (2-2)
A ¹ and A ² are each independently alkyl, aryl or heteroaryl which may be substituted, A ¹ and A ² may be combined to form a ring,
R ¹ to R ⁴ and R ⁵ to R ⁸ are each independently hydrogen, alkyl, aryl, heteroaryl or diaryl substituted amino, and these groups may be substituted and R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ^7, and R ⁷ and R ⁸ may be independently bonded to form a ring,
The hydrogen in the fluorene compound represented by the formula (1) may be substituted with fluorine, chlorine, bromine, iodine or alkoxy. In this case, in the formula (2-1) or The corresponding hydrogen in the OH precursor to be displayed is similarly substituted. 3. The method according to claim 1 or 2,
Wherein the carrier is an inorganic oxide or a metal sulfate,
Wherein said acid is sulfuric acid, phosphoric acid, polyphosphoric acid or sulfonic acid,
Wherein the fixed catalyst is a sulfonated resin or a surface-sulfonated porous material. 3. The method according to claim 1 or 2,
Wherein the carrier is a porous material. 3. The method of claim 2,
Of the formulas (1), (2-1) and (2-2)
A ¹ and A ² are each independently alkyl, aryl or heteroaryl, A ¹ and A ² may be bonded to form an aliphatic or aromatic ring,
R ¹ to R ⁴ and R ⁵ to R ⁸ are each independently hydrogen, alkyl, aryl, heteroaryl or diaryl substituted amino, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ and R ⁷ and R ⁸ may be independently bonded to form an aromatic ring,
The hydrogen in the fluorene skeleton of the fluorene compound represented by the formula (1) may be substituted with fluorine, chlorine, bromine, iodine or alkoxy. In this case, in the formula (2-1) or -2) in which the corresponding hydrogen in the OH precursor is equally substituted,
Gt; 3. The method of claim 2,
Of the formulas (1), (2-1) and (2-2)
A ¹ and A ² are each independently alkyl, aryl or heteroaryl,
R ¹ to R ⁴ are each independently hydrogen, alkyl, aryl, heteroaryl, diaryl substituted amino or fluorine, at least one of R ¹ to R ⁴ is fluorine,
R ⁵ to R ⁸ are each independently hydrogen, alkyl, aryl, heteroaryl, diaryl substituted amino, chlorine, bromine, iodine or alkoxy, and at least one of R ⁵ to R ⁸ is chlorine, bromine, Alkoxy,
Gt; A fluorene-based compound represented by the following general formula (1).

In the formula (1)
A ¹ and A ² are each independently alkyl, aryl or heteroaryl,
R ¹ to R ⁴ are each independently hydrogen, alkyl, aryl, heteroaryl, diaryl substituted amino or fluorine, at least one of R ¹ to R ⁴ is fluorine,
R ⁵ to R ⁸ are each independently hydrogen, alkyl, aryl, heteroaryl, diaryl substituted amino, chlorine, bromine, iodine or alkoxy, and at least one of R ⁵ to R ⁸ is chlorine, bromine, Lt; / RTI &gt; 8. The method of claim 7,
In the formula (1)
A ¹ and A ² are each independently alkyl,
R ¹ to R ⁴ are each independently hydrogen, alkyl, aryl, heteroaryl, diaryl substituted amino or fluorine, at least one of R ¹ to R ⁴ is fluorine,
R ⁵ to R ⁸ are each independently hydrogen, alkyl, aryl, heteroaryl, diaryl substituted amino, chlorine, bromine, iodine or alkoxy, and at least one of R ⁵ to R ⁸ is chlorine, bromine, Alkoxy,
Fluorene compound.