KR102331357B1 - (arylmethyl)arenes and a production process thereof - Google Patents

Abstract

화학식 3에서 Ar₁= 벤젠, 나프탈렌, 안트라센, 페난트렌, 피렌, 퍼릴렌, 바이페닐, 바이페닐 에테르 또는 바이페닐 설파이드; R₁=H, C1~C4의 알킬기 또는 페닐기; R₂ = H, F, Cl, Br, C1~C4의 알킬기 또는 (CH₂)_qSi(R₃)p(OR₃)_3-p(q= 0, 1, 2이고 p는 0, 1, 2이다); R₃ =H, C1~C8의 알킬기나 페닐기를 포함하는 알킬기; R₄=H, F, Cl, Br, I, 탄소수가 1~6개인 알킬기; X=Cl, Br 또는 I; Ar₂는 벤젠, 알킬벤젠, 할로벤젠, 아니솔, 사이오아니솔, 바이페닐, 플루오렌, 터페닐렌, 나프탈렌, 1-메틸나프탈렌, 2-메틸나프탈렌, 1,2-디메틸나프탈렌, 안트라센, 안트론, 2-(t-부틸)안트라퀴논, 2-(t-부틸)안트라센, 9-메틸안트라센, 9,10-디메틸안트라센, 페난트렌, 바이페닐, 바이페닐에테르, 바이페닐설파이드, 피렌, 퍼릴렌. 테트라센, 펜타센 또는 벤젠고리가 1~8인 아로마틱 화합물이 되고, n=1 또는 2가 될 수 있다.The present invention relates to a (arylmethyl) arene compound synthesized by Friedel-Crafts benzylation reaction and a method for preparing the same. The (arylmethyl) arene compound of the present invention may be represented by the formula (3).
[Formula 3]

_{Ar 1} in Formula 3 = benzene, naphthalene, anthracene, phenanthrene, pyrene, perylene, biphenyl, biphenyl ether or biphenyl sulfide; R ₁ =H, C1-C4 alkyl group or phenyl group; R ₂ = H, F, Cl, Br, C1-C4 alkyl group or (CH ₂ ) _q Si(R ₃ )p(OR ₃ ) _3-p (q= 0, 1, 2 and p is 0, 1, 2); R ₃ =H, an alkyl group including a C1-C8 alkyl group or a phenyl group; R ₄ =H, F, Cl, Br, I, an alkyl group having 1 to 6 carbon atoms; X=Cl, Br or I; Ar ₂ is benzene, alkylbenzene, halobenzene, anisole, thioanisole, biphenyl, fluorene, terphenylene, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 1,2-dimethylnaphthalene, anthracene, Anthrone, 2-(t-butyl)anthraquinone, 2-(t-butyl)anthracene, 9-methylanthracene, 9,10-dimethylanthracene, phenanthrene, biphenyl, biphenyl ether, biphenylsulfide, pyrene, Perylene. It becomes an aromatic compound having 1 to 8 tetracene, pentacene or benzene rings, and n=1 or 2.

Description

(arylmethyl) arene compound and its manufacturing method

The present invention relates to an (arylmethyl) arene compound synthesized by Friedel-Crafts benzylation reaction and a method for preparing the same, and specifically, to an organophosphine compound as a catalyst, and to Friedel-Crafts benzylation of a halomethylaromatic compound and an aromatic compound It relates to a (arylmethyl) arene compound produced by reaction through a reaction and a method for preparing the same.

The Friedel-Crafts reaction, which introduces organic substituents into aromatic compounds, is a very important reaction in organic synthesis and has been widely used for over a century (Roberts, Royston M; Khalaf, Ali, Friedel-Crafts Alkylation Chemistry, Marcel Dekker, Inc., New York). , New York, USA, 1984 ).

It is known that such a Friedel-Crafts reaction necessarily requires a Lewis acid catalyst. The Lewis acid catalyst uses inorganic chlorides such as aluminum, boron, and iron. As for the Lewis acid catalyst, an anthracene having three benzene rings or an aromatic compound starting material having more benzene rings than that of an aromatic compound to introduce an organic group forms a coordination bond with the Lewis acid as a catalyst, and thus the activity of the catalyst is greatly reduced, making it impractical. If the product contains several phenyl groups, it is difficult to remove from the organic matter after the reaction because it coordinates with the Lewis acid. Therefore, in order to introduce an organic substituent by reacting an aromatic compound coordinating with a Lewis acid with an allyl halide, an alkyl halide or a benzyl halide, a neutral compound should be used instead of an acid catalyst. As a neutral catalyst, a catalyst that facilitates electrophilic substitution reaction by activating carbon and halogen bonds is required.

(Arylmethyl) arene compounds are synthesized by a Friedel-Kraft type alkylation reaction using a Lewis acid such as boron trichloride or aluminum trichloride as a catalyst for a halomethyl aromatic compound to an aromatic compound. A product having a lot of phenyl groups is not easy to remove from organic matter because it coordinates with a Lewis acid. Therefore, it has been reported that when benzene is synthesized with benzyl chloride and diphenylmethane through Friedel-Crafts reaction, an inorganic solid, acidic silica, is used as a carrier for a Lewis acid catalyst to facilitate removal of the catalyst after the reaction (Selvaraj, M.; Lee). , TG Journal of Molecular Catalysis A: Chemical 2006 , 243(2) , 176-182).

On the other hand, using organophosphonium chloride as a catalyst, the alkyl halide and trichlorosilane are reacted to remove the halogen from the alkyl halide, hydrogen is taken from the trichlorosilane to generate hydrogen halide, and the alkyl group is formed by dehydrohalogenation Si-C bonding reaction. The synthesis of silane-substituted alkylchlorosilanes is known (Yeon Seok Cho, YS; Kang, S.-H.; Han, JS; Yoo, BR; Jung, IN, J. Am. Chem. Soc. 2001 , 123 , 5584).

As disclosed in the prior art above, organophosphonium chloride used as a catalyst in the synthesis of alkylchlorosilane in which an alkyl halide and trichlorosilane are reacted to substitute an alkyl group to silane by a dehydrohalogenation Si-C bonding reaction is an organic salt. is neutral with Also, tertiary trialkylphosphines belong to Lewis bases, not Lewis acids. When this organophosphonium chloride is used for the reaction of an aromatic compound and a halomethylaromatic compound, it can be expected that a dehydrohalogenation C-C bond reaction that takes halogen from the halomethylaromatic compound and removes hydrogen from the aromatic ring to generate HX can occur. In addition, since the catalyst has different physical properties from the reactant or product, it is easy to recover and can be reused. Therefore, it has been reported that an allyl arene compound can be prepared in a very economical and high yield using trialkylphosphine or organophosphonium chloride as a catalyst (Korean Patent Application No. 2019-0171734 (December 20, 2019)). In the prior art, in which an allyl halide is reacted with an aromatic compound by a Friedel-Crafts reaction using an organophosphine catalyst to synthesize an allyl aromatic compound by a dehydrohalogenation CC bonding reaction, a benzyl halide having an active halomethyl group is used instead of an allyl halide. The present invention has been completed by paying attention to the fact that the synthesis of (arylmethyl) arene compounds can be expected by dehydrohalogenation CC bonding reaction, and has the following objects.

Prior Art 1: Jung, I. N.; Cho, K. D.; Lim, J. C. Yoo, B. R. US Patent 4,613,491 Prior Art 2: Il-Nam Jung, A-Ra Jo, Young-Min Kim, Seung-Hwan Kang, Korean Patent Application No. 2019-0171734 (December 20, 2019)

Prior Art 1: Roberts, Royston M; Khalaf, Ali, Friedel-Crafts Alkylation Chemistry, Marcel Dekker, Inc., New York, New York, USA, 1984 Prior art 2: Selvaraj, M.; Lee, T. G. Journal of Molecular Catalysis A: Chemical 2006, 243(2), 176-182 Prior Art 3: Yeon Seok Cho, Y. S.; Kang, S.-H.; Han, J. S.; Yoo, B. R.; Jung, I. N., and J. Am. Chem. Soc. 2001, 123, 5584

An object of the present invention is to provide an (arylmethyl) arene compound produced by reacting a halomethylaromatic compound with an aromatic compound using an organophosphine compound as a catalyst and a method for preparing the same.

The present invention relates to a method for preparing a compound represented by [Formula 3] produced by reacting a compound represented by the following [Formula 1] and [Formula 2].

[Formula 1]

[Formula 2]

[Formula 3]

_{Ar 1} in formulas 1, 2 and 3 = benzene, naphthalene, anthracene, phenanthrene, pyrene, perylene, biphenyl, biphenyl ether or biphenyl sulfide; R ₁ =H, C1-C4 alkyl group or phenyl group; R ₂ = H, F, Cl, Br, C1-C4 alkyl group or (CH ₂ ) _q Si(R ₃ )p(OR ₃ ) _3-p (q= 0, 1, 2 and p is 0, 1, 2); R ₃ =H, an alkyl group including a C1-C8 alkyl group or a phenyl group; R ₄ =H, F, Cl, Br, I, or an alkyl group having 1 to 6 carbon atoms; X=Cl, Br or I;

Ar ₂ is benzene, alkylbenzene, halobenzene, anisole, thioanisole, biphenyl, fluorene, terphenylene, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 1,2-dimethylnaphthalene, anthracene, Anthrone, 2-(t-butyl)anthraquinone, 2-(t-butyl)anthracene, 9-methylanthracene, 9,10-dimethylanthracene, phenanthrene, biphenyl, biphenyl ether, biphenylsulfide, pyrene, Perylene. It is one compound selected from among tetracene, pentacene, and aromatic compounds having 1 to 8 benzene rings, and n=1 or 2 may be present.

According to one embodiment of the present invention, there is provided a (arylmethyl) arene compound represented by [Formula 3].

[Formula 3]

_{Ar 1} in Formula 3 = benzene, naphthalene, anthracene, phenanthrene, pyrene, perylene, biphenyl, biphenyl ether or biphenyl sulfide; R ₁ =H, C1-C4 alkyl group or phenyl group; R ₂ = H, F, Cl, Br, C1-C4 alkyl group or (CH ₂ ) _q Si(R ₃ )p(OR ₃ ) _3-p (q= 0, 1, 2 and p is 0, 1, 2); R ₃ = H, a C1-C8 alkyl group or an alkyl group including a phenyl group; R ₄ =H, F, Cl, Br, I, an alkyl group having 1 to 6 carbon atoms;

Ar ₂ is benzene, alkylbenzene, halobenzene, anisole, thioanisole, biphenyl, fluorene, terphenylene, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 1,2-dimethylnaphthalene, anthracene, Anthrone, 2-(t-butyl)anthraquinone, 2-(t-butyl)anthracene, 9-methylanthracene, 9,10-dimethylanthracene, phenanthrene, biphenyl, biphenyl ether, biphenylsulfide, pyrene, Perylene. An aromatic compound having 1 to 8 tetracene, pentacene or benzene rings, and a compound in which n = 1 or 2,

Diphenylmethane, 1-benzyl-4-methylbenzene, 1-benzyl-4-butylbenzene, 1-benzyl-4-fluorobenzene, 1-benzyl-4-bromobenzene, 1-benzyl-4-iodo Benzene, 2-benzyl-1,4-dimethylbenzene, 2-benzylnaphthalene, 9-benzylanthracene, 1-benzylpyrene, 4-benzyl-1,1`-biphenyl, 1-benzyl-4-methoxybenzene, 1-(2,5-dimethylbenzyl)naphthalene, di(1-naphthalenyl)methane, 1-(4-methylbenzyl)naphthalene, 1-(4-fluorobenzyl)naphthalene, 1-(4-chlorobenzyl) ) Naphthalene, 1-(4-bromobenzyl) naphthalene, 9-(1-naphthyl) anthracene, 3-(1-naphthalenylmethyl) pyrene, 1-([1,1`-biphenyl]-4 -methyl) naphthalene, 9- (4-methylbenzyl) anthracene, 9- (4-chlorobenzyl) anthracene, 9- (4-fluorobenzyl) anthracene, di (9-anthracenyl) methane, 9- (4- Methoxybenzyl) anthracene, triphenylmethane, (p-torylmethylene) dibenzene, ((4-fluorophinyl) methylene) dibenzene, ((4-chlorophenyl) methylene) dibenzene, ((4-bromo Phenyl) methylene) dibenzene, ((2,5-dimethylphenyl) methylene) dibenzene, 1-benzhydrylnaphthalene, 9-benzhydryl anthracene, 3-(2,2-diphenylmethyl) pyrene, 4- Benzhydryl-1,1`-biphenyl, tetraphenylmethane, 1-(diphenyl(p-tolyl)methyl)benzene, 1-((4-methoxyphenyl)diphenylmethyl)benzene, 4-(4 -Methylbenzyl)-1,1'-biphenyl and 4-(4-fluorobenzyl)-1,1'-biphenyl are excluded from the (arylmethyl)arene compound of the present invention.

According to one embodiment of the present invention, there is provided a method for preparing (arylmethyl) arene in which the reaction molar ratio of the compound represented by Formula 1 to the compound represented by Formula 2 is 4:1 to 1:3.

According to an embodiment of the present invention, the compound represented by [Formula 4] is used as a catalyst,

[Formula 4]

P(R") ₃ ,

In Formula 4, R″ may include an alkyl group or alkenyl group having 1 to 12 carbon atoms, and different R″ is a cyclic structure connected by a covalent bond.

According to an embodiment of the present invention, the compound represented by [Formula 5] is used as a catalyst,

[Formula 5]

P(R") ₄ X'

In Formula 5, R″ may include an alkyl group or alkenyl group having 1 to 12 carbon atoms and a phenyl group. Methods for preparing phosphorus (arylmethyl)arenes are provided.

According to an embodiment of the present invention, the compound represented by [Formula 6] is used as a catalyst,

[Formula 6]

X'(R") ₃ PYP(R") ₃ X

In Formula 6, R″ may include an alkyl group or alkenyl group having 1 to 12 carbon atoms and a phenyl group, different R″ are cyclic structures linked by a covalent bond, X′=Cl, Br or I, Y=carbon Provided is a method for producing (arylmethyl) arene, which is an alkyl group having 1 to 12 numbers, an alkyl group including an aromatic group, or an aromatic group.

According to one embodiment of the present invention, there is provided a method for producing (arylmethyl) arene in which the concentration of the catalyst is 5 to 20 mol% based on the compound represented by Formula 1.

According to an embodiment of the present invention, there is provided a method for preparing an (arylmethyl) arene compound having a reaction temperature of 100 to 250°C.

According to an embodiment of the present invention, in reacting the compound of Formula 1 with the compound of Formula 2, using one or more solvents selected from aliphatic hydrocarbons, ethers, dimethoxyethane (DME), and THF ( A method for preparing an arylmethyl) arene compound is provided.

According to an embodiment of the present invention, there is provided a method for preparing an (arylmethyl) arene compound in which a compound of Formula 1 and a compound of Formula 2 are reacted without a solvent.

Metal chlorides, such as aluminum, boron, iron, and copper, which are typically used as Lewis acid catalysts, have lower catalyst activity, making it difficult to smoothly perform Friedel-Crafts reaction. However, in the present invention, the (arylmethyl) arene compound can be obtained by smoothly performing the Friedel-Crafts reaction using an organophosphine catalyst, which is a neutral catalyst, not a metal compound. The catalyst compound group used in the present invention may be a quaternary salt of a nitrogen or phosphorus compound of Group 5 in organic matter. Using a quaternary organophosphonium salt as a catalyst, alkyl chloride and chlorosilane having Si-H bond are reacted, and various alkylsilanes can be synthesized by dehydrohalogenation Si-C bond reaction. In the method according to the present invention, the catalyst as described above may be used to synthesize (arylmethyl) arene by reacting a halomethylaromatic compound with an aromatic compound based on this process. Such a catalyst can act very effectively in the process of synthesis of (arylmethyl) arene by dehydrohalogenation C-C bond reaction, and has the advantage that the catalyst can be easily recovered and recycled. Anthracene having three benzene rings and organosilicon compounds substituted with aromatic compounds having more benzene rings have fluorescence. The fluorescent organosilicon compound according to the present invention can be usefully used for the development of new functional silicone products.

The (arylmethyl) arene compound according to the present invention is useful as an electronic material because it has fluorescence, and a silicone binder having fluorescence can be synthesized by directly reacting the (arylmethyl) arene compound with a phenylsilane compound having a chloromethyl group. The silicone binder according to the present invention has high adhesion while having fluorescence. The fluorescent tetracene or pentacene compound according to the present invention can be usefully used to develop new organic light emitting diode (OLED) products.

The present invention reacts a halomethylaromatic compound of Formula 1 with an aromatic compound of Formula 2 using a tertiary organophosphine or quaternary organophosphonium salt as a catalyst as shown in Scheme 1 below, which is represented by Formula 3 (arylmethyl) Arene compounds can be prepared.

<화학식 1> <화학식 2> <화학식 3>[Scheme 1]

<Formula 1><Formula2><Formula3>

Ar ₁ = benzene, naphthalene, anthracene, phenanthrene, pyrene, perylene in formula (1), biphenyl, biphenyl ether, or biphenyl sulfide; R ₁ =H, C1-C4 alkyl group or phenyl group; R ₂ = H, F, Cl, Br, I, C1-C4 alkyl group or (CH ₂ ) _q Si(R ₃ )p(OR ₃ ) _3-p (q= 0, 1, 2 and p is 0, 1, 2); X=Cl, Br, or I.

In Formula 2, R ₃ = H, a C1-C8 alkyl group or an alkyl group including a phenyl group; R ₄ =H, F, Cl, Br, I, an alkyl group having 1 to 6 carbon atoms; Ar ₂ = benzene, alkylbenzene, halobenzene, anisole, thioanisole, biphenyl, fluorene, terphenylene, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 1,2-dimethylnaphthalene, anthracene, Anthrone, 2-(t-butyl)anthraquinone, 2-(t-butyl)anthracene, 9-methylanthracene, 9,10-dimethylanthracene, phenanthrene, biphenyl, biphenyl ether, biphenylsulfide, pyrene, Perylene. It may be an aromatic compound having 1 to 8 tetracene, pentacene or benzene rings. In Formula 3, R ₁ to R ₃ may be any of the above compounds and n=1 or 2.

The (arylmethyl) arene compound according to the present invention is represented by Formula 3,

[Formula 3]

_{Ar 1} in Formula 3 = benzene, naphthalene, anthracene, phenanthrene, pyrene, perylene, biphenyl, biphenyl ether or biphenyl sulfide; R ₁ =H, C1-C4 alkyl group or phenyl group; R ₂ = H, F, Cl, Br, C1-C4 alkyl group or (CH ₂ ) _q Si(R ₃ )p(OR ₃ ) _3-p (q= 0, 1, 2 and p is 0, 1, 2); R ₃ = H, a C1-C8 alkyl group or an alkyl group including a phenyl group; R ₄ =H, F, Cl, Br, I, an alkyl group having 1 to 6 carbon atoms; Ar ₂ = benzene, alkylbenzene, halobenzene, anisole, thioanisole, biphenyl, fluorene, terphenylene, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 1,2-dimethylnaphthalene, anthracene, Anthrone, 2-(t-butyl)anthraquinone, 2-(t-butyl)anthracene, 9-methylanthracene, 9,10-dimethylanthracene, phenanthrene, biphenyl, biphenyl ether, biphenylsulfide, pyrene, Perylene. It becomes an aromatic compound having 1 to 8 tetracene, pentacene or benzene rings, and n=1 or 2.

The tertiary organophosphine used as a catalyst in Scheme 1 may be, for example, represented by Chemical Formula 4, and the quaternary organophosphine salt may be represented by Chemical Formula 5 or Chemical Formula 6.

[Formula 4]

P(R") ₃

In Formula 4, R″ may include a phenyl group while being an alkyl or alkenyl group having 1 to 12 carbon atoms. Two R″ may be connected to each other by a covalent bond to have a cyclic structure, and each R″ may be the same as each other. or have a different structure.

[Formula 5]

P(R") ₄ X'

In Formula 5, X′=Cl, Br, or I, R″ is the same as the compound of Formula 4, R″ may be covalently linked to each other to have a cyclic structure, and each R″ is the same as or different from each other can have a structure.

[Formula 6]

X'(R") ₃ PYP(R") ₃ X'

In Formula 6, X' and R" are the same as in the compound of Formula 5, respectively, and Y= may be an alkyl group or an aromatic group having 1 to 12 carbons or an alkyl group or an aromatic group, and two R" are covalently linked to each other to form a cyclic structure, and each R″ may have the same or different structure from each other.

The tertiary organophosphine as a catalyst is trimethylphosphine, triethylphosphine, tributylphosphine, methyldiphenylphosphine, tricyclohexylphosphine, triisopropylphosphine, tripropylphosphine, dimethylphenylphosphine , ethyldiphenylphosphine, t-butyldiphenylphosphine, t-butyldiisopropyl, isopropyldiphenylphosphine, dicyclohexylphenylphosphine, benzyldiphenylphosphine, cyclohexyldiphenylphosphine, tri cyclopentylphosphine, di-t-butylneopentylphosphine, di-t-butylphenylphosphine, di-t-butylmethylphosphine and t-butyldicyclohexylphosphine may include at least one compound selected from the group consisting of have.

Quaternary organophosphonium salts include benzyltributylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodine, tetramethylphosphonium bromide, tetraethylphosphonium chloride, (4-ethylbenzyl) Triphenylphosphonium chloride, hexyltriphenylphosphonium chloride, benzyltriphenylphosphonium chloride, tetraphenylphosphonium chloride, bis(benzyldimethylphosphonium chloride)ethane, bis(benzyldimethylphosphonium chloride)butane or silica or silicone resin , silicon silsesquioxene, and quaternary alkylphosphonium chloride immobilized on an organic polymer may include at least one compound selected from the group consisting of.

On the other hand, since the boiling point of the aromatic compound having a halomethyl group of Formula 1 or the aromatic compound of Formula 2 is lower than the reaction temperature of 250° C. in the manufacturing process of the (arylmethyl) arene compound, it is difficult to react at normal pressure, and a certain level A reaction tank made of stainless steel that can withstand the pressure of

After preparing the aromatic compound having a halomethyl group of [Formula 1] and the aromatic compound of [Formula 2], the tertiary organophosphine or quaternary organophosphonium salt used as a catalyst is added in an amount of 5 to 20 mol% based on the compound of formula 1 Add to range and mix. Thereafter, when the reaction mixture is heated to 100 to 250° C., preferably 150 to 220° C., an (arylmethyl) arene compound such as Chemical Formula 3 in [Scheme 1] can be synthesized. At this time, the tertiary organophosphine used as a catalyst in the present invention reacts with a halomethylaromatic compound during the reaction to become a quaternary organophosphine halide salt.

In addition, the quaternary organophosphonium salt used as the catalyst is easily recovered from the reaction mixture, and for example, when the reaction product is distilled under reduced pressure after completion of the reaction, the catalyst remains and can be simply recovered. The catalyst can be recovered to a level of 80% of the amount initially used, and the recovered catalyst can be recrystallized with a suitable solvent and reused.

A typical synthesis process of the present invention is a stainless steel tube that puts the halomethylaromatic compound of [Formula 1] and the aromatic compound of [Formula 2] under a nitrogen atmosphere and withstands pressure with a tertiary organophosphine or quaternary organophosphonium salt catalyst. After putting it in the reaction tank, the stopper is closed and the reaction proceeds by heating to the reaction temperature. In this case, the halomethyl aromatic compound of [Formula 1] and the aromatic compound of [Formula 2] are preferably mixed in a molar ratio of 4:1 to 1:3.

On the other hand, the tertiary organophosphine represented by Chemical Formula 4 or the quaternary organophosphonium salt catalyst represented by Chemical Formula 5 or Chemical Formula 6 used as a catalyst is preferably 5 to 20 mol% based on the compound of Chemical Formula 1. In this process, the reaction solvent may be, for example, a reaction solvent such as an aliphatic hydrocarbon or a solvent such as ether, dimethoxyethane (DME), or THF depending on the reactant.

When the reaction solvent as described above is used, the reactants can be uniformly distributed, and in particular, when THF is used, the ring is opened by HX, a by-product, and halobutyl alcohol is generated, and then halobutyl ether is generated through the condensation reaction of the alcohol. There is an advantageous advantage in the reaction in that the by-product HCl gas can be removed.

However, a solvent may not be used when reacting the substances of Formulas 1 and 2, in which case the reactant is in a liquid state. There is an advantage in terms of an increase in quantity and the like. The reaction temperature is preferably 100 to 250 °C, more preferably 150 to 220 °C. After reacting for 1 to 48 hours under these conditions, when the reaction is completed, the stopper is opened to discharge the hydrogen halide, and the product is separated by distillation or recrystallization under normal pressure or reduced pressure to obtain the desired product.

When cyclic THF is used as a solvent, the ring structure of THF is opened by HX, which is a by-product, and halobutyl alcohol is produced.

According to the present invention, the catalyst and the product are separated in order to prepare the product, separate the catalyst, and then recycle it as described above. Even if a tertiary organophosphine is used instead of a quaternary phosphonium salt as a catalyst, it reacts with an aromatic compound having a halomethyl group during the reaction to form a quaternary phosphonium salt, so the catalyst can be separated from the reaction product and reused without any difficulty. have. The recovery rate of the quaternary organophosphonium salt, which is a catalyst, can be recovered up to 80% and reused, which is economically very advantageous. If the organic phosphonium salt is immobilized on a silicone resin, silica or zeolite, it is very convenient to recover and reuse it after the reaction.

The halomethylaromatic compound of Formula 1 for the reaction is 9-chloromethylanthracene, 1-chloromethylnaphthalene, 1-chloromethyl-2-methylnaphthalene, chloromethylbenzene (alpha-chlorotoluene), 4-phenylbenzylchloride, 2 -Methylbenzyl chloride, benzyl chloride, 4-methylbenzyl chloride, 2,5-dimethylbenzyl chloride, 3,4-dimethylbenzyl chloride, diphenylmethyl bromide, benzyl bromide, 9-bromomethylanthracene, 1-bromomethyl Naphthalene, 4-phenylthiobenzyl chloride, 4-methoxybenzyl chloride, 3-methylbenzyl chloride. At least one material selected from ρ-(trimethoxysilyl)benzylchloride, ((chloromethyl)phenylethyl)methyldimethoxysilane, and ((chloromethyl)phenylethyl)trimethoxysilane may be used.

All of these compounds are commercially produced materials or compounds whose synthesis methods are known in the literature. The compound represented by Formula 2 is a compound that can be commercially produced or easily synthesized, and includes benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, ethylbenzene, propylbenzene, n -Butylbenzene, isobutylbenzene, t-butylbenzene, 1,2,4,5-tetramethylbenzene, fluorobenzene, bromobenzene, iodobenzene, anisole, thioanisole, biphenyl, fluorene , o-terphenylene, m-terphenylene, p-terphenylene, naphthalene, 1-methylnaphthalene, 1-methyl-2-methylnaphthalene, biphenyl ether, biphenyl sulfide, anthracene, 9-bromoanthracene , 9-methylanthracene, 9,10-dimethylanthracene, pyrene, 1,6-dimethylpyrene, 2,7-dimethylpyrene, 1,6-diphenylpyrene, 2,7-dibenzylpyrene, 2,7-bis At least one material selected from (diphenylmethyl)pyrene, perylene, dimethylperylene, tetracene, and pentacene may be used.

Since the halomethylaromatic compound of Formula 1 may be substituted as much as the number of hydrogens bonded to the benzene ring of the aromatic compound of Formula 2, various types of products may be obtained depending on the reaction molar ratio. When the halomethylaromatic compound of Formula 1 is used in excess, that is, when the compounds of Formulas 1 and 2 are reacted in a molar ratio of 4:1, a plurality of methylarenes may be substituted in the aromatic compound of Formula 2, When the aromatic compound of is used in excess relative to the halomethylaromatic compound, that is, when the compounds of Formulas 1 and 2 are reacted in a molar ratio of 1:3, a compound in which one methylarene is substituted can be obtained as a main product.

In this process, the tertiary organophosphine used as a catalyst may be reacted with a halomethylaromatic compound in the reaction process to form a quaternary organophosphine chloride salt. The quaternary organophosphonium salt used as a catalyst corresponds to a salt with excellent activity and has different physical properties from reactants or products, so it can be easily separated and reused.

For the reaction, a solvent may not be added separately, and hydrocarbons, dimethoxyethane (DME), or THF may optionally be used as the reaction solvent. When the reaction is completed, the compound represented by Formula 3 may be obtained by distillation or recrystallization under normal or reduced pressure. Hereinafter, examples in which specific methods and conditions for the production of Chemical Formula 3 according to the present invention are described will be described.

<Example>

Example 1: Synthesis of 1-benzylnaphthalene

60g (0.47mol) of naphthalene and 30.4g (0.24mol) of benzyl chloride, 4.7g (0.024mol) of tetrabutylphosphonium chloride corresponding to 10% of the number of moles of benzyl chloride in a high-temperature, high-pressure reactor with 290ml stainless steel tube, THF 100ml was added and reacted at 200°C for 4 hours. The solution was taken out in a round-bottom flask, and 23.6 g (0.14 mol, yield 60%) of 1-benzylnaphthalene was obtained through distillation under reduced pressure. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis of the obtained product, Ph- CH ₂ -Ph at 4.0 ppm (s, 2H) and Ph- H at 7.2-7.3 ppm (m, 5H) were confirmed.

Example 2: Synthesis of diphenylmethane

In the same manner as in Example 1, 50 g (0.64 mol) of benzene, 81 g (0.64 mol) of 1-(chloromethyl) benzene, and 8.3 g (0.06 mol) of dimethylphenylphosphine were added, and reacted at 200° C. for 3 hours to 59.2 diphenylmethane. g (0.35 mol, yield 55%) was obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis of the obtained product, Ph- CH ₂ -Ph at 3.8 ppm (s, 2H) and Ph- H at 7.0-7.1 ppm (m, 10H) were confirmed.

Example 3: Synthesis of 1-benzyl-4-methoxybenzene

In the same manner as in Example 1, 80 g (0.74 mol) of anisole, 93.7 g (0.74 mol) of benzyl chloride, and 20.7 g (0.07 mol) of tetrabutylphosphonium chloride were added and reacted at 200° C. for 5 hours to react 1-benzyl-4- 79.3 g (0.48 mol, yield 64.3%) of methoxybenzene was obtained. As a result of hydrogen nuclear magnetic resonance analysis of the obtained product at 300 MHz, C- OCH ₃ at 3.8 ppm (s, 3H), Ph-CH ₂ -Ph at 4.1 ppm (s, 2H), Ph-CH 2 -Ph at 6.9-7.3 ppm (m, 9H) - H peak was confirmed.

Example 4: Synthesis of 4-benzyl-1,1`-biphenyl

In the same manner as in Example 1, 50 g (0.32 mol) of 1,1`-biphenyl, 54.7 g (0.32 mol) of (bromomethyl) benzene, 6.1 g (0.03 mol) of tributylphosphine, and 100 ml of THF were added, and 200 ° C. was reacted for 5 hours to obtain 38.8 g (0.16 mol, yield 49.7%) of 4-benzyl-1,1`-biphenyl. As a result of the 300 MHz hydrogen nuclear magnetic resonance analysis of the obtained product, Ph- CH ₂ -Ph at 4.1 ppm (s, 2H) and Ph- H at 7.2-7.8 ppm (m, 14H) were confirmed.

Example 5: Synthesis of di(naphthalenyl)methane

In the same manner as in Example 1, 50 g (0.39 mol) of naphthalene, 68.9 g (0.39 mol) of 1-(chloromethyl) naphthalene, 4.7 g (0.04 mol) of triethylphosphine, and 100 ml of THF were added and reacted at 200° C. for 5 hours. 74.3 g (0.28 mol, yield 71%) of di(naphthalenyl)methane was obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis of the obtained product, Ph- CH ₂ -Ph at 4.7 ppm (s, 2H) and Naph- H at 7.1-7.8 ppm (m, 14H) were confirmed.

Example 6: Synthesis of 1-benzhydrylnaphthalene

In the same manner as in Example 1, 30 g (0.23 mol) of naphthalene, 56.8 g (0.23 mol) of diphenylmethyl bromide, 4.5 g (0.023 mol) of tetrabutylphosphonium chloride, and 60 ml of THF were added, and reacted at 200 ° C. for 4 hours. 35.3 g (0.12 mol, yield 50%) of benzhydryl naphthalene was obtained. The obtained product was confirmed from H Ph- Ph- CH -Ph, 6.9-8.1ppm (m, 17H) from 300MHz 1H magnetic resonance analysis, 5.5ppm (s, 1H).

Example 7: Synthesis of 1,5-dibenzhydrylnaphthalene

In the same manner as in Example 1, 20 g (0.16 mol) of naphthalene, 97.3 g (0.48 mol) of diphenylmethyl chloride, 4.9 g (0.024 mol) of tributylphosphine corresponding to 5% of diphenylmethyl chloride, and 60 ml of THF were added. After reacting at 200° C. for 5 hours, 36.8 g (0.08 mol, yield 49.4%) of 1,5-dibenzhadryl naphthalene was obtained. As a result of hydrogen nuclear magnetic resonance analysis of the obtained product at 300 MHz, C- CH- C at 5.5ppm (s, 2H), Ph-H at 7.1-7.3ppm (m, 20H), Naph- at 7.0-8.0 (m, 6H) H peak was confirmed.

Example 8: Synthesis of ((4-methoxyphenyl)methylene)dibenzene

In the same manner as in Example 1, 50 g (0.46 mol) of anisole, 93.2 g (0.46 mol) of diphenylmethyl chloride, 14.8 g (0.05 mol) of tetrabutylphosphonium chloride, and 100 ml of THF were added and reacted at 200° C. for 4 hours ( 66.9 g (0.24 mol, yield 53%) of (4-methoxyphenyl) methylene) dibenzene was obtained. The obtained product in the 300MHz 1H magnetic resonance analysis, 3.7ppm (s, 3H) O- CH 3, 5.3ppm (s, 1H) from Ph- CH -Ph, 6.6-7.1ppm (m, 14H) from Ph - H was confirmed.

Example 9: Synthesis of 9-benzylanthracene

In the same manner as in Example 1, 50 g (0.28 mol) of anthracene, 35.4 g (0.28 mol) of (chloromethyl) benzene, 6.1 g (0.03 mol) of tributylphosphine, and 100 ml of THF were added, and reacted at 200° C. for 4 hours. 37.6 g (0.14 mol, yield 50%) of benzylanthracene was obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was Ph- CH ₂ -Ph at 4.3 ppm (s, 2H), Ph- H at 7.0-7.2 ppm (m, 5H), and 7.3-7.7 ppm (m, 9H) at Anth- H was confirmed.

Example 10: Synthesis of 1-((2-methyl-5-naphthalenyl)methyl)naphthalene

In the same manner as in Example 1, 50 g (0.35 mol) of 2-methylnaphthalene, 61.8 g (0.35 mol) of (chloromethyl) naphthalene, 11.8 g (0.04 mol) of tetrabutylphosphonium chloride, and 100 ml of THF were added, followed by 4 hours at 200 ° C. 78.1 g (0.28 mol, yield 79%) of 1-((2-methyl-5-naphthalenyl)methyl)naphthalene was obtained by reaction. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was Ph- CH ₃ at 2.5ppm (s, 3H), Ph- CH ₂ -Ph at 4.7ppm (s, 2H), Naph at 7.1-7.7ppm (m, 13H) - H was confirmed.

Example 11: Synthesis of 9-triphenylmethylanthracene

50 g (0.28 mol) of anthracene, 78.1 g (0.28 mol) of trityl chloride, 6.1 g (0.03 mol) of tetrabutylphosphonium chloride, and 80 ml of THF were put in a high-temperature, high-pressure reactor made of 290 ml stainless steel tube, and reacted at 200 ° C for 5 hours. did. This solution was taken out in a round-bottom flask, filtered, and distilled under reduced pressure to remove THF. THF was removed using methylene chloride, the remaining solid was dissolved, and then the catalyst was removed by treatment with water. It was distilled under reduced pressure to remove methylene chloride, and recrystallized by adding toluene to obtain 75.7 g (0.18 mol, yield 64.3%) of 9-triphenylmethylanthracene. As a result of hydrogen nuclear magnetic resonance analysis of the obtained product at 300 MHz, Ph- H at 7.2 ppm (m, 15H) and Anth-H peak at 7.5-8.3 ppm (m, 9H) were confirmed.

Example 12: Synthesis of 1-triphenylmethylnaphthalene

In the same manner as in Example 11, 30 g (0.23 mol) of naphthalene, 64.1 g (0.23 mol) of triphenylmethyl chloride, 4.5 g (0.023 mol) of tetrabutylphosphonium chloride, and 60 ml of THF were added, and reacted at 200° C. for 4 hours. 48.2 g (0.13 mol, yield 55%) of triphenylmethylnaphthalene was obtained. The obtained product was confirmed as Ph-H and Naph- H at 6.9-8.1 ppm (m, 22H) as a result of hydrogen nuclear magnetic resonance analysis at 300 MHz.

Example 13: Synthesis of 9-benzhydrylanthracene

In the same manner as in Example 11, 50 g (0.28 mol) of anthracene, 69.2 g (0.28 mol) of diphenylmethyl bromide, 8.9 g (0.03 mol) of tetrabutylphosphonium chloride, and 100 ml of THF were added and reacted at 200 ° C. for 4 hours. 48.2 g (0.14 mol, yield 50%) of benzhydryl anthracene was obtained. The obtained product 300MHz 1H magnetic resonance analysis, 5.3ppm (s, 1H) Ph- H, 7.3-7.7ppm (m, 9H) from Ph- CH -Ph, 7.0-7.1ppm (m, 10H) from Anth - H was confirmed.

Example 14: Synthesis of 9,10-dibenzhydrylanthracene

In the same manner as in Example 11, 20 g (0.11 mol) of anthracene, 66.9 g (0.33 mol) of benzhydryl chloride, 6.5 g (0.022 mol) of tetrabutylphosphonium chloride, and 40 ml of THF were added and reacted at 200 ° C. for 5 hours 9, 30.6 g (0.06 mol, yield 54.5%) of 10-dibenzhydryl anthracene was obtained. As a result of 300MHz hydrogen nuclear magnetic resonance analysis of the obtained product, C- CH- C at 5.5ppm (s, 2H), Ph-H at 7.0-7.3ppm (m, 20H), Anth at 7.5-8.2ppm (m, 8H) - H peak was confirmed.

Example 15: Synthesis of di(9-anthracenyl)methane

In the same manner as in Example 11, 30 g (0.17 mol) of anthracene, 38.5 g (0.17 mol) of chloromethyl anthracene, 5.6 g (0.02 mol) of tricyclohexylphosphine, and 60 ml of THF were added, and reacted at 200° C. for 4 hours to di(9) -Anthracenyl)methane 33.2g (0.09mol, yield 50%) was obtained. As a result of the 300 MHz hydrogen nuclear magnetic resonance analysis of the obtained product, Ph- CH ₂ -Ph at 4.7 ppm (s, 2H) and Anth-H at 7.3-7.7 pm (m, 18H) were confirmed.

Example 16: Synthesis of 9-(4-phenylbenzyl)anthracene

In the same manner as in Example 11, 50 g (0.28 mol) of anthracene, 56.8 g (0.28 mol) of 4-chloromethyl-1,1'-biphenyl, 8.9 g (0.03 mol) of tetrabutylphosphonium chloride, and 100 ml of THF were added, and 200 58.6 g (0.17 mol, yield 60%) of 9-(4-phenylbenzyl)anthracene was obtained by reaction at ℃ for 5 hours. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was Ph- CH ₂ -Ph at 4.3 ppm (s, 2H), Ph- H at 7.0-7.5 ppm (m, 9H), and 7.3-7.7 ppm (m, 9H) at anth- H was confirmed.

Example 17: Synthesis of 4-benzhydryl-1,1`-biphenyl

In the same manner as in Example 11, 50 g (0.32 mol) of 1,1`-biphenyl, 64.9 g (0.32 mol) of diphenylmethyl chloride, 5.1 g (0.03 mol) of tetramethylphosphonium bromide, and 100 ml of THF were put at 200 ° C. After reaction for 5 hours, 49.2 g (0.15 mol, yield 48%) of 4-benzhydryl-1,1`-biphenyl was obtained. The obtained product was confirmed from H Ph- Ph- CH -Ph, 7.0-7.5ppm (m, 19H) from 300MHz 1H magnetic resonance analysis, 5.3ppm (s, 1H).

Example 18: Synthesis of 4-benzyl-9-anthracenone

In the same manner as in Example 11, 50 g (0.26 mol) of anthrone, 32.9 g (0.26 mol) of (chloromethyl) benzene, 8.9 g (0.03 mol) of tetrabutylphosphonium chloride, and 100 ml of THF were added and reacted at 200° C. for 4 hours. 38.4 g (0.14 mol, yield 52%) of 4-benzyl-9-anthracenone was obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis of the obtained product, Ph- CH ₂ -Ph at 4.1-4.4 ppm (d, 4H) and Ph-H at 7.0-7.6 ppm (m, 12H) were confirmed.

Example 19: Synthesis of 1-benzylpyrene

In the same manner as in Example 11, 50 g (0.25 mol) of pyrene, 31.6 g (0.25 mol) of (chloromethyl) benzene, 8.9 g (0.03 mol) of tetrabutylphosphonium chloride, and 100 ml of THF were added and reacted at 200 ° C. for 4 hours. - 51.9 g (0.18 mol, yield 71%) of benzylpyrene was obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was Ph- CH ₂ -Ph at 4.3 ppm (s, 2H), Ph- H at 7.0-7.1 ppm (m, 5H), and 7.6-8.1 ppm (m, 9H) at Pyrene- H was confirmed.

Example 20: Synthesis of 10-((1-naphthalenyl)methyl)anthracene

In the same manner as in Example 11, 50 g (0.28 mol) of anthracene and 50. (0.28 mol) of 1-(chloromethyl) naphthalene, 8.9 g (0.03 mol) of tetrabutylphosphonium chloride, and 100 ml of THF were added and reacted at 200° C. for 4 hours. 52.9 g (0.17 mol, yield 59%) of 10-((1-naphthalenyl)methyl)anthracene was obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was Ph- CH ₂ -Ph at 4.7ppm (s, 2H), Naph-H at 7.1-7.8ppm (m, 7H), and 7.1-7.8ppm (m, 9H) at Anth- H was confirmed.

Example 21: Synthesis of 6-benzylpentacene

In the same manner as in Example 11, 50 g (0.18 mol) of pentacene, 61.4 g (0.36 mol) of 1-(bromomethyl) benzene, 10.6 g (0.036 mol) of tetrabutylphosphonium chloride, and 100 ml of THF were added, followed by 3 at 200°C. The reaction time was followed to obtain 36.4 g (0.1 mol, yield 55%) of 6-benzylpentacene. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis of the obtained product, Ph- CH ₂ -Ph at 4.3 ppm (s, 2H) and Ph- H and Pentacene- H at 7.0-7.7 ppm (m, 18H) were confirmed.

Example 22: Synthesis of 5-benzyltetracene

In the same manner as in Example 11, 50 g (0.22 mol) of tetracene, 75 g (0.44 mol) of 1-(bromomethyl) benzene, 12.9 g (0.043 mol) of tetrabutylphosphonium chloride, and 100 ml of THF were added, and 3 hours at 200 ° C. By reaction, 37 g (0.1 mol, yield 53%) of 5-benzyltetracene was obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis of the obtained product, Ph- CH ₂ -Ph at 4.3 ppm (s, 2H), Ph- H at 7.0-7.7 ppm (m, 16H), and Tetracene- H were confirmed.

Example 23: Synthesis of 2-benzylperylene

In the same manner as in Example 11, 50 g (0.2 mol) of perylene, 86.4 g (0.4 mol) of 1-(iodomethyl) benzene, 11.7 g (0.04 mol) of tetrabutylphosphonium chloride, and 100 ml of THF were added at 200 ° C. The reaction time was followed to obtain 27.8 g (0.08 mol, yield 41%) of 2-benzylperylene. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis of the obtained product, Ph- CH ₂ -Ph at 3.9 ppm (s, 2H) and Ph- H and perylene- H at 7.0-9.0 ppm (m, 16H) were confirmed.

Example 24: Synthesis of (4-(9-anthracenylmethyl)phenyl)trimethoxysilane

Anthracene 50g (0.28mol) and ((4-chloromethyl)phenyl)trimethoxysilane 69.1g (0.28mol), dimethylphenylphosphine 6g (0.03mol), n- 100ml of Decane was added and reacted at 200°C for 3 hours. This solution was taken out in a round-bottom flask, filtered, and distilled under reduced pressure to obtain 69.9 g (0.18 mol, yield 64.3%) of (4-(9-anthracenylmethyl)phenyl)trimethoxysilane. As a result of 300MHz hydrogen nuclear magnetic resonance analysis, the obtained product was O- CH ₃ at 3.5 ppm (s, 9H), Ph-CH ₂ -Ph at 4.3 ppm (s, 2H), Ph-CH 2 -Ph at 7.1-7.2 ppm (m, 4H) -H , Anth-H was confirmed at 7.3-7.7ppm (m, 9H).

Example 25: Synthesis of [(4-(1-naphthalenylmethyl)phenyl)trimethoxysilane]

In the same manner as in Example 24, 50 g (0.39 mol) of naphthalene, 96.2 g (0.39 mol) of (4- (chloromethyl) phenyl) trimethoxysilane, 4.7 g (0.04 mol) of triethylphosphine, and 100 ml of n-Decane were prepared in the same manner as in Example 24. and reacted at 200° C. for 4 hours to obtain 93.7 g (0.28 mol, yield 71%) of trimethoxy(4-(5-naphthalenyl)methyl)phenyl)silane. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was O- CH ₃ at 3.6 ppm (s, 9H), Ph-CH ₂ -Ph at 4.3 ppm (s, 2H ), Ph- H at 7.1 ppm (m, 4H) , Naph-H was confirmed at 7.1-7.8 ppm (m, 7H).

Claims (10)

Dehydrohalogenation using the halomethylaromatic compound represented by [Formula 1] and the aromatic compound represented by [Formula 2] as a catalyst using the organophosphine compound represented by [Formula 4], [Formula 5] or [Formula 6] as a catalyst A method for preparing an (arylmethyl) arene compound represented by [Formula 3] by a CC bond reaction.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]
P(R") ₃
[Formula 5]
P(R") ₄ X'
[Formula 6]
X'(R") ₃ PYP(R") ₃ X'

provided that, in Formulas 1, 2 and 3, Ar ₁ =benzene, naphthalene, anthracene, phenanthrene, pyrene, perylene, biphenyl, biphenyl ether or biphenyl sulfide; R ₁ =H, C1-C4 alkyl group or phenyl group; R ₂ = H, F, Cl, Br, C1-C4 alkyl group or (CH ₂ ) _q Si(R ₃ )p(OR ₃ ) _3-p ) R ₃ =H, including C1-C8 alkyl group or phenyl group an alkyl group; R ₄ =H, F, Cl, Br, I, or an alkyl group having 1 to 6 carbon atoms; X=Cl, Br or I; Ar ₂ is benzene, alkylbenzene, halobenzene, anisole, thioanisole, biphenyl, fluorene, terphenylene, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 1,2-dimethylnaphthalene, anthracene, Anthrone, 2-(t-butyl)anthraquinone, 2-(t-butyl)anthracene, 9-methylanthracene, 9,10-dimethylanthracene, phenanthrene, biphenyl, biphenyl ether, biphenylsulfide, pyrene, Perylene. It is one compound selected from among tetracene, pentacene, and aromatic compounds having 1 to 8 benzene rings, and n=1 or 2.
In Formulas 4, 5, and 6, R″ may include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or a phenyl group, each R″ may be the same as or different from each other, and different R″ may be shared It may be a cyclic structure connected by a bond, X'=Cl, Br, or I, and Y=alkylene having 1 to 12 carbon atoms, an alkyl group including an aromatic group, or an aromatic group.
(arylmethyl) arene compound represented by [Formula 3].
[Formula 3]

provided that Ar ₁ =benzene, naphthalene, anthracene; Ar ₂ =naphthalene, biphenyl, anthracene, phenanthrene, pyrene, perylene, tetracene, pentacene, fluorene; R ₁ =H; R ₂ =Si(OMe) ₃ , Si(OEt) ₃ , CH ₂ Si(OMe) ₃ , CH ₂ Si(OEt) ₃ , CH ₂ SiMe(OMe) ₂ , CH ₂ CH ₂ Si(OMe) _{3 ,} CH ₂ CH ₂ Si(OEt) ₃ , CH ₂ CH ₂ SiMe(OMe) ₂ ; R ₃ and R ₄ =H; n=1 or 2.
or Ar ₁ =naphthalene, anthracene, pyrene, biphenyl, perylene; Ar ₂ =phenanthrene, perylene, tetracene, pentacene, fluorene; R ₁ = H; R ₂ = H, n-propyl, iso-propyl, n-butyl, t-butyl; R ₃ and R ₄ = H; n=1 or 2.
According to claim 1,
A method for producing (arylmethyl) arene, characterized in that the reaction molar ratio of the compound represented by Formula 1 to the compound represented by Formula 2 is 4:1 to 1:3. delete delete delete According to claim 1,
The method for producing (arylmethyl) arene, characterized in that the concentration of the catalyst is 5 to 20 mol% based on the compound of Formula 1. According to claim 1,
The reaction temperature is a method for producing an (arylmethyl) arene compound, characterized in that 100 ~ 250 ℃. According to claim 1,
(arylmethyl) arene compound, characterized in that at least one solvent selected from among aliphatic hydrocarbons, ether, dimethoxyethane (DME), and THF is used to react the compound of Formula 1 with the compound of Formula 2 manufacturing method. According to claim 1,
A method for producing an (arylmethyl) arene compound, characterized in that the compound of Formula 1 and the compound of Formula 2 are reacted without a solvent when they are in a liquid phase.