KR102346347B1 - Allylarenes and a Method for Producing the Same - Google Patents

Abstract

. The present invention relates to an allylaromatic association and a method for preparing the same. Allyl aromatic compound is represented by the formula (3)
Formula 3:

.

Description

Allylaromatic compound and its preparation method {Allylarenes and a Method for Producing the Same}

The present invention relates to an allyl aromatic compound and a method for preparing the same, and more particularly, to an allyl aromatic compound produced by reaction of an allyl halide with an aromatic compound using an organophosphine compound catalyst and a method for preparing the same.

The Friedel-Crafts alkylation reaction in which an alkyl group is substituted for an aromatic compound by reacting an alkyl halide with an aromatic compound using a Lewis acid catalyst is widely used as a very important reaction in organic synthesis (Roberts, Royston M; Khalaf, Ali, Friedel-Crafts) Alkylation Chemistry, Marcel Dekker, Inc., New York, New York, USA, 1984 ). However, the Friedel-Crafts alkylation reaction has a disadvantage in that the number of alkyl groups may change due to the displacement of the alkyl group of the alkyl aromatic compound from the aromatic ring or from one aromatic ring to the other by the Lewis acid catalyst. Anthracene having three rings or an aromatic compound having more rings than that of an aromatic compound for alkylation is not practical because the activity of the catalyst is greatly reduced by coordination with the catalyst Lewis acid. In addition, when an allyl group is substituted in an aromatic compound using an allyl halide, a reaction in which the carbon-carbon double bond of the allyl halide interacts with a Lewis acid as a catalyst to be added to the ring of the aromatic compound may occur first. Due to this, a compound to which a haloalkyl group is added, not a compound substituted with an allyl group, may be obtained. When an allyl group is directly substituted in the Friedel-Crafts type alkylation reaction using a Lewis acid such as boron trichloride or aluminum trichloride as a catalyst, allyl alcohol or allyl ether must be used instead of allyl halide. Instead of using an acid catalyst for the allylation of an aromatic compound with an allyl halide, a neutral compound should be used. In addition, there is a need for a catalyst in which carbon and halogen bonds are activated by a neutral catalyst to facilitate substitution. Using organophosphonium chloride as a catalyst, the alkyl halide and trichlorosilane are reacted to remove the halogen from the alkyl halide, and hydrogen is taken from the trichlorosilane to generate hydrogen halide. The synthesis of substituted alkylchlorosilanes is known (Yeon Seok Cho, YS; Kang, S.-H.; Han, JS; Yoo, BR; Jung, IN, J. Am. Chem. Soc. 2001 , 123 , 5584). Referring to the prior art above, in the case of an alkyl halide reaction with high activity such as allyl chloride or benzyl chloride, alkylchlorosilane is synthesized in a good yield at 130 to 150° C., and when an inactive alkyl halide unsubstituted with a functional group is reacted 30 Alkylchlorosilanes can be synthesized in high yield at a higher temperature condition of about ~50°C. In addition, even if quaternary organophosphonium chloride is not used as a catalyst and tertiary trialkylphosphine is used, it reacts with alkyl chloride as a reactant during the reaction to generate quaternary organophosphonium chloride, so the scope of the catalyst is tertiary organophosphine includes As disclosed in the prior art, the quaternary organophosphonium chloride used as a catalyst in the synthesis reaction of alkylchlorosilane in which an alkyl group is replaced with a silane by a dehydrohalogenation Si-C bond reaction by reacting an alkyl halide with trichlorosilane is an organic salt becomes 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 an allyl halide, a dehydrohalogenation CC bonding reaction that separates halogen from the allyl halide and hydrogen from the aromatic ring to generate HX may occur. As described above, without using a Lewis acid as a catalyst, by using a tertiary organophosphine or a quaternary organophosphonium salt as a catalyst, the allyl halide is reacted with an aromatic compound to synthesize an arylaromatic compound by dehydrohalogenation CC bonding reaction. , an appropriate amount of catalyst may be used. In addition, since the catalyst has different physical properties from the reactant or product, it is easy to recover and reuse. Due to this, the allyl aromatic compound can be prepared in a very economical and high yield compared to known manufacturing methods. Therefore, the present invention is based on the above idea 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: Roberts, Royston M; Khalaf, Ali, Friedel-Crafts Alkylation Chemistry, Marcel Dekker, Inc., New York, New York, USA, 1984 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 allyl aromatic compound synthesized by a C-C bond reaction of hydrogen halide to generate HX by reacting an allyl halide with an aromatic compound using an organophosphine compound catalyst, and a method for preparing the same.

According to a suitable embodiment of the present invention, the allyl aromatic compound is represented by Formula 3,

Formula 3:

,

,

_{R 1} =H, Me, CH ₂ Cl or CH ₂ Br in Formula 3; R ₂ = H, Me, Ph, CH ₂ Cl or CH ₂ Br; R ₃ = H, Me, CH ₂ Cl or CH ₂ Br; R ₄ = H or Me; Ar ₁ = benzene, alkylbenzene, halobenzene, 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, 9-benzylanthracene, 9,10-dibenzylanthracene, 9-(diphenylmethyl)anthracene, phenanthrene, biphenyl, biphenylether, biphenylsulfide, pyrene, perylene. tetracene, pentacene or aromatic compounds having 1 to 8 rings; R ₅ = H, X, a phenyl group substituted with a phenyl group or an alkyl group having 1 to 8 carbon atoms; X=F, Cl, Br or I; R ₆ = H, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a benzyl group or a diphenylmethyl group; R ₇ = H or Me; R ₈ = H or Me; R ₉ = an allyl group represented by Formula 1 having an allyl group, a methyl group, or a phenyl group as a substituent, and n is 0, 1 or 2.

According to another suitable embodiment of the present invention, the compound represented by Formula 1 and Formula 2 is reacted to produce a compound represented by Formula 3,

Formula 1:

Formula 2:

,

,

_{R 1} =H, Me, CH ₂ Cl or CH ₂ Br in formulas 1, 2 and 3; R ₂ = H, Me, Ph, CH ₂ Cl or CH ₂ Br; R ₃ = H, Me, CH ₂ Cl or CH ₂ Br; R ₄ = H or Me; Ar ₁ = benzene, alkylbenzene, halobenzene, 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 _, 9-benzylanthracene, 9,10-dibenzylanthracene, 9-(diphenylmethyl)anthracene, phenanthrene, biphenyl ether, biphenylsulfide, pyrene , perylene, tetracene, pentacene or aromatic compounds having 1 to 8 rings; R ₅ = H, X, a phenyl group substituted with a phenyl group or an alkyl group having 1 to 8 carbon atoms; X=F, Cl, Br or I; R ₆ = H, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a benzyl group or a diphenylmethyl group; R ₇ = H or Me; R ₈ = H or Me; R ₉ = an allyl group represented by Formula 1 having an allyl group, a methyl group or a phenyl group as a substituent, and n is 0, 1, or 2 is provided a method for producing an allyl aromatic compound.

According to another suitable embodiment of the present invention, the compound represented by Formula 4 may be used as a catalyst,

Formula 4:

P(R") _3,

In Formula 4, 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, and R″ different from each other becomes a cyclic structure connected by a covalent bond.

According to another suitable 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 having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or a phenyl group, and R″ different from each other becomes a cyclic structure connected by a covalent bond, and X′=Cl, Br or I.

According to another suitable 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 having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or a phenyl group, and R" different from each other becomes a cyclic structure connected by a covalent bond, and X'=Cl, Br or I and Y = an alkylene group having 1 to 12 carbon atoms, an alkylene group having 1 to 12 carbon atoms including an aromatic group, or an aromatic group.

According to another suitable embodiment of the present invention, the reaction temperature is 100-250 °C.

According to another suitable embodiment of the present invention, the reaction solvent is an aliphatic hydrocarbon, ether, dimethoxyethane (DME) or THF, or is reacted without a solvent.

The present invention can replace the process of obtaining an allyl aromatic compound by reacting an aromatic compound with an allyl halide using a known Lewis acid catalyst corresponding to a metal chloride such as aluminum, boron, iron, or copper. For the known reaction, an aromatic compound substituted with a haloalkyl group in which a carbon-carbon double bond is added to an aromatic ring is produced. Therefore, a catalyst corresponding to neutrality, not a metal compound, is required instead of the above catalyst. Such a group of compounds may be a quaternary salt of a nitrogen or phosphorus compound of Group 5 among organic substances. Using a quaternary organophosphonium salt as a catalyst, alkyl chloride and chlorosilane having a 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 an allyl aromatic compound by reacting an allyl halide with an aromatic compound based on this process. Such a catalyst can act very effectively in the process of synthesizing an allyl aromatic compound by dehydrohalogenation C-C bonding reaction, and has the advantage that the catalyst can be easily recovered and recycled. In the allyl aromatic compound according to the present invention, an allyl group and an aromatic ring form a ring again to prepare a compound in which an aromatic ring is increased, or an organosilicon compound in which an aromatic compound is substituted with an allyl functional group by a hydrogen silylation reaction can be prepared. Organosilicon compounds substituted with three-ring anthracene and aromatic compounds having more rings have fluorescence. The fluorescent organosilicon compound according to the present invention can be usefully used for the development of new functional silicone products.

Hereinafter, the present invention will be described in detail with reference to the presented examples, but the examples are for a clear understanding of the present invention, and the present invention is not limited thereto.

Allyl aromatic compound according to the present invention is represented by Formula 3,

Formula 3:

,

,

_{R 1} =H, Me, CH ₂ Cl or CH ₂ Br in Formula 3; R ₂ = H, Me, Ph, CH ₂ Cl or CH ₂ Br; R ₃ = H, Me, CH ₂ Cl or CH ₂ Br; R ₄ = H or Me; Ar ₁ = Benzene _, alkylbenzene _, halobenzene _, biphenyl, fluorene, terphenylene _, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 1,2-dimethylnaphthalene, anthracene, anthrone, 2-(t-butyl)anthraene Quinone, 2-(t-butyl)anthracene, 9-methylanthracene, 9,10-dimethylanthracene _, 9-benzylanthracene, 9,10-dibenzylanthracene, 9-(diphenylmethyl)anthracene, phenanthrene, biphenyl , biphenyl ether, biphenyl sulfide, pyrene, perylene. tetracene, pentacene or aromatic compounds having 1 to 8 rings; R ₅ = HX, or a phenyl group having 1 to 8 carbon atoms or a phenyl group substituted with an alkyl group; X=F, Cl, Br or I; R ₆ = H, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a benzyl group or a diphenylmethyl group; R ₇ = H or Me; R ₈ = H or Me; R ₉ = an allyl group represented by Formula 1 having an allyl group, a methyl group, or a phenyl group as a substituent, and n is 0, 1 or 2.

The allyl aromatic compound represented by Formula 3 may be produced by reacting the allyl halide of Formula 1 below with the aromatic compound of Formula 2 using a tertiary organophosphine or a quaternary organophosphonium salt as a catalyst.

Scheme 1:

,

,

<Formula 1> <Formula 2> <Formula 3>

_{R 1} =H, Me, CH ₂ Cl or CH ₂ Br in Formula 1; R ₂ = H, Me, Ph, CH ₂ Cl or CH ₂ Br; R ₃ = H, Me, CH ₂ Cl or CH ₂ Br; R ₄ = H or Me; and X = Cl, Br or I. In Formula 2, Ar ₁ = Benzene _, alkylbenzene _, halobenzene _, biphenyl, fluorene, terphenylene _, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 1,2-dimethylnaphthalene, anthracene, anthrone, 2-(t-butyl)anthraene Quinone, 2-(t-butyl)anthracene, 9-methylanthracene, 9,10-dimethylanthracene _, 9-benzylanthracene, 9,10-dibenzylanthracene, 9-(diphenylmethyl)anthracene, phenanthrene, biphenyl , diphenyl ether, diphenyl sulfide, pyrene, perylene. It may be tetracene or pentacene, and may be, for example, an aromatic compound having 1 to 8 rings or a phenyl group having 1 to 8 carbon atoms substituted with a phenyl group or an alkyl group. and R ₅ = H or X, and X = F, Cl, Br or I. R ₆ = H, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a benzyl group or a diphenylmethyl group, R ₇ = H or Me; R ₈ = H or Me, and each R may have the same or different structures. In Formula 3, R ₁ to R ₈ may be the above compounds, and R ₉ = H or an allyl group having an allyl group, a methyl group, or a phenyl group as a substituent, for example, is the same as the allyl group of Formula 1, (R ₉ ) _n of n can be 0, 1 or 2.

In the process of preparing the allyl aromatic compound, a reaction between the aromatic compound and allyl halide may be induced by using a Lewis acid catalyst of a metal such as aluminum, boron, iron, or copper or a metal chloride. However, in this process, an aromatic compound substituted with a haloalkyl group, not an allylaromatic compound, may be generated. In contrast, when an organic tertiary organophosphine or a neutral quaternary organophosphonium salt is used as a catalyst for the allylation reaction, a dehydrohalogenation CC bonding reaction is induced, so that an allyl aromatic compound can be effectively produced, and the catalyst can be easily recovered It has the advantage that it can be reused. According to the present invention, since the boiling point of allyl halide is lower than 200° C. corresponding to the reaction temperature, it is difficult to react at normal pressure, and it is advantageous to use a reactor used for high pressure reaction. The tertiary organophosphine or quaternary organophosphonium salt corresponding to the allyl halide compound of Formula 1, the aromatic compound of Formula 2 and the catalyst in the high-pressure reactor is 1 to 100 mol%, preferably 5 to 20 mol%, compared to the compound of Formula 1 mole % may be added. The reactor may be heated to a temperature of 100 to 250 °C, preferably 150 to 220 °C, whereby an allyl aromatic compound such as Chemical Formula 3 according to Scheme 1 can be synthesized. In this reaction process, the tertiary organophosphine used as a catalyst reacts with allyl halide during the reaction to become a quaternary organophosphine chloride salt. The quaternary organophosphonium salt used as a catalyst has excellent activity and can be easily separated and reused because it is a salt compound and has different physical properties from reactants or products. Therefore, it is advantageous to synthesize the allyl aromatic compound of Formula 3 by the reaction of the aromatic compound of Formula 2 with the allyl halide of Formula 1 using a tertiary organophosphine or quaternary organophosphonium salt as a catalyst. For the reaction process, the allyl halide of Formula 1 and the aromatic compound of Formula 2 are added under a nitrogen atmosphere, and a tertiary organophosphine or quaternary organophosphonium salt catalyst is added to, for example, a stainless steel tube material that can withstand high pressure can be The stopper can then be closed and the reactor can be heated to the reaction temperature. In order to induce an appropriate reaction, the molar ratio of the aromatic compound of Formula 2 to the allyl halide of Formula 1 may be 1 to 2 times. In addition, the tertiary organophosphine or quaternary organophosphonium salt catalyst may be 1 to 100 mol%, preferably 5 to 20 mol%, based on the compound of Formula 1. The reaction solvent may be appropriately selected depending on the reactant, and for example, a reaction solvent such as an aliphatic hydrocarbon may be used, or a solvent such as ether, dimethoxyethane (DME) or THF may be used as the reaction solvent. Optionally, the reaction may be induced in the absence of a reaction solvent. The reaction temperature may be 100 to 250 °C, preferably 150 to 220 °C, and at this reaction temperature, the reaction takes place for 1 to 48 hours, and after the reaction is completed, the stopper is opened and hydrogen halide gas can be discharged. In addition, the reaction tank is at atmospheric pressure or reduced pressure, and the product is separated by distillation or recrystallization to obtain the compound of Formula 3. When cyclic THF is used as a solvent, the ring is opened by HX, which is a by-product, and halobutyl alcohol can be produced, and halobutyl ether is generated through the condensation reaction of the alcohol, and HX gas corresponding to the by-product is removed. can be After the product of Formula 3 is generated and separated, the product is separated for recycling the catalyst, and the remaining compound can be used again as a catalyst without any additional process, so the quaternary organophosphonium salt used as a catalyst can be simply recovered. have. The recovery rate can be at the level of 80 wt% of the amount used, and it is economically very advantageous. When the organic phosphonium salt is used after being immobilized on a silicone resin, silica or zeolite, it is recovered after completion of the reaction and has the advantage of being very convenient for reuse.

The allyl halide of Formula 1 for the reaction may include the following compounds:

Allyl chloride, allyl bromide, allyl iodide, 3-chloro-1-butene, 3-bromo-1-butene, 3-iodo-1-butene, 1-chloro-2-butene, 1-bromo- 2-Butene, 1-iodo-2-butene, 3-chloro-2-methyl-1-propene, 3-bromo-2-methyl-1-propene, 3-iodo-2-methyl-1 -propene, (3-chloro-propenyl)benzene, (3-bromo-propenyl)benzene, (3-iodo-propenyl)benzene, 1,4-dichloro-2-butene, 1,4- Dibromo-2-butene.

All such compounds are commercially available or readily synthesized compounds. The compound represented by Formula 2 may include the following compounds that are commercially available or can be easily synthesized:

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, biphenyl, fluorene, o-terphenylene, m-terphenylene, p-terphenylene, naphthalene, 1-methylnaphthalene, 1-methyl-2-methylnaphthalene, biphenyl, 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(diphenylmethyl)pyrene, triphenylene, perylene, dimethylperylene, tetracene, pentane sen.

Since the allyl halide of Formula 1 may be substituted as much as the number of hydrogens bonded to the ring of the aromatic compound of Formula 2, various types of products may be obtained depending on the reaction molar ratio. When the allyl halide of Formula 1 is used in excess, a plurality of allyl groups may be substituted in the aromatic compound of Formula 2, and when used in an appropriate amount, a compound in which allyl groups are substituted by the number of hydrogens bonded to the ring may be obtained. Since the allyl group substituted in the aromatic compound having two or more rings can form a hexagonal ring with the aromatic ring, a compound having an increased aromatic ring can be obtained. On the other hand, when the aromatic compound of Formula 2 is used in excess relative to the allyl halide, a compound in which one allyl group is substituted may be obtained as a main product.

The tertiary organophosphine used as a catalyst may be, for example, represented by Chemical Formula 4, and the quaternary organophosphonium 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, 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″ has the same or different structure can have

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 = an alkylene group having 1 to 12 carbon atoms; an alkylene group having 1 to 12 carbon atoms including an aromatic group; or an aromatic group; , two R″ may be covalently linked to each other to have a cyclic structure, and each R″ may have the same or different structures. The tertiary organophosphine as a catalyst is trimethylphosphine, triethyl Phosphine, tributylphosphine, methyldiphenylphosphine, tricyclohexylphosphine, triisopropylphosphine, tripropylphosphine, dimethylphenylphosphine, ethyldiphenylphosphine, t-butyldiphenylphosphine, t-butyldiisopropyl, isopropyldiphenylphosphine, dicyclohexylphenylphosphine, benzyldiphenylphosphine, cyclohexyldiphenylphosphine, tricyclopentylphosphine, di-t-butylneopentylphosphine, di-t-butylphenylphosphine, di-t-butylmethylphosphine or t-butyldicyclohexylphosphine The quaternary organophosphonium salt is for example 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, silicone silsesquoxene or organic polymer immobilized on 4 The quaternary organophosphonium salt used as a catalyst can be easily recovered from the reaction mixture, 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 up to a level of 80% of the amount initially used, and the recovered catalyst can be reused by recrystallization with an appropriate solvent. In the course of the reaction, tertiary organophosphine or quaternary organophosphonium The salt catalyst is 1 to 100 mol%, preferably 5 to 20 mol% may be added, and when the reaction is carried out at a temperature of 100 to 250 °C, preferably 150 to 220 °C, an allyl aromatic compound represented by Chemical Formula 3 of Scheme 1 may be produced. In this process, the tertiary organophosphine used as a catalyst reacts with allyl halide 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. According to another suitable embodiment of the present invention, the reaction temperature of the compounds represented by Chemical Formulas 1 and 2 is 10 to 250 °C, preferably 150 to 220 °C, and the reaction may proceed for 1 to 48 hours. For the reaction, the tertiary organophosphine or quaternary organophosphonium salt catalyst may be added in an amount of 1 to 100 mol%, preferably 5 to 20 mol%. For the reaction, a solvent may not be separately added, and optionally hydrocarbon or dimethoxyethane (DME) may be used as the reaction solvent. When the reaction is completed, the compound represented by Chemical Formula 3 may be obtained by distillation under normal or reduced pressure. Examples for the production of compounds according to the invention are described below.

Example

Example 1: Synthesis of allylbenzene

50 g (0.64 mol) of benzene, 24.5 g (0.32 mol) of allyl chloride, and 9.4 g (0.032 mol) of tetrabutylphosphonium chloride corresponding to 10% of the number of moles of allyl chloride were added to a high-temperature, high-pressure reactor with a stainless steel tube with a capacity of 290 ml. and reacted at 200°C for 5 hours. This solution was taken out in a round-bottom flask, and 18.7 g (0.16 mol, yield 49.5%) of allylbenzene was obtained through distillation under reduced pressure. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was C- CH ₂ -C at 3.3 ppm (d, 2H), CH ₂ =C at 4.8-5.1 ppm (m, 2H), and C at 5.9 ppm (m, 1H). - CH = C, Ph was confirmed at 7.1-7.3 ppm (m, 5H).

Example 2: Synthesis of 1,3-diphenyl-1-propene

In the same manner as in Example 1, 50 g (0.64 mol) of benzene, 48.8 g (0.32 mol) of cinnamyl chloride, and 9.4 g (0.032 mol) of tetrabutylphosphonium chloride were added and reacted at 200° C. for 5 hours to 1,3-diphenyl -1-propene 41.9 g (0.22 mol, yield 67.4%) was obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was C- CH ₂ -C at 3.3 ppm (d, 2H), C= CH -C at 6.3 ppm (d, 1H), C- at 6.7 ppm (m, 1H) CH = C, Ph was confirmed at 7.2-7.3 ppm (m, 10H).

Example 3: Synthesis of 1-allylnaphthalene

In the same manner as in Example 1, 50 g (0.39 mol) of naphthalene, 14.9 g (0.20 mol) of allyl chloride, 5.7 g (0.02 mol) of tetrabutylphosphonium chloride, and 60 ml of decane were added, and reacted at 200° C. for 6 hours, followed by 1-allylnaphthalene 25.3 g (0.15 mol, 77.1%) was obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was C- CH ₂ -C at 3.7 ppm (d, 2H), CH ₂ =C at 5.0 ppm (m, 2H), C-CH at 6.3 ppm (m, 1H) =C, Naph peak was confirmed at 7.1-7.8 ppm (m, 7H). In addition, it was confirmed by GC/MS analysis that hydrogen was removed from diallylnaphthalene and diallylnaphthalene as by-products and dihydropyrene, a cyclized compound, was generated.

Example 4: Synthesis of 1-(2-methylallyl)naphthalene

In the same manner as in Example 1, 40 g (0.31 mol) of naphthalene, 14.1 g (0.16 mol) of 3-chloro-2-methyl-1-propene, 5.4 g (0.016 mol) of tetrabutylphosphonium bromide, and 60 ml of decane were added and 200 The reaction was carried out at ℃ for 6 hours to obtain 22.8 g (0.12 mol, yield 80.2%) of 1-(2-methylallyl)naphthalene. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was CH ₃ -C at 1.7 ppm (s, 3H), C- CH ₂ -C at 3.7 ppm (s, 2H), CH ₂ = at 4.7 ppm (m, 2H) C, Naph peak was confirmed at 7.1-7.8 ppm (m, 7H).

Example 5: Synthesis of 1-cinnamylnaphthalene

In the same manner as in Example 1, 30 g (0.23 mol) of naphthalene, 17.9 g (0.12 mol) of cinnamyl chloride, 4.1 g (0.012 mol) of tetrabutylphosphonium bromide, and 60 ml of decane were added, and reacted at 200° C. for 6 hours to react 1-cinnamyl. 20.4 g (0.08 mol, yield 69.7%) of naphthalene was obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was C- CH ₂ -C at 3.7 ppm (d, 2H), C= CH -C at 6.3 ppm (d, 1H), C- at 6.7 ppm (m, 1H) A Naph peak was identified at CH = C, 7.1-7.8 ppm (m, 12H).

Example 6: Synthesis of 1-allyl-5-bromonaphthalene

In the same manner as in Example 1, 50 g (0.24 mol) of 1-bromonaphthalene, 9.2 g (0.12 mol) of allyl chloride, 3.5 g (0.012 mol) of tetrabutylphosphonium chloride, and 50 ml of THF were added, and reacted at 200° C. for 6 hours. -Allyl-5-bromonaphthalene 18.5g (0.07mol, yield 62.3%) was obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was C- CH ₂ -C at 3.8 ppm (d, 2H), CH ₂ =C at 5.0 ppm (m, 2H ), C= CH at 6.0 ppm (m, 1H) Naph peak was confirmed at -C, 7.0-8.0 ppm (m, 6H).

Example 7: Synthesis of 1-bromo-5-(2-butenyl)naphthalene

In the same manner as in Example 1, 50 g (0.24 mol) of 1-bromonaphthalene, 10.9 g (0.12 mol) of 1-chloro-2butene, 3.5 g (0.012 mol) of tetrabutylphosphonium chloride, and 50 ml of THF were added at 200°C 6 The reaction was conducted over time to obtain 20.4 g (0.08 mol, yield 65%) of 1-bromo-5-(2-butenyl)naphthalene. The obtained product 300MHz 1H magnetic resonance analysis, 1.6ppm (d, 3H) in _{CH 3 -C, 3.8ppm (d,} 2H) C- CH 2 -C, 5.4ppm (m, 1H) from the C- CH A Naph peak was observed at =C, 6.0 ppm (m, 1H) at C = CH -C, 7.0-8.1 ppm (m, 6H).

Example 8: Synthesis of 9-allylanthracene

In the same manner as in Example 1, 40 g (0.22 mol) of anthracene, 8.6 g (0.11 mol) of allyl chloride, 3.2 g (0.011 mol) of tetrabutylphosphonium chloride, and 50 ml of THF were added, and reacted at 200° C. for 5 hours to 14.9 9-allyl anthracene. g (0.07 mol, yield 62.1%) was obtained. The obtained product 300MHz 1H magnetic resonance analysis, 3.8ppm (d, 2H) CH 2 = C, 6.0ppm (m, 1H) In _{Anth- CH 2 -C, 5.0ppm (m} , 2H) from the C- CH Anth peak was confirmed at =C, 7.5-8.3 ppm (m, 9H).

Example 9: Synthesis of 9-(1-methyl-2-propenyl)anthracene

In the same manner as in Example 1, 40 g (0.22 mol) of anthracene, 10 g (0.11 mol) of 3-chloro-1-butene, 3.2 g (0.011 mol) of tetrabutylphosphonium chloride, and 50 ml of THF were added, and reacted at 200° C. for 5 hours. 17.8 g (0.08 mol, yield 69.7%) of -(1-methyl-2-propenyl)anthracene was obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was CH ₃ -C at 1.4 ppm (d, 3H), C-CH -C at 3.6 ppm (m, 1H), and CH ₂ = C at 5.0 ppm (m, 2H). , C-CH = C at 6.3 ppm (m, 1H ), Anth peak was confirmed at 7.5-8.3 ppm (m, 9H).

Example 10: Synthesis of 9-cinnamylanthracene

In the same manner as in Example 1, 40 g (0.22 mol) of anthracene, 16.8 g (0.11 mol) of cinnamyl chloride, 3.2 g (0.011 mol) of tetrabutylphosphonium chloride, and 50 ml of THF were added and reacted at 200° C. for 5 hours to react with 9-cinnamyl. Anthracene 18.8 g (0.06 mol, yield 58.2%) was obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was C- CH ₂ -C at 3.8 ppm (d, 2H), C= CH -Ph at 6.3 ppm (d, 1H), C- at 6.7 ppm (m, 1H) CH = C, Ph at 7.2-7.3 ppm (m, 5H ), Anth peak was confirmed at 7.5-8.3 ppm (m, 9H).

Example 11: Synthesis of diallylanthracene

In the same manner as in Example 1, 30 g (0.17 mol) of anthracene, 38.63 g (0.50 mol) of allyl chloride, 7.4 g (0.025 mol) of tetrabutylphosphonium chloride, and 50 ml of THF were added, and reacted at 200° C. for 5 hours to 18.7 g of diallylanthracene. (0.07 mol, yield 43%) was obtained.

The obtained compound was analyzed through GC/MS and it was confirmed that it contained isomers. In addition, it was confirmed that dihydroperylene, a cyclized compound, was generated.

Example 12: Synthesis of 3-allylanthrone

In the same manner as in Example 1, 30 g (0.15 mol) of anthrone, 5.9 g (0.08 mol) of allyl chloride, 3.1 g (0.008 mol) of benzyl triphenyl phonium chloride, and 50 ml of DME were added, and reacted at 200 ° C. for 5 hours. Allylanthrone 13.5g (0.06mol, yield 72%) was obtained. The obtained product was obtained by 300 MHz hydrogen nuclear magnetic resonance analysis, C- CH ₂ -C at 3.3 ppm (d, 2H), Ph- CH ₂ -Ph at 4.4 ppm (s, 2H), 4.8-5.0 ppm (m, 2H) At CH ₂ =C, 6.0 ppm (m, 1H) at C = CH -C, Ph peak was confirmed at 7.4-8.4 ppm (m, 7H).

Example 13: Synthesis of 3,6-Diallylanthrone

In the same manner as in Example 1, 30 g (0.15 mol) of anthrone, 35.5 g (0.46 mol) of allyl chloride, 6.2 g (0.016 mol) of benzyl triphenyl phonium chloride, and 30 ml of DME were added, and reacted at 200 ° C. for 7 hours 3, 22.5 g (0.08 mol, yield 54.6%) of 6-diallylanthrone was obtained. The obtained product 300MHz 1H magnetic resonance analysis, 3.3ppm (d, 4H) C- CH 2 -C, 4.4ppm (s, 2H) from _{Ph- CH 2 -Ph, 5.0ppm (m} , 4H) in CH _{At 2} = C, 6.0 ppm (m, 2H), C = CH -C, Ph peak was confirmed at 7.4-7.7 ppm (m, 6H).

Example 14: Synthesis of 3-(2-methylallyl)anthrone

In the same manner as in Example 1, 30 g (0.15 mol) of anthrone, 7.2 g (0.08 mol) of 3-chloro-2-methyl-propene, 2.4 g (0.008 mol) of tetrabutylphosphonium chloride, and 40 ml of DME were added, and 200° C. After reaction for 5 hours, 13.2 g (0.05 mol, yield 66.2%) of 3-(2-methylallyl)anthrone was obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was CH ₃ -C at 1.8 ppm (s, 3H), C- CH ₂ -C at 3.2 ppm (s, 2H), Ph- CH at 4.4 ppm (s, 2H) ₂ -Ph, CH ₂ =C at 5.0ppm (d, 2H ), Ph peak was confirmed at 7.4-8.4ppm (m, 7H).

Example 15: Synthesis of 1-allylpyrene

In the same manner as in Example 1, 40 g (0.19 mol) of pyrene, 7.6 g (0.10 mol) of allyl chloride, 2.9 g (0.01 mol) of tetrabutylphosphonium chloride, and 50 ml of THF were added, and reacted at 200° C. for 5 hours, followed by 1-allylpyrene 19.1 g (0.08 mol, yield 78.8%) was obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was C- CH ₂ -C at 3.7 ppm (d, 2H), CH ₂ =C at 4.8-5.0 ppm (m, 2H), C at 6.0 ppm (m, 1H) = CH -C, Pyrene peak was confirmed at 7.7-8.3 ppm (m, 9H).

Example 16: Synthesis of 2-(3-butenyl)pyrene

In the same manner as in Example 1, 40 g (0.19 mol) of pyrene, 9.1 g (0.10 mol) of 3-chloro-1-butene, 2.9 g (0.01 mol) of tetrabutylphosphonium chloride, and 50 ml of THF were added and reacted at 200° C. for 5 hours. 1-(2-(3-butenyl))pyrene 19.2 g (0.07 mol, yield 74.9%) was obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was CH ₃ -C at 1.4 ppm (d, 3H), C-CH -C at 3.6 ppm (m, 1H), and CH ₂ =C at 5.0 ppm (m, 2H). , C = CH -C at 6.3 ppm (m, 1H ), Pyrene peak was confirmed at 7.7-8.3 ppm (m, 9H).

Example 17: Synthesis of 1-cinnamylpyrene

In the same manner as in Example 1, 40 g (0.19 mol) of pyrene, 15.3 g (0.10 mol) of cinnamyl chloride, 2.9 g (0.01 mol) of tetrabutylphosphonium chloride, and 50 ml of THF were added and reacted at 200 ° C. for 5 hours to react 1-cinnamyl p. Rennes 24.5 g (0.08 mol, yield 77%) were obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was C- CH ₂ -C at 3.8 ppm (d, 2H), C- CH =C at 6.4-6.7 ppm (m, 2H), 7.2-7.3 ppm (m, 5H) ) at Ph , Pyrene peak was confirmed at 7.7-8.3 ppm (m, 9H).

Example 18: Synthesis of 1-(2-methylallyl)pyrene

In the same manner as in Example 1, 40 g (0.19 mol) of pyrene, 9.1 g (0.10 mol) of 3-chloro-2methyl-1-propene, 2.9 g (0.01 mol) of tetrabutylphosphonium chloride, and 50 ml of THF were added, and 200° C. After reaction for 5 hours, 20.3 g (0.08 mol, yield 79.2%) of 1-(2-methylallyl)pyrene was obtained. The obtained product 300MHz 1H magnetic resonance analysis, 1.8ppm (s, 3H) in _{CH 3 -C, 3.7ppm (s,} 2H) CH at _{C- CH 2 -C, 4.9-5.0ppm (d} , 2H) from ₂ = C, Pyrene peak was confirmed at 7.7-8.3 ppm (m, 9H).

Example 19: Synthesis of 1-(2-butenyl)pyrene

In the same manner as in Example 1, 40 g (0.19 mol) of pyrene, 9.1 g (0.10 mol) of 1-chloro-2-butene, 2.9 g (0.01 mol) of tetrabutylphosphonium chloride, and 50 ml of THF were added and reacted at 200° C. for 5 hours. 20.2 g (0.08 mol, yield 78.9%) of 1-(2-butenyl)pyrene was obtained. The obtained product 300MHz 1H magnetic resonance analysis, 1.8ppm (d, 3H) in _{CH 3 -C, 3.7ppm (d,} 2H) C- CH 2 -C, 5.4ppm (m, 1H) from the C- CH =C, Pyrene peak was confirmed at 6.1ppm (m, 1H) at C= CH- C, 7.7-8.3ppm (m, 9H).

Example 20: Synthesis of 2-(t-butyl)-10-allylanthracene

In the same manner as in Example 1, 40 g (0.17 mol) of 2-(t-butyl) anthracene, 6.5 g (0.09 mol) of allyl chloride, 2.7 g (0.009 mol) of tetrabutylphosphonium chloride, and 50 ml of THF were added, and 200° C. for 6 hours. By reaction, 17.5 g (0.06 mol, yield 71%) of 2-(t-butyl)-10-allylanthracene was obtained. The obtained product 300MHz 1H magnetic resonance analysis, 1.5ppm (s, 9H) in _{CH 3 -C, 3.8ppm (d,} 2H) CH at _{C- CH 2 -C, 4.8-5.0ppm (m} , 2H) from Anth peak was confirmed at ₂ = C, 6.0 ppm (m, 1H) at C- CH = C, 7.4-8.3 ppm (m, 8H).

Example 21: Synthesis of 2-(t-butyl)-10-(2-butenyl)anthracene

In the same manner as in Example 1, 40 g (0.17 mol) of 2-(t-butyl) anthracene, 8.1 g (0.09 mol) of 1-chloro-2-butene, 2.7 g (0.009 mol) of tetrabutylphosphonium chloride, and 50 ml of THF were prepared. and reacted at 200° C. for 6 hours to obtain 18.2 g (0.06 mol, yield 70.2%) of 2-(t-butyl)-10-(2-butenyl)anthracene. The obtained product 300MHz 1H magnetic resonance analysis, 1.5ppm (s, 9H) in _{CH 3 -C, 1.7ppm (d,} 1H) in _{CH 3 -C, 3.8ppm (d,} 2H) C- CH 2 in the - Anth peaks were identified at C, C- CH =C at 5.4 ppm (m, 1H), C = CH- C at 6.1 ppm (m, 1H), and 7.4-8.3 ppm (m, 8H).

Example 22: Synthesis of 10-allyl-9-methylanthracene

In the same manner as in Example 1, 40 g (0.20 mol) of 9-methylanthracene, 8.0 g (0.10 mol) of allyl chloride, 3.0 g (0.01 mol) of tetrabutylphosphonium chloride, and 50 ml of THF were added, and reacted at 200 ° C. for 6 hours. 18.7 g (0.08 mol, yield 80%) of allyl-9-methylanthracene was obtained. The obtained product 300MHz 1H magnetic resonance analysis, 2.7ppm (s, 3H) C- CH 3, 3.8ppm (d, 2H) CH at _{C- CH 2 -C, 4.8-5.0ppm (m} , 2H) from Anth peak was confirmed at ₂ = C, 6.0 ppm (m, 1H) at C = CH -C, 7.5-8.2 ppm (m, 8H).

Example 23: Synthesis of 10-cinnamyl-9-methylanthracene

In the same manner as in Example 1, 40 g (0.20 mol) of 9-methylanthracene, 15.3 g (0.10 mol) of cinnamyl chloride, 3.0 g (0.01 mol) of tetrabutylphosphonium chloride, and 50 ml of THF were added, and reacted at 200° C. for 6 hours. -Cinnamyl-9-methylanthracene 21.2g (0.07mol, yield 68.7%) was obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was C- CH ₃ at 2.7 ppm (s, 3H), C-CH ₂ -C at 3.8 ppm (d, 2H ), C= CH at 6.4 ppm (d, 1H) -Ph, C-CH = C at 6.7ppm (m, 1H), Ph at 7.2-7.3ppm (m, 5H ), Anth peak at 7.5-8.2ppm (m, 8H) was confirmed.

Example 24: Synthesis of 1-allyl-4-phenoxyder

In the same manner as in Example 1, 60 g (0.35 mol) of diphenyl ether, 13.5 g (0.18 mol) of allyl chloride, and 5.2 g (0.018 mol) of tetrabutylphosphonium chloride were added and reacted at 200° C. for 7 hours to 1-allyl-4 24.3 g (0.12 mol, yield 64.2%) of phenoxyider was obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was C- CH ₂ -C at 3.3 ppm (d, 2H), CH ₂ = C at 5.0 ppm (m, 2H ), C = CH at 5.9 ppm (m, 1H) A Ph peak was confirmed at -C, 7.1-7.4 ppm (m, 9H).

Example 25: Synthesis of 1-(2-butenyl)-4-phenoxyder

In the same manner as in Example 1, 60 g (0.35 mol) of diphenyl ether, 16.3 g (0.18 mol) of 1-chloro-2-butene, and 5.2 g (0.018 mol) of tetrabutylphosphonium chloride were added and reacted at 200° C. for 7 hours. 1-(2-butenyl)-4-phenoxyider 24.3g (0.11mol, yield 60.3%) was obtained. The obtained product 300MHz 1H magnetic resonance analysis, 1.7ppm (d, 3H) in _{CH 3 -C, 3.3ppm (d,} 2H) C- CH 2 -C, 5.4ppm (m, 1H) from the C- CH A Ph peak was observed at =C, 6.1 ppm (m, 1H) at C = CH -C, 7.1-7.4 ppm (m, 9H).

Example 26: Synthesis of 2-(3-butenyl)-4-phenoxyder

In the same manner as in Example 1, 60 g (0.35 mol) of diphenyl ether, 16.3 g (0.18 mol) of 1-chloro-2-butene, and 5.2 g (0.018 mol) of tetrabutylphosphonium chloride were added and reacted at 200° C. for 7 hours. 2-(2-(3-butenyl))-4-phenoxyider 28.7 g (0.13 mol, yield 71%) was obtained. As a result of 300 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was CH ₃ -C at 1.4 ppm (d, 3H), C-CH -C at 3.6 ppm (m, 1H), and CH ₂ =C at 5.0 ppm (m, 2H). , C = CH -C at 6.3 ppm (m, 1H ), Ph peak was confirmed at 7.1-7.4 ppm (m, 9H).

Although the present invention has been described in detail above with reference to the presented embodiment, those skilled in the art will be able to make various modifications and modified inventions without departing from the technical spirit of the present invention with reference to the presented embodiment. . The present invention is not limited by such variations and modifications, but only by the claims appended hereto.

Claims (7)

Chemical formula synthesized by dehydrohalogenation CC bonding reaction by reaction of an allyl halide compound represented by Formula 1 and an aromatic compound represented by Formula 2 using an organophosphine compound represented by Formula 4, Formula 5 or Formula 6 as a catalyst becomes an allyl aromatic compound represented by 3,
Formula 1

Formula 2

Formula 3:

,
_{R 1} =H, Me, CH ₂ Cl or CH ₂ Br in formulas 1, 2 and 3; R ₂ = H, Me, Ph, CH ₂ Cl or CH ₂ Br; R ₃ = H, Me, CH ₂ Cl or CH ₂ Br; R ₄ = H or Me; Ar ₁ = benzene, alkylbenzene, halobenzene, 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, 9-benzylanthracene, 9,10-dibenzylanthracene, 9-(diphenylmethyl)anthracene, phenanthrene, biphenyl, biphenylether, biphenylsulfide, pyrene, perylene, tetracene, pentacene or a ring 1-8 aromatic compounds; R ₅ = H, X, a phenyl group substituted with a phenyl group or an alkyl group having 1 to 8 carbon atoms; X=F, Cl, Br or I; R ₆ = H, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a benzyl group or a diphenylmethyl group; R ₇ = H or Me; R ₈ = H or Me; R ₉ is an allyl group of the allyl halide compound represented by Formula 1, n is 0.1, or 2;
Formula 4:
P(R") ₃ ,
Formula 5:
P(R") ₄ X',
Formula 6:
X'(R") ₃ PYP(R") ₃ X',
In Formulas 4, 5 and 6, R” is an alkyl group having 1 to 12 carbon atoms; an alkenyl group having 2 to 12 carbon atoms; or a phenyl group, each R″ is the same as or different from each other, X′=Cl, Br or I, and Y is an alkylene group having 1 to 12 carbon atoms; an alkylene group having 1 to 12 carbon atoms including an aromatic group; or an aromatic group,
The compound of formula 3 is 10-allyl-2-(tert-butyl)anthracene; 9-cinnamyl-10-methylanthracene; 10-(but-2-en-1-yl)-2-(tert-butyl)anthracene; 4-(but-2-en-1-yl)pyrene; 4-cinnamylpyrene; allylpentacene; diallylpentacene; allyltetracene; Or allyl aromatic compound, characterized in that diallyltetracene. Formula 3 by reaction of an allyl halide compound represented by Formula 1 and an aromatic compound represented by Formula 2 using an organophosphine compound represented by Formula 4, Formula 5 or Formula 6 as a catalyst, as a CC bonding reaction of hydrogen halide to produce the allylaromatic compound shown,
Formula 1:

Formula 2:

Formula 3:

,
_{R 1} =H, Me, CH ₂ Cl or CH ₂ Br in formulas 1, 2 and 3; R ₂ = H, Me, Ph, CH ₂ Cl or CH ₂ Br; R ₃ = H, Me, CH ₂ Cl or CH ₂ Br; R ₄ = H or Me; Ar ₁ = benzene, alkylbenzene, halobenzene, 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, 9-benzylanthracene, 9,10-dibenzylanthracene, 9-(diphenylmethyl)anthracene, phenanthrene, biphenylether, biphenylsulfide, pyrene, perylene, tetracene, pentacene or 1 to 8 rings phosphorus aromatic compounds; R ₅ = H, X, a phenyl group substituted with a phenyl group or an alkyl group having 1 to 8 carbon atoms; X=F, Cl, Br or I; R ₆ = H, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a benzyl group or a diphenylmethyl group; R ₇ = H or Me; R ₈ = H or Me; R ₉ is an allyl group of the allyl halide compound represented by Formula 1, n is 0, 1 or 2,
Formula 4:
P(R") ₃ ,
Formula 5:
P(R") ₄ X',
Formula 6:
X'(R") ₃ PYP(R") ₃ X',
In Formulas 4, 5 and 6, R” is an alkyl group having 1 to 12 carbon atoms; an alkenyl group having 2 to 12 carbon atoms; or a phenyl group, each R″ is the same as or different from each other, X′=Cl, Br or I, and Y is an alkylene group having 1 to 12 carbon atoms; an alkylene group having 1 to 12 carbon atoms including an aromatic group; Or a method for producing an allyl aromatic compound that becomes an aromatic group. delete delete delete The method for producing an allyl aromatic compound according to claim 2, wherein the reaction temperature is 100 to 250 °C. The method according to claim 2, wherein the reaction solvent is an aliphatic hydrocarbon, ether, dimethoxyethane (DME), or THF, or the reaction is performed without a solvent.