JP5889030B2 - Method for producing polycyclic aromatic compound - Google Patents

Description

  The present invention relates to a method for producing a polycyclic aromatic compound.

  Polycyclic aromatic compounds used in various industries are synthesized by many techniques such as, for example, Gomberg-Bachmann reaction, Guttermann reaction, Ullmann reaction, Wurtz-Fittig reaction. However, the above method has disadvantages such as low compatibility with functional groups, generation of many homo-coupled products as by-products, and high temperature for the reaction, which are disadvantageous in cost. Many.

  On the other hand, in the presence of a palladium catalyst, an aromatic compound having an anionic leaving group such as an aromatic metal, an organic metal compound such as aromatic magnesium, aromatic zinc or aromatic tin, or an organic boron compound. Various cross-coupling reactions have been developed (see Non-Patent Document 1, for example). Among them, the coupling reaction between an aromatic boron compound and an aromatic compound having an anionic leaving group (Suzuki-Miyaura cross-coupling method) (for example, see Non-Patent Document 2) has compatibility with a functional group. In addition, compared with tin, zinc compounds and the like, borons are easily used for waste liquids, and have been widely used in recent years.

  For example, in addition to academic fields such as the synthesis of natural products having complex molecular structures to the creation of conjugated oligomers and polymers having novel structures and functions, medicines and agrochemicals and intermediates thereof, liquid crystals, organic light-emitting diodes and organic Many application examples have been reported in industrial production fields such as electronic and optical materials such as conductive materials (see Non-Patent Document 3, for example).

  In recent years, a cross-coupling reaction in a system using only a small amount of a palladium catalyst has also been reported (see, for example, Patent Document 1). Furthermore, for the purpose of facilitating the removal of palladium, a catalyst in which palladium is fixed to carbon particles or the like (Patent Document 2) has also been reported.

  On the other hand, a polycyclic aromatic compound having a halogen atom is used as a gelling agent that gels various non-aqueous solvents (see, for example, Patent Documents 3 and 4), and as an electrolyte material for a lithium ion secondary battery ( For example, see Patent Document 5). The polycyclic aromatic compound having a halogen atom enables gelation of the system with a small addition of 10% or less with respect to the non-aqueous solvent. Therefore, for example, when used as an electrolyte solution material for a lithium ion secondary battery, it is possible to achieve both high battery characteristics and high safety (see Patent Document 5).

JP 2001-89402 A JP 2007-238447 A International Publication No. 2007/083843 International Publication No. 2009/078268 International Publication No. 2010/095572

Shinjiro, “Organic Synthesis Opened by Transition Metals”, p25-37, Chemical Doujin, 1997 Synthetic Communications, Volume 11, p513-519, 1981 Akira Suzuki, TCI Mail, No. 142, April 2009

  However, in the methods disclosed in Non-Patent Documents 1 and 2, it is necessary to use an expensive palladium catalyst in an amount of 1 mol% or more based on the organoboron compound or aromatic halide, and there is a problem that the raw material cost increases. Also, the process of removing the palladium remaining after the reaction is complicated, and it is difficult to remove the palladium to an allowable concentration or less, and problems such as reducing the yield of the product in the process of removing the palladium occur. There are also many. Furthermore, the method disclosed in Patent Document 1 is achieved only with a limited substrate, and is not necessarily suitable for the synthesis of a polycyclic aromatic compound having a halogen atom. Further, the method disclosed in Patent Document 2 cannot solve the problem of high raw material costs because the amount of palladium catalyst to be used is not reduced.

  Therefore, when synthesizing a polycyclic aromatic compound having a halogen atom as disclosed in Patent Documents 3 to 5, the raw material cost is low and the yield is high, and purification such as removal of palladium is easy. It is desired to establish a method for producing a certain polycyclic aromatic compound.

  The present invention has been made in view of the above circumstances. A polycyclic aromatic compound having a halogen atom can be produced at a low raw material cost and in a high yield, and can be easily purified. An object is to provide a manufacturing method.

（上記式中、Ｒ¹は下記一般式（３）で表される基を示し、Ｘは臭素原子を示し、Ｌはスルホニル基を示し、Ｒ²は炭素数１〜２０のアルコキシ基を示し、Ｚはホウ素原子を有する１価の基を示し、前記ホウ素原子はベンゼン環に直接結合している。）

（上記式中、ｎは２〜８の整数を示し、ｍは１〜２０の整数を示す。）
［２］Ｒ²は、炭素数が１〜２０のアルコキシ基である、［１］の多環式芳香族化合物の製造方法。
［３］前記式（３）において、ｍは、１、２、４又は６である、［１］又は［２］の多環式芳香族化合物の製造方法。
［４］前記式（３）において、ｍは、４又は６である、［１］又は［２］の多環式芳香族化合物の製造方法。

In order to solve the above problems, the present inventors have studied the synthesis of a polycyclic aromatic compound having a halogen atom, selected a compound having a specific structure, and selected suitable synthesis conditions for the compound. By using it, it came to solve said subject.
That is, the present invention is as follows.
[1] Of the first compound and the second compound, a first compound represented by the following general formula (1) and a second compound represented by the following general formula (2): A step of reacting in the presence of 0.0001 to 1 mol% of a metal-containing compound, a solvent, and a base with respect to the amount of the smaller compound on a molar basis, and the metal contained in the metal-containing compound is a palladium method of polycyclic aromatic compounds.

(In the formula, R ¹ is a group represented by the following general formula (3), X represents a bromine atom, L is shown a scan Ruhoniru group, R ² represents an alkoxy group having 1 to 20 carbon atoms Z represents a monovalent group having a boron atom, and the boron atom is directly bonded to the benzene ring.)

(In the above formula, n represents an integer of 2 to 8, and m represents an integer of 1 to 20.)
[2] The method for producing a polycyclic aromatic compound according to [1], wherein R ² is an alkoxy group having 1 to 20 carbon atoms.
[3] The method for producing a polycyclic aromatic compound of [1] or [2], wherein in the formula (3), m is 1, 2, 4 or 6 .
[4] The method for producing a polycyclic aromatic compound of [1] or [ 2 ], wherein m is 4 or 6 in the formula (3) .

  According to the present invention, it is possible to provide a method for producing a polycyclic aromatic compound, which can produce a polycyclic aromatic compound having a halogen atom at a low raw material cost and a high yield and can be easily purified. Become.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.

  The method for producing a polycyclic aromatic compound according to the present embodiment includes a specific aromatic boron compound and a specific aromatic compound having a halogen atom and an anionic leaving group, whichever is smaller on a molar basis. This is a method having a step of reacting in the presence of 0.0001 to 1 mol% of a metal-containing compound, a solvent and a base with respect to the amount of the compound (if the same amount, the amount of any compound, the same applies hereinafter). .

  The specific aromatic compound having a halogen atom and an anionic leaving group is a compound represented by the following general formula (1) (hereinafter, this compound is also referred to as “first compound”).

式（１）中、Ｘはアニオン性脱離基を示す。ここで、「アニオン性脱離基」とは、本実施形態の製造方法において、第１の化合物の反応時に第１の化合物から脱離するアニオン性の基を意味する。アニオン性脱離基としては、例えば、フッ素原子、塩素原子、臭素原子及びヨウ素原子などのハロゲン原子、トリフラート基（ＣＦ₃ＳＯ₃−）、パーフルオロアルキルスルホナート基（Ｃ_pＦ_2p+1ＳＯ₃−；ｐは１〜２０の整数を示す。）が挙げられる。これらの中で、アニオン性脱離基は、多環式芳香族化合物の合成の容易さの観点から、好ましくはハロゲン原子であり、更に好ましくは臭素原子、ヨウ素原子又は塩素原子であり、特に好ましくは臭素原子である。

In formula (1), X represents an anionic leaving group. Here, the “anionic leaving group” means an anionic group capable of leaving from the first compound during the reaction of the first compound in the production method of the present embodiment. Examples of the anionic leaving group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, triflate group (CF ₃ SO ₃ —), perfluoroalkyl sulfonate group (C _p F _{2p + 1} SO). _3- ; p represents an integer of 1 to 20.). Among these, the anionic leaving group is preferably a halogen atom, more preferably a bromine atom, an iodine atom or a chlorine atom, particularly preferably from the viewpoint of ease of synthesis of the polycyclic aromatic compound. Is a bromine atom.

  In the above formula (1), the position of X on the aromatic ring may be any of the ortho-position, meta-position and para-position with respect to the sulfur atom in L described later, but ease of synthesis of the polycyclic aromatic compound. From this point of view, it is preferably in the para position.

In the formula (1), L represents a sulfide group (—S—), a sulfinyl group (—S (═O) —) or a sulfonyl group (—SO ₂ —), and is a gelling agent for polycyclic aromatic compounds. From the viewpoint of utility as a sulfonyl group, a sulfonyl group is preferred.

In the formula (1), R ¹ represents an alkyl group, an alkoxy group or an aryl group, and these groups are obtained by substituting one or more hydrogen atoms with halogen atoms. Among these, from the viewpoint of solubility in a solvent, preferably, one or more hydrogen atoms is an alkyl group substituted with a halogen atom, and the number of carbon atoms in the group is preferably 1 to 28, more Preferably it is 3-12, More preferably, it is 6-8. From the viewpoint of usefulness as a gelling agent for polycyclic aromatic compounds, the halogen atom is preferably a fluorine atom, more preferably R ¹ is a group containing a perfluoroalkyl chain moiety, and more preferably R. ¹ is a group represented by the following general formula (3), more preferably -LR ¹ is a group represented by the following general formula (4).

  In the first compound, one or more hydrogen atoms are substituted with halogen atoms, so that a desired polycyclic aromatic compound as a final product is easily precipitated and is dissolved in an organic phase. Separation from compounds, ligands and raw materials is easier, and the purification process can be further simplified.

In said Formula (3) and (4), n is an integer of 0-8, Preferably it is an integer of 2-4, More preferably, it is 2. Moreover, m is an integer of 1-20, Preferably it is an integer of 1-8, More preferably, it is an integer of 1-6, More preferably, it is 1, 2, 4 or 6, Especially preferably, it is 4 Or 6. By employing a perfluoro group in which m is in the above range, raw materials can be obtained at low cost.
The first compound may be obtained as a commercial product or synthesized by a conventional method. The manufacturing method of this embodiment can use 1 type of 1st compound individually or in combination of 2 or more types.

The specific aromatic boron compound in the present embodiment is a compound represented by the following general formula (2) (hereinafter, this compound is also referred to as “second compound”).

ここで、式（５）中、Ｑ¹及びＱ²は互いに同じでも異なっていてもよい１価の基であり、その基としては、例えば、水酸基、アルキル基、アルコキシ基、ハロゲン原子で置換されていてもよいフェニル基、アルコキシ基で置換されていてもよいフェニル基、アルキル基で置換されていてもよいフェニル基及びハロゲン原子が挙げられる。上記アルキル基及びアルコキシ基の炭素数は、好ましくは１〜１０である。また、Ｑ¹及びＱ²は互いに結合してホウ素原子と共に環を形成してもよい。Ｑ¹及びＱ²が互いに結合した基としては、例えば、アルキル基で置換されていてもよいアルキレンジオキシ基、アルキル基で置換されていてもよいアルキレン基が好ましい。アルキル基で置換されていてもよいアルキレンジオキシ基（−Ｏ−Ｒ−Ｏ−；Ｒはアルキレン基）の主鎖の炭素数は好ましくは２〜６であり、より好ましくは２〜３であり、特に好ましくは２である。また、アルキル基で置換されていてもよいアルキレン基の主鎖の炭素数は好ましくは２〜１１であり、より好ましくは４〜７である。さらに、置換するアルキル基の炭素数は好ましくは１〜８であり、より好ましくは１〜３であり、特に好ましくは１である。また、主鎖の１つの炭素原子に対して置換したアルキル基の数は単数であっても複数であってもよい。Ｑ¹及びＱ²が互いに結合した基としては、例えば下記式（５Ａ）〜（５Ｄ）で表される基が挙げられる。 In formula (2), Z represents a monovalent group having a boron atom, and the boron atom is directly bonded to the benzene ring. Z is preferably a functional group represented by the following general formula (5).

Here, in the formula (5), Q ¹ and Q ² are monovalent groups which may be the same or different from each other. Examples of the group include a hydroxyl group, an alkyl group, an alkoxy group, and a halogen atom. A phenyl group which may be substituted, a phenyl group which may be substituted with an alkoxy group, a phenyl group which may be substituted with an alkyl group, and a halogen atom. Preferably the carbon number of the said alkyl group and alkoxy group is 1-10. Q ¹ and Q ² may be bonded to each other to form a ring together with the boron atom. The group in which Q ¹ and Q ² are bonded to each other is preferably, for example, an alkylenedioxy group which may be substituted with an alkyl group or an alkylene group which may be substituted with an alkyl group. The number of carbon atoms in the main chain of the alkylenedioxy group (—O—R—O—; R is an alkylene group) optionally substituted with an alkyl group is preferably 2 to 6, more preferably 2 to 3. Particularly preferably 2. Moreover, carbon number of the main chain of the alkylene group which may be substituted by the alkyl group becomes like this. Preferably it is 2-11, More preferably, it is 4-7. Furthermore, carbon number of the alkyl group to substitute becomes like this. Preferably it is 1-8, More preferably, it is 1-3, Especially preferably, it is 1. The number of alkyl groups substituted for one carbon atom of the main chain may be singular or plural. Examples of the group in which Q ¹ and Q ² are bonded to each other include groups represented by the following formulas (5A) to (5D).

ここで、式（６）及び（６Ａ）中、Ｒ³、Ｒ⁴及びＲ⁵は、それぞれ独立に、１価の有機基を示し、好ましくは、水素原子、水酸基及び−Ｐｈ−Ｒ²（Ｐｈはベンゼン環であり、Ｒ²は上記式（２）におけるものと同義である。）で表される基である。式（６）において、Ｒ³及びＲ⁴の両方が−Ｐｈ−Ｒ²で表される基であるか、Ｒ³及びＲ⁴のいずれか一方が−Ｐｈ−Ｒ²で表される基であり、他方が水酸基であるとより好ましく、Ｒ³及びＲ⁴の両方が−Ｐｈ−Ｒ²で表される基であると更に好ましい。Ｒ³及びＲ⁴の両方が−Ｐｈ−Ｒ²で表される基である場合、上記一般式（２）で表される化合物における３つのＲ²が全て同じ基であると特に好ましい。また、式（６Ａ）において、Ｒ³、Ｒ⁴及びＲ⁵が、それぞれ独立に、水酸基又は−Ｐｈ−Ｒ²で表される基であると好ましく、いずれか１つが水酸基であって、他の２つが−Ｐｈ−Ｒ²で表される基であるか、いずれも−Ｐｈ−Ｒ²で表される基であるとより好ましく、いずれも−Ｐｈ−Ｒ²で表される基であると更に好ましい。この場合も、Ｒ²が全て同じ基であると特に好ましい。 Alternatively, the functional group represented by the general formula (5) is preferably a monovalent group derived from a boronic acid analog, and more preferably a monovalent group represented by the following general formula (6). In this specification, a boronic acid analog is represented by boronic acid, a compound in which one or more hydrogen atoms of boronic acid are substituted, a boronic acid ester which may form a ring, and the following general formula (6A). And a compound containing a boroxan ring.

Here, in the formulas (6) and (6A), R ³ , R ⁴ and R ⁵ each independently represent a monovalent organic group, preferably a hydrogen atom, a hydroxyl group and —Ph—R ² (Ph Is a benzene ring, and R ² is a group represented by the above formula (2). In Formula (6), both R ³ and R ⁴ are groups represented by —Ph—R ² , or one of R ³ and R ⁴ is a group represented by —Ph—R ² . More preferably, the other is a hydroxyl group, and it is even more preferred that both R ³ and R ⁴ are groups represented by —Ph—R ² . When both R ³ and R ⁴ are groups represented by —Ph—R ² , it is particularly preferred that all three R ² in the compound represented by the general formula (2) are the same group. In formula (6A), R ³ , R ⁴ and R ⁵ are each independently preferably a hydroxyl group or a group represented by —Ph—R ² , and any one of them is a hydroxyl group, two of or a group represented by -Ph-R ^2, and more preferable to be a group both represented by -Ph-R ^2, further if is a group both represented by -Ph-R ² preferable. Also in this case, it is particularly preferred that all R ² are the same group.

In the formula (2), R ² is an alkyl group or an alkoxy group. Preferably carbon number of an alkyl group and an alkoxy group is 1-20. R ² is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 2 to 14 carbon atoms, still more preferably an alkoxy group having 3 to 12 carbon atoms, and particularly preferably a carbon number. 3 to 10 alkoxy groups. When the carbon number is within the above range, the affinity with the solvent becomes better, the purification becomes easier, and the target polycyclic aromatic compound can be easily obtained with higher purity.

In the above formula (2), the position of Z on the aromatic ring may be any of the ortho-position, meta-position and para-position with respect to R ² , but it is useful as a gelling agent for polycyclic aromatic compounds. From this point of view, it is preferably in the para position.
The second compound may be obtained as a commercial product or synthesized by a conventional method. The manufacturing method of this embodiment can use 1 type of a 2nd compound individually or in combination of 2 or more types.

  The mixing ratio of the first compound and the second compound in the reaction system is such that when the amount of the first compound is 100 mol%, the amount of the second compound is preferably 50 to 200 mol%, more preferably Is a blending ratio of 80 to 120 mol%, more preferably 90 to 110 mol%.

  The metal-containing compound used in the production method of the present embodiment is a compound containing one or more metals selected from the group consisting of palladium, nickel, and iron, and is used alone or in combination of two or more. Among these, preferred metal-containing compounds are palladium-containing compounds.

  The palladium-containing compound is not particularly limited as long as it has palladium, and examples thereof include zero-valent or divalent palladium metals and palladium salts containing complexes. The palladium-containing compound may be supported on a carrier such as activated carbon, carbon particles, aluminum oxide, hydroxyapatite, and a porous body. Examples of the palladium-containing compound preferably used include palladium (0) / carbon, palladium (II) acetate, palladium (II) chloride, bis (triphenylphosphine) palladium (II) chloride, tetrakis (triphenylphosphine) palladium ( 0), palladium ketonate, palladium acetylacetonate, nitrile palladium halide, palladium halide, allyl palladium halide, palladium biscarboxylate. Among these, palladium (II) acetate and palladium (II) chloride are more preferable, and palladium (II) acetate is more preferably used. A palladium-containing compound is used individually by 1 type or in combination of 2 or more types.

  A commercially available product may be obtained for the palladium-containing compound, or it may be produced by a conventional method. In the case of production, for example, palladium (II) acetate can be produced by reaction of palladium (II) chloride and sodium acetate.

  The nickel-containing compound is not particularly limited as long as it is a compound having nickel in its structure, and examples thereof include a nickel salt containing a zero-valent or divalent nickel metal and a complex. The nickel-containing compound may be supported on a carrier such as activated carbon, carbon particles, aluminum oxide, hydroxyapatite, and a porous body. Examples of the nickel salt include a salt of nickel and an inorganic acid or an organic acid. More specifically, examples of the inorganic acid salt of nickel include nickel halides such as nickel chloride (II), nickel bromide (II) and nickel iodide (II), nickel nitrate (II), nickel sulfate ( II), nickel nickel sulfate (II), and nickel (II) hypophosphite. Examples of the organic acid salt of nickel include nickel acetate (II), nickel formate (II), nickel (II) stearate, cyclohexane butyrate nickel (II), nickel citrate (II), and nickel naphthenate (II ). Examples of the divalent nickel complex include amine complexes of divalent nickel such as hexaamminenickel chloride (II) and hexaamminenickel iodide (II), and nickel acetylacetonate which is an acetylacetone complex of divalent nickel. Can be mentioned. Examples of the divalent nickel π complex include bis (η3-allyl) nickel (II), bis (η-cyclopentadienyl) nickel (II), and allylnickel chloride dimer. As the zero-valent nickel complex, the zero-valent nickel complex may be used as it is, or a nickel salt may be reacted in the presence of a reducing agent to produce zero-valent nickel in the system to obtain a zero-valent nickel complex. In the latter case, examples of the nickel salt include nickel chloride and nickel acetate, and examples of the reducing agent include zinc, sodium hydride, hydrazine and derivatives thereof, and lithium aluminum hydride. Furthermore, ammonium iodide, lithium iodide, potassium iodide, or the like may be used as an additive as necessary. Examples of the zerovalent nickel complex include bis (1,5-cyclooctadiene) nickel (0), (ethylene) bis (triphenylphosphine) nickel (0), tetrakis (triphenylphosphine) nickel and nickelcarbonyl (0 ). The nickel-containing compound may be a nickel hydroxide, and examples of the nickel hydroxide include nickel hydroxide (II). Examples of the nickel-containing compound include [1,2-bis (diphenylphosphino) ethane] dichloronickel (II), [1,3-bis (diphenylphosphino) propane] dichloronickel (II), and tetrakis (tri Phenylphosphine) nickel is also mentioned.

  An iron-containing compound will not be specifically limited if it is a compound which has iron in the structure, For example, the iron salt containing an iron metal and a complex is mentioned. Further, the iron-containing compound may be supported on a carrier such as activated carbon, carbon particles, aluminum oxide, hydroxyapatite, and a porous body. Examples of the iron-containing compound used include iron halides such as iron chloride.

  The metal-containing compound is 0.0001 to 1 mol%, preferably 0.0001 to 0.1 mol%, based on the amount (100 mol%) of the first compound and the second compound, which is smaller on a molar basis. More preferably, 0.001 to 0.1 mol% is used. When the amount of the metal-containing compound used is in this range, the target polycyclic aromatic compound can be obtained in a higher yield, and the amount of metal contained in the product can be reduced. Purification becomes easy.

  In this embodiment, examples of the base include alkali metal or alkaline earth metal hydroxides, carbonates, hydrogen carbonates, phosphates, carboxylates, alkoxides, and tertiary amines that are organic bases ( For example, triethylamine) can be used. From the viewpoint of facilitating the synthesis and purification of the polycyclic aromatic compound, the base is preferably an alkali metal or alkaline earth metal hydroxide, carbonate, bicarbonate, phosphate and carboxylate. More preferred are alkali metal or alkaline earth metal carbonates, hydrogen carbonates, phosphates and carboxylates, and still more preferred are alkali metal or alkaline earth metal carbonates and hydrogen carbonates. . Examples of alkali metal or alkaline earth metal carbonates and bicarbonates include lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, barium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate and cesium bicarbonate. Are preferable, and lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate are more preferable.

  The base may be a compound added independently in the reaction system, or may be added in a state of being included in the raw material, catalyst, ligand and the like. The base is preferably used in an amount of 10 to 5000 mol%, more preferably 50 to 2000 mol%, based on the amount of the compound (100 mol%) of the first compound and the second compound, which is smaller on a molar basis. Moreover, a base is used individually by 1 type or in combination of 2 or more types.

  In this embodiment, each raw material, product, and by-product may exist in any state of solid and liquid. The reaction system may be a single phase or may be separated into two or more phases. For example, the reaction system may be separated into a liquid and a solid. When separated into two or more phases, at least one phase contains a liquid, and if the liquid and the solid are separated, there is no need to use a solvent or the like for dissolving the solid, thus improving productivity. To do. In addition, when the raw material is liquid or a solvent is used, and all phases are liquid, the control of the reaction progress is facilitated.

  The solvent contained in the reaction system is preferably an organic solvent, and may be a water-insoluble organic solvent or a water-soluble organic solvent. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, chlorobenzene Halogenated aromatic hydrocarbon solvents such as dichloromethane, halogenated aliphatic hydrocarbon solvents such as dichloromethane and chloroform, perfluoro-2-butyltetrahydrofuran, perfluorooctane, perfluorotributylamine, perfluorohexane, and perfluorobenzene. Fluorine-containing solvents such as solvents having a fluoro group, ester solvents such as alkyl acetates such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate and isopropyl acetate, N, N-dimethylacetamide, N-methylpyrrolidinone and dimethylformamide Amide solvent Ether solvents such as diethyl ether, diglyme, dimethoxyethane, 1,4-dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, diethoxymethane, diisopropyl ether, anisole and methyl t-butyl ether, acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone Ketone solvents, alkane solvents such as hexane and cyclohexane, methanol, ethanol, 1,2-propanediol, isopropyl alcohol, alcohol solvents such as t-butyl alcohol, n-butyl alcohol and t-amyl alcohol, nitrile solvents such as acetonitrile, 1,3-dimethyl-2-imidazolidinone, pyridine, nitromethane, dimethyl sulfoxide, N-methylpyrrolidone, acetic acid and trie Triethanolamine and the like.

  When a water-insoluble organic solvent is included as a solvent used in the reaction system, examples of the water-insoluble organic solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene, and halogenated aromatic hydrocarbons such as chlorobenzene. Solvents, halogenated aliphatic hydrocarbon solvents such as dichloromethane and chloroform, solvents containing perfluoro groups such as perfluoro-2-butyltetrahydrofuran, perfluorooctane, perfluorotributylamine, perfluorohexane, and perfluorobenzene. Fluorine solvents, ester solvents such as alkyl acetates such as butyl acetate, isobutyl acetate and isopropyl acetate, diethyl ether, 2-methyltetrahydrofuran, diethoxymethane, diisopropyl ether, anisole and methyl t-butyl ether Ether solvents, methyl isobutyl ketone, ketone solvents such as methyl ethyl ketone and cyclohexanone, alkane solvents such as hexane and cyclohexane, 1,3-dimethyl-2-imidazolidinone, as well as triethylamine. The water-insoluble organic solvent is more preferably a solvent having a solubility in water at 20 ° C. of 20% by mass or less, and more preferably 20 ° C. from the viewpoint of separation of the aqueous phase and the organic phase during purification. Is a solvent having a solubility in water of 5% by mass or less. The water-insoluble organic solvent is still more preferably an aromatic hydrocarbon solvent, a halogenated aromatic hydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent, a fluorine-containing solvent, and an ether solvent. The water-insoluble organic solvent is particularly preferably toluene, xylene, chlorobenzene and methylene chloride from the viewpoint of availability of the solvent. Since a water-insoluble organic solvent is easily separated from water, it is effective in that water-soluble by-products and impurities can be easily washed. Further, even when the water-insoluble organic solvent used in the reaction is reused by distillation or the like, it is also effective in that it can be easily purified because it contains little water.

  When a water-soluble organic solvent is included as a solvent used in the reaction system, examples of the water-soluble organic solvent include amide solvents such as N, N-dimethylacetamide, N-methylpyrrolidinone and dimethylformamide, diglyme, dimethoxyethane, Ether solvents such as 1,4-dioxane and tetrahydrofuran, ketone solvents such as acetone and methyl ethyl ketone, methanol, ethanol, 1,2-propanediol, isopropyl alcohol, t-butyl alcohol, n-butyl alcohol and t-amyl alcohol Examples include alcohol solvents, nitrile solvents such as acetonitrile, 1,3-dimethyl-2-imidazolidinone, pyridine, nitromethane, dimethyl sulfoxide, N-methylpyrrolidone, and acetic acid.

  The water-soluble organic solvent is preferably a solvent having a solubility in water at 20 ° C. of more than 20% by mass. From the viewpoint of solubility during purification, the solubility in water at 20 ° C. is more preferably 50% by mass or more. It is a solvent, more preferably a solvent that is arbitrarily miscible with water at 20 ° C. More specifically, methanol, ethanol, 1,2-propanediol, isopropyl alcohol, t-butyl alcohol, n-butyl alcohol, t-amyl alcohol, nitromethane, acetonitrile, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, The solvent is preferably at least one solvent selected from the group consisting of acetone, acetic acid, pyridine, 1,2-dimethoxyethane, tetrahydrofuran and 1,4-dioxane. Since the water-soluble organic solvent is easily mixed with water, the target product can be precipitated or the precipitation can be promoted in the purification step. In addition, the water-soluble organic solvent can dissolve and remove a by-product salt by adding water.

  An organic solvent is used individually by 1 type or in combination of 2 or more types.

  Moreover, a polycyclic aromatic compound can be synthesized even in the presence of water together with an organic solvent in the reaction system. When water is allowed to coexist as a solvent, the amount of water is preferably 100 parts by mass or less with respect to 100 parts by mass of the organic solvent. When water and an organic solvent are used, it is preferable that they are separated into an aqueous phase and an organic solvent phase from the viewpoint of simplification of purification.

  The amount of the solvent in the reaction system is 500 to 5000% by mass with respect to the mass (100% by mass) of the larger one of the first compound and the second compound from the viewpoint of solubility during the reaction. It is preferable and it is more preferable in it being 500-3000 mass%.

In this embodiment, a ligand may be added in the reaction system. Examples of the ligand include triphenylphosphine (PPh ₃ ), methyldiphenylphosphine (Ph ₂ PCH ₃ ), trifurylphosphine (P (2-furyl) ₃ ), tri (o-tolyl) phosphine (P (o -Tol) ₃ ), tri (cyclohexyl) phosphine (PCy ₃ ), dicyclohexylphenylphosphine (PhPCy ₂ ), tri (t-butyl) phosphine (PtBu ₃ ), 2,2′-bis (diphenylphosphino) -1, 1'-binaphthyl (BINAP), 2,2'-bis [(diphenylphosphino) diphenyl] ether (DPEphos) (see Tetrahedron Letters 39, 5327 (1998)), Diphenylphosphinoferrocene (DPPF), 1,1′-bis Di-t-butylphosphino) ferrocene (DtBPF), N, N-dimethyl-1- [2- (diphenylphosphino) ferrocenyl] ethylamine, 1- [2- (diphenylphosphino) ferrocenyl] ethyl methyl ether, 2 -Dicyclohexylphosphino-2'-dimethylamino-1,1'-biphenyl (see Journal of the American Chemical Society, Volume 120, page 9722 (1998)) Spiro-type phosphonium salts (see Angewante Chemie International Edition, vol. 37, p. 481 (1998)) -Based ligands, phosphine mimic ligands such as imidazol-2-ylidenecarbenes (Angewandte Chemie International Edition in English, Volume 36, 2163 (1997) Year))). In addition, the ligand reacts with the metal contained in the metal-containing compound and a substituent on the ligand to form a palladacycle (Angevante Chemie International Edition in English) when the metal is palladium. (Angewandte Chemie international Edition in England) Vol. 34, p. 1844 (1995)) may be formed.

  Furthermore, examples of the ligand include nitrogen-containing ligands such as 2,2'-bipyridyl, 1,10-phenanthroline, methylenebisoxazoline and N, N'-tetramethylethylenediamine.

  When the first compound has a chlorine atom as an anionic leaving group of X, from the viewpoint of improving the yield, trifurylphosphine, tri (o-tolyl) phosphine (palladacycle is formed as a ligand. ), Tri (cyclohexyl) phosphine, tri (t-butyl) phosphine, dicyclohexylphenylphosphine, 1,1′-bis (di-t-butylphosphino) ferrocene, 2-dicyclohexylphosphino-2′-. It is preferable to use phosphine mimic ligands such as dimethylamino-1,1′-biphenyl and imidazol-2-ylidenecarbenes.

  The amount of the ligand in the reaction system is preferably 0.0001 to 4 mol%, more preferably 0, with respect to the amount of the smaller compound (100 mol%) of the first compound and the second compound. 0.0001 to 0.4 mol%, more preferably 0.001 to 0.4 mol%. A ligand is used individually by 1 type or in combination of 2 or more types.

  The reaction temperature for reacting the first compound and the second compound is preferably 0 to 200 ° C., more preferably 20 to 150 ° C., and still more preferably, from the viewpoint of the boiling point of the solvent and the solubility of the raw material. 40-130 ° C. The atmosphere around the reaction system may be an air atmosphere, but from the viewpoint of reducing by-products, it is preferably an atmosphere substituted with an inert gas. From the viewpoint of cost, the atmosphere around the reaction system is more preferably an atmosphere substituted with nitrogen gas. The reaction between the first compound and the second compound can proceed under normal pressure, or can proceed under reduced pressure or high pressure.

  The degree of progress of the reaction can be confirmed by analysis such as thin layer chromatography, NMR, gas chromatography, liquid chromatography and the like.

In the present embodiment, a known purification method can be used as the purification after the synthesis of the polycyclic aromatic compound. For example, among known purification methods consisting of distillation, recrystallization, filtration, solvent washing, solvent distillation under reduced pressure, and drying, one can be used alone, or two or more can be used in combination.
As the purification operation, for example, after the reaction in the above step, the salt and the water-soluble raw material contained in the reaction mixture can be dissolved in water to remove the salt and the water-soluble raw material. Further, when water is not used and the organic phase is a liquid, the salt can be separated by filtration. Further, the target product can be obtained by mixing the organic phase and a solvent in which the target product is insoluble to precipitate the target product and further filtering.

In the production method of the present embodiment, additives such as a reaction catalyst, a cocatalyst, a reaction accelerator, an emulsifier and an antifoaming agent may be used as necessary. In addition, in order to suppress side reactions and unintended reactions, compounds that have an effect as a negative catalyst for those reactions may be used as necessary.
Examples of the reaction catalyst include a phase transfer catalyst. The phase transfer catalyst effectively performs the reaction by the effect of solubilizing the reactive species or collecting it at the interface in the reaction between the substrates or reagents that are not mixed with each other, such as liquid-liquid and solid-liquid. It is a catalyst used for this purpose. Examples of the phase transfer catalyst include quaternary ammonium salts, phosphonium salts, amines, crown ethers, cryptands, and chain polyethylene glycol derivatives.
An emulsifier is an additive that efficiently performs a reaction by dispersing one substrate or reagent in another substrate or reagent between substrates or reagents that do not mix with each other. Examples of the emulsifier include fatty acid esters, higher alcohols, sulfonium salts, quaternary ammonium salts, phosphonium salts, amines, and glycols.

These additives are used singly or in combination of two or more.
Further, the same additive may be used in all of the above steps, or different additives may be used in each step.

  Polycyclic aromatic compounds obtained by the production method of the present embodiment are used in non-aqueous electrolyte secondary battery materials, organic EL materials, liquid crystal materials, nonlinear optical materials, photographic additives, sensitizing dyes, pharmaceuticals, etc. They can be used or can be useful as synthetic intermediates for these materials.

  As mentioned above, although the form for implementing this invention was demonstrated, this invention is not limited to the said this embodiment. The present invention can be variously modified without departing from the gist thereof.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

(Production Example of First Compound)
[Production Example 1]
15.5 g (82 mmol) of 4-bromobenzenethiol, 40.9 g (86.3 mmol) of 2- (perfluorohexyl) ethyl iodide, 100 mL of 1,2-dimethoxyethane, and 17 g (123.4 mmol) of potassium carbonate were reacted. The solution was put into a container and stirred at 50 ° C. for 3 hours under atmospheric pressure. Then, white powder was obtained through filtration and solvent removal. To the obtained powder, 165 mL of acetic acid and 40 g of 35% aqueous hydrogen peroxide were added, and the mixture was further stirred at 70 ° C. for 3 hours under atmospheric pressure. Then, it filtered and stirred and washed in hexane. Subsequently, the compound (1A) which has the following structure was obtained in the state of white powder through filtration and solvent removal. The yield was 42 g, and the yield was 90%. The yield results are shown in Table 1.

[Production Examples 2-3]
Compound (1B) and Compound (1C) having the above structure were obtained in the same manner as in Production Example 1 except that 82 mmol of the raw material shown in Table 1 was used instead of 82 mmol of 2- (perfluorohexyl) ethyl iodide. It was. The yield results are shown in Table 1.

(Production Example of Second Compound)
[Production Example 4]
4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenol 15 g (68.2 mmol), 1-bromohexane 14.1 g (85.2 mmol), potassium carbonate 14 0.1 g (102.3 mmol) and 230 mL of 3-pentanone were charged into a reaction vessel, and the mixture was stirred while refluxing at 120 ° C. for 14 hours under atmospheric pressure. Thereafter, the compound (2A) having the following structure was obtained in a brown solid state through filtration and solvent removal. The yield was 20.9 g, and the yield was 100%. The yield results are shown in Table 2.

[Production Examples 5 to 7]
The compound (2B), the compound (2C) and the compound (2D) having the structure described above were prepared in the same manner as in Production Example 4 except that 85.2 mmol of the raw material shown in Table 2 was used instead of 85.2 mmol of 1-bromohexane. Respectively. The yield results are shown in Table 2.

[Example 1]
Compound (1A) 27.7 g (48.8 mmol), Compound (2A) 15 g (49.3 mmol), palladium acetate 2.2 mg (0.0098 mmol), triphenylphosphine 9.0 mg (0.034 mmol), sodium carbonate 52 g (488 mmol), 450 mL of 1,4-dioxane and 250 mL of distilled water were mixed in a reaction vessel, and the atmosphere around the reaction system was replaced with nitrogen gas, and then the solution was stirred at 95 ° C. for 40 minutes under atmospheric pressure. Subsequently, the deposit obtained by allowing to cool was washed twice with water, and further washed twice with hexane. Thereafter, the solvent was removed to obtain a compound (a) having the following structure in a pale pink solid state. The yield was 29.4 g, and the yield was 91%. The results are shown in Table 3. Further, the structure of the obtained compound (a) was confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.
¹ H-NMR (CDCl ₃ ) 0.92 (3H, m), 1.48 (6H, m), 1.81 (2H, m), 2.65 (2H, m), 3.33 (2H, m), 4.02 (2H, m), 7.01 (2H, d, J = 8.0 Hz), 7.56 (2H, d, J = 8.0 Hz), 7.76 (2H, d, J = 8.0 Hz), 7.95 (2H, d, J = 8.0 Hz) ppm

[Examples 2 to 11]
The materials shown in Table 3 were used instead of the compound (1A) and the compound (2A) as raw materials, the amount of palladium acetate as a palladium-containing compound was changed to the amount shown in Table 3, and the amount of triphenylphosphine was changed to Table 3. Compound (a), Compound (b), Compound (c), Compound (d), Compound (e), Compound (f) and Compound (g) were obtained in the same manner as in Example 1 except that the amount shown was changed. I got each. The results are shown in Table 3. The amount of the palladium-containing compound and the amount of triphenylphosphine in Table 3 are the amount of compound (1A) or compound (1B) which is the smaller of the first compound and the second compound on a molar basis (100 mol%). Is the value for. The structures of the compounds (a), (c) and (d) obtained in Examples 2, 4, 5, 6 and 11 were confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.

(Example 2)
¹ H-NMR (CDCl ₃ ) 0.93 (3H, m), 1.48 (6H, m), 1.80 (2H, m), 2.63 (2H, m), 3.35 (2H, m), 4.02 (2H, m), 7.01 (2H, d, J = 8.0 Hz), 7.56 (2H, d, J = 8.0 Hz), 7.77 (2H, d, J = 8.0 Hz), 7.95 (2H, d, J = 8.0 Hz) ppm
(Example 3)
¹ H-NMR (CDCl ₃ ) 0.88 (3H, m), 1.48 (10H, m), 1.80 (2H, m), 2.65 (2H, m), 3.35 (2H, m), 4.02 (2H, m), 7.01 (2H, d, J = 8.0 Hz), 7.56 (2H, d, J = 8.0 Hz), 7.77 (2H, d, J = 8.0 Hz), 7.95 (2H, d, J = 8.0 Hz) ppm
Example 4
¹ H-NMR (CDCl ₃ ) 1.07 (3H, m), 1.84 (2H, m), 2.63 (2H, m), 3.34 (2H, m), 3.98 (2H, m), 7.02 (2H, d, J = 8.0 Hz), 7.57 (2H, d, J = 8.0 Hz), 7.77 (2H, d, J = 8.0 Hz), 7.95 (2H, d, J = 8.0 Hz) ppm
(Example 5)
¹ H-NMR (CDCl ₃ ) 1.00 (3H, m), 1.52 (2H, m), 1.81 (2H, m), 2.65 (2H, m), 3.36 (2H, m), 4.03 (2H, m), 7.01 (2H, d, J = 8.0 Hz), 7.56 (2H, d, J = 8.0 Hz), 7.77 (2H, d, J = 8.0 Hz), 7.95 (2H, d, J = 8.0 Hz) ppm
(Example 6)
¹ H-NMR (CDCl ₃ ) 1.00 (3H, m), 1.51 (2H, m), 1.81 (2H, m), 2.63 (2H, m), 3.35 (2H, m), 4.02 (2H, m), 7.01 (2H, d, J = 8.0 Hz), 7.56 (2H, d, J = 8.0 Hz), 7.77 (2H, d, J = 8.0 Hz), 7.95 (2H, d, J = 8.0 Hz) ppm
(Example 7)
¹ H-NMR (CDCl ₃ ) 1.00 (3H, m), 1.51 (2H, m), 1.81 (2H, m), 2.64 (2H, m), 3.36 (2H, m), 4.03 (2H, m), 7.01 (2H, d, J = 8.0 Hz), 7.56 (2H, d, J = 8.0 Hz), 7.77 (2H, d, J = 8.0 Hz), 7.95 (2H, d, J = 8.0 Hz) ppm
(Example 8)
¹ H-NMR (CDCl ₃ ) 0.93 (3H, m), 1.48 (6H, m), 1.81 (2H, m), 2.65 (2H, m), 3.35 (2H, m), 4.02 (2H, m), 7.01 (2H, d, J = 8.0 Hz), 7.56 (2H, d, J = 8.0 Hz), 7.76 (2H, d, J = 8.0 Hz), 7.94 (2H, d, J = 8.0 Hz) ppm
Example 9
¹ H-NMR (CDCl ₃ ) 0.88 (3H, m), 1.48 (10H, m), 1.80 (2H, m), 2.65 (2H, m), 3.35 (2H, m), 4.01 (2H, m), 7.01 (2H, d, J = 8.0 Hz), 7.56 (2H, d, J = 8.0 Hz), 7.76 (2H, d, J = 8.0 Hz), 7.94 (2H, d, J = 8.0 Hz) ppm
(Example 10)
¹ H-NMR (CDCl ₃ ) 0.88 (3H, m), 1.47 (14H, m), 1.80 (2H, m), 2.64 (2H, m), 3.35 (2H, m), 4.02 (2H, m), 7.01 (2H, d, J = 8.0 Hz), 7.56 (2H, d, J = 8.0 Hz), 7.77 (2H, d, J = 8.0 Hz), 7.95 (2H, d, J = 8.0 Hz) ppm
(Example 11)
¹ H-NMR (CDCl ₃ ) 1.00 (3H, m), 1.51 (2H, m), 1.81 (2H, m), 2.65 (2H, m), 3.35 (2H, m), 4.03 (2H, m), 7.01 (2H, d, J = 8.0 Hz), 7.56 (2H, d, J = 8.0 Hz), 7.76 (2H, d, J = 8.0 Hz), 7.95 (2H, d, J = 8.0 Hz) ppm
(Example 12)
¹ H-NMR (CDCl ₃ ) 0.93 (3H, m), 1.48 (6H, m), 1.81 (2H, m), 2.63 (2H, m), 3.34 (2H, m), 4.01 (2H, m), 7.01 (2H, d, J = 8.0 Hz), 7.56 (2H, d, J = 8.0 Hz), 7.77 (2H, d, J = 8.0 Hz), 7.95 (2H, d, J = 8.0 Hz) ppm

[Example 12]
Compound (a) was obtained in the same manner as in Example 1 except that palladium acetate as a palladium-containing compound was changed to palladium chloride. The results are shown in Table 3.

[Example 13]
Compound (1A) 300 g (529 mmol), p-propoxyphenylboronic acid 100 g (555 mmol), palladium acetate 11.9 mg (0.0529 mmol), triphenylphosphine 48.6 mg (0.185 mmol), potassium carbonate 291 g (2116 mmol), 4000 mL of acetonitrile and 2 L of distilled water were put into the reaction vessel. Next, the atmosphere around the reaction system was replaced with nitrogen gas, and then the liquid was stirred at 90 ° C. for 2 hours under atmospheric pressure. Subsequently, the deposit obtained by allowing to cool was washed twice with water, and further washed twice with hexane. Thereafter, the solvent was removed to obtain a compound (c) in a white solid state. The yield was 296 g, and the yield was 90%. The results are shown in Table 3. Further, the structure of the obtained compound (c) was confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.
¹ H-NMR (CDCl ₃ ) 1.07 (3H, m), 1.84 (2H, m), 2.63 (2H, m), 3.34 (2H, m), 3.98 (2H, m), 7.02 (2H, d, J = 8.0 Hz), 7.57 (2H, d, J = 8.0 Hz), 7.77 (2H, d, J = 8.0 Hz), 7.95 (2H, d, J = 8.0 Hz) ppm

[Example 14]
The same procedure was carried out as in Example 13, except that 100 g (555 mmol) of p-propoxyphenylboronic acid and 4000 mL of acetonitrile were changed to 123 g (555 mmol) of p-hexoxyphenylboronic acid and 4000 mL of diethylene glycol dimethyl ether, respectively. (C) was obtained. The yield was 316 g, and the yield was 90%. The results are shown in Table 3. Further, the structure of the obtained compound (c) was confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.
¹ H-NMR (CDCl ₃ ) 0.93 (3H, m), 1.48 (6H, m), 1.80 (2H, m), 2.63 (2H, m), 3.35 (2H, m), 4.02 (2H, m), 7.01 (2H, d, J = 8.0 Hz), 7.56 (2H, d, J = 8.0 Hz), 7.77 (2H, d, J = 8.0 Hz), 7.95 (2H, d, J = 8.0 Hz) ppm

[Example 15]
Compound (1A) 300 g (529 mmol), p-butoxyphenylboronic acid 108 g (555 mmol), palladium acetate 23.8 mg (0.106 mmol), triphenylphosphine 97.1 mg (0.370 mmol), sodium bicarbonate 355 g (4230 mmol) Then, 1.71 g (5.29 mmol) of tetrabutylammonium bromide, 1600 mL of toluene, and 2 L of distilled water were charged into the reaction vessel. Next, the atmosphere around the reaction system was replaced with nitrogen gas, and then the liquid was stirred at 90 ° C. for 2 hours under atmospheric pressure. Thereafter, the aqueous phase was removed from the separated toluene phase and aqueous phase. Next, 2 L of distilled water was put into the reaction vessel, stirred at 90 ° C. for 5 minutes, and then the operation of removing the aqueous phase from the separated toluene phase and aqueous phase was repeated three times. Next, 2 L of hexane at 0 ° C. was stirred, and the toluene phase heated to 90 ° C. was dropped into the hexane to obtain a precipitate. After filtration and solvent removal, compound (d) was obtained as a white solid. The yield was 320 g, and the yield was 95%. The results are shown in Table 3. The structure of the obtained compound (d) was confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.
¹ H-NMR (CDCl ₃ ) 1.00 (3H, m), 1.51 (2H, m), 1.81 (2H, m), 2.64 (2H, m), 3.36 (2H, m), 4.03 (2H, m), 7.01 (2H, d, J = 8.0 Hz), 7.56 (2H, d, J = 8.0 Hz), 7.77 (2H, d, J = 8.0 Hz), 7.95 (2H, d, J = 8.0 Hz) ppm

[Comparative Example 1]
Compound (1A) 18.65 g (32.89 mmol), Compound (2A) 10 g (32.89 mmol), Palladium acetate 1.48 g (6.58 mmol), Triphenylphosphine 5.9 mg (22.5 mmol), Sodium carbonate 31 .8 g (300 mmol), 1,4-dioxane 300 mL, and distilled water 150 mL were mixed in a reaction vessel and stirred at 95 ° C. for 90 minutes under atmospheric pressure. Next, distilled water was added thereto, and the precipitate was filtered. Furthermore, after washing with water, it dried at 90 degreeC. Next, the mixture was filtered while using ethyl acetate, and the resulting precipitate was washed four times with hexane. Furthermore, it wash | cleaned alternately with ethyl acetate and hexane, and the compound (a) was obtained in the state of yellow solid through solvent removal. The yield was 6.64 g, and the yield was 30%. The results are shown in Table 4.

[Comparative Examples 2 to 5]
The materials shown in Table 4 were used instead of the compound (1A) and the compound (2A) as raw materials, the amount of palladium acetate as a palladium-containing compound was changed to the amount shown in Table 4, and the amount of triphenylphosphine was changed to Table 4. A compound (a), a compound (f), a compound (e) and a compound (h) were obtained in the same manner as in Comparative Example 1 except that the amount was changed. However, in Comparative Example 4, no reaction product compound was obtained. The results are shown in Table 4. The amount of the palladium-containing compound and the amount of triphenylphosphine in Table 4 are those of the compound (1A), the compound (1B) or the compound (1C) which is the smaller of the first compound and the second compound on a molar basis. It is a value with respect to the amount (100 mol%).

  The present invention is a polycyclic aromatic useful as a non-aqueous electrolyte secondary battery material, organic EL material, liquid crystal material, nonlinear optical material, photographic additive, sensitizing dye, pharmaceutical, etc., or a synthetic intermediate thereof. Use as a compound production method is expected.

Claims (4)

The first compound represented by the following general formula (1) and the second compound represented by the following general formula (2) are on a molar basis among the first compound and the second compound. It has a metal-containing compound of 0.0001～1Mol% relative to the amount of lesser compound, a solvent, a base, a step of reacting in the presence of a metal contained in the metal-containing compound, palladium A process for producing a polycyclic aromatic compound.

(In the formula, R ¹ is a group represented by the following general formula (3), X represents a bromine atom, L is shown a scan Ruhoniru group, R ² represents an alkoxy group having 1 to 20 carbon atoms Z represents a monovalent group having a boron atom, and the boron atom is directly bonded to the benzene ring.)

(In the above formula, n represents an integer of 2 to 8, and m represents an integer of 1 to 20.) The method for producing a polycyclic aromatic compound according to claim 1, wherein R ² is an alkoxy group having 1 to 20 carbon atoms. The method for producing a polycyclic aromatic compound according to claim 1, wherein m is 1, 2, 4 or 6 in the formula (3) . In the said Formula (3), m is 4 or 6, The manufacturing method of the polycyclic aromatic compound of Claim 1 or 2 .