JP5837843B2 - Method for producing polycyclic aromatic compound having halogen atom - Google Patents

Description

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

  Polycyclic aromatic compounds are used in various industrial fields, for example, non-aqueous electrolyte secondary battery materials, organic EL materials, liquid crystal materials, nonlinear optical materials, photographic additives, sensitizing dyes, pharmaceuticals, etc. Are widely used as synthetic intermediates thereof.

  Among them, a polycyclic aromatic compound having a halogen atom is used as a gelling agent that gels various nonaqueous solvents (see, for example, Patent Documents 1 and 2), and as an electrolyte material for a lithium ion secondary battery. (See, for example, Patent Document 3). When a polycyclic aromatic compound having a halogen atom is used as a gelling agent, the addition of a small amount of 10% or less with respect to the nonaqueous solvent enables the system to gel. Therefore, the function by gelation can be imparted without substantially deteriorating the characteristics inherent to the non-aqueous solvent used. For example, when such a compound is used as an electrolyte material for a lithium ion secondary battery, it is possible to achieve both high battery characteristics and high safety (see, for example, Patent Document 3).

  As a method for producing a polycyclic aromatic compound, a coupling reaction between an aromatic boron compound and an aromatic compound having an anionic leaving group (Suzuki-Miyaura cross-coupling method) (see, for example, Non-Patent Document 1) In recent years, it has been widely used because of its high compatibility with functional groups.

  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 In industrial production fields such as electronic and optical materials such as conductive materials, many application examples of the reaction have been reported (for example, see Non-Patent Document 2).

  Further, in the industrial production field, purification and removal of waste liquid are important issues, and means for easily separating a by-product from a target product is required. In the coupling reaction between an aromatic boron compound and an aromatic compound having an anionic leaving group, in order to facilitate the removal of by-product salts, cross-linking in a two-phase system using a water-insoluble solvent A coupling reaction has been reported (see, for example, Patent Document 4).

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

Synthetic Communications, Volume 11, p513-519, 1981 Akira Suzuki, TCI Mail, No. 142, April 2009

However, Patent Document 3 does not disclose a method suitable for industrial production, and particularly does not disclose an industrial production method of a polycyclic aromatic compound having a halogen atom.
Further, even the method disclosed in Patent Document 4 does not show a method suitable for industrial production, and in particular, it is difficult to separate and purify the target product.

  Therefore, when synthesizing a polycyclic aromatic compound having a halogen atom as disclosed in Patent Documents 1 to 3, the yield is high and purification such as removal of by-products is easy. It is desired to establish a method for producing a ring aromatic compound.

  The present invention has been made in view of the above circumstances, and a polycyclic aromatic compound having a halogen atom can be produced in a high yield with a method suitable for industrial production, and can be easily purified. It aims at providing the manufacturing method of an aromatic compound.

（式（１）、（２）、（３）、（４）、（５）及び（６）中、Ｒ¹は、１つ以上の水素原子がハロゲン原子で置換されたアルキル基、１つ以上の水素原子がハロゲン原子で置換されたアルコキシ基、又は、１つ以上の水素原子がハロゲン原子で置換されたアリール基を示し、Ｒ²はアルキル基又はアルコキシ基を示し、Ｌはスルフィニル基又はスルホニル基を示し、Ｘ¹及びＸ²は、それぞれ独立にアニオン性の１価の脱離基を示し、Ｙ¹は脱離可能な元素又は１価の基を示し、Ｚは式（６）に示されるベンゼン環に直接結合したホウ素原子を有する１価の基を示す。）
［２］１つ以上の前記工程において用いられる溶媒が、水を含む、［１］に記載の多環式芳香族化合物の製造方法。
［３］１つ以上の前記工程において用いられる溶媒が、非水溶性有機溶媒を含む、［１］又は［２］に記載の多環式芳香族化合物の製造方法。
［４］前記第１の工程及び前記第２の工程において用いられる溶媒が、互いに同一の非水溶性有機溶媒を含む、［１］〜［３］のいずれかに記載の多環式芳香族化合物の製造方法。
［５］前記第２の工程及び前記第３の工程において用いられる溶媒が、互いに同一の非水溶性有機溶媒を含む、［１］〜［４］のいずれかに記載の多環式芳香族化合物の製造方法。
［６］全ての前記工程において用いられる溶媒が、互いに同一の非水溶性有機溶媒を含む、［１］〜［５］のいずれか１項に記載の多環式芳香族化合物の製造方法。
［７］前記非水溶性有機溶媒の２０℃における水への溶解度が２０質量％以下である、［３］〜［６］のいずれかに記載の多環式芳香族化合物の製造方法。
［８］前記非水溶性有機溶媒の２０℃における水への溶解度が５質量％以下である、［３］〜［６］のいずれかに記載の多環式芳香族化合物の製造方法。
［９］前記非水溶性有機溶媒が、芳香族炭化水素溶媒、ハロゲン化芳香族炭化水素溶媒、ハロゲン化脂肪族炭化水素溶媒、含フッ素溶媒及びエーテル溶媒からなる群より選ばれる少なくとも１種の溶媒である、［３］〜［８］のいずれかに記載の多環式芳香族化合物の製造方法。
［１０］前記非水溶性有機溶媒が、トルエン、キシレン、クロロベンゼン及び塩化メチレンからなる群より選ばれる少なくとも１種の溶媒である、［９］に記載の多環式芳香族化合物の製造方法。
［１１］前記相間移動触媒が、第四級アンモニウム塩、ホスホニウム塩、アミン類、クラウンエーテル、クリプタンド及び鎖状ポリエチレングリコール誘導体からなる群より選ばれる１種以上の触媒である、［１］〜［１０］のいずれかに記載の多環式芳香族化合物の製造方法。
［１２］前記相間移動触媒が、第四級アンモニウム塩である、［１１］に記載の多環式芳香族化合物の製造方法。
［１３］前記相間移動触媒が、テトラブチルアンモニウムブロミドである、［１１］に記載の多環式芳香族化合物の製造方法。
［１４］前記第２の工程において、酸化剤として過酸化水素水及びモノ過硫酸水素カリウムのうちの少なくとも一方を用いる、［１］〜［１３］のいずれかに記載の多環式芳香族化合物の製造方法。
［１５］前記Ｒ²は、炭素数が１〜２０のアルコキシ基である、［１］〜［１４］のいずれかに記載の多環式芳香族化合物の製造方法。
［１６］前記Ｒ¹における前記ハロゲン原子がフッ素原子である、［１］〜［１５］のいずれかに記載の多環式芳香族化合物の製造方法。
［１７］前記Ｒ¹は、パーフルオロアルキル鎖部位を含む、［１］〜［１６］のいずれかに記載の多環式芳香族化合物の製造方法。
［１８］前記Ｒ¹は、下記一般式（７）で表される基である、［１］〜［１７］のいずれかに記載の多環式芳香族化合物の製造方法。

（式（７）中、ｎは０〜８の整数を示し、ｍは１〜２０の整数を示す。）
［１９］前記Ｌはスルホニル基である、［１］〜［１８］のいずれかに記載の多環式芳香族化合物の製造方法。
［２０］前記Ｘ¹は、臭素原子、ヨウ素原子又は塩素原子である、［１］〜［１９］のいずれかに記載の多環式芳香族化合物の製造方法。
［２１］前記Ｘ²は、臭素原子、ヨウ素原子又は塩素原子である、［１］〜［２０］のいずれかに記載の多環式芳香族化合物の製造方法。 In order to solve the above-mentioned 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 used a phase transfer catalyst for the compound. The above-described problems have been solved by using the synthesis conditions used.
That is, the present invention is as follows.
[1] A method for producing a polycyclic aromatic compound represented by the following general formula (1):
In a two-phase system using a plurality of solvents, a compound (2) represented by the following general formula (2) is reacted with a compound (3) represented by the following general formula (3) to obtain the following general formula: A first step of producing the compound (4) represented by (4);
A second step of producing a compound (5) represented by the following general formula (5) by oxidizing the third compound in a two-phase system using a plurality of solvents ;
In a two-phase system using a plurality of solvents, the third step of reacting the compound (5) with the compound (6) represented by the following general formula (6),
A production method using a phase transfer catalyst in all the steps.

(Equation (1), (2), (3), (4), (5) and (6), R ¹ is an alkyl group in which one or more hydrogen atoms are substituted with halogen atoms, one or more Represents an alkoxy group in which a hydrogen atom is substituted with a halogen atom , or an aryl group in which one or more hydrogen atoms are substituted with a halogen atom , R ² represents an alkyl group or an alkoxy group, L represents a sulfinyl group or a sulfonyl group X ¹ and X ² each independently represents an anionic monovalent leaving group, Y ¹ represents a detachable element or a monovalent group, and Z represents the formula (6). A monovalent group having a boron atom directly bonded to the benzene ring.)
[2] The method for producing a polycyclic aromatic compound according to [1], wherein the solvent used in one or more of the steps includes water.
[3] The method for producing a polycyclic aromatic compound according to [1] or [2], wherein the solvent used in one or more of the steps includes a water-insoluble organic solvent.
[4] The polycyclic aromatic compound according to any one of [1] to [3], wherein the solvents used in the first step and the second step include the same water-insoluble organic solvent. Manufacturing method.
[5] The polycyclic aromatic compound according to any one of [1] to [4], wherein the solvents used in the second step and the third step include the same water-insoluble organic solvent. Manufacturing method.
[6] The method for producing a polycyclic aromatic compound according to any one of [1] to [5], wherein the solvents used in all the steps include the same water-insoluble organic solvent.
[7] The method for producing a polycyclic aromatic compound according to any one of [3] to [6], wherein the water-insoluble organic solvent has a solubility in water at 20 ° C. of 20% by mass or less.
[8] The process for producing a polycyclic aromatic compound according to any one of [3] to [6], wherein the water-insoluble organic solvent has a solubility in water at 20 ° C. of 5% by mass or less.
[9] The water-insoluble organic solvent is at least one solvent selected from the group consisting of aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, halogenated aliphatic hydrocarbon solvents, fluorine-containing solvents, and ether solvents. The method for producing a polycyclic aromatic compound according to any one of [3] to [8].
[10] The method for producing a polycyclic aromatic compound according to [9], wherein the water-insoluble organic solvent is at least one solvent selected from the group consisting of toluene, xylene, chlorobenzene and methylene chloride.
[11] The phase transfer catalyst is one or more catalysts selected from the group consisting of quaternary ammonium salts, phosphonium salts, amines, crown ethers, cryptands, and chain polyethylene glycol derivatives. [10] The method for producing a polycyclic aromatic compound according to any one of [10].
[12] The method for producing a polycyclic aromatic compound according to [11], wherein the phase transfer catalyst is a quaternary ammonium salt.
[13] The method for producing a polycyclic aromatic compound according to [11], wherein the phase transfer catalyst is tetrabutylammonium bromide.
[14] The polycyclic aromatic compound according to any one of [1] to [13], wherein in the second step, at least one of hydrogen peroxide and potassium monohydrogen persulfate is used as an oxidizing agent. Manufacturing method.
[15] The method for producing a polycyclic aromatic compound according to any one of [1] to [14], wherein R ² is an alkoxy group having 1 to 20 carbon atoms.
[16] The method for producing a polycyclic aromatic compound according to any one of [1] to [15], wherein the halogen atom in R ¹ is a fluorine atom.
[17] The method for producing a polycyclic aromatic compound according to any one of [1] to [16], wherein R ¹ includes a perfluoroalkyl chain moiety.
[18] The method for producing a polycyclic aromatic compound according to any one of [1] to [17], wherein R ¹ is a group represented by the following general formula (7).

(In formula (7), n represents an integer of 0 to 8, and m represents an integer of 1 to 20.)
[19] The method for producing a polycyclic aromatic compound according to any one of [1] to [18], wherein L is a sulfonyl group.
[20] The method for producing a polycyclic aromatic compound according to any one of [1] to [19], wherein X ¹ is a bromine atom, an iodine atom or a chlorine atom.
[21] The method for producing a polycyclic aromatic compound according to any one of [1] to [20], wherein X ² is a bromine atom, an iodine atom or a chlorine atom.

  According to the present invention, there is provided a method for producing a polycyclic aromatic compound, which can produce a polycyclic aromatic compound having a halogen atom in a high yield with a method suitable for industrial production and can be easily purified. It becomes possible.

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

The production method of the polycyclic aromatic compound represented by the following general formula (1) of the present embodiment (hereinafter also referred to as “compound (1)”) is a compound represented by the following general formula (2). (Hereinafter also referred to as “compound (2)”) and a compound represented by the following general formula (3) (hereinafter also referred to as “compound (3)”) are reacted to give the following general formula: The first step for producing the compound represented by (4) (hereinafter also referred to as “compound (4)”) and the compound (4) are oxidized to be represented by the following general formula (5). A second step for producing a compound (hereinafter also referred to as “compound (5)”), a compound (5), and a compound represented by the following general formula (6) (hereinafter referred to as “compound (6)”) And a third step of reacting with each other using a phase transfer catalyst in all of the first, second and third steps. It is a manufacturing method.

Here, in the formulas (1), (2), (3), (4), (5) and (6), R ¹ is an alkyl group or alkoxy group in which one or more hydrogen atoms are substituted with halogen atoms. Or an aryl group, R ² represents an alkyl group or an alkoxy group, L represents a sulfinyl group or a sulfonyl group, X ¹ and X ² each independently represents an anionic monovalent leaving group, Y ¹ represents a detachable element or a monovalent group, and Z represents a monovalent group having a boron atom directly bonded to the benzene ring represented by the formula (6).

  In the present embodiment, the reaction solvent used in the first, second and third steps may be water, an organic solvent, or a combination of the two.

In the formula (1), L represents a sulfinyl group (—S (═O) —) or a sulfonyl group (—SO ₂ —), and from the viewpoint of utility as a gelling agent of a polycyclic aromatic compound, 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 utility in various uses as a polycyclic aromatic compound, 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 (7), particularly preferably -LR ¹ is a group represented by the following general formula (8).

  In Formula (7) and (8), 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.

  In Formula (1), when one or more hydrogen atoms are substituted with halogen atoms, the desired polycyclic aromatic compound, which is the final product, is likely to precipitate, and the metal-containing metal dissolved in the organic phase Separation from compounds, ligands and raw materials is easier, and the purification process can be further simplified.

In the formula (1), R ² represents 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 formula (1), the combination of R ¹ , R ² and L may be any combination of the groups shown above for each, and —LR ¹ and R ² may be any of the benzene rings. It may be bound to a site.

In formula (2), X ¹ represents an anionic monovalent leaving group (hereinafter also simply referred to as “anionic leaving group”). Here, the “anionic monovalent leaving group” is a monovalent chemical species (atom and group) that is eliminated from the raw material compound as an anion when two or more compounds react. In the production method of this embodiment, X ¹ means an anionic monovalent chemical species that is eliminated from the compound (4) during the reaction of the compound (5) and the compound (6). 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 formula (2), the position of X ¹ on the aromatic ring may be any of the ortho, meta, and para positions with respect to the sulfur atom in L described above, but ease of synthesis of the polycyclic aromatic compound. From this point of view, it is preferably in the para position.

In formula (2), Y ¹ represents a detachable element or a monovalent group. Here, the “leaving element or monovalent group” refers to an element or monovalent that is eliminated from the compound (2) during the reaction between the compound (2) and the compound (3) in the production method of the present embodiment. Means the group of Examples of such chemical species include a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, and tetraethylammonium. From the viewpoint of availability, a hydrogen atom, a sodium atom or a potassium atom is preferable, and a hydrogen atom is more preferable.

In the formula (2), the combination of Y ¹ and X ¹ may be any combination of the groups shown above for each, and —S—Y ¹ is bonded to any part of the benzene ring. There may be.

In the formula (3), X ² represents an anionic leaving group. In the production method of this embodiment, X ² means an anionic monovalent chemical species that is eliminated from the compound (3) during the reaction of the compound (2) and the compound (3). 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 formula (3), the combination of R ¹ and X ² may be any combination of the groups shown above for each.

  In formula (6), Z represents a monovalent group having a boron atom directly bonded to the benzene ring represented by formula (6). Z is preferably a functional group represented by the following general formula (9).

ここで、式（９）中、Ｑ¹及びＱ²は互いに同じでも異なっていてもよい１価の基である。その１価の基としては、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。１価の基は、好ましくは水酸基及びアルコキシ基であり、より好ましくは水酸基である。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、及び、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（１０Ａ）、（１０Ｂ）、（１０Ｃ）及び（１０Ｄ）で表される基が挙げられる。

Here, in formula (9), Q ¹ and Q ² are monovalent groups which may be the same or different from each other. Examples of the monovalent group include a hydroxyl group, an alkyl group, an alkoxy group, a phenyl group which may be substituted with a halogen atom, a phenyl group which may be substituted with an alkoxy group, and an alkyl group. Good phenyl groups and halogen atoms are mentioned. Preferably the carbon number of the said alkyl group and alkoxy group is 1-10. The monovalent group is preferably a hydroxyl group and an alkoxy group, and more preferably a hydroxyl group. Q ¹ and Q ² may be bonded to each other to form a ring together with the boron atom. As the group in which Q ¹ and Q ² are bonded to each other, for example, an alkylenedioxy group that may be substituted with an alkyl group and an alkylene group that may be substituted with an alkyl group are preferable. 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 Q1 and Q2 are bonded to each other include groups represented by the following formulas (10A), (10B), (10C), and (10D).

Alternatively, the functional group represented by the general formula (9) is preferably a monovalent group derived from a boronic acid analog, and more preferably a monovalent group represented by the following general formula (11). 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 (11A). And a compound containing a boroxan ring.

Here, in the formulas (11) and (11A), 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 (6). In formula (11), 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 preferable that all three R ² in the compound (6) are the same group. In Formula (11A), 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 (6), the position of Z on the aromatic ring may be any of the ortho, meta, and para positions relative to R ² , but it is useful as a gelling agent for polycyclic aromatic compounds. From the viewpoint, it is preferably in the para position.

In the formula (6), the combination of R ² and Z may be any combination of the groups shown above for each, and R ² may be bonded to any part of the benzene ring. .

  Compound (6) may be obtained as a commercial product, or may be synthesized by a conventional method. The manufacturing method of this embodiment can use 1 type of a compound (6) individually or in combination of 2 or more types.

  In the production method of the present invention, a phase transfer catalyst is used in all of the first, second and third steps. The phase transfer catalyst is used to effectively carry out the reaction by 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. The catalyst used. Here, examples of the liquid include a solution in which a substrate or a reagent is dissolved in a solvent, or a substrate or a reagent that is liquid without a solvent during the reaction. Examples of the phase transfer catalyst include quaternary ammonium salts, phosphonium salts, amines, crown ethers, cryptands, and chain polyethylene glycol derivatives. More specifically, as a quaternary ammonium salt, for example, tetrabutylammonium salt such as tetrabutylammonium bromide, tetrabutylammonium iodide, tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrahexylammonium salt , Tetraoctylammonium salt, tetradecylammonium salt, hexadecyltriethylammonium salt, dodecyltrimethylammonium salt, trioctylmethylammonium salt, octyltriethylammonium salt, benzyltrimethylammonium salt, benzyltriethylammonium salt, benzyltributylammonium salt, benzyldimethyl Octadecyl ammonium salt, phenyltrimethyl ammonium salt, STARKS 'cat For example, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, tetrabutylphosphonium salt, tetramethylphosphonium salt, tetraethylphosphonium salt, tetrapropylphosphonium salt, tetrahexylphosphonium salt, tetradecylphosphonium salt, tetra Octylphosphonium salt, triethyloctadecylphosphonium salt, trioctylethylphosphonium salt, hexadecyltriethylphosphonium salt, tetraphenylphosphonium salt, methyltriphenylphosphonium salt, amines, crown ethers such as 18-crown-6, dibenzo-18- Crown-6, dicyclohexyl-18-crown-6, cryptand, for example, [2.2.2] cryptan Examples of the chain and chain polyethylene glycol derivatives include PEG-200, PEG-400, and PEG-6000. From the viewpoint of availability, a quaternary ammonium salt is preferable, and tetrabutylammonium bromide is more preferable.

  A phase transfer catalyst is used individually by 1 type or in combination of 2 or more types.

  As the phase transfer catalyst, the same phase transfer catalyst may be used in all the above steps, or different phase transfer catalysts may be used in each step. When the same phase transfer catalyst is used in all the steps, purification in each step is simplified. When phase-transfer catalysts different from each other are used in each step, it is possible to select an optimum phase-transfer catalyst for each step, and it is possible to reduce the reaction time and the amount of addition of the phase-transfer catalyst.

  In addition to the phase transfer catalyst, a co-catalyst that enhances the catalytic activity and other catalysts may be included. For example, a quaternary ammonium salt as a phase transfer catalyst may be combined with a metal catalyst (see 11 SEPTEMBER, 1998, VOL281, SCIENCE, p. 1646).

  The amount of the phase transfer catalyst added may be any amount as long as the desired reaction in each step proceeds. From the viewpoint of ease of purification and reaction rate, the addition amount is preferably 0.001 to 40 mol% with respect to the amount of the smaller compound on a molar basis in the reaction raw materials in each step. More preferably, it is 0.01-20 mol%, More preferably, it is 0.1-10 mol%.

  In this embodiment, each raw material, product, and by-product may exist in any state of solid or liquid. The reaction system is separated into two or more phases. For example, the reaction system may be separated into a liquid and a solid, or may be separated into a liquid and a liquid. When at least one phase contains a liquid and the liquid and the solid are separated, productivity is improved by not using a solvent or the like for dissolving the solid. In addition, when the raw material is liquid or a solvent or the like is used and all phases are liquid, the reaction can be easily controlled.

  In one or more of the first, second, and third steps, the solvent contained in the reaction system preferably contains water. Use of water dissolves by-produced salts and facilitates separation and purification from the reaction target product. When water and an organic solvent are used, it is preferable to select the organic solvent so that they are separated into an aqueous phase and an organic solvent phase from the viewpoint of simplification of purification. The amount of water is preferably 1000 parts by mass or less with respect to 100 parts by mass of the compound (1).

  In one or more of the first, second, and third steps, it is preferable that the solvent contained in the reaction system includes an organic solvent. Examples of the organic solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene, halogenated aromatic hydrocarbon solvents such as chlorobenzene, halogenated aliphatic hydrocarbon solvents such as dichloromethane and chloroform, and perfluoro-2-butyl. Fluorine-containing solvents such as tetrahydrofuran, perfluorooctane, perfluorotributylamine, perfluorohexane and perfluorobenzene-containing solvents such as perfluoro groups, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, and alkyl acetates such as isopropyl acetate Ester solvents such as N, N-dimethylacetamide and amide solvents such as N-methylpyrrolidinone, diethyl ether, diglyme, dimethoxyethane, 1,4-dioxane, tetrahydrofuran, 2-methyltetrahydride Ether solvents such as furan, diethoxymethane, diisopropyl ether, anisole and methyl t-butyl ether, ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, alkane solvents such as hexane and cyclohexane, 1,3-dimethyl-2- Examples include imidazolidinone, acetonitrile, pyridine, and triethylamine. From the viewpoint of simplification of the purification process and recovery of the solvent, the organic solvent preferably contains a water-insoluble organic solvent. The water-insoluble organic solvent is an organic solvent that undergoes phase separation from water at the reaction temperature in each of the above steps or in the purification step.

  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, esters such as 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.

  The organic solvent contained in the reaction system is used alone or in combination of two or more.

  When an organic solvent is used in a plurality of the above steps, different organic solvents may be used in each step, and an optimal organic solvent can be selected for each step. Among the above steps, two or more successive steps, that is, a first step and a second step, a second step and a third step, as well as a first step, a second step and a third step. It is preferable that the solvent used in the step includes the same water-insoluble organic solvent. This eliminates the need for removal of the water-insoluble organic solvent contained in the reaction product in the previous step, simplifies purification, and also when the water-insoluble organic solvent is recovered and reused by distillation or the like. It can be purified by a simple process. It is further preferable that the solvents used in all the steps, that is, the first step, the second step, and the third step contain the same water-insoluble organic solvent.

  In the production method of the present embodiment, in the first step, the compound (4) is produced by reacting the compound (2) with the compound (3).

  The compounding ratio of the compound (2) and the compound (3) in the first step is preferably such that the amount of the compound (3) is 50 to 200 mol%, when the amount of the compound (2) is 100 mol%. Is a blending ratio of 80 to 120 mol%, more preferably 90 to 110 mol%. When the blending ratio is within this range, there are few remaining raw materials after completion of the reaction, and purification becomes easy.

  In the first step, a base can be used as a catalyst in addition to the phase transfer catalyst. Examples of such catalysts include alkali metal or alkaline earth metal hydroxides, carbonates, hydrogen carbonates, phosphates, carboxylates and alkoxides, as well as tertiary amines that are organic bases (for example, Triethylamine). 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. Lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate and potassium bicarbonate are preferred.

  In the first step, the reaction temperature when reacting the compound (2) and the compound (3) is preferably 0 to 200 ° C., more preferably 20 to 20 ° C. from the viewpoint of the boiling point of the solvent and the solubility of the raw material. It is 150 degreeC, More preferably, it is 40-130 degreeC. The atmosphere around the reaction system may be an air atmosphere, but from the viewpoint of reducing by-products, an atmosphere substituted with an inert gas is preferable. From the viewpoint of cost, the atmosphere around the reaction system is more preferably an atmosphere substituted with nitrogen gas. The reaction can proceed under normal pressure, or it can proceed under reduced pressure or high pressure.

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

  In the second step, compound (4) is oxidized to produce compound (5).

  In the second step, examples of the oxidizing agent for oxidizing the compound (4) include hydrogen peroxide solution, potassium monohydrogen persulfate, organic peroxide, metallized oxide, sodium hypochlorite and air. Can be used. Among these, hydrogen peroxide is preferable from the viewpoint of easy availability and purification, and potassium hydrogen persulfate is preferable from the viewpoint of easy handling. An oxidizing agent is used individually by 1 type or in combination of 2 or more types. The compounding ratio of the oxidizing agent other than air and the compound (4) is preferably 100 to 2000 mol%, more preferably 100 to 800 mol, when the amount of the compound (4) is 100 mol%. %.

  In the second step, the reaction temperature for reacting compound (4) 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 the reaction may be performed in an atmosphere substituted with an inert gas. From the viewpoint of cost, the atmosphere around the reaction system is preferably an atmosphere substituted with nitrogen gas. The reaction can proceed under normal pressure, or can proceed under reduced pressure or high pressure.

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

  In the third step, compound (5) is reacted with compound (6).

  The compounding ratio of the compound (5) and the compound (6) in the third step is such that the amount of the compound (6) is preferably 50 to 200 mol% when the amount of the compound (5) is 100 mol%. The blending ratio is preferably 80 to 120 mol%, more preferably 90 to 110 mol%.

In the third step, a metal-containing compound, a ligand and a base can be used as a catalyst in addition to the phase transfer catalyst.
Examples of the metal-containing compound include a palladium-containing compound, a nickel-containing compound, and an iron-containing compound.

  The palladium-containing compound is not particularly limited as long as it is a compound having palladium in its structure, and examples thereof include a palladium salt containing a zero-valent or divalent palladium metal and a complex. 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 ketonates, palladium acetylacetonates, nitrile palladium halides, palladium halides, allyl palladium halides and palladium biscarboxylates. 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 preferably 0.0001 to 1 mol%, more preferably 0.0001 to the amount (100 mol%) of the compound (5) and the compound (6) which is smaller on a molar basis. 0.1 mol%, more preferably 0.001 to 0.1 mol% is used. When the usage-amount of a metal-containing compound exists in the said range, the metal amount contained in a product can be decreased and subsequent refinement | purification becomes easy.

  In the third (3), a base can also be used. 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. . 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. Lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate and potassium bicarbonate are more preferred.

  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 (100 mol%) of the compound (5) and compound (6), 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 the third step, 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. When compound (5) has a chlorine atom as an anionic leaving group for X ¹ , trifurylphosphine, tri (o-tolyl) phosphine (forms a palladacycle) as a ligand from the viewpoint of improving the yield. ), 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.

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

  The amount of the ligand in the reaction system is preferably 0.0001 to 4 mol%, more preferably 0, relative to the amount of the smaller compound (100 mol%) of compound (5) and compound (6). 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 compound (5) with compound (6) 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 can proceed under normal pressure, and can proceed under reduced pressure or high pressure.

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

  In the production method of the present embodiment, the product obtained through any of the first, second, and third steps may be purified. That is, purification may be performed after any step. For example, purification may be performed every time the above steps are completed, purification may be performed both after the second step and after the third step, and purification is performed only after the third step. May be.

  In the production method of the present embodiment, by using a phase transfer catalyst in all of the first, second and third steps, the target product and the salt by-product are present in different phases, and therefore, by a simple operation. The target product can be purified.

  As purification, a known purification method can be used. 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 are removed by dissolving the salt and the water-soluble raw material contained in the reaction mixture in water and separating the aqueous phase. it can. 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 precipitating the target product by mixing the organic phase and a solvent in which the target product is insoluble, and filtering.

  For example, when the solvent used in the next step includes the solvent used in the previous step, the solvent may be distilled off, the organic phase is used as it is, or concentration or addition of a solvent is performed. Thus, the following process may be performed.

  According to this embodiment, it is not necessary to employ a method suitable for industrial production of the compound (1), more specifically, disadvantageous conditions for industrial production such as low temperature, for example, general synthesis equipment such as Further, it can be produced by equipment that can be replaced with an inert atmosphere or that can be used in a temperature range corresponding to a general heating method using steam or the like. For example, it is not necessary to employ a complicated operation such as an extraction operation of a product with an extraction solvent, and the target product can be easily separated and purified as described above. That is, with the production method of the present embodiment, compound (1) can be produced in high yield and can be easily purified. Moreover, according to the manufacturing method of this embodiment, it becomes possible to suppress raw material cost more.

  The polycyclic aromatic compound (compound (1)) obtained by the production method of the present embodiment comprises a non-aqueous electrolyte secondary battery material, an organic EL material, a liquid crystal material, a nonlinear optical material, a photographic additive, an additive It can be used in dyes and pharmaceuticals, or can be useful as a synthetic intermediate 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 1]
(First step)
4-bromobenzenethiol 100 g (529 mmol), 2- (perfluorohexyl) ethyl iodide 260 g (556 mmol), tetrabutylammonium bromide 34 g (106 mmol), toluene 2 L, sodium hydroxide 32 g (794 mmol), and distilled water 400 mL The reaction vessel was charged and stirred at 50 ° C. for 2 hours under atmospheric pressure. Thereafter, the aqueous phase was removed from the separated toluene phase and aqueous phase. Next, 400 mL of distilled water was put into the reaction vessel, stirred at 50 ° C. for 5 minutes, and then the operation of removing the aqueous phase from the separated toluene phase and aqueous phase was repeated twice.

(Second step)
To the obtained toluene phase, 850 mL of distilled water, 813 g (1323 mmol) of potassium hydrogen persulfate (trade name “Oxone”, manufactured by DuPont, the same shall apply hereinafter), and 8.53 g (26.5 mmol) of tetrabutylammonium bromide Was further stirred at 70 ° C. for 14 hours under atmospheric pressure. Thereafter, the aqueous phase was removed from the separated toluene phase and aqueous phase. Next, 850 mL of distilled water was put into the reaction vessel, stirred at 70 ° C. for 5 minutes, and then the operation of removing the aqueous phase from the separated toluene phase and aqueous phase was repeated twice. The obtained toluene phase was added dropwise to 1 L of hexane at room temperature, and further, a powder was obtained by filtration and solvent removal.

(Third step)
In a reaction vessel containing the obtained powder, 108 g (555 mmol) of p-butoxyphenylboronic acid, 23.8 mg (0.106 mmol) of palladium acetate, 97.1 mg (0.370 mmol) of triphenylphosphine, 449 g of sodium carbonate ( 4230 mmol), 1.71 g (5.29 mmol) of tetrabutylammonium bromide, 1600 mL of toluene, and 2 L of distilled water were added. After the atmosphere around the reaction system was replaced with nitrogen gas, 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. Through filtration and solvent removal, a compound having a structure represented by the following formula (a) in a white solid state (hereinafter referred to as “compound (a)”) was obtained. The yield was 320 g, and the yield was 95%. The structure of the obtained compound (a) was confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.

NMR of the final product
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

[Production Example 2]
(First step)
4-bromobenzenethiol 100 g (529 mmol), 2- (perfluorohexyl) ethyl iodide 260 g (556 mmol), tetrabutylammonium bromide 1.71 g (5.29 mmol), toluene 200 mL, sodium hydroxide 32 g (794 mmol), and Distilled water (330 mL) was charged into the reaction vessel and stirred at 50 ° C. for 2 hours under atmospheric pressure. Thereafter, the aqueous phase was removed from the separated toluene phase and aqueous phase. Next, 400 mL of distilled water was put into the reaction vessel, stirred at 50 ° C. for 5 minutes, and then the operation of removing the aqueous phase from the separated toluene phase and aqueous phase was repeated twice.

(Second step)
After further adding 450 mL of toluene to the obtained toluene phase, the same treatment as in the second step of Production Example 1 was performed.

(Third step)
In the same manner as in Production Example 1, compound (a) was obtained in the form of a white solid. The yield was 316 g, and the yield was 94%. The structure of the obtained compound (a) was confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.

NMR of the final product
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

[Production Example 3]
In the first step, compound (a) was obtained in the form of a white solid in the same manner as in Production Example 1 except that 110 g (794 mmol) of potassium carbonate was used instead of 32 g (794 mmol) of sodium hydroxide. The yield was 323 g, and the yield was 96%. The structure of the obtained compound (a) was confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.

NMR of the final product
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), 4.03 (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), 7.96 (2H, d, J = 8.0 Hz) ppm

[Production Example 4]
(First step)
100 g (529 mmol) of 4-bromobenzenethiol, 260 g (556 mmol) of 2- (perfluorohexyl) ethyl iodide, 1.71 g (5.29 mmol) of tetrabutylammonium bromide, 110 g (794 mmol) of potassium carbonate, and 330 mL of distilled water The reaction vessel was charged and stirred at 50 ° C. for 2 hours under atmospheric pressure. Then, the water phase was removed among the separated water phase and another phase (organic phase). Next, 400 mL of distilled water was put into the reaction vessel, stirred for 5 minutes at 50 ° C., and then the operation of removing the aqueous phase from the separated aqueous phase and organic phase was repeated twice.

(Second step)
To the obtained organic phase, 650 mL of toluene, 850 mL of distilled water, 813 g (1323 mmol) of potassium hydrogen persulfate, and 8.53 g (26.5 mmol) of tetrabutylammonium bromide were added, and further, at 70 ° C. for 14 hours under atmospheric pressure. Stir. Thereafter, the aqueous phase was removed from the separated toluene phase and aqueous phase. Next, 850 mL of distilled water was put into the reaction vessel, stirred at 70 ° C. for 5 minutes, and then the operation of removing the aqueous phase from the separated toluene phase and aqueous phase was repeated twice. The obtained toluene phase was added dropwise to 1 L of hexane at room temperature, and further, a powder was obtained by filtration and solvent removal.

(Third step)
In a reaction vessel containing the obtained powder, 123 g (555 mmol) of p-hexoxyphenylboronic acid, 23.8 mg (0.106 mmol) of palladium acetate, 97.1 mg (0.370 mmol) of triphenylphosphine, 449 g of sodium carbonate. (4230 mmol), 1.71 g (5.29 mmol) of tetrabutylammonium bromide, 1600 mL of toluene, and 1.5 L of distilled water were added. After the atmosphere around the reaction system was replaced with nitrogen gas, 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, 1.5 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. Through filtration and solvent removal, a compound having a structure represented by the following formula (b) in a white solid state (hereinafter referred to as “compound (b)”) was obtained. The yield was 330 g, and the yield was 94%. The structure of the obtained compound (b) was confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.

NMR of the final product
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

[Production Example 5]
(First step)
100 g (529 mmol) of 4-bromobenzenethiol, 260 g (556 mmol) of 2- (perfluorohexyl) ethyl iodide, 1.71 g (5.29 mmol) of tetrabutylammonium bromide, and 110 g (794 mmol) of potassium carbonate were put in a reaction vessel. The mixture was added and stirred at 50 ° C. for 2 hours under atmospheric pressure. Next, 400 mL of distilled water was put into the reaction vessel, stirred for 5 minutes at 50 ° C., and then the operation of removing the aqueous phase from the separated aqueous phase and another phase (organic phase) was repeated twice. .

(Second step and third step)
In the same manner as in Production Example 4, a compound (b) having the following structure in a white solid state was obtained. The yield was 334 g, and the yield was 95%. The structure of the obtained compound (b) was confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.

NMR of the final product
¹ H-NMR (CDCl ₃ ) 0.93 (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

[Production Example 6]
(First step)
Reaction of 100 g (529 mmol) of 4-bromobenzenethiol, 260 g (556 mmol) of 2- (perfluorohexyl) ethyl iodide, 1.71 g (5.29 mmol) of tetrabutylammonium bromide, 110 g (794 mmol) of potassium carbonate, and 200 mL of toluene It put in the container and stirred at 50 degreeC under atmospheric pressure for 2 hours. Next, 400 mL of distilled water was put into the reaction vessel, stirred at 50 ° C. for 5 minutes, and then the operation of removing the aqueous phase from the separated toluene phase and aqueous phase was repeated twice.

(Second step)
After further adding 450 mL of toluene to the obtained toluene phase, the same treatment as in the second step of Production Example 4 was performed.

(Third step)
In the same manner as in Production Example 4, a compound (b) having the following structure in a white solid state was obtained. The yield was 330 g, and the yield was 94%. The structure of the obtained compound (b) was confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.

NMR of the final product
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

[Production Example 7]
(First step)
4-bromobenzenethiol 100 g (529 mmol), 2- (perfluorohexyl) ethyl iodide 260 g (556 mmol), tetrabutylammonium bromide 1.71 g (5.29 mmol), potassium carbonate 110 g (794 mmol), toluene 100 mL, and distillation 90 mL of water was put into the reaction vessel and stirred at 50 ° C. for 2 hours under atmospheric pressure. Thereafter, the aqueous phase was removed from the separated toluene phase and aqueous phase. Next, 90 mL of distilled water was put into the reaction vessel, stirred for 5 minutes at 50 ° C., and then the operation of removing the aqueous phase from the separated toluene phase and aqueous phase was repeated twice.

(Second step)
To the obtained toluene phase, 550 mL of toluene, 1800 mL of distilled water, 813 g (1323 mmol) of potassium monohydrogen persulfate, and 8.53 g (26.5 mmol) of tetrabutylammonium bromide were added, and further, at 70 ° C. under atmospheric pressure for 14 hours. Stir. Thereafter, the aqueous phase was removed from the separated toluene phase and aqueous phase. Next, 1800 mL of distilled water was put into the reaction vessel, stirred for 5 minutes at 70 ° C., and then the operation of removing the aqueous phase from the separated toluene phase and aqueous phase was repeated twice. The obtained toluene phase was added dropwise to 1 L of hexane at room temperature, and further, a powder was obtained by filtration and solvent removal.

(Third step)
In a reaction vessel containing the obtained powder, 123 g (555 mmol) of p-hexoxyphenylboronic acid, 23.8 mg (0.106 mmol) of palladium acetate, 97.1 mg (0.370 mmol) of triphenylphosphine, 584 g of potassium carbonate. (4230 mmol), 1.71 g (5.29 mmol) of tetrabutylammonium bromide, 1600 mL of toluene, and 1 L of distilled water were added. After the atmosphere around the reaction system was replaced with nitrogen gas, 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, 1 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. Through filtration and solvent removal, compound (b) was obtained in the form of a white solid. The yield was 337 g, and the yield was 96%. The structure of the obtained compound (b) was confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.

NMR of the final product
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), 7.76 (2H, d, J = 8.0 Hz), 7.95 (2H, d, J = 8.0 Hz) ppm

[Production Example 8]
In the third step, instead of 123 g (555 mmol) of p-hexoxyphenylboronic acid, 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) hexoxybenzene Compound (b) was obtained in the form of a white solid in the same manner as in Production Example 7 except that 169 g (555 mmol) was used. The yield was 330 g, and the yield was 94%. The structure of the obtained compound (b) was confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.

NMR of the final product
¹ H-NMR (CDCl ₃ ) 0.92 (3H, m), 1.48 (6H, m), 1.81 (2H, m), 2.64 (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), 7.96 (2H, d, J = 8.0 Hz) ppm

[Production Example 9]
In the third step, compound (b) was obtained in the form of a white solid in the same manner as in Production Example 7, except that 292 g (2115 mmol) of potassium carbonate was used instead of 584 g (4230 mmol) of potassium carbonate. The yield was 330 g, and the yield was 94%. The structure of the obtained compound (b) was confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.

NMR of the final product
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

[Production Example 10]
In the first step, 208 g (556 mmol) of 2- (perfluorobutyl) ethyl iodide was used instead of 260 g (556 mmol) of 2- (perfluorohexyl) ethyl iodide, and p-hexyl was used in the third step. It is represented by the following formula (c) in the form of a white solid in the same manner as in Production Example 7 except that 139 g (555 mmol) of p-octoxyphenylboronic acid is used in place of 123 g (555 mmol) of sooxyphenylboronic acid. A compound having a structure (hereinafter referred to as “compound (c)”) was obtained. The yield was 295 g, and the yield was 94%. The structure of the obtained compound (c) was confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.

NMR of the final product
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

[Production Example 11]
In the first step, 208 g (556 mmol) of 2- (perfluorobutyl) ethyl iodide was used instead of 260 g (556 mmol) of 2- (perfluorohexyl) ethyl iodide, and p-hexyl was used in the third step. A structure represented by the following formula (d) in the form of a white solid in the same manner as in Production Example 7 except that 84 g (555 mmol) of p-methoxyphenylboronic acid was used in place of 123 g (555 mmol) of sooxyphenylboronic acid (Hereinafter, referred to as “compound (d)”) was obtained. The yield was 246 g, and the yield was 94%. The structure of the obtained compound (d) was confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.

NMR of the final product
¹ H-NMR (CDCl ₃ ) 2.65 (2H, m), 3.35 (2H, m), 3.87 (3H, s), 7.02 (2H, d, J = 8.0 Hz), 7.57 (2H, d, J = 8.0 Hz), 7.76 (2H, d, J = 8.0Hz), 7.95 (2H, d, J = 8.0 Hz) ppm

[Production Example 12]
In the first step, 208 g (556 mmol) of 2- (perfluorobutyl) ethyl iodide was used instead of 260 g (556 mmol) of 2- (perfluorohexyl) ethyl iodide, and p-hexyl was used in the third step. It is represented by the following formula (e) in the form of a white solid in the same manner as in Production Example 7 except that 100 g (555 mmol) of 4-isopropoxyphenylboronic acid is used instead of 123 g (555 mmol) of sooxyphenylboronic acid. A compound having a structure (hereinafter referred to as “compound (e)”) was obtained. The yield was 260 g, and the yield was 94%. The structure of the obtained compound (e) was confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.

NMR of the final product
¹ H-NMR (CDCl ₃ ) 1.38 (6H, m), 2.64 (2H, m), 3.35 (2H, m), 4.62 (1H, m), 6.99 (2H, d, J = 8.0 Hz), 7.55 ( 2H, d, J = 8.0 Hz), 7.76 (2H, d, J = 8.0 Hz), 7.94 (2H, d, J = 8.0 Hz) ppm

[Production Example 13]
(First step)
4-bromobenzenethiol 100 g (529 mmol), 2- (perfluorohexyl) ethyl iodide 260 g (556 mmol), tetrabutylammonium bromide 1.71 g (5.29 mmol), potassium carbonate 110 g (794 mmol), toluene 100 mL, and distillation 90 mL of water was put into the reaction vessel and stirred at 50 ° C. for 2 hours under atmospheric pressure. Thereafter, the aqueous phase was removed from the separated toluene phase and aqueous phase. Next, 90 mL of distilled water was put into the reaction vessel, stirred for 5 minutes at 50 ° C., and then the operation of removing the aqueous phase from the separated toluene phase and aqueous phase was repeated twice.

(Second step)
To the obtained toluene phase, 550 mL of toluene, 1800 mL of distilled water, 813 g (1323 mmol) of potassium monohydrogen persulfate, and 8.53 g (26.5 mmol) of tetrabutylammonium bromide were added, and further, at 70 ° C. under atmospheric pressure for 14 hours. Stir. Thereafter, the aqueous phase was removed from the separated toluene phase and aqueous phase. Next, 1800 mL of distilled water was put into the reaction vessel, stirred for 5 minutes at 70 ° C., and then the operation of removing the aqueous phase from the separated toluene phase and aqueous phase was repeated twice.

(Third step)
In a reaction vessel containing the resulting toluene phase, 123 g (555 mmol) of p-hexoxyphenylboronic acid, 23.8 mg (0.106 mmol) of palladium acetate, 97.1 mg (0.370 mmol) of triphenylphosphine, potassium carbonate 584 g (4230 mmol), 1.71 g (5.29 mmol) of tetrabutylammonium bromide, 950 mL of toluene, and 1 L of distilled water were added. After the atmosphere around the reaction system was replaced with nitrogen gas, 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, 1 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. Through filtration and solvent removal, compound (b) was obtained in the form of a white solid. The yield was 334 g, and the yield was 95%. The structure of the obtained compound (b) was confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.

NMR of the final product
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), 4.01 (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), 7.95 (2H, d, J = 8.0 Hz) ppm

[Comparative Example 1]
In the first step, the same procedure as in Production Example 7 was performed except that tetrabutylammonium bromide was not used and the stirring time of the first stirring was changed from 2 hours to 9 hours. After the first step, toluene was distilled off from the solution sampled from the toluene phase, and its ¹ H-NMR (CDCl ₃ ) was measured, and it was confirmed that the reaction did not proceed. The second and third steps were not performed.

[Comparative Example 2]
In the first step, except that tetrabutylammonium bromide was not used and the initial stirring was performed under toluene reflux, the reaction was not proceeded in the same manner as in Comparative Example 1 except that the reaction was not performed. . Since the reaction did not proceed, the second and third steps were not performed.

[Comparative Example 3]
In the first step, except that tetrabutylammonium bromide was not used and the stirring time for the first stirring was changed from 2 hours to 9 hours, the reaction was performed in the same manner as in Production Example 6 except that the reaction time was the same as in Comparative Example 1. Did not progress. Since the reaction did not proceed, the second and third steps were not performed.

[Comparative Example 4]
In the first step, except that tetrabutylammonium bromide was not used, and the stirring time of the first stirring was changed from 2 hours to 9 hours, the reaction was performed in the same manner as in Production Example 4 except that the reaction time was the same as in Comparative Example 1. Did not progress. Since the reaction did not proceed, the second and third steps were not performed.

[Comparative Example 5]
In the first step, tetrabutylammonium bromide was not used, and the same stirring as in Production Example 5 was conducted except that the stirring time of the first stirring was changed from 2 hours to 9 hours. Did not progress. Since the reaction did not proceed, the second and third steps were not performed.

[Comparative Example 6]
The first step was performed in the same manner as in Production Example 7. Subsequently, in the 2nd process, it carried out similarly to manufacture example 7 except not having used tetrabutylammonium bromide. The chemical structure of the powder obtained after completion of the second step was confirmed by ¹ H-NMR (CDCl ₃ ). As a result, (4-bromophenyl) -2- (perfluorohexyl) ethyl sulfide, which is the raw material of this step, was obtained. It was found that more than 50% remained. Therefore, the third step was not performed.

[Comparative Example 7]
The first and second steps were performed in the same manner as in Production Example 7. Subsequently, in the 3rd process, it carried out like manufacture example 7 except not having used tetrabutylammonium bromide. As a result of confirming the chemical structure of the powder obtained after completion of the third step by ¹ H-NMR (CDCl ₃ ), (4-bromophenyl) -2- (perfluorohexyl) ethylsulfone which is a raw material of this step Was found to remain over 25%.

  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 (21)

A method for producing a polycyclic aromatic compound represented by the following general formula (1):
In a two-phase system using a plurality of solvents, a compound (2) represented by the following general formula (2) is reacted with a compound (3) represented by the following general formula (3) to obtain the following general formula: A first step of producing the compound (4) represented by (4);
A second step of producing a compound (5) represented by the following general formula (5) by oxidizing the compound (4) in a two-phase system using a plurality of solvents ;
In a two-phase system using a plurality of solvents, the third step of reacting the compound (5) with the compound (6) represented by the following general formula (6),
A production method using a phase transfer catalyst in all the steps.

(Equation (1), (2), (3), (4), (5) and (6), R ¹ is an alkyl group in which one or more hydrogen atoms are substituted with halogen atoms, one or more Represents an alkoxy group in which a hydrogen atom is substituted with a halogen atom , or an aryl group in which one or more hydrogen atoms are substituted with a halogen atom , R ² represents an alkyl group or an alkoxy group, L represents a sulfinyl group or a sulfonyl group X ¹ and X ² each independently represents an anionic monovalent leaving group, Y ¹ represents a detachable element or a monovalent group, and Z represents the formula (6). A monovalent group having a boron atom directly bonded to the benzene ring.)   The method for producing a polycyclic aromatic compound according to claim 1, wherein the solvent used in one or more of the steps comprises water.   The method for producing a polycyclic aromatic compound according to claim 1 or 2, wherein the solvent used in one or more of the steps comprises a water-insoluble organic solvent.   The manufacturing method of the polycyclic aromatic compound of any one of Claims 1-3 in which the solvent used in the said 1st process and the said 2nd process contains the mutually same water-insoluble organic solvent. .   The method for producing a polycyclic aromatic compound according to any one of claims 1 to 4, wherein the solvent used in the second step and the third step contains the same water-insoluble organic solvent. .   The manufacturing method of the polycyclic aromatic compound of any one of Claims 1-5 in which the solvent used in all the said processes contains the mutually same water-insoluble organic solvent.   The method for producing a polycyclic aromatic compound according to any one of claims 3 to 6, wherein the solubility of the water-insoluble organic solvent in water at 20 ° C is 20% by mass or less.   The method for producing a polycyclic aromatic compound according to any one of claims 3 to 6, wherein the solubility of the water-insoluble organic solvent in water at 20 ° C is 5% by mass or less.   The water-insoluble organic solvent is at least one solvent selected from the group consisting of an aromatic hydrocarbon solvent, a halogenated aromatic hydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent, a fluorine-containing solvent, and an ether solvent. The manufacturing method of the polycyclic aromatic compound of any one of Claims 3-8.   The method for producing a polycyclic aromatic compound according to claim 9, wherein the water-insoluble organic solvent is at least one solvent selected from the group consisting of toluene, xylene, chlorobenzene and methylene chloride.   The phase transfer catalyst is one or more kinds of catalysts selected from the group consisting of quaternary ammonium salts, phosphonium salts, amines, crown ethers, cryptands, and chain polyethylene glycol derivatives. A method for producing the polycyclic aromatic compound according to item 1.   The method for producing a polycyclic aromatic compound according to claim 11, wherein the phase transfer catalyst is a quaternary ammonium salt.   The method for producing a polycyclic aromatic compound according to claim 11, wherein the phase transfer catalyst is tetrabutylammonium bromide.   The method for producing a polycyclic aromatic compound according to any one of claims 1 to 13, wherein in the second step, at least one of hydrogen peroxide and potassium hydrogen persulfate is used as an oxidizing agent. . 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 the halogen atom in R ¹ is a fluorine atom. Wherein R ¹ comprises a perfluoroalkyl chain site, a manufacturing method of a polycyclic aromatic compound according to any one of claims 1 to 16. Wherein R ¹ is a group represented by the following general formula (7), the production method of the polycyclic aromatic compound according to any one of claims 1-17.

(In formula (7), n represents an integer of 0 to 8, and m represents an integer of 1 to 20.)   The method for producing a polycyclic aromatic compound according to any one of claims 1 to 18, wherein L is a sulfonyl group. 20. The method for producing a polycyclic aromatic compound according to claim 1, wherein X ¹ is a bromine atom, an iodine atom, or a chlorine atom. Said X < ² > is a manufacturing method of the polycyclic aromatic compound of any one of Claims 1-20 which is a bromine atom, an iodine atom, or a chlorine atom.