JP2014024777A - Method for producing polycyclic aromatic compound having halogen atom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polycyclic aromatic compound, capable of easily producing a polycyclic aromatic compound having a halogen atom at low raw material costs.SOLUTION: The method for producing a polycyclic aromatic compound includes the steps of: mixing a compound represented by R-Ph-Xand a compound having a metal such as lithium to obtain a compound represented by R-Ph-M; and mixing a compound represented by R-Ph-Mand a compound represented by R-L-Ph-Xto obtain a compound represented by R-L-Ph-Ph-R(where Rrepresents an alkyl group or the like in which at least one hydrogen atom is substituted by a halogen atom, Xand Xeach independently represents an anionic monovalent leaving group, L represents a sulfide group or the like, Rrepresents an alkyl group or the like, Ph represents a phenylene group, Mrepresents a monovalent group having a metal such as lithium or the like, and the metal is directly bound to the Ph).

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.

  As a method for producing a polycyclic aromatic compound used in various industries, a coupling reaction between an aromatic boron compound and an aromatic compound having an anionic leaving group (Suzuki-Miyaura cross-coupling method) (for example, Non-patent document 1) and coupling reactions of aromatic magnesium compounds with compounds having an anionic leaving group (Kumada-Tamao-Coriu cross-coupling method) (for example, refer to non-patent document 2) are widely known. Yes. By using these coupling reactions, various aromatic compounds can be produced.

  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 1 and 2), and also as an electrolyte material for a lithium ion secondary battery (for example, This is useful as Patent Document 3). The polycyclic aromatic compound having a halogen atom enables gelation of the system with a small amount of 10% by mass or less based on the non-aqueous solvent. Therefore, for example, when used as an electrolyte solution material of a lithium ion secondary battery, it is possible to achieve both high battery characteristics and high safety (see Patent Document 3).

International Publication No. 2007/083843 International Publication No. 2009/078268 International Publication No. 2010/095572

Miyaura, N., Yanagi, T., Suzuki, A., Synthetic Communications, 1981, Vol. 11, p513-519 Tamao, K., Sumitani, K., Kumada, M., J. Am. Chem. Soc., 1972, 94, p4374

  The Suzuki-Miyaura cross-coupling method has the advantage that the desired product can be obtained in a high yield by a simple operation. However, it is difficult to obtain an aromatic boron compound used as a raw material for the coupling reaction, and it may take time and effort, which may be disadvantageous in cost.

  In contrast, the Kumada-Tamao-Coriu cross-coupling method is advantageous in terms of cost because the raw materials used are often inexpensive and can be easily obtained and manufactured. However, impurities after the coupling reaction may increase, and the production apparatus and the purification apparatus may be large and complicated, and the conditions for production and purification may be complicated.

  In addition, when a polycyclic aromatic compound having a halogen atom is produced by the method disclosed in Non-Patent Document 1, it is necessary to use an expensive raw material (aromatic boron compound). On the other hand, when a method such as that disclosed in Non-Patent Document 2 is used, it is difficult to separate the reaction raw material magnesium and the reaction target product after the reaction, and it takes time for purification. Not suitable for manufacturing.

  Therefore, in the synthesis of a polycyclic aromatic compound having a halogen atom as disclosed in Patent Documents 1 to 3, production of a polycyclic aromatic compound that is easy to produce and purify using an inexpensive raw material It is desirable to establish a method.

  The present invention has been made in view of the above circumstances, and provides a method for producing a polycyclic aromatic compound, which can easily produce and purify a polycyclic aromatic compound having a halogen atom at a low raw material cost. For the purpose.

  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.

（式（７）中、ｎは０〜８の整数を示し、ｍは１〜２０の整数を示す。）
［９］前記Ｌは、スルホニル基である、上記製造方法。
［１０］前記Ｘ¹は、臭素原子、ヨウ素原子又は塩素原子である、上記製造方法。
［１１］前記第２の工程において、上記式（３）で表される化合物と、上記式（４）で表される化合物とを、それらの化合物のうちモル基準で少ない方の化合物の量に対して０．０００１〜１ｍｏｌ％の、パラジウム、ニッケル及び鉄からなる群より選ばれる１種以上の金属を有する化合物の存在下に反応させる、上記製造方法。
［１２］前記パラジウム、ニッケル及び鉄からなる群より選ばれる１種以上の金属を有する化合物は、パラジウムを有する化合物である、上記製造方法。
［１３］前記第２の工程において、上記式（３）で表される化合物と、上記式（４）で表される化合物とを、添加剤の存在下に反応させる、上記製造方法。
［１４］前記添加剤が、上記式（３）で表される化合物及び上記式（４）で表される化合物のうちモル基準で少ない方の化合物の量に対して０．０００１〜４ｍｏｌ％の、リンを有する化合物である、上記製造方法。
［１５］前記第１の工程及び前記第２の工程のうち少なくとも一方において、水溶性有機溶媒を用いる、上記製造方法。
［１６］前記第１の工程及び前記第２の工程のうち少なくとも一方おいて、非水溶性有機溶媒を用いる、上記製造方法。
［１７］前記第１の工程及び前記第２の工程のうち少なくとも一方において、非プロトン性有機溶媒を用いる、上記製造方法。 That is, the present invention is as follows.
[1] The following general formula (1):
R ¹ -L-Ph-Ph-R ² (1)
A process for producing a polycyclic aromatic compound represented by:
The following general formula (2):
R ² -Ph-X ² (2)
Is reacted with a compound having one or more metals selected from the group consisting of lithium, magnesium and zinc, and the following general formula (3):
R ² -Ph-M ¹ (3)
A first step of obtaining a compound represented by:
The compound represented by the above formula (3) and the following general formula (4):
R ¹ -L-Ph-X ¹ (4)
And a second step of obtaining a compound represented by the above formula (1) by reacting with the compound represented by formula (1).
(In the formulas (1), (2), (3) and (4), R ¹ represents an alkyl group, an alkoxy group or an aryl group in which one or more hydrogen atoms are substituted with a halogen atom, and X ¹ and X ² independently represents an anionic monovalent leaving group, L represents a sulfide group, a sulfinyl group or a sulfonyl group, R ² represents an alkyl group or an alkoxy group, Ph represents a phenylene group, M ¹ represents a monovalent group having one or more metals selected from the group consisting of lithium, magnesium and zinc, and in the formula (3), the metal is directly bonded to the Ph.
[2] The said manufacturing method whose said metal is lithium or magnesium.
[3] The said manufacturing method whose compound which has the said metal is organic lithium, metallic lithium, organic magnesium, or metallic magnesium.
[4] The above production method, wherein R ² is an alkoxy group having 1 to 20 carbon atoms.
[5] The above production method, wherein X ² is a bromine atom, an iodine atom or a chlorine atom.
[6] The said manufacturing method whose said halogen atom in said R < ¹ > is a fluorine atom.
[7] The above production method, wherein R ¹ includes a perfluoroalkyl chain moiety.
[8] The above production method, 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.)
[9] The above production method, wherein L is a sulfonyl group.
[10] The above production method, wherein X ¹ is a bromine atom, an iodine atom or a chlorine atom.
[11] In the second step, the compound represented by the above formula (3) and the compound represented by the above formula (4) are reduced to the amount of the smaller compound on a molar basis among these compounds. The said manufacturing method made to react in presence of the compound which has 1 or more types of metals chosen from the group which consists of palladium, nickel, and iron with respect to 0.0001-1 mol%.
[12] The above production method, wherein the compound having one or more metals selected from the group consisting of palladium, nickel and iron is a compound having palladium.
[13] The production method as described above, wherein in the second step, the compound represented by the formula (3) is reacted with the compound represented by the formula (4) in the presence of an additive.
[14] The additive is 0.0001 to 4 mol% based on the amount of the compound represented by the above formula (3) and the compound represented by the above formula (4), which is smaller on a molar basis. The said manufacturing method which is a compound which has phosphorus.
[15] The above production method using a water-soluble organic solvent in at least one of the first step and the second step.
[16] The above production method using a water-insoluble organic solvent in at least one of the first step and the second step.
[17] The production method as described above, wherein an aprotic organic solvent is used in at least one of the first step and the second step.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the manufacturing method of a polycyclic aromatic compound which can manufacture and refine | purify the polycyclic aromatic compound which has a halogen atom easily at low raw material cost.

  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 the polycyclic aromatic compound of the present embodiment is represented by the following general formula (1):
R ¹ -L-Ph-Ph-R ² (1)
A polycyclic aromatic compound represented by the following (hereinafter simply referred to as “compound (1)”):
R ² -Ph-X ² (2)
And a compound having at least one metal selected from the group consisting of lithium, magnesium and zinc (hereinafter referred to as “comprising M ¹ compound”). And the following general formula (3):
R ² -Ph-M ¹ (3)
A first step of obtaining a compound represented by formula (hereinafter simply referred to as “compound (3)”), a compound represented by the above formula (3), and the following general formula (4):
R ¹ -L-Ph-X ¹ (4)
And a second step of obtaining a compound represented by the above formula (1) by reacting with a compound represented by formula (hereinafter simply referred to as “compound (4)”).
Here, in the formulas (1), (2), (3) and (4), R ¹ represents an alkyl group, an alkoxy group or an aryl group in which one or more hydrogen atoms are substituted with a halogen atom, and X ¹ And X ² each independently represents an anionic monovalent leaving group, L represents a sulfide group, sulfinyl group or sulfonyl group, R ² represents an alkyl group or an alkoxy group, and Ph represents a phenylene group. , M ¹ represents a monovalent group having at least one metal selected from the group consisting of lithium, magnesium and zinc, and in the formula (3), the metal is directly bonded to the Ph.

(1) In the first step this embodiment, by reacting mixed compound (2) and containing M ¹ compound to provide compound (3). Here, in the above formulas, Ph represents a phenylene group.

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.

X ² represents an anionic monovalent leaving group (hereinafter referred to as “anionic leaving group”). Here, the “anionic leaving group” means an anionic monovalent group that is eliminated from the compound during the reaction 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 —), and 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, from the viewpoint of easy synthesis of a polycyclic aromatic compound and availability of raw materials. And particularly preferably a bromine atom or a chlorine atom.

The position of X ² bonded to Ph may be any of the ortho-position, meta-position and para-position relative to R ² , but from the viewpoint of utility as a gelling agent for polycyclic aromatic compounds, the para-position It is preferable that it exists in.

  Compound (2) 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 compound (2) individually or in combination of 2 or more types.

Containing M ¹ compound, Compound (2) and by mixing the containing M ¹ compound reaction, in a first step to obtain the compound (3), the X ² is an anionic leaving group desorbed, If it is a compound which can obtain a compound (3), it will not specifically limit. Examples of the M ¹ -containing compound include organic lithium, lithium halide, metallic lithium, organic magnesium, lithium halide, metallic magnesium, organic zinc, zinc halide and metallic zinc. Among these, organic lithium, metallic lithium, organic magnesium or metallic magnesium is preferable from the viewpoint of more effectively and reliably achieving the effects of the present invention. The M ¹ -containing compound may be obtained as a commercial product or synthesized by a conventional method. In the production method of the present embodiment, ^one of the M ¹ -containing compounds can be used alone or in combination of two or more.

  The organic lithium is preferably alkyllithium having 1 to 10 carbon atoms or phenyllithium, and more preferably hexyllithium, n-butyllithium, s-butyllithium, t-butyl from the viewpoint of availability. Lithium, methyllithium, ethyllithium, or phenyllithium.

  The organic magnesium is preferably an alkyl magnesium having 1 to 10 carbon atoms, an alkyl magnesium halide having 1 to 10 carbon atoms, a vinyl magnesium halide, an allyl magnesium halide, or a phenyl magnesium halide. More preferably, methyl magnesium chloride, methyl magnesium bromide, methyl magnesium iodide, ethyl magnesium bromide, propyl magnesium chloride, isopropyl magnesium, butyl magnesium chloride, vinyl magnesium chloride, allyl magnesium bromide, allyl magnesium chloride , Phenylmagnesium bromide, or phenylmagnesium chloride.

  The organic zinc is preferably alkyl zinc having 1 to 10 carbon atoms, halogenated alkyl zinc having 1 to 10 carbon atoms, or phenyl zinc halide, and more preferably bromide from the viewpoint of availability. Propyl zinc, butyl zinc bromide, cyclohexyl zinc bromide, 3-ethoxy-3-oxopropyl zinc bromide, phenyl zinc bromide, 2-pyridyl zinc bromide, or 2-thienyl zinc bromide.

Compounding ratio of the compound in the reaction system and (2) and containing M ¹ compound, 100 mol% of the compound (2), the amount of containing M ¹ compound is preferably 50～200Mol%, more preferably 90~150mol %, And more preferably 100 to 120 mol%.

In the compound (3), M ¹ represents a monovalent group having one or more metals selected from the group consisting of lithium, magnesium and zinc. In the compound (3), the metal is directly bonded to Ph. In M ¹ , the metal is preferably lithium or magnesium from the viewpoint of more effectively and reliably achieving the effects of the present invention. M ¹ may be the metal itself or a group having another chemical species together with the metal. Examples of such groups include an alkyl metal group, an alkoxy metal group, and a halogenated metal group.

(2) Second Step In this embodiment, compound (1) is obtained by mixing and reacting compound (3) obtained in the first step and compound (4).

R ¹ represents an alkyl group, an alkoxy group or an aryl group, in which one or more hydrogen atoms are substituted with a halogen atom. 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 as a gelling agent for 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).

In R ¹ , one or more hydrogen atoms are substituted with a halogen atom, so that a desired polycyclic aromatic compound as a final product is easily precipitated, and a metal-containing compound dissolved in an organic phase, Separation from ligands and raw materials becomes easier, and the purification process can be further simplified.

  In said formula (7), 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 group in which m is in the above range, the raw material can be obtained at a lower cost.

ここで、式（８）中、ｎ及びｍは、上記式（７）におけるものと同義である。 L represents a sulfide group (—S—), a sulfinyl group (—S (═O) —) or a sulfonyl group (—SO ₂ —), and a viewpoint of utility as a gelling agent for a polycyclic aromatic compound Therefore, a sulfonyl group is preferable. Therefore, -LR ¹ is preferably a group represented by the following general formula (8).

Here, in Formula (8), n and m are synonymous with those in Formula (7).

X ¹ represents an anionic leaving group. Here, the “anionic leaving group” means an anionic monovalent group that is eliminated from the compound during the reaction 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 —), and 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, from the viewpoint of easy synthesis of a polycyclic aromatic compound and availability of raw materials. And particularly preferably a bromine atom or a chlorine atom.

The position of X ¹ bonded to Ph may be any of the ortho-position, meta-position and para-position with respect to the sulfur atom in L described later, but from the viewpoint of ease of synthesis of the polycyclic aromatic compound, It is preferable that it exists in.

  Compound (4) 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 compound (4) individually or in combination of 2 or more types.

  The compounding ratio of the compound (3) and the compound (4) in the reaction system is such that the amount of the compound (4) is preferably 50 to 200 mol%, more preferably 80 to 120 mol, relative to 100 mol% of the compound (3). %, More preferably 90 to 110 mol%.

In the second step, compound (3) and compound (4) are compounds having at least one metal selected from the group consisting of palladium, nickel and iron (hereinafter referred to as “M ² -containing compound”). It is preferable to make it react in presence of. The abundance of the M ² -containing compound is preferably 0.0001 to 1 mol%, more preferably the amount of the compound (3) and the compound (4), which is smaller on a molar basis (100 mol%). It is 0.0001-0.1 mol%, More preferably, it is 0.001-0.1 mol%. When the abundance of the M ² -containing compound 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 further reduced. Subsequent purification becomes easier.

The M ² -containing compound 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, a preferable M ² -containing compound is a compound having palladium (hereinafter referred to as “palladium-containing compound”).

  The palladium-containing compound is not particularly limited as long as it has palladium, and examples thereof include zero-valent or divalent palladium metal and a palladium salt containing 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. Preferable palladium-containing compounds include, for example, those in which palladium (0) is supported on a carbon substance (for example, activated carbon and carbon particles) as a carrier, palladium (II) acetate, palladium (II) chloride, bis (tri Phenylphosphine) palladium (II) chloride, tetrakis (triphenylphosphine) palladium (0), palladium ketonate, palladium acetylacetonate, nitrile palladium halide, palladium halide, allyl palladium halide, and palladium biscarboxylate. It is done. 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.

  The palladium-containing compound may be a commercially available product or may be synthesized by a conventional method. For synthesis, for example, palladium (II) acetate can be produced by reaction of palladium (II) chloride with sodium acetate.

  The nickel-containing compound is not particularly limited as long as it is a compound having nickel, 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 a zero-valent nickel complex, a 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. Good. 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 zero-valent 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, 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.

In the production method of this embodiment, in the second step, compound (3) and compound (4) may be reacted in the presence of an additive. By using an additive, it becomes easier to control and accelerate the reaction. That is, the additive functions as a reaction control agent or a reaction accelerator for the reaction between the compound (3) and the compound (4). The additive used is used individually by 1 type or in combination of 2 or more types. The additive is preferably a compound having phosphorus from the viewpoint of more effectively and reliably achieving the effects of the present invention. Examples of such phosphorus-containing compounds include triphenylphosphine (PPh ₃ ), methyldiphenylphosphine (Ph ₂ PCH ₃ ), trifurylphosphine (P (2-furyl) ₃ ), and 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) (Tatrahedron Letters, 39, 5327 (1998) )), Diphenylphosphinoferrocene (DP) PF), 1,1′-bis (di-t-butylphosphino) ferrocene (DtBPF), N, N-dimethyl-1- [2- (diphenylphosphino) ferrocenyl] ethylamine, 1- [2- (diphenyl) Phosphino) ferrocenyl] ethyl methyl ether, 2-dicyclohexylphosphino-2′-dimethylamino-1,1′-biphenyl (Journal of the American Chemical Society, vol. 120, 9722 (1998)), spiro-type phosphonium salt (Angewandte Chemie international Edition) 37, 481 (1998) Phosphine-based ligands such as imidazole-2-ylidenecarbenes (Angewandte Chemie international edition in English), Vol. 36, 2163 (1997)).

  The ligand as an additive reacts with the metal contained in the metal-containing compound and a substituent on the ligand to produce a palladacycle (Angevante Chemie International Edition) when the metal is palladium. -You may form compounds, such as in English (Angewandte Chemie international Edition in England) vol. 34, p. 1844 (1995)).

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

  In the second step, the amount of the additive present in the reaction system is preferably 0.1% relative to the amount (100 mol%) of the compound (3) and the compound (4), which is smaller on a molar basis. It is 0001-4 mol%, More preferably, it is 0.0001-0.4 mol%, More preferably, it is 0.001-0.4 mol%. An additive is used individually by 1 type or in combination of 2 or more types. When the amount of the additive is within the above range, the reaction can be promoted or controlled more reliably, and purification can be performed more easily.

  Each raw material, product, and by-product in the first step and the second step of the present embodiment 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.

  In the first step and the second step, a solvent may be present in the reaction system, and the solvent is preferably an organic solvent, and is a water-soluble organic solvent or a water-insoluble organic solvent. Also good. A water-insoluble organic solvent is effective in that it can be easily separated from water and can easily wash water-soluble by-products and impurities. 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. On the other hand, since the water-soluble organic solvent is easily miscible with water, the target product can be precipitated or promoted in the purification step. Further, by using a water-soluble organic solvent, it becomes possible to dissolve and remove the metal and by-product salt by adding water and an aqueous solution.

  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 solvents having a perfluoro group such as tetrahydrofuran, perfluorooctane, perfluorotributylamine, perfluorohexane and perfluorobenzene, diethyl ether, diglyme, dimethoxyethane, 1,4-dioxane, tetrahydrofuran, 2- Ether solvents such as methyltetrahydrofuran, diethoxymethane, diisopropyl ether, anisole and methyl t-butyl ether, alkane solvents such as hexane and cyclohexane, triethylamine, N, N Diisopropylethylamine, pyridine, N, include tertiary amine solvent such as N- dimethyl-4-aminopyridine. An organic solvent is used individually by 1 type or in combination of 2 or more types.

  The water-insoluble organic solvent is a solvent having a solubility in water at 20 ° C. of 20% by mass or less at the reaction temperature in each of the above steps or at the purification temperature in the subsequent purification step, more preferably at 20 ° C. From the viewpoint of separation of the aqueous phase and the organic phase in the solvent, more preferably, the solvent has a solubility in water at 20 ° C. of 5% by mass or less.

  Examples of the water-insoluble 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. Fluorine-containing solvents such as solvents having a perfluoro group such as butyltetrahydrofuran, perfluorooctane, perfluorotributylamine, perfluorohexane and perfluorobenzene, diethyl ether, 2-methyltetrahydrofuran, diisopropyl ether, anisole and methyl t- Examples include ether solvents such as butyl ether, alkane solvents such as hexane and cyclohexane, and tertiary amine solvents such as triethylamine and N, N-dimethyl-4-aminopyridine. A water-insoluble organic solvent is used individually by 1 type or in combination of 2 or more types.

  The water-soluble organic solvent is a solvent having a solubility in water of more than 20% by mass at 20 ° C. in the reaction temperature of each of the above steps or in the purification step, and further from the viewpoint of solubility during purification. A solvent having a solubility in water at 20 ° C. of 50% by mass or more is preferable, and a solvent arbitrarily mixed with water at 20 ° C. is more preferable.

  Examples of the water-soluble organic solvent include ether solvents such as diglyme, dimethoxyethane, 1,4-dioxane, tetrahydrofuran and diethoxymethane, and tertiary amine solvents such as N, N-diisopropylethylamine and pyridine. A water-soluble organic solvent is used individually by 1 type or in combination of 2 or more types.

  An aprotic organic solvent is a solvent that does not have a highly acidic hydrogen atom bonded to an oxygen atom, a nitrogen atom, or a sulfur atom. The aprotic organic solvent may be water-soluble or water-insoluble. By not having hydrogen with high acidity, it is possible to suppress the formation of by-products.

  Examples of the aprotic 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- Fluorinated solvents such as solvents having perfluoro groups such as 2-butyltetrahydrofuran, perfluorooctane, perfluorotributylamine, perfluorohexane and perfluorobenzene, diethyl ether, diglyme, dimethoxyethane, 1,4-dioxane, tetrahydrofuran Ether solvents such as 2-methyltetrahydrofuran, diethoxymethane, diisopropyl ether, anisole and methyl t-butyl ether, alkane solvents such as hexane and cyclohexane, triethyl alcohol Emissions, N, N- diisopropylethylamine, pyridine, N, a tertiary amine solvent such as N- dimethyl-4-aminopyridine, and dimethyl sulfoxide and the like. The aprotic organic solvent may be used alone or in combination of two or more.

  The solvents used in the first step and the second step may be the same as or different from each other. Moreover, the same or different solvent as the solvent contained in the solution may be added to the solution after the reaction in the first step, and the process may move to the second step.

  The reaction temperature in the first step is preferably -80 ° C to 200 ° C, more preferably -20 to 150 ° C, still more preferably 20 to 100 ° C, particularly preferably from the viewpoint of the boiling point of the solvent and the solubility of the raw material. Is 30 ° C to 80 ° C.

  The reaction temperature in the second step is preferably from −80 ° C. to 200 ° C., more preferably from −20 to 150 ° C., still more preferably from 20 to 100 ° C., particularly preferably from the viewpoint of the boiling point of the solvent and the solubility of the raw material. Is 30 ° C to 80 ° C.

  In the first step and the second step, 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, and can proceed under reduced pressure or high pressure.

  The degree of reaction progress in the first step and the second step can be confirmed by analysis of 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 first step or the second step, the salt or water-soluble raw material contained in the reaction mixture can be dissolved in water, and the salt or water-soluble raw material can be removed. . 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 other than the above, such as a reaction catalyst, a cocatalyst, a reaction accelerator, an emulsifier, and an antifoaming agent, may be further 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.

  Examples of the reaction accelerator include dibromoethane, iodoethane, lithium chloride and the like.

  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.

  According to this embodiment, a polycyclic aromatic compound having a halogen atom can be easily produced and purified at a low raw material cost.

  The polycyclic aromatic compound obtained by the production method of the present embodiment includes, for example, materials for non-aqueous electrolyte secondary batteries (preferably lithium ion secondary batteries) such as gelling agents for electrolytic solutions, organic EL materials, It can be used for liquid crystal materials, nonlinear optical materials, photographic additives, sensitizing dyes, pharmaceuticals, etc., 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]
Reaction of 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 The solution was put into a container and stirred at 50 ° C. for 3 hours under atmospheric pressure. Thereafter, the product was filtered and the solvent was removed to obtain a white powder. The obtained white powder, 165 mL of acetic acid, and 40 g of 35% aqueous hydrogen peroxide were mixed, and further stirred at 70 ° C. for 3 hours under atmospheric pressure. Thereafter, the product was filtered and stirred and washed in hexane. Subsequently, the product (1A) which has the following structure was obtained in the state of white powder through filtration of a product and solvent removal. The yield was 42 g, and the yield was 90%.

[Production Example 2]
4-Bromophenol 20 g (115.6 mmol), 1-bromohexane 23.84 g (144.5 mmol), potassium carbonate 23.93 g (173.4 mmol), and 3-pentanone 300 mL were charged into the reaction vessel, and the atmospheric pressure The mixture was stirred at 120 ° C. for 8 hours while refluxing. Thereafter, the product was filtered and the solvent was removed to obtain a compound (2A) having the following structure in a brown solid state. The yield was 29.6 g, and the yield was 100%.

[Example 1]
0.44 g (18 mmol) of metal magnesium was put in the reaction vessel 1 and the atmosphere around the reaction system was replaced with nitrogen gas, 5 mL of tetrahydrofuran was added, and the mixture was stirred at 60 ° C. for 5 minutes. Next, 0.2 mL (2.34 mmol) of 1,2-dibromoethane was added to the reaction vessel 1 and stirred at 60 ° C. for 510 minutes. Next, a mixed solution of 2.6 g (10.11 mmol) of the compound (2A) and 10 mL of tetrahydrofuran was dropped into the reaction vessel 1 and stirred at 60 ° C. for 2 hours to obtain a solution.

  Subsequently, 3.36 g (10.11 mmol) of the compound (1A), 11.4 mg (0.0505 mmol) of palladium acetate, and 46.5 mg (0.177 mmol) of triphenylphosphine were added to a reaction vessel 2 different from the reaction vessel 1. The atmosphere around the reaction system was replaced with nitrogen gas, and then 20 mL of tetrahydrofuran was added to the reaction vessel 2 and stirred at 60 ° C. for 10 minutes.

Then, the solution in the reaction container 1 was dripped in the reaction container 2, and it stirred at 60 degreeC for 2 hours. Subsequently, when 30 mL of water was added to the reaction vessel 2 and allowed to cool, a white gel substance precipitated. The obtained precipitate 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 5.25, and the yield was 75%. 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

  The present invention relates to materials for non-aqueous electrolyte secondary batteries (preferably lithium ion secondary batteries) such as electrolyte gelling agents, organic EL materials, liquid crystal materials, nonlinear optical materials, photographic additives, and sensitizing dyes. It is expected to be used as a method for producing a polycyclic aromatic compound useful as a pharmaceutical product or a synthetic intermediate thereof.

Claims (17)

The following general formula (1):
R ¹ -L-Ph-Ph-R ² (1)
A process for producing a polycyclic aromatic compound represented by:
The following general formula (2):
R ² -Ph-X ² (2)
Is reacted with a compound having one or more metals selected from the group consisting of lithium, magnesium and zinc, and the following general formula (3):
R ² -Ph-M ¹ (3)
A first step of obtaining a compound represented by:
The compound represented by the above formula (3) and the following general formula (4):
R ¹ -L-Ph-X ¹ (4)
And a second step of obtaining a compound represented by the above formula (1) by reacting with the compound represented by formula (1).
(In the formulas (1), (2), (3) and (4), R ¹ represents an alkyl group, an alkoxy group or an aryl group in which one or more hydrogen atoms are substituted with a halogen atom, and X ¹ and X ² independently represents an anionic monovalent leaving group, L represents a sulfide group, a sulfinyl group or a sulfonyl group, R ² represents an alkyl group or an alkoxy group, Ph represents a phenylene group, M ¹ represents a monovalent group having one or more metals selected from the group consisting of lithium, magnesium and zinc, and in the formula (3), the metal is directly bonded to the Ph.   The manufacturing method according to claim 1, wherein the metal is lithium or magnesium.   The method according to claim 1 or 2, wherein the metal-containing compound is organic lithium, metallic lithium, organic magnesium, or metallic magnesium. The said R < ² > is a manufacturing method of any one of Claims 1-3 which is a C1-C20 alkoxy group. Said X < ² > is a manufacturing method of any one of Claims 1-4 which is a bromine atom, an iodine atom, or a chlorine atom. The halogen atom in the R ¹ is a fluorine atom, a manufacturing method according to any one of claims 1 to 5. Wherein R ¹ comprises a perfluoroalkyl chain site production method according to any one of claims 1-6. Wherein R ¹ is a group represented by the following general formula (7) A process according to any one of claims 1 to 7.

(In formula (7), n represents an integer of 0 to 8, and m represents an integer of 1 to 20.)   The manufacturing method according to claim 1, wherein L is a sulfonyl group. Wherein X ¹ is a bromine atom, an iodine atom or a chlorine atom, a manufacturing method according to any one of claims 1-9.   In the second step, the compound represented by the above formula (3) and the compound represented by the above formula (4) are reduced with respect to the amount of the smaller compound on a molar basis among these compounds. The manufacturing method of any one of Claims 1-10 made to react in presence of the compound which has 1 or more types of metals chosen from the group which consists of 0.0001-1 mol% of palladium, nickel, and iron.   The manufacturing method according to claim 11, wherein the compound having at least one metal selected from the group consisting of palladium, nickel, and iron is a compound having palladium.   The said 2nd process WHEREIN: The compound represented by the said Formula (3) and the compound represented by the said Formula (4) are made to react in presence of an additive. The production method according to item.   The additive contains 0.0001 to 4 mol% of phosphorus with respect to the amount of the compound represented by the above formula (3) and the compound represented by the above formula (4), which is smaller on a molar basis. The manufacturing method of Claim 13 which is a compound which has.   The manufacturing method according to claim 1, wherein a water-soluble organic solvent is used in at least one of the first step and the second step.   The manufacturing method according to claim 1, wherein a water-insoluble organic solvent is used in at least one of the first step and the second step.   The manufacturing method according to any one of claims 1 to 14, wherein an aprotic organic solvent is used in at least one of the first step and the second step.