JP2014024778A - Method for producing aromatic boron compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an aromatic boron compound at raw material costs and a high yield, suitable for industrial manufacturing.SOLUTION: The method for producing an aromatic boron compound includes the steps of: causing a compound represented by R-Ph-Xand a compound having a metal such as lithium to react with each other to obtain a compound represented by R-Ph-M; and causing a compound represented by R-Ph-Mand a compound having a boron atom to react with each other to obtain a compound represented by R-Ph-Z, and in each step, a solvent and a first additive having a hetero atom are present in a reaction system (where Rrepresents an alkyl group or the like, Ph represents a phenylene group, Z represents a monovalent group having a boron atom, Xrepresents an anionic monovalent leaving group, Mrepresents a monovalent group having a metal such as lithium, the metal is directly bound to the Ph, and the boron atom is directly bound to the Ph).

Description

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

  Aromatic boron compounds are used in various industries. 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 uses as synthetic intermediates and objects have been reported (for example, see Non-Patent Document 1). For example, an aromatic boron compound is used as a raw material for a coupling reaction with an aromatic compound having an anionic leaving group (Suzuki-Miyaura cross-coupling method) (for example, see Non-Patent Document 2). Since the waste liquid can be easily treated, it has been widely used in recent years from such a viewpoint.

  The aromatic boron compound can be produced, for example, by a reaction between an aromatic Grignard reagent and an alkyl borate (see, for example, Patent Document 1). An aromatic boron compound can also be produced by a reaction between diboron having an alkoxy group and an aromatic halide (see, for example, Non-Patent Document 3).

Special table 2002-517503 gazette

Suzuki Akira, TCI Mail, April 2009, No. 142 Miyaura, N., Yanagi, T., Suzuki, A., Synthetic Communications, 1981, Vol. 11, p513-519 T. Ishiyama, J. Org. Chem., 1995, 60, p7508

  However, in the method disclosed in Patent Document 1, it is necessary to perform the reaction at a low temperature of 0 ° C. or lower, which is disadvantageous in industrial production. Further, in the method disclosed in Non-Patent Document 3, there is a problem that the diboron compound is poorly available and the raw material cost is high.

  Therefore, it is desired to establish a method for producing an aromatic boron compound that is suitable for industrial production at a low raw material cost.

  The present invention has been made in view of the above circumstances, and is a method for producing an aromatic boron compound that is low in raw material cost and suitable for industrial production, and can produce an aromatic boron compound in a high yield. It aims to provide a method.

[1] The following general formula (1):
R ² -Ph-Z (1)
A 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 second step of obtaining a compound represented by the above formula (1) by reacting a compound represented by the above formula (3) with a compound having a boron atom. And in the first step and / or the second step, a solvent and a first additive having a hetero atom are present in the reaction system.
(In the formulas (1), (2) and (3), R ² represents an alkyl group or an alkoxy group, Ph represents a phenylene group, Z represents a monovalent group having a boron atom, and X ² represents an anion. 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 the Ph (In the formula (1), the boron atom 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 said manufacturing method whose compound which has the said boron atom is an alkoxy borate.
[6] The above production method, wherein the hetero atom in the first additive is one or more atoms selected from the group consisting of a nitrogen atom, a phosphorus atom, and an oxygen atom.
[7] The above production method, wherein the first additive includes one or more selected from the group consisting of an ether compound, an organic nitrogen compound, an ammonium salt, an organic phosphorus compound, and a phosphonium salt.
[8] The above production method, wherein the solvent is an aprotic non-nucleophilic solvent.
[9] The above production method, wherein the solvent includes one or more solvents selected from the group consisting of toluene, xylene, chlorobenzene, and methylene chloride.
[10] The above production method, wherein a reaction temperature in at least one of the first step and the second step is −20 ° C. or higher.
[11] The said manufacturing method whose reaction temperature in at least one of the said 1st process and the said 2nd process is 30 degreeC or more.
[12] The above production method, wherein X ² is a bromine atom, an iodine atom or a chlorine atom.
[13] The following general formula (4):
R ¹ -L-Ph-Ph-R ² (4)
A compound represented by the following general formula (5):
R ¹ -L-Ph-X ¹ (5)
And a compound represented by the following general formula (1):
R ² -Ph-Z (1)
The manufacturing method which has a 3rd process of making the compound represented by these react, and obtaining the compound represented by the said Formula (4).
(In the above formulas (4), (5) and (1), 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 is an anionic 1 R represents a sulfide group, sulfinyl group or sulfonyl group, R ² represents an alkyl group or an alkoxy group, Ph represents a phenylene group, and Z represents a monovalent group having a boron atom. In the formula (1), the boron atom is directly bonded to the Ph.)
[14] The above production method, wherein the halogen atom in R ¹ is a fluorine atom.
[15] The above production method, wherein R ¹ includes a perfluoroalkyl chain moiety.
[16] The above production method, wherein L is a sulfonyl group.
[17] The above production method, wherein X ¹ is a bromine atom, an iodine atom or a chlorine atom.
[18] In the third step, the compound represented by the above formula (1) and the compound represented by the above formula (5) 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%.
[19] The above production method, wherein the compound having one or more metals selected from the group consisting of palladium, nickel and iron is palladium.
[20] The production method, wherein in the third step, the compound represented by the formula (1) and the compound represented by the formula (5) are reacted in the presence of a second additive. .
[21] The production method described above, wherein in the third step, the compound represented by the formula (1) is reacted with the compound represented by the formula (5) in the presence of a base.
[22] The production method described above, wherein, in the third step, the compound represented by the formula (1) and the compound represented by the formula (5) are reacted in the presence of a phase transfer catalyst.
[23] The above production method using a water-insoluble organic solvent in the third step.
[24] The above production method using a water-soluble organic solvent in the third step.

  According to the present invention, it is possible to provide a method for producing an aromatic boron compound that is low in raw material cost and suitable for industrial production, and that can produce the aromatic boron compound in a high yield. .

  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 an aromatic boron compound of the present embodiment has the following general formula (1):
R ² -Ph-Z (1)
(Hereinafter simply referred to as “compound (1)”), which is represented by the following general formula (2):
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 the formula (hereinafter simply referred to as “compound (3)”), a compound represented by the above formula (3) and a compound having a boron atom (hereinafter referred to as “Z-containing compound”). And a second step of obtaining a compound represented by the above formula (1), and in the first step and / or the second step, in the reaction system, a solvent and And a first additive having a heteroatom.

(1) In the first step this embodiment, than to react by mixing the compound (2) and containing M ¹ compound to provide compound (3). Here, in each of the above general formulas, Ph represents a phenylene group.

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 ease of synthesis of the aromatic boron compound and availability of raw materials. Particularly preferred is 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 described later. However, when an aromatic boron compound is used as a gelling agent raw material, it is in the para-position. It is preferable.

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 is further improved, the purification becomes easier, and the target aromatic boron compound can be obtained with higher purity.

  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.

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 alkyl metal groups, alkoxy metal groups, and halogenated metal groups.

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%.

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

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

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 group include a hydroxyl group, an alkyl group, an alkoxy group, and a halogen atom. which may be a phenyl group, a phenyl group optionally substituted with an alkoxy group, an alkyl phenyl group which may be substituted with a group include groups represented by halogen atoms and -Ph-R ^2. Here, Ph and R ² are synonymous with those in the above formula (1). Preferably the carbon number of the said alkyl group and alkoxy group is 1-10. Z is more preferably an alkoxy group, and the alkoxy group preferably has 1 to 6 carbon atoms. When Q ¹ or Q ² is a group represented by —Ph—R ² , the plurality of R ² may be the same as or different from each other.

Q ¹ and Q ² may be bonded to each other to form a ring together with the boron atom. The group in which Q ¹ and Q ² are bonded to each other is preferably, for example, an alkylenedioxy group which may be substituted with an alkyl group, or an alkylene group which may be substituted with an alkyl group. The number of carbon atoms in the main chain of the alkylenedioxy group (—O—R—O—; R is an alkylene group) optionally substituted with an alkyl group is preferably 2 to 6, more preferably 2 to 3. Particularly preferably 2. Moreover, carbon number of the main chain of the alkylene group which may be substituted by the alkyl group becomes like this. Preferably it is 2-11, More preferably, it is 4-7. Furthermore, carbon number of the alkyl group to substitute becomes like this. Preferably it is 1-8, More preferably, it is 1-3, Especially preferably, it is 1. The number of alkyl groups substituted for one carbon atom of the main chain may be singular or plural.

Examples of the group in which Q ¹ and Q ² are bonded to each other include groups represented by the following formulas (9A) to (9D).

  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 (6). In this specification, a boronic acid analog is represented by boronic acid, a compound in which one or more hydrogen atoms of boronic acid are substituted, a boronic acid ester which may form a ring, and the following general formula (6A). And a compound containing a boroxan ring.

ここで、式（６）及び（６Ａ）中、Ｒ³、Ｒ⁴及びＲ⁵は、それぞれ独立に、１価の有機基を示し、好ましくは、水素原子、水酸基、アルコキシ基及び−Ｐｈ−Ｒ²（Ｐｈはフェニレン基であり、Ｒ²は上記式（１）におけるものと同義である。）で表される基である。式（６）において、Ｒ³及びＲ⁴の両方が−Ｐｈ−Ｒ²で表される基であるか、Ｒ³及びＲ⁴のいずれか一方が−Ｐｈ−Ｒ²で表される基であり、他方が水酸基もしくはアルコキシ基であるとより好ましく、Ｒ³及びＲ⁴の両方が−Ｐｈ−Ｒ²で表される基であると更に好ましい。Ｒ³及びＲ⁴の両方が−Ｐｈ−Ｒ²で表される基である場合、上記式（６）で表される化合物における３つのＲ²が全て同じ基であると特に好ましい。また、式（６Ａ）において、Ｒ³、Ｒ⁴及びＲ⁵が、それぞれ独立に、水酸基、アルコキシ基又は−Ｐｈ−Ｒ²で表される基であると好ましく、いずれか１つが水酸基又はアルコキシ基であって、他の２つが−Ｐｈ−Ｒ²で表される基であるか、いずれも−Ｐｈ−Ｒ²で表される基であるとより好ましく、いずれも−Ｐｈ−Ｒ²で表される基であると更に好ましい。この場合も、Ｒ²が全て同じ基であると特に好ましい。

Here, in the formulas (6) and (6A), R ³ , R ⁴ and R ⁵ each independently represent a monovalent organic group, preferably a hydrogen atom, a hydroxyl group, an alkoxy group and —Ph—R. ² (Ph is a phenylene group, and R ² has the same meaning as in the above formula (1)). In Formula (6), both R ³ and R ⁴ are groups represented by —Ph—R ² , or one of R ³ and R ⁴ is a group represented by —Ph—R ² . The other is more preferably a hydroxyl group or an alkoxy group, and more preferably both R ³ and R ⁴ are groups represented by —Ph—R ² . When both R ³ and R ⁴ are groups represented by —Ph—R ² , it is particularly preferred that all three R ² in the compound represented by the formula (6) are the same group. In Formula (6A), R ³ , R ⁴ and R ⁵ are each independently preferably a hydroxyl group, an alkoxy group or a group represented by —Ph—R ² , and any one of them is a hydroxyl group or an alkoxy group. a is, other two or a group represented by -Ph-R ^2, either more preferably a group represented by -Ph-R ^2, both represented by -Ph-R ² More preferably, it is a group. Also in this case, it is particularly preferred that all R ² are the same group.

The compound (1) can be obtained by eliminating M ¹ in the second step of obtaining the compound (1) by mixing and reacting the compound (3) and the Z-containing compound. If it is a compound, it will not specifically limit. Preferably, the Z-containing compound is a compound represented by the following general formula (10).

ここで、Ｑ³、Ｑ⁴及びＱ⁵は、互いに同じであっても異なっていてもよい１価の基であり、それらの基としては、例えば、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。Ｑ³、Ｑ⁴及びＱ⁵は、より好ましくはアルコキシ基であり、アルコキシ基の炭素数は１〜６である。入手性の観点から、含Ｚ化合物はアルコキシボレートであると好ましく、トリアルコキシボレートであるとより好ましい。

Here, Q ³ , Q ⁴ and Q ⁵ are monovalent groups which may be the same or different from each other. Examples of these groups include alkyl groups, alkoxy groups, and halogen atoms. A phenyl group which may be substituted, a phenyl group which may be substituted with an alkoxy group, a phenyl group which may be substituted with an alkyl group, and a halogen atom. Preferably the carbon number of the said alkyl group and alkoxy group is 1-10. Q ³ , Q ⁴ and Q ⁵ are more preferably an alkoxy group, and the alkoxy group has 1 to 6 carbon atoms. From the viewpoint of availability, the Z-containing compound is preferably an alkoxyborate, more preferably a trialkoxyborate.

Q ³ , Q ⁴ and Q ⁵ may be bonded to each other to form a ring together with the boron atom. The group bonded to each other is preferably, for example, an alkylenedioxy group which may be substituted with an alkyl group or an alkylene group which may be substituted with an alkyl group. The number of carbon atoms in the main chain of the alkylenedioxy group (—O—R—O—; R is an alkylene group) optionally substituted with an alkyl group is preferably 2 to 6, more preferably 2 to 3. Particularly preferably 2. Moreover, carbon number of the main chain of the alkylene group which may be substituted by the alkyl group becomes like this. Preferably it is 2-11, More preferably, it is 4-7. Furthermore, carbon number of the alkyl group to substitute becomes like this. Preferably it is 1-8, More preferably, it is 1-3, Especially preferably, it is 1. The number of alkyl groups substituted for one carbon atom of the main chain may be singular or plural.

  In the first step and / or the second step, the hetero atom in the first additive having a hetero atom present in the reaction system is preferably nitrogen from the viewpoint of more effectively and reliably achieving the effects of the present invention. One or more atoms selected from the group consisting of an atom, a phosphorus atom and an oxygen atom. The 1st additive used in the manufacturing method of this embodiment is used individually by 1 type or in combination of 2 or more types. The first additive may have a plurality of different or the same heteroatoms in one molecule.

  Examples of the first additive include ether compounds, organic nitrogen compounds, ammonium salts, organic phosphorus compounds, and phosphonium salts. More preferably, the first additive is an ether compound having a structure in which an oxygen atom and a hydrogen atom are not directly bonded, an organic nitrogen compound having a structure in which a nitrogen atom and a hydrogen atom are not directly bonded, an ammonium salt, and an amine. Compounds, urea compounds, amide compounds, imide compounds, organic phosphorus compounds having a structure in which phosphorus atoms and hydrogen atoms are not directly bonded, and phosphonium salts having a structure in which phosphorus atoms and hydrogen atoms are not directly bonded.

  Examples of the first additive having a nitrogen atom as a hetero atom include nitrogen compounds having an alkyl group such as trimethylamine, triethylamine, tripropylamine, and tributylamine, triethylamine, tetramethylethylenediamine, and substituted imidazolidine. Nitrogen compounds having an alkyl group having a plurality of nitrogen atoms, pyridine, 2,2′-bipyridyl, substituted 2,2′-bipyridyl, 1,10-phenanthroline, phenylpyridin-2-ylmethylenamine, terpyridyl, N, Examples thereof include nitrogen-containing heterocyclic compounds such as N-dimethylaniline and quinoline, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone.

  Examples of the ammonium salt include tetrabutylammonium salts such as tetrabutylammonium bromide and tetrabutylammonium iodide, tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrahexylammonium salt, tetraoctylammonium salt, tetradecyl Ammonium salt, hexadecyltriethylammonium salt, dodecyltrimethylammonium salt, trioctylmethylammonium salt, octyltriethylammonium salt, benzyltrimethylammonium salt, benzyltriethylammonium salt, benzyltributylammonium salt, benzyldimethyloctadecylammonium salt, phenyltrimethylammonium salt And STARKS 'catalyst It is.

  The nitrogen-containing heterocyclic compound has one or more, usually 1 to 4, nitrogen atoms as heteroatoms in the heterocyclic ring. Further, the nitrogen-containing heterocyclic compound may be a monocyclic compound or a bicyclic compound, and is usually composed of 1 to 4 5- to 7-membered rings that are a heterocyclic ring and a homocyclic ring. Is. Examples of the heterocyclic ring include monocyclic 5-membered rings such as pyrrole ring, imidazole ring, pyrazole ring and triazole ring, and 6-membered rings such as pyridine ring, pyrimidine ring and triazine ring. Examples of the bicyclic ring include an indole ring, a benzimidazole ring, a benztriazole ring, a quinoline ring, a bipyridyl ring, and a phenanthroline ring. These heterocycles may be condensed with an allocyclic ring composed only of aromatic carbon such as a benzene ring and a naphthalene ring. Among nitrogen-containing heterocyclic compounds, those having aromaticity are particularly preferred, and examples of such compounds include pyridine ring, pyrrole ring, imidazole ring, triazole ring, indole ring, quinoline ring, bipyridyl ring, Or the nitrogen-containing heterocyclic compound containing a phenanthroline ring is mentioned. Further, the nitrogen-containing heterocycle may have a substituent such as an alkyl group, a hydroxyl group and a cyano group.

  Among the nitrogen-containing heterocyclic compounds, examples of monocyclic compounds include pyridine derivatives such as pyridine, pyrimidine, pyridazine and pyrazine, pyrrole derivatives such as pyrrole and pyrazole, imidazole derivatives such as imidazole and 1-methylimidazole, and 1H- And triazole derivatives such as 1,2,3-triazole, 2H-1,2,3-triazole, 2H-1,2,4-triazole, and 4H-1,2,4-triazole. In addition, examples of the multicyclic compound include indole derivatives such as indole, isoindole, 1H-indazole, 2H-indazole, and purine, benzimidazole derivatives such as benzimidazole and 1-methylbenzimidazole, benzotriazole, and 1 -Benztriazole derivatives such as methylbenzotriazole, quinoline derivatives such as quinoline, isoquinoline, phthalazine, cinnoline, quinazoline, quinoxaline, 1,8-naphthyridine, and pteridine, 2,2'-dipyridyl, 2,3'-dipyridyl, 2 , 4′-dipyridyl and 3,3′-dipyridyl and the like, and acridine, phenazine and phenanthroline derivatives such as 1,10-phenanthroline and the like.

Examples of the first additive having a phosphorus atom as a hetero atom 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), 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, spiro Type phosphonium salts and imidazol-2-ylidenecarbenes.

  Examples of the phosphonium salt include tetrabutylphosphonium salts such as tetrabutylphosphonium bromide and tetrabutylphosphonium iodide, tetramethylphosphonium salt, tetraethylphosphonium salt, tetrapropylphosphonium salt, tetrahexylphosphonium salt, tetradecylphosphonium salt, tetraoctyl. Examples include phosphonium salts, triethyloctadecylphosphonium salts, trioctylethylphosphonium salts, hexadecyltriethylphosphonium salts, tetraphenylphosphonium salts, and methyltriphenylphosphonium salts.

  Examples of the first additive having an oxygen atom as a hetero atom include an ether compound. Examples of the ether compound include diethyl ether, diglyme, dimethoxyethane, 1,4-dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, diethoxymethane, diisopropyl ether, anisole, methyl t-butyl ether, crown ether, cribandand, and chain Examples include polyethylene glycol derivatives. Examples of the crown ether include 18-crown-6, dibenzo-18-crown-6, and dicyclohexyl-18-crown-6. Examples of the cryptand include [2.2.2] cryptand. Examples of the chain polyethylene glycol derivative include PEG-200, PEG-400, and PEG-6000.

  In the present embodiment, the first additive is preferably used in an amount of 30 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less with respect to 100 parts by mass of the solvent in the reaction system. The first additive is preferably used in the range of 20 to 500 mol%, more preferably 20 to 300 mol%, and still more preferably 50 to 200 mol% with respect to 100 mol% of the compound (1). When the first additive has a plurality of heteroatoms in one molecule, the amount of the first additive based on mol may be within the above preferable range, and the amount of the first additive based on mol The value divided by the number of heteroatoms in one molecule may be within the above preferred range.

  In the first step and / or the second step, the solvent present in the reaction system is preferably an organic solvent, and may be a water-insoluble organic solvent or a water-soluble organic solvent. An organic solvent may be used. 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. In this embodiment, the solvent excludes those used as the first additive.

  The water-insoluble organic solvent is preferably 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 in the subsequent purification step. From the viewpoint of separation from the organic phase, a solvent having a solubility in water at 20 ° C. of 5% by mass or less is more preferable.

  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, tertiary amine solvents such as triethylamine and N, N-dimethyl-4-aminopyridine, and the like. 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 atoms with high acidity, it is possible to suppress the generation of side reactions.

  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 solvent is preferably an aprotic non-nucleophilic solvent. By using an aprotic non-nucleophilic solvent, side reactions can be further suppressed even at room temperature or higher or at a high temperature. Examples of the aprotic non-nucleophilic 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, Examples thereof include fluorine-containing solvents such as solvents having a perfluoro group such as fluorooctane, perfluorohexane and perfluorobenzene, and alkane solvents such as hexane and cyclohexane. From the viewpoint of availability, benzene, toluene, xylene, chlorobenzene, dichloromethane, chloroform, hexane, heptane, and cyclohexane are more preferable, and toluene, xylene, chlorobenzene, and methylene chloride are more preferable.

  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.

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

  The reaction temperature in at least one of the first step and the second step is preferably −20 ° C. or higher, more preferably 30 ° C. or higher, from the viewpoint of ease of temperature control.

  The reaction temperature in the first step is preferably −80 ° C. to 200 ° C., more preferably −20 to 150 ° C. from the viewpoints of reduction of side reaction, ease of temperature control, boiling point of solvent and solubility of raw materials. More preferably, it is 20-100 degreeC, Most preferably, it is 30-80 degreeC.

  The reaction temperature in the second step is preferably −80 ° C. to 200 ° C., more preferably −20 to 150 ° C., from the viewpoints of reduction of side reactions, ease of temperature control, boiling point of solvent and solubility of raw materials. More preferably, it is 20-100 degreeC, Most preferably, it is 30-80 degreeC.

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

(3) Third Step In this embodiment, the compound (1) obtained through the second step and the following general formula (5):
R ¹ -L-Ph-X ¹ (5)
And a compound represented by the following formula (hereinafter simply referred to as “compound (5)”) and reacted to give the following general formula (4):
R ¹ -L-Ph-Ph-R ² (4)
The polycyclic aromatic compound represented by these can be manufactured. Here, in the above formulas, Ph represents a phenylene group, and in formula (4), R ² has the same meaning as in formula (1).

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 —), 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.

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.

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.

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, an alkyl group in which one or more hydrogen atoms are substituted with a halogen atom, preferably halogen is fluorine, and the number of carbons in the group is preferably Is 1-28, 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), and more preferably a group represented by -LR ¹ is a group represented by the following general formula (8).

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

  Compound (5) 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 (5) individually or in combination of 2 or more types.

  The compounding ratio of the compound (1) and the compound (5) in the reaction system is such that the amount of the compound (5) is preferably 50 to 200 mol%, more preferably 80 to 120 mol, relative to 100 mol% of the compound (1). %, More preferably 90 to 110 mol%.

In the third step, compound (1) and compound (5) 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. Among these, a preferable M ² -containing compound is a compound having palladium (hereinafter referred to as “palladium-containing compound”). Containing M ² compounds are used alone or in combination of two or more thereof.

  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. Palladium-containing compounds preferably used include, for example, palladium (supporting 0, palladium acetate (II), palladium chloride (II), bis (triphenyl) on a carbon substance (for example, activated carbon and carbon particles) as a carrier. Phosphine) palladium (II) chloride, tetrakis (triphenylphosphine) palladium (0), palladium ketonate, palladium acetylacetonate, nitrile palladium halide, palladium halide, allyl palladium halide, and palladium biscarboxylate. Among these, palladium acetate (II) and palladium chloride (II) are more preferable, and palladium acetate (II) is more preferably used.Palladium-containing compounds may be used alone or in combination of two or more. Used by.

  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.

Abundance of containing M ² compound, among the compounds (1) and the compound (5), relative to the amount of the compound of the lesser molar basis (100 mol%), preferably to be 0.0001~1mol%, 0 More preferably, it is 0.0001 to 0.1 mol%, and even more preferably 0.001 to 0.1 mol%. When the abundance of the M2 containing compound is within the above 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. Purification becomes easier.

In the production method of the present embodiment, in the third step, compound (1) and compound (5) may be reacted in the presence of the second additive. By using the second additive, it becomes easier to control and accelerate the reaction. That is, the second additive functions as a reaction control agent or a reaction accelerator for the reaction between the compound (1) and the compound (5). A 2nd additive is used individually by 1 type or in combination of 2 or more types. The second 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 the second additive reacts with a metal contained in the metal-containing compound and a substituent on the ligand to produce a palladacycle in the case where the metal is palladium (Angevante Chemie, A compound such as International Edition in English (see 34, 1844 (1995)) may be formed.

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

  In the third step, the amount of the second additive present in the reaction system is preferably relative to the amount (100 mol%) of the compound (1) and the compound (5), which is smaller on a molar basis. Is 0.0001 to 4 mol%, more preferably 0.0001 to 0.4 mol%, still more preferably 0.001 to 0.4 mol%. A 2nd additive is used individually by 1 type or in combination of 2 or more types. When the amount of the second additive is within the above range, the reaction can be promoted or the reaction can be controlled more reliably, and purification can be performed more easily.

  Each raw material, product, and by-product in the third step of the present embodiment may exist in any state of a solid and a 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 third step, compound (1) and compound (5) may be reacted in the presence of a base. Examples of the base include alkali metal or alkaline earth metal hydroxides, carbonates, hydrogen carbonates, phosphates, carboxylates, alkoxides, and tertiary amines that are organic bases (for example, triethylamine). Can be used. From the viewpoint of facilitating the synthesis and purification of the polycyclic aromatic compound, the base is preferably an alkali metal or alkaline earth metal hydroxide, carbonate, bicarbonate, phosphate and carboxylate. More preferred are alkali metal or alkaline earth metal carbonates, hydrogen carbonates, phosphates and carboxylates, and still more preferred are alkali metal or alkaline earth metal carbonates and hydrogen carbonates. . Examples of alkali metal or alkaline earth metal carbonates and bicarbonates include lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, barium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate and cesium bicarbonate. Are preferable, and lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate are more preferable.

  The base may be a compound added independently in the reaction system, or may be added in a state of being included in the raw material, catalyst, ligand and the like. The amount of the base is preferably 10 to 5000 mol%, more preferably 50 to 2000 mol%, based on the amount of the compound (1) and compound (5), which is smaller on a molar basis (100 mol%). is there. Moreover, a base is used individually by 1 type or in combination of 2 or more types.

  In the third step of the production method of the present embodiment, the compound (1) and the compound (5) may be reacted in the presence of a phase transfer catalyst. 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, phenyl trimethyl ammonium salt, STARKS 'ca alyst, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, tetrabutylphosphonium salt, tetramethylphosphonium salt, tetraethylphosphonium salt, tetrapropylphosphonium salt, tetrahexylphosphonium salt, tetradecylphosphonium salt, tetradecylphosphonium salt 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] crypter 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.

  In the third step, in addition to the phase transfer catalyst, the reaction system may contain a co-catalyst that enhances the catalytic activity and other catalysts. 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 compound (100 mol%) on the molar basis, which is smaller among the reaction raw materials, More preferably, it is 0.01-20 mol%, More preferably, it is 0.1-10 mol%.

  In the third step, a solvent may be present in the reaction system, and the solvent is preferably an organic solvent, and may be a water-insoluble organic solvent or a water-soluble 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, amide solvents such as N-methylpyrrolidinone and dimethylformamide, diethyl ether, diglyme, dimethoxyethane, 1,4-dioxane, tetrahydrofuran Ether solvents such as 2-methyltetrahydrofuran, 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, methanol, ethanol, 1 , 2-propanediol, isopropyl alcohol, t-butyl alcohol, n-butyl alcohol and t-amyl alcohol, alcohol solvents such as acetonitrile, 1,3-dimethyl-2-imidazolidinone, pyridine, nitromethane, Examples include dimethyl sulfoxide, N-methylpyrrolidone, acetic acid and triethylamine. An organic solvent is used individually by 1 type or in combination of 2 or more types.

  When a water-insoluble organic solvent is included as a solvent used in the reaction system in the third step, examples of the water-insoluble organic solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene, chlorobenzene and the like. Perfluoro groups such as halogenated aromatic hydrocarbon solvents, halogenated aliphatic hydrocarbon solvents such as dichloromethane and chloroform, perfluoro-2-butyltetrahydrofuran, perfluorooctane, perfluorotributylamine, perfluorohexane and perfluorobenzene A fluorine-containing solvent such as a solvent having a solvent, an ester solvent such as alkyl acetate such as butyl acetate, isobutyl acetate and isopropyl acetate, diethyl ether, 2-methyltetrahydrofuran, diethoxymethane, diisopropyl ether, anisole and methyl t Ether solvents such as ether, 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. A water-insoluble 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 of each of the above steps or a purification temperature in the subsequent purification step, more preferably 20 ° C. From the viewpoint of separation of the aqueous phase and the organic phase, a solvent having a solubility in water at 20 ° C. of 5% by mass or less is more preferable. The water-insoluble organic solvent is still more preferably an aromatic hydrocarbon solvent, a halogenated aromatic hydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent, a fluorine-containing solvent, and an ether solvent. The water-insoluble organic solvent is particularly preferably toluene, xylene, chlorobenzene and methylene chloride from the viewpoint of availability of the solvent. Since a water-insoluble organic solvent is easily separated from water, it is effective in that water-soluble by-products and impurities can be easily washed. Further, even when the water-insoluble organic solvent used in the reaction is reused by distillation or the like, it is also effective in that it can be easily purified because it contains little water.

  When a water-soluble organic solvent is included as a solvent used in the reaction system in the third step, examples of the water-soluble organic solvent include amide solvents such as N, N-dimethylacetamide, N-methylpyrrolidinone and dimethylformamide. Ether solvents such as diglyme, dimethoxyethane, 1,4-dioxane and tetrahydrofuran, ketone solvents such as acetone and methyl ethyl ketone, methanol, ethanol, 1,2-propanediol, isopropyl alcohol, t-butyl alcohol, n-butyl alcohol and Examples include alcohol solvents such as t-amyl alcohol, nitrile solvents such as acetonitrile, 1,3-dimethyl-2-imidazolidinone, pyridine, nitromethane, dimethyl sulfoxide, N-methylpyrrolidone, and acetic acid. A water-soluble 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 the reaction temperature of each of the above steps, or a purification temperature in the subsequent purification step, preferably 20 ° C., and has a solubility during purification. From the viewpoint, a solvent having a solubility in water at 20 ° C. of 50% by mass or more is more preferable, and a solvent arbitrarily mixed with water at 20 ° C. is more preferable. More specifically, methanol, ethanol, 1,2-propanediol, isopropyl alcohol, t-butyl alcohol, n-butyl alcohol, t-amyl alcohol, nitromethane, acetonitrile, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, The solvent is preferably at least one solvent selected from the group consisting of acetone, acetic acid, pyridine, 1,2-dimethoxyethane, tetrahydrofuran and 1,4-dioxane. Since the water-soluble organic solvent is easily mixed with water, the target product can be precipitated or the precipitation can be promoted in the purification step. In addition, the water-soluble organic solvent can dissolve and remove a by-product salt by adding water.

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

  The amount of the solvent in the reaction system in the third step is 500 to 500% with respect to the amount (100% by mass) of the compound (1) and the compound (5) that are contained in a larger amount from the viewpoint of solubility during the reaction. It is preferable in it being 5000 mass%, and it is more preferable in it being 500-3000 mass%.

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

  The reaction temperature in the third step is preferably 0 to 200 ° C, more preferably 20 to 150 ° C, and still more preferably 40 to 130 ° C, from the viewpoint of the boiling point of the solvent and the solubility of the raw materials.

  In the third step, 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 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 each of the above steps, the salt and water-soluble raw material contained in the reaction mixture can be dissolved in water, and the salt and 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 those described above such as a reaction catalyst, a cocatalyst, a reaction accelerator, an emulsifier, and an antifoaming agent may be used as necessary in each step. 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.

  As a reaction catalyst, the phase transfer catalyst in a 1st process and a 2nd process is mentioned, for example. 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 the above steps, or different additives may be used in each step.

  According to this embodiment, it is possible to provide a method for producing an aromatic boron compound that is low in raw material cost and suitable for industrial production, and that can produce an aromatic boron compound in a high yield. . More specifically, “suitable for industrial production” means that refining and the like are easy and can reduce labor, that large-scale or complicated equipment is not required for production and purification, and cryogenic / ultra-high pressure. This means not using special conditions.

  The aromatic boron compound obtained by the production method of the present embodiment includes, for example, a material for a nonaqueous electrolyte secondary battery (preferably a lithium ion secondary battery) such as an electrolyte gelling agent, an organic EL material, and a liquid crystal material. It can be used for 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%.

[Example 1]
After putting 0.5 g (1.95 mmol) of p-bromo (hexyloxy) benzene into the reaction vessel and substituting the atmosphere around the reaction system with nitrogen gas, N, N, N ′, N′-tetramethylethylenediamine 0 .45 g (3.9 mmol) and 10 mL of toluene were added, and the mixture was stirred at 40 ° C. for 5 minutes. Next, 1.34 mL (2.15 mmol) of a 1.6 mol / L butyl lithium hexane solution was added, and the mixture was stirred at 40 ° C. for 30 minutes. Next, 0.55 g (2.92 mmol) of triisopropyl borate was added to the reaction vessel and stirred at 40 ° C. for 30 minutes. Subsequently, 40 mL of 0.1 mol / L hydrochloric acid aqueous solution was added to the reaction vessel, and after stirring for 5 minutes, the aqueous layer was removed, and this was repeated twice. Furthermore, 40 mL of water was added to the reaction vessel, and after stirring for 5 minutes, the aqueous layer was removed, and this was repeated twice. Then, solvent removal was obtained and p-hexoxyphenyl boronic acid was obtained in the state of white solid. The yield was 0.39 g and the yield was 90%. The structure of the obtained compound was confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.
¹ H-NMR (CDCl ₃ ) 0.90 (3H, m), 1.40 (6H, m), 1.80 (2H, m), 4.00 (2H, m), 6.97 (2H, d, J = 8.0 Hz), 8.13 ( 2H, d, J = 8.0 Hz) ppm

[Example 2]
P-Hexoxyphenylboronic acid was obtained in the same manner as in Example 1 except that 2 mL of tetrahydrofuran was used instead of N, N, N ′, N′-tetramethylethylenediamine and the reaction temperature was changed to -10 ° C. It was. The yield was 0.33 g, and the yield was 75%. The structure of the obtained compound was confirmed by ¹ H-NMR (CDCl ₃ ). The results were as follows.
¹ H-NMR (CDCl ₃ ) 0.90 (3H, m), 1.40 (6H, m), 1.80 (2H, m), 4.00 (2H, m), 6.97 (2H, d, J = 8.0 Hz), 8.13 ( 2H, d, J = 8.0 Hz) ppm

[Example 3]
After putting 1 g (3.84 mmol) of p-bromo (hexyloxy) benzene into the reaction vessel and substituting the atmosphere around the reaction system with nitrogen gas, 0.9 g of N, N, N ′, N′-tetramethylethylenediamine was added. (7.8 mmol) and 30 mL of toluene were added, and the mixture was stirred at 40 ° C. for 5 minutes. Next, 2.38 mL (4.3 mmol) of a 1.6 mol / L butyl lithium hexane solution was added, and the mixture was stirred at 40 ° C. for 30 minutes. Next, 1.1 g (5.83 mmol) of triisopropyl borate was added to the reaction vessel and stirred at 40 ° C. for 30 minutes. Subsequently, 40 mL of 0.1 mol / L hydrochloric acid aqueous solution was added to the reaction vessel, and after stirring for 5 minutes, the aqueous layer was removed, and this was repeated twice. Furthermore, 40 mL of water was added to the reaction vessel, and after stirring for 5 minutes, the aqueous layer was removed, and this was repeated twice. Then, compound (1A) 2.21 g (3.84 mmol), palladium acetate 4.4 mg (0.019 mmol), triphenylphosphine 12.7 mg (0.049 mmol), sodium carbonate 1.06 g (7.68 mmol), ethanol 20 mL and 20 mL 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, 40 mL 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, 20 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. Then, the compound which has a structure represented by following formula (4A) in the state of white solid was obtained through filtration and solvent removal. The yield was 2 g, and the yield was 80%. The structure of the obtained compound 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

[Comparative Example 1]
Example 1 was repeated except that N, N, N ′, N′-tetramethylethylenediamine was not used. The target product was not obtained.

[Comparative Example 2]
N, N, N ′, N′-Tetraethylenediamine was not used, and the same procedure as in Example 1 was performed except that the reaction temperature was changed to −72 ° C. The target product was not obtained.

  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 aromatic boron compounds useful as pharmaceuticals, etc., or synthetic intermediates thereof.

Claims (24)

The following general formula (1):
R ² -Ph-Z (1)
A process for producing a 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:
A second step of reacting the compound represented by the above formula (3) with a compound having a boron atom to obtain a compound represented by the above formula (1),
The manufacturing method in which a solvent and a first additive having a hetero atom are present in the reaction system in the first step and / or the second step.
(In the formulas (1), (2) and (3), R ² represents an alkyl group or an alkoxy group, Ph represents a phenylene group, Z represents a monovalent group having a boron atom, and X ² represents an anion. 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 the Ph (In the formula (1), the boron atom 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.   The manufacturing method of any one of Claims 1-4 whose compound which has the said boron atom is an alkoxy borate.   The production method according to any one of claims 1 to 5, wherein the heteroatom in the first additive is one or more atoms selected from the group consisting of a nitrogen atom, a phosphorus atom, and an oxygen atom.   The said 1st additive is a manufacture of any one of Claims 1-6 containing 1 or more types chosen from the group which consists of an ether compound, an organic nitrogen compound, an ammonium salt, an organic phosphorus compound, and a phosphonium salt. Method.   The manufacturing method according to claim 1, wherein the solvent is an aprotic non-nucleophilic solvent.   The said solvent is a manufacturing method of any one of Claims 1-8 containing 1 or more types of solvents chosen from the group which consists of toluene, xylene, chlorobenzene, and a methylene chloride.   The production method according to claim 1, wherein a reaction temperature in at least one of the first step and the second step is −20 ° C. or higher.   The manufacturing method of any one of Claims 1-10 whose reaction temperature in at least one of the said 1st process and the said 2nd process is 30 degreeC or more. Said X < ² > is a manufacturing method of any one of Claims 1-11 which is a bromine atom, an iodine atom, or a chlorine atom. The following general formula (4):
R ¹ -L-Ph-Ph-R ² (4)
A process for producing a compound represented by
The following general formula (5):
R ¹ -L-Ph-X ¹ (5)
And a compound represented by the following general formula (1):
R ² -Ph-Z (1)
The manufacturing method which has a 3rd process of making the compound represented by these react, and obtaining the compound represented by the said Formula (4).
(In the above formulas (4), (5) and (1), 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 is an anionic 1 R represents a sulfide group, sulfinyl group or sulfonyl group, R ² represents an alkyl group or an alkoxy group, Ph represents a phenylene group, and Z represents a monovalent group having a boron atom. In the formula (1), the boron atom is directly bonded to the Ph.) The method according to claim 13, wherein the halogen atom in R ¹ is a fluorine atom. The production method according to claim 13 or 14, wherein R ¹ includes a perfluoroalkyl chain moiety.   The said L is a manufacturing method of any one of Claims 13-15 which is a sulfonyl group. The production method according to claim 13, wherein X ¹ is a bromine atom, an iodine atom, or a chlorine atom.   In the third step, the compound represented by the above formula (1) and the compound represented by the above formula (5) are reduced by 0 with respect to the amount of the smaller compound on a molar basis. The manufacturing method of any one of Claims 13-17 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 any one of claims 13 to 18, wherein the compound having at least one metal selected from the group consisting of palladium, nickel, and iron is palladium.   In the third step, the compound represented by the formula (1) and the compound represented by the formula (5) are reacted in the presence of a second additive. The manufacturing method of any one of Claims.   The said 3rd process WHEREIN: The compound represented by the said Formula (1) and the compound represented by the said Formula (5) are made to react in presence of a base. The manufacturing method as described in.   In the third step, the compound represented by the formula (1) and the compound represented by the formula (5) are reacted in the presence of a phase transfer catalyst. 2. The production method according to item 1.   The manufacturing method according to any one of claims 13 to 22, wherein a water-insoluble organic solvent is used in the third step.   The manufacturing method according to any one of claims 13 to 22, wherein a water-soluble organic solvent is used in the third step.