JP2018083174A - Etherification catalyst composition and method for producing ether compound using the etherification catalyst composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an ether compound from an alcohol using an etherification catalyst composition.SOLUTION: The present invention provides a method for producing an ether compound using a catalyst composition containing a transition metal complex represented by formula (1) [Ar is aromatic compound or cyclopentadienyl group; Mis Ru, Rh or Ir; L is sulfoxide, amide, nitrogen-containing aromatic ring, amine, ether, nitrile or aquo ligand; dashed line is, together with a solid line, single bond or double bond; Yis anion, preferably alkyl sulfonic acid ion, bis(sulfonyl) imide ion, or a (sulfonyl) methide ion].SELECTED DRAWING: None

Description

The present invention relates to an etherification catalyst composition and a method for producing an ether compound using the etherification catalyst composition.

  Conventionally, ether compounds are used in a wide range of fields such as pharmaceuticals, agricultural chemicals, surfactants, and polymer materials. As a method for producing an ether compound, for example, a method of alkylating an alcohol compound with an alkyl halide is widely known (Non-Patent Document 1). However, in this method, an alcohol compound is reacted with an alkali metal such as sodium to form an alkali metal alcoholate, and then an alkyl halide is reacted. In this reaction, an equal amount of inorganic salt is discharged as a by-product. Alkyl halides are generally highly toxic. Thus, the subject remains in industrially implementing the method of a nonpatent literature 1.

  On the other hand, production examples of ether compounds that do not require alkyl halides using transition metal catalysts have been reported (Non-patent Documents 2 and 3). In Non-Patent Document 2, an ether compound is produced by reacting an alcohol compound using a ruthenium complex as a catalyst. However, the ruthenium complex used as a catalyst is unstable to oxygen, needs to be handled in a special facility that can keep the oxygen concentration extremely low, and has a highly toxic carbonyl coordination as a ligand. There is a problem in industrial implementation because of the use of a child or an alkylphosphine ligand. In Non-Patent Document 3, ether synthesis is studied using an iridium complex having a nitrogen-containing heterocyclic carbene ligand, but using silver trifluoromethanesulfonate having high photosensitivity as an additive together with the iridium complex. Therefore, it is necessary to shield from light when performing the reaction, and there is a problem in industrial implementation. In addition, referring to Non-Patent Document 3, the present inventors used an iridium complex obtained by reacting an iridium complex having a nitrogen-containing heterocyclic carbene ligand and silver trifluoromethanesulfonate in advance to produce an ether compound. Production was attempted, but the yield was very low (see Comparative Examples below).

J. et al. March, Advanced Organic Chemistry Reactions, Mechanisms and Structure, 6th ed. , Wiley, New York, 2007, pp. 529-531. ACS Catal. 2014, 4, 3881-3985. Chem. Eur. J. et al. 2008, 14, 11474-11479.

  An object of the present invention is to provide an etherification catalyst composition that is simple and safe and suitable for industrial implementation, and to provide a method for producing an ether compound from an alcohol compound using the etherification catalyst composition. To do.

  The present inventor has intensively studied to solve the above problems. As a result, the present inventors have found a transition metal complex having a nitrogen-containing heterocyclic carbene ligand that is stable in air and does not contain highly toxic carbonyl ligands or alkylphosphine ligands. Furthermore, it has been found that by reacting various alcohol compounds in the presence of the transition metal complex, an ether compound can be obtained without producing a large amount of by-products, and the present invention has been completed.

  That is, the present invention relates to the following [1] to [15].

[1] An etherification catalyst composition containing a transition metal complex represented by the general formula (1) or (2).

General formula (1):

General formula (2):

［一般式（１）及び（２）中、Ａｒは、置換基を有してもよい芳香族化合物又は置換基を有していてもよいシクロペンタジエニル基、Ｍ^１は、ルテニウム、ロジウム又はイリジウム、Ｒ^１は置換基を有していてもよい炭素数１〜２０の炭化水素基、Ｒ^２〜Ｒ^７は、互いに独立して、水素原子、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシ基、アミノ基、スルホ基、メルカプト基、カルボキシル基、カルバモイル基又は置換基を有していてもよい炭素数１〜２０の炭化水素基を示す。Ｒ^２とＲ^３、Ｒ^３とＲ^４、若しくは隣接するＲ^４〜Ｒ^７は互いに結合して、環を形成してもよい。Ｌは、スルホキシド配位子、アミド配位子、含窒素芳香環配位子、アミン配位子、エーテル配位子、ニトリル配位子及びアコ配位子からなる群から選択される配位子を示す。破線は、実線と共に、単結合又は二重結合を形成していることを示す。Ｙ⁻はアニオンを示す。］
［２］ Ａｒが１，２，３，４，５−ペンタメチルシクロペンタジエニル基である［１］に記載のエーテル化触媒組成物。
［３］ Ｍ^１がイリジウムである［１］又は［２］に記載のエーテル化触媒組成物。
［４］ Ｙ⁻が一般式（３）：
Ｒ^８ＳＯ_３ ⁻ （３）
（一般式（３）中、Ｒ^８は炭素数１〜２０のアルキル基、炭素数１〜２０のパーフルオロアルキル基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基又は炭素数６〜２０のパーフルオロアリール基である。）
で表されるスルホン酸イオン、一般式（４）：

[In the general formulas (1) and (2), Ar is an aromatic compound which may have a substituent or a cyclopentadienyl group which may have a substituent, M ¹ is ruthenium, rhodium or Iridium, R ¹ is an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and R ^{2 to} R ⁷ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, hydroxy group , An amino group, a sulfo group, a mercapto group, a carboxyl group, a carbamoyl group or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. R ² and R ³ , R ³ and R ⁴ , or adjacent R ^{4 to} R ⁷ may be bonded to each other to form a ring. L is a ligand selected from the group consisting of a sulfoxide ligand, an amide ligand, a nitrogen-containing aromatic ring ligand, an amine ligand, an ether ligand, a nitrile ligand, and an aco ligand Indicates. A broken line shows that the single bond or the double bond is formed with the solid line. Y ⁻ represents an anion. ]
[2] The etherification catalyst composition according to [1], wherein Ar is a 1,2,3,4,5-pentamethylcyclopentadienyl group.
[3] The etherification catalyst composition according to [1] or [2], wherein M ¹ is iridium.
[4] Y ⁻ represents the general formula (3):
R ⁸ SO ₃ ^- ₍₃₎
(In General Formula (3), R ⁸ is an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or (It is a C6-C20 perfluoroaryl group.)
A sulfonate ion represented by the general formula (4):

（一般式（４）中、Ｒ^９、Ｒ^１０は互いに同じ若しくは異なっていてもよい炭素数１〜２０のアルキル基、炭素数１〜２０のパーフルオロアルキル基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基、炭素数６〜２０のパーフルオロアリール基又はフッ素原子を示し、Ｒ^９とＲ^１０は互いに結合して、環を形成していてもよい。）
で表されるビス（スルホニル）イミドイオン又は一般式（５）：
（Ｒ^１１ＳＯ_２）_３Ｃ⁻ （５）
（一般式（５）中、Ｒ^１１は炭素数１〜２０のアルキル基、炭素数１〜２０のパーフルオロアルキル基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基又は炭素数６〜２０のパーフルオロアリール基である。）
で表されるトリス（スルホニル）メチドイオンである［１］〜［３］のいずれかに記載のエーテル化触媒組成物。
［５］ Ｙ⁻が一般式（４）で表されるビス（スルホニル）イミドイオンである［１］〜［４］のいずれかに記載のエーテル化触媒組成物。
［６］ Ｌがアコ配位子である［１］〜［５］のいずれかに記載のエーテル化触媒組成物。
［７］ Ｒ^７がヒドロキシ基である［１］〜［６］のいずれかに記載のエーテル化触媒組成物。
［８］ Ｒ^２〜Ｒ^６が水素原子である［１］〜［７］のいずれかに記載のエーテル化触媒組成物。
［９］ Ｒ^１が炭素数１〜６のアルキル基である［１］〜［８］のいずれかに記載のエーテル化触媒組成物。
［１０］ ［１］〜［９］のいずれかに記載のエーテル化触媒組成物存在下、２分子以上のアルコール化合物同士を反応させるエーテル化合物の製造方法。
［１１］ ［１］〜［９］のいずれかに記載のエーテル化触媒組成物存在下、一般式（６）：

(In the general formula (4), R ⁹ and R ¹⁰ may be the same or different from each other, and the alkyl group having 1 to 20 carbon atoms, the perfluoroalkyl group having 1 to 20 carbon atoms, and the cycloalkyl having 3 to 20 carbon atoms. A group, an aryl group having 6 to 20 carbon atoms, a perfluoroaryl group having 6 to 20 carbon atoms, or a fluorine atom, and R ⁹ and R ¹⁰ may be bonded to each other to form a ring.)
A bis (sulfonyl) imide ion represented by the general formula (5):
_{^{(R 11 SO 2) 3 C}} - (5)
(In the general formula (5), R ¹¹ is an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or (It is a C6-C20 perfluoroaryl group.)
The etherification catalyst composition according to any one of [1] to [3], which is a tris (sulfonyl) methide ion represented by:
[5] The etherification catalyst composition according to any one of [1] to [4], wherein Y ⁻ is a bis (sulfonyl) imide ion represented by the general formula (4).
[6] The etherification catalyst composition according to any one of [1] to [5], wherein L is an acoligand.
[7] The etherification catalyst composition according to any one of [1] to [6], wherein R ⁷ is a hydroxy group.
[8] The etherification catalyst composition according to any one of [1] to [7], wherein R ^{2 to} R ⁶ are hydrogen atoms.
[9] The etherification catalyst composition according to any one of [1] to [8], wherein R ¹ is an alkyl group having 1 to 6 carbon atoms.
[10] A method for producing an ether compound in which two or more alcohol compounds are reacted with each other in the presence of the etherification catalyst composition according to any one of [1] to [9].
[11] In the presence of the etherification catalyst composition according to any one of [1] to [9], the general formula (6):

［一般式（６）中、Ｒ^１２は置換基を有していてもよい炭素数１〜２０の炭化水素基又は置換基を有していてもよい炭素数１〜２０の複素環基、Ｒ^１３は水素原子、置換基を有していてもよい炭素数１〜２０の炭化水素基又は置換基を有していてもよい炭素数１〜２０の複素環基であって、Ｒ^１２とＲ^１３が互いに結合して環を形成していてもよい。］
で表されるアルコール化合物と、一般式（７）：

[In General Formula (6), R ¹² is an optionally substituted hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted heterocyclic group having 1 to 20 carbon atoms, R ¹³ is a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted heterocyclic group having 1 to 20 carbon atoms, and R ¹² and R ¹³ may be bonded to each other to form a ring. ]
An alcohol compound represented by formula (7):

［一般式（７）中、Ｒ^１４は置換基を有していてもよい炭素数１〜２０の炭化水素基又は置換基を有していてもよい炭素数１〜２０の複素環基、Ｒ^１５は水素原子、置換基を有していてもよい炭素数１〜２０の炭化水素基又は置換基を有していてもよい炭素数１〜２０の複素環基であって、Ｒ^１４とＲ^１５が互いに結合して環を形成していてもよい。］
で表されるアルコール化合物を反応させる一般式（８）：

[In General Formula (7), R ¹⁴ is a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a heterocyclic group having 1 to 20 carbon atoms which may have a substituent, R ¹⁵ is a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted heterocyclic group having 1 to 20 carbon atoms, and R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. ]
General formula (8) in which an alcohol compound represented by the formula is reacted:

［一般式（８）中、Ｒ^１２〜Ｒ^１５は、前記に同じ。］
で表されるエーテル化合物の製造方法。
［１２］ さらに一般式（９）：
Ｍ^２・Ｎ（ＺＳＯ_２）_２ （９）
［一般式（９）中、Ｍ^２はＬｉ、Ｎａ、Ｋ、であり、Ｚはフッ素原子又は炭素数１〜２０のパーフルオロアルキル基を示す。Ｚは互いに結合して、環を形成していてもよい。］
で表されるアルカリ金属化合物存在下で反応させる［１０］又は［１１］に記載のエーテル化合物の製造方法。
［１３］ 反応の際に副生する水を反応系外に排出しながら行う［１０］〜［１２］に記載のエーテル化合物の製造方法。
［１４］ 炭化水素溶媒存在下で反応を行う［１０］〜［１３］のいずれかに記載のエーテル化合物の製造方法。
［１５］ 水素ガス雰囲気下で反応を行う［１０］〜［１４］のいずれかに記載のエーテル化合物の製造方法。

[In general formula (8), R < ¹² > -R < ¹⁵ > is the same as the above. ]
The manufacturing method of the ether compound represented by these.
[12] Further, the general formula (9):
M ² · N (ZSO ₂ ) ₂ (9)
[In General Formula (9), M ² is Li, Na, K, and Z represents a fluorine atom or a C 1-20 perfluoroalkyl group. Z may be bonded to each other to form a ring. ]
[10] The method for producing an ether compound according to [11], wherein the reaction is performed in the presence of an alkali metal compound.
[13] The method for producing an ether compound according to [10] to [12], wherein water produced as a by-product during the reaction is discharged out of the reaction system.
[14] The method for producing an ether compound according to any one of [10] to [13], wherein the reaction is performed in the presence of a hydrocarbon solvent.
[15] The method for producing an ether compound according to any one of [10] to [14], wherein the reaction is performed in a hydrogen gas atmosphere.

  ADVANTAGE OF THE INVENTION According to this invention, while providing the etherification catalyst composition which is simple and safe and suitable for industrial implementation, the manufacturing method of the ether compound from the alcohol compound which uses this etherification catalyst composition can be provided.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

  The transition metal complex represented by the general formula (1) or (2) (hereinafter referred to as transition metal complex (A)) will be described.

  In General Formulas (1) and (2), Ar represents an aromatic ring compound which may have a substituent or a cyclopentadienyl group which may have a substituent. A cyclopentadienyl group which may have a substituent is preferable.

  Specific examples of the aromatic ring compound which may have a substituent include, but are not limited to, benzene, toluene, o-xylene, m-xylene, p-xylene, o-cymene, m-cymene, p-cymene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, 1,3,5-triethylbenzene, 1,2,3,4-tetramethyl Examples include benzene, 1,2,4,5-tetramethylbenzene, 1,3,4,5-tetramethylbenzene, pentamethylbenzene, hexamethylbenzene, naphthalene, anthracene, and the like, preferably p-cymene, 3,5-trimethylbenzene and hexamethylbenzene.

Specific examples of the cyclopentadienyl group which may have a substituent include, but are not limited to, a cyclopentadienyl group (Cp), a methylcyclopentadienyl group, and an ethylcyclopentadienyl group. , Isopropylcyclopentadienyl group, phenylcyclopentadienyl group, benzylcyclopentadienyl group, 1,2- and 1,3-dimethylcyclopentadienyl group, 1,2,3- and 1,2,4 -Trimethylcyclopentadienyl group, 1,2,3,4-tetramethylcyclopentadienyl group, 1,2,3,4,5-pentamethylcyclopentadienyl group (Cp ^* ), 1,2, Examples include 3,4,5-pentaphenylcyclopentadienyl group, indenyl group, fluorenyl group and the like. Preferred are a cyclopentadienyl group (Cp) and 1,2,3,4,5-pentamethylcyclopentadienyl group (Cp ^* ), and particularly preferred is 1,2,3,4,5-penta. It is a methylcyclopentadienyl group (Cp ^* ).

In the general formulas (1) and (2), M ¹ is ruthenium, rhodium or iridium, preferably iridium.

In general formulas (1) and (2), R ¹ represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms. R ^{2 to} R ⁷ may each independently have a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a sulfo group, a mercapto group, a carboxyl group, a carbamoyl group, or a substituent. A good hydrocarbon group having 1 to 20 carbon atoms is preferred, and a hydrogen atom is preferred. As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, Preferably they are a fluorine atom and a chlorine atom. R ² and R ³ , R ³ and R ⁴ , or adjacent R ^{4 to} R ⁷ may be bonded to each other to form a ring. When forming a ring, a ring having a double bond may be formed.

R ¹ Examples of the hydrocarbon group having 1 to 20 carbon atoms that may have a substituent at to R ^7, alkyl group having 1 to 20 carbon atoms that may have a substituent, a substituent An optionally substituted cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, C1-C20 heterocyclyl group which may have a substituent, C2-C20 alkenyl group which may have a substituent, C2-C20 which may have a substituent An alkynyl group having 1 to 20 carbon atoms which may have a substituent, preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a substituent. Optionally having a cycloalkyl group having 3 to 20 carbon atoms and a substituent. An aryl group of prime 6-20, which may have a substituent aralkyl group having 7 to 20 carbon atoms, particularly preferably an alkyl group having 1 to 20 carbon atoms that may have a substituent.

In the case where the hydrocarbon group having 1 to 20 carbon atoms in R ^{1 to} R ⁷ has a substituent, the substituent is not limited thereto, but halogen such as fluorine atom, chlorine atom, bromine atom, iodine atom, etc. Atom, nitro group, cyano group, hydroxy group, amino group, sulfo group, mercapto group, carboxyl group, carbamoyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, Isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, vinyl, allyl, 3-butenyl, ethynyl, 2- Propynyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, 4-methylphenyl group, 4-methoxyphenyl group 4- (dimethylamino) phenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4-trifluoromethylphenyl group, benzyl group, cyclohexyl group, trifluoromethyl group, acetyl group, pivaloyl group, benzoyl group, methoxy Group, ethoxy group, n-propoxy group, isopropoxy group, tert-butoxy group, benzyloxy group, acetyloxy group, pivaloyloxy group, benzoyloxy group, dimethylamino group, trifluoromethanesulfonyl group, trimethoxysilyl group, triethoxy A silyl group etc. are mentioned.

In the case where the hydrocarbon group having 1 to 20 carbon atoms in R ^{1 to} R ⁷ has a substituent, the number of substituents is not particularly limited, but for example 1 to 5, preferably 1 to 3, and the position is The position is not particularly limited as long as it can be substituted.

The alkyl group having 1 to 20 carbon atoms which may have a substituent in R ^{1 to} R ⁷ may be linear or branched, preferably an alkyl group having 1 to 12 carbon atoms. More preferably an alkyl group having 1 to 6 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms include, but are not limited to, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl , Hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, 2-methoxyethyl group, 3-methoxypropyl group, 2- (trimethoxysilyl) ethyl group, 3- (trimethoxysilyl) propyl group and the like. A methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a tert-butyl group are preferable, and a methyl group is particularly preferable.

Specific examples of the cycloalkyl group having 3 to 20 carbon atoms that may have a substituent in R ^{1 to} R ⁷ include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and cyclohexyl. Group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, adamantyl group and the like. Preferably, they are a cyclopentyl group and a cyclohexyl group.

Specific examples of the aryl group having 6 to 20 carbon atoms that may have a substituent in R ^{1 to} R ⁷ include, but are not limited to, a phenyl group, a naphthyl group, an anthryl group, 4-methyl group. Phenyl group, 4-methoxyphenyl group, 4- (dimethylamino) phenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4-trifluoromethylphenyl group, mesityl group, 2,6-dimethylphenyl group, 2 , 6-diisopropylphenyl group, biphenyl group and the like. Preferable examples include phenyl group, naphthyl group, 4-methoxyphenyl group, 4- (dimethylamino) phenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4-trifluoromethylphenyl group and the like.

Specific examples of the aralkyl group having 7 to 20 carbon atoms which may have a substituent in R ^{1 to} R ⁷ include, but are not limited to, benzyl group, 4-methylbenzyl group, 4-methoxy group. Benzyl group, 4-fluorobenzyl group, 4-chlorobenzyl group, 4-trifluoromethylbenzyl group, pentafluorobenzyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-anthrylmethyl group, 2-an Examples include a thrylmethyl group, a 9-anthrylmethyl group, a 1-phenylethyl group, a 2-phenylethyl group, and a 3-phenylpropyl group. Of these, a benzyl group, a 4-methoxybenzyl group, a 4-fluorobenzyl group, a 4-chlorobenzyl group, and a 4-trifluoromethylbenzyl group are preferable.

Specific examples of the heterocyclyl group having 1 to 20 carbon atoms that may have a substituent in R ^{1 to} R ⁷ include, but are not limited to, a furyl group, a thienyl group, a pyrrolinyl group, a pyridyl group, Examples include 1-pyrrolidinyl group, 1-piperidinyl group, 4-morpholinyl group and the like. Preferably, they are a furyl group and a thienyl group.

Specific examples of the alkenyl group having 2 to 20 carbon atoms which may have a substituent in R ^{1 to} R ⁷ include, but are not limited to, a vinyl group, an allyl group, a 3-butenyl group, 4 -Pentenyl group, 5-hexenyl group, 6-heptenyl group, 7-octenyl group, 8-nonenyl group, 9-decenyl group are mentioned. Preferred are vinyl group, allyl group, and 3-butenyl.

Specific examples of the alkynyl group having 2 to 20 carbon atoms which may have a substituent in R ^{1 to} R ⁷ include, but are not limited to, an ethynyl group, a 2-propynyl group, and a 3-butynyl group. 4-pentynyl group, 5-hexynyl group, 6-heptynyl group, 7-octynyl group, 8-nonynyl group, and 9-decynyl group. Preferably, they are an ethynyl group and a 2-propynyl group.

Specific examples of the acyl group having 1 to 20 carbon atoms that may have a substituent in R ^{1 to} R ⁷ include, but are not limited to, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, Examples include a pivaloyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a 2-ethylhexanoyl group, a nonanoyl group, a decanoyl group, and a benzoyl group. An acetyl group, a pivaloyl group, and a benzoyl group are preferable.

  In the general formulas (1) and (2), L represents a sulfoxide ligand, an amide ligand, a nitrogen-containing aromatic ring ligand, an amine ligand, an ether ligand, a nitrile ligand, and an aco-coordination. A ligand selected from the group consisting of children is shown. An acoligand is preferable in terms of easy handling.

  Examples of the sulfoxide ligand include dimethyl sulfoxide (DMSO), methylphenyl sulfoxide, and diphenyl sulfoxide.

  N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), 1-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI) as amide ligands 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone (DMPU).

  Examples of the nitrogen-containing aromatic ring ligand include pyridine, picoline, chloropyridine, methoxypyridine, 2,6-lutidine, and 2,6-di-tert-butylpyridine.

  Examples of the amine ligand include triethylamine, diisopropylethylamine, aniline, N, N-dimethylaniline, toluidine, and anisidine.

  Examples of the ether ligand include diethyl ether, dibutyl ether, diisopropyl ether, cyclopentyl methyl ether (CPME), tert-butyl methyl ether (TBME), tetrahydrofuran (THF), 2-methyltetrahydrofuran (MeTHF), anisole, diphenyl ether. 1,4-dioxane.

  Examples of the nitrile ligand include acetonitrile, benzonitrile, propionitrile, butyronitrile, and the like.

  In the general formulas (1) and (2), the broken line indicates that a single bond or a double bond is formed together with the solid line.

Specific examples of the cation of the organometallic complex (A) include the structures shown below, but the present invention is not limited thereto. In the following specific examples, Ar, R ¹ and L are the same as described above, and Me represents a methyl group.

In the general formulas (1) and (2), Y ⁻ represents an anion. Preferably, general formula (3):
R ⁸ SO ₃ ^- ₍₃₎
(In General Formula (3), R ⁸ is an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or (It is a C6-C20 perfluoroaryl group.)
A sulfonate ion represented by the following formula (hereinafter referred to as sulfonate ion (3)), general formula (4):

（一般式（４）中、Ｒ^９、Ｒ^１０は互いに同じ若しくは異なっていてもよい炭素数１〜２０のアルキル基、炭素数１〜２０のパーフルオロアルキル基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基、炭素数６〜２０のパーフルオロアリール基又はフッ素原子を示し、Ｒ^９とＲ^１０は互いに結合して、環を形成していてもよい。）
で表されるビス（スルホニル）イミドイオン（以下、ビス（スルホニル）イミドイオン（４）という。）又は一般式（５）：
（Ｒ^１１ＳＯ_２）_３Ｃ⁻ （５）
（一般式（５）中、Ｒ^１１は炭素数１〜２０のアルキル基、炭素数１〜２０のパーフルオロアルキル基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基又は炭素数６〜２０のパーフルオロアリール基である。）
で表されるトリス（スルホニル）メチドイオン（以下、トリス（スルホニル）メチドイオン（５）という。）であり、特に好ましくは一般式（４）で表されるビス（スルホニル）イミドイオンである。

(In the general formula (4), R ⁹ and R ¹⁰ may be the same or different from each other, and the alkyl group having 1 to 20 carbon atoms, the perfluoroalkyl group having 1 to 20 carbon atoms, and the cycloalkyl having 3 to 20 carbon atoms. A group, an aryl group having 6 to 20 carbon atoms, a perfluoroaryl group having 6 to 20 carbon atoms, or a fluorine atom, and R ⁹ and R ¹⁰ may be bonded to each other to form a ring.)
A bis (sulfonyl) imide ion represented by the following (hereinafter referred to as bis (sulfonyl) imide ion (4)) or general formula (5):
_{^{(R 11 SO 2) 3 C}} - (5)
(In the general formula (5), R ¹¹ is an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or (It is a C6-C20 perfluoroaryl group.)
Is a tris (sulfonyl) methide ion (hereinafter referred to as tris (sulfonyl) methide ion (5)), particularly preferably a bis (sulfonyl) imide ion represented by the general formula (4).

In general formula (3), R ⁸ is an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or carbon. It is a perfluoroaryl group of several 6-20. Preferably, R ⁸ is an alkyl group having 1 to 20 carbon atoms and a perfluoroalkyl group having 1 to 20 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 20 carbon atoms.

  The alkyl group having 1 to 20 carbon atoms which may have a substituent may be linear or branched, preferably an alkyl group having 1 to 12 carbon atoms, more preferably a carbon number. 1 to 6 alkyl groups. Specific examples of the alkyl group having 1 to 20 carbon atoms include, but are not limited to, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl , Hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, 2-methoxyethyl group, 3-methoxypropyl group, 2- (trimethoxysilyl) ethyl group, 3- (trimethoxysilyl) propyl group and the like. A methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a tert-butyl group are preferable, and a methyl group is particularly preferable.

  The perfluoroalkyl group having 1 to 20 carbon atoms is preferably a perfluoroalkyl group having 1 to 12 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 6 carbon atoms. Specific examples of the C 1-20 perfluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, and the like, preferably a trifluoromethyl group, a pentafluoroethyl group. Group, more preferably a trifluoromethyl group.

  Specific examples of the cycloalkyl group having 3 to 20 carbon atoms include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group. And an adamantyl group. Preferably, they are a cyclopentyl group and a cyclohexyl group.

  Specific examples of the aryl group having 6 to 20 carbon atoms include, but are not limited to, a phenyl group, a naphthyl group, an anthryl group, a 4-methylphenyl group, a 4-methoxyphenyl group, and 4- (dimethylamino). A phenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4-trifluoromethylphenyl group, mesityl group, 2,6-dimethylphenyl group, 2,6-diisopropylphenyl group, biphenyl group and the like can be mentioned. Preferable examples include phenyl group, naphthyl group, 4-methoxyphenyl group, 4- (dimethylamino) phenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4-trifluoromethylphenyl group and the like.

  Specific examples of the C 6-20 perfluoroaryl group include, but are not limited to, a pentafluorophenyl group, a 1-heptafluoronaphthyl group, a 2-heptafluoronaphthyl group, and a nonafluoroanthracenyl group. , Nonafluoropyrenyl group, heptafluoro-4-methylphenyl group, heptafluoro-3-methylphenyl group, heptafluoro-2-methylphenyl group, nonafluoroethylphenyl group, nonafluorodimethylphenyl group, etc. Preferably, it is a pentafluorophenyl group.

Specific examples of the sulfonate ion (3) include, but are not limited to, methanesulfonate (CH ₃ SO ₃ ⁻ ), ethanesulfonate (C ₂ H ₅ SO ₃ ⁻ ), trifluoromethanesulfonate ( CF ₃ SO ₃ ^-), pentafluoroethane sulfonate ^{_{(C 2 F 5 SO 3 -}} ), heptafluoropropane sulfonate ^{_{(C 3 F 7 SO 3 -}} ), nonafluorobutanesulfonate _{(C 4} F 9 SO ₃ ^- ), Undecafluoropentanesulfonate (C ₅ F ₁₁ SO ₃ ⁻ ), tridecafluorohexanesulfonate (C ₆ F ₁₃ SO ₃ ⁻ ), pentadecafluoroheptanesulfonate (C ₇ F ₁₅ SO ₃ ⁻ ), heptadecafluorooctanesulfonic sulfonate ^{_{(C 8 F 17 SO 3 -}} ), benzenesulfonate Trainer ^{_{(C 6 H 5 SO 3 -}} ), p- toluenesulfonate _{(CH 3 C 6 H 4 SO} 3 -), dodecyl benzenesulfonate ^{_{(C 18 H 29 SO 3 -}} ), pentafluorophenyl benzenesulfonate _(C 6 F ₅ SO ₃ ⁻ ), fluorosulfonate (FSO ₃ ⁻ ) and the like. Preferred are trifluoromethane sulfonate, pentafluoroethane sulfonate, heptafluoropropane sulfonate, nonafluorobutane sulfonate, and p-toluene sulfonate, and particularly preferred is trifluoromethane sulfonate.

In General Formula (4), R ⁹ and R ¹⁰ may be the same or different from each other, and may be the same or different from each other. , An aryl group having 6 to 20 carbon atoms, a perfluoroaryl group having 6 to 20 carbon atoms, or a fluorine atom, preferably an alkyl group having 1 to 20 carbon atoms or a perfluoroalkyl group having 1 to 20 carbon atoms. More preferably, it is a C 1-20 perfluoroalkyl group. R ⁹ and R ¹⁰ may be bonded to each other to form a ring.

  The alkyl group having 1 to 20 carbon atoms which may have a substituent may be linear or branched, preferably an alkyl group having 1 to 12 carbon atoms, more preferably a carbon number. 1 to 6 alkyl groups. Specific examples of the alkyl group having 1 to 20 carbon atoms include, but are not limited to, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl , Hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, 2-methoxyethyl group, 3-methoxypropyl group, 2- (trimethoxysilyl) ethyl group, 3- (trimethoxysilyl) propyl group and the like. A methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a tert-butyl group are preferable, and a methyl group is particularly preferable.

  The perfluoroalkyl group having 1 to 20 carbon atoms is preferably a perfluoroalkyl group having 1 to 12 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 6 carbon atoms. Specific examples of the C 1-20 perfluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, and the like, preferably a trifluoromethyl group, a pentafluoroethyl group. Group, more preferably a trifluoromethyl group.

  Specific examples of the cycloalkyl group having 3 to 20 carbon atoms include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group. And an adamantyl group. Preferably, they are a cyclopentyl group and a cyclohexyl group.

  Specific examples of the aryl group having 6 to 20 carbon atoms include, but are not limited to, a phenyl group, a naphthyl group, an anthryl group, a 4-methylphenyl group, a 4-methoxyphenyl group, and 4- (dimethylamino). A phenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4-trifluoromethylphenyl group, mesityl group, 2,6-dimethylphenyl group, 2,6-diisopropylphenyl group, biphenyl group and the like can be mentioned. Preferable examples include phenyl group, naphthyl group, 4-methoxyphenyl group, 4- (dimethylamino) phenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4-trifluoromethylphenyl group and the like.

  Specific examples of the C 6-20 perfluoroaryl group include, but are not limited to, a pentafluorophenyl group, a 1-heptafluoronaphthyl group, a 2-heptafluoronaphthyl group, and a nonafluoroanthracenyl group. , Nonafluoropyrenyl group, heptafluoro-4-methylphenyl group, heptafluoro-3-methylphenyl group, heptafluoro-2-methylphenyl group, nonafluoroethylphenyl group, nonafluorodimethylphenyl group, etc. Preferably, it is a pentafluorophenyl group.

Specific examples of the bis (sulfonyl) imide ion (4) include, but are not limited to, bis (trifluoromethanesulfonyl) imidate ((CF ₃ SO ₂ ) ₂ N ⁻ ), bis (pentafluoroethanesulfonyl) imidate. ((C ₂ F ₅ SO ₂ ) ₂ N ⁻ ), bis (heptafluoropropanesulfonyl) imidate ((C ₃ F ₇ SO ₂ ) ₂ N ⁻ ), bis (nonafluorobutanesulfonyl) imidate ((C ₄ F ₉ SO _{2) 2} N ^-), bis (undecapeptide fluorosilicone pentane sulfonyl) imidate _{((C 5 F 11 SO 2} ) 2 N -), bis (tridecanol fluorosilicone hexane sulfonyl) imidate _{((C 6 F} 13 SO ₂ ) ₂ N ⁻ ), bis (pentadecafluoroheptanesulfonyl) imidate ((C ₇ F _{1 ^{5 SO 2) 2 N -)}} , bis (heptadecafluoro fluorosilicone C1-12alkyl) imidate _{((C 8 F 17 SO 2} ) 2 N -), nonafluoro -N - [(trifluoromethane) sulfonyl] butane sulfonyl amidate (( CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ) N ⁻ ), bis (fluorosulfonyl) imidate ((FSO ₂ ) ₂ N ⁻ ) and the like. Preferred are bis (trifluoromethanesulfonyl) imidate, bis (pentafluoroethanesulfonyl) imidate, bis (heptafluoropropanesulfonyl) imidate, bis (nonafluorobutanesulfonyl) imidate, and particularly preferred is bis (trifluoromethanesulfonyl) imidate It is.

When R ⁹ and R ¹⁰ are bonded to each other to form a ring, specific examples of the bis (sulfonyl) imide ion (4) include 1,1,2,2,3,3-hexafluoropropane-1 , 3-Disulfonimidate (CF ₂ (CF ₂ SO ₂ ) ₂ N ⁻ ), 1,1,2,2-butafluoroethane-1,2-disulfonimidate ((CF ₂ SO ₂ ) ₂ N ⁻ ) Etc.

In General Formula (5), R ¹¹ is an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or carbon. It is a perfluoroaryl group of several 6-20. Preferably they are a C1-C20 perfluoroalkyl group, a C6-C20 perfluoroaryl group, More preferably, it is a C6-C20 perfluoroaryl group.

  The alkyl group having 1 to 20 carbon atoms which may have a substituent may be linear or branched, preferably an alkyl group having 1 to 12 carbon atoms, more preferably a carbon number. 1 to 6 alkyl groups. Specific examples of the alkyl group having 1 to 20 carbon atoms include, but are not limited to, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl , Hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, 2-methoxyethyl group, 3-methoxypropyl group, 2- (trimethoxysilyl) ethyl group, 3- (trimethoxysilyl) propyl group and the like. A methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a tert-butyl group are preferable, and a methyl group is particularly preferable.

  The perfluoroalkyl group having 1 to 20 carbon atoms is preferably a perfluoroalkyl group having 1 to 12 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 6 carbon atoms. Specific examples of the C 1-20 perfluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, and the like, preferably a trifluoromethyl group, a pentafluoroethyl group. Group, more preferably a trifluoromethyl group.

  Specific examples of the cycloalkyl group having 3 to 20 carbon atoms include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group. And an adamantyl group. Preferably, they are a cyclopentyl group and a cyclohexyl group.

  Specific examples of the aryl group having 6 to 20 carbon atoms include, but are not limited to, a phenyl group, a naphthyl group, an anthryl group, a 4-methylphenyl group, a 4-methoxyphenyl group, and 4- (dimethylamino). A phenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4-trifluoromethylphenyl group, mesityl group, 2,6-dimethylphenyl group, 2,6-diisopropylphenyl group, biphenyl group and the like can be mentioned. Preferable examples include phenyl group, naphthyl group, 4-methoxyphenyl group, 4- (dimethylamino) phenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4-trifluoromethylphenyl group and the like.

  Specific examples of the C 6-20 perfluoroaryl group include, but are not limited to, a pentafluorophenyl group, a 1-heptafluoronaphthyl group, a 2-heptafluoronaphthyl group, and a nonafluoroanthracenyl group. , Nonafluoropyrenyl group, heptafluoro-4-methylphenyl group, heptafluoro-3-methylphenyl group, heptafluoro-2-methylphenyl group, nonafluoroethylphenyl group, nonafluorodimethylphenyl group, etc. Preferably, it is a pentafluorophenyl group.

Specific examples of the tris (sulfonyl) methide ion (5) include, but are not limited to, tris (trifluoromethanesulfonyl) methide ((CF ₃ SO ₂ ) ₃ C ⁻ ), tris (pentafluorobenzenesulfonyl) methide. _{((C 6 F 5 SO 2} ) 3 C -) , and the like.

Specific examples of the transition metal complex (A) are shown below, but the present invention is not limited thereto. In this specific example, bis (trifluoromethanesulfonyl) imide ion is TFSI ⁻ , trifluoromethanesulfonate ion is OTf ⁻ , 1,2,3,4,5-pentamethylcyclopentadienyl group is Cp ^* , and methyl group is Me. Abbreviated.

  In the present invention, the transition metal complex (A) can be produced by various methods. As a typical method, it can be produced by steps 1 and 2 shown in the following reaction formula 1.

  Reaction formula 1:

（上記反応式１中、Ａｒ、Ｒ^１〜Ｒ^７、Ｌ及びＹ⁻は前記に同じである。）

(In the above reaction scheme 1, Ar, R ^{1 to} R ⁷ , L and Y ⁻ are the same as described above.)

・ Process 1
A pyridine compound represented by the general formula (10) (hereinafter referred to as pyridine compound (10)) and silver oxide (Ag ₂ O) are reacted (reaction a), and then in the reaction formula 1, the general formula (11 Step of obtaining a transition metal complex represented by the general formula (12) by reacting (reaction b) with a transition metal halide represented by (hereinafter referred to as transition metal halide (11)).

・ Process 2
A silver salt represented by the general formula (13) (hereinafter referred to as silver salt (13)) is added to the transition metal complex represented by the general formula (12) obtained in step 1 (hereinafter referred to as transition metal complex (12)). ).) To obtain a transition metal complex represented by the general formula (1).

  In addition to the above production method, in order to obtain the transition metal complex represented by the general formula (1), protection and deprotection can be performed as necessary, and a commonly used method (Protective Groups in Organic Synthesis Edition, (John Wiley & Sons, Inc.). In addition, functional group conversion can be performed as necessary, and a generally used method (Comprehensive Organic Transformations, John Wiley & Sons, Inc.) may be referred to.

In addition, the transition metal complex represented by the general formula (2) is generated by an equilibrium reaction of a transition metal complex in which R ⁷ is a hydroxyl group in the general formula (1).

  Hereinafter, each step will be described.

[Step 1-Reaction a]
In General Formula (10), the bonds represented by R ^{1 to} R ⁷ and the broken line are the same as described above. X ^a− is a halogen ion, and represents a fluorine ion, a chlorine ion, a bromine ion, or an iodine ion, preferably an iodine ion.

Examples of the pyridine compound (10) include the following structures. In the following formulae, R ^{1 to} R ⁷ , the bond represented by a broken line, and X ^a- are the same as described above.

In step 1-reaction a, a commercially available silver oxide (Ag ₂ O) can be used. The amount of silver oxide (Ag ₂ O) used may be appropriately adjusted. For example, it is generally 0.1 to 2 mol, preferably 0.4 to 0.6 mol, more preferably, relative to 1 mol of the pyridine compound (10). Is 0.45 to 0.55 mol.

  Step 1—Reaction a is usually carried out in the presence of a solvent, and the solvent is not particularly limited as long as it does not affect the reaction. Examples of the solvent used include ketone solvents such as acetone and 2-butanone, alcohol solvents such as methanol and ethanol, ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran (THF), and 1,4-dioxane, benzene, and toluene. , Aromatic hydrocarbon solvents such as xylene, aliphatic hydrocarbon solvents such as pentane, hexane, cyclohexane, petroleum ether, ester solvents such as ethyl acetate, halogenated hydrocarbon solvents such as dichloromethane, chloroform, 1,2-dichloroethylene, Examples thereof include water, halogenated hydrocarbon solvents are preferred, dichloromethane and chloroform are more preferred, and dichloromethane is particularly preferred. Among these, it can use individually or in combination of 2 or more types. Of these, halogenated hydrocarbon solvents are preferred, dichloromethane and chloroform are more preferred, and dichloromethane is particularly preferred.

  What is necessary is just to adjust suitably as the usage-amount of a solvent, for example, generally 0-100L with respect to 1 mol of pyridine compounds (10), Preferably it is 0-20L.

  Step 1—Reaction a is preferably carried out in the dark. The light shielding method is not particularly limited as long as the reaction mixture in the reactor is not irradiated with light such as a fluorescent lamp or the sun. Moreover, it can carry out in the atmosphere of inert gas, such as nitrogen and argon.

  The reaction pressure is not particularly limited, and the reaction may be performed at normal pressure or may be performed under pressure.

  Reaction temperature is 0-100 degreeC normally, Preferably it is 10-80 degreeC, More preferably, it is 20-50 degreeC.

The mixing order of the pyridine compound (10), silver oxide (Ag ₂ O), and the solvent is not particularly limited. For example, the pyridine compound (10) and the solvent are charged into the reactor, and the silver oxide (Ag ₂ O) is charged with stirring. The method of doing is mentioned.

  After completion of the reaction, it may be used for Step 1-Reaction b after performing known purification and isolation operations such as distillation, filtration, and centrifugation, and the mixture after the reaction without the purification and isolation steps. You may use for process 1-reaction b as it is (one-pot synthesis | combination).

[Step 1-Reaction b]
In general formula (11), Ar and M ¹ are the same as described above. ^Xb is a halogen atom, which is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and preferably a chlorine atom. Specific examples of the transition metal halide (11) include (pentamethylcyclopentadienyl) iridium (III) dichloride (dimer) ([Cp ^* IrCl ₂ ] ₂ ), diiodo (pentamethylcyclopentadienyl) iridium ( III) (dimer) ([Cp ^* Irl ₂ ] ₂ ), benzene ruthenium (II) dichloride (dimer), (hexamethylbenzene) ruthenium (II) dichloride (dimer), dichloro (p-cymene) ruthenium (II) ( Dimer), (pentamethylcyclopentadienyl) rhodium (III) dichloride (dimer) ([Cp ^* RhCl ₂ ] ₂ ) and the like. Commercial products can be used for these reagents.

  The amount of the transition metal halide (11) used may be appropriately adjusted. For example, it is generally 0.1 to 2 mol, preferably 0.4 to 0.6 mol, more preferably, relative to 1 mol of the pyridine compound (10). Is 0.45 to 0.55 mol.

  The reaction of step 1-reaction b is usually carried out in the presence of a solvent, and when a solvent is used, the solvent is not particularly limited as long as it does not affect this reaction. Examples of the solvent used include ketone solvents such as acetone and 2-butanone, alcohol solvents such as methanol and ethanol, ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran (THF), and 1,4-dioxane, benzene, and toluene. , Aromatic hydrocarbon solvents such as xylene, aliphatic hydrocarbon solvents such as pentane, hexane, cyclohexane, petroleum ether, ester solvents such as ethyl acetate, halogenated hydrocarbon solvents such as dichloromethane, chloroform, 1,2-dichloroethylene, Examples thereof include water, halogenated hydrocarbon solvents are preferred, dichloromethane and chloroform are more preferred, and dichloromethane is particularly preferred. Among these, it can use individually or in combination of 2 or more types. When the above-described one-pot synthesis method is employed, the solvent in Step 1-Reaction a can be used as it is as the solvent in Step 1-Reaction b.

  What is necessary is just to adjust suitably the usage-amount of a solvent, for example, generally 0.1-100L with respect to 1 mol of compounds represented by a pyridine compound (10), Preferably it is 5-20L.

  Step 1—Reaction b is preferably carried out in the dark. The light shielding method is not particularly limited as long as the reaction mixture in the reactor is not irradiated with light such as a fluorescent lamp or the sun.

  Step 1-Reaction b can be performed in an atmosphere of an inert gas such as nitrogen or argon.

  The reaction pressure is not particularly limited, and the reaction may be performed at normal pressure or may be performed under pressure.

  Reaction temperature is 0-100 degreeC normally, Preferably it is 10-80 degreeC, More preferably, it is 20-50 degreeC.

  The mixing order of the raw materials is not particularly limited, and examples thereof include a method in which the transition metal halide (11) is added to the reaction mixture obtained in Step 1-reaction a with stirring (one-pot reaction).

  After completion of the reaction, the desired transition metal complex (12) can be taken out through known purification and isolation operations such as distillation, filtration, and centrifugation.

In General Formula (12), the bonds represented by R ^{1 to} R ⁷ , M ¹ , Ar, and the broken line are the same as described above. X ^b− is a halogen ion, which is a fluorine ion, a chlorine ion, a bromine ion or an iodine ion, and preferably a chlorine ion.

In the general formula (13), Y ⁻ is the same as described above. Specific examples of the silver salt (13) include silver methanesulfonate, silver ethanesulfonate, silver trifluoromethanesulfonate, silver pentafluoroethanesulfonate, silver heptafluoropropanesulfonate, silver nonafluorobutanesulfonate, undeca Silver fluoropentanesulfonate, silver tridecafluorohexanesulfonate, silver pentadecafluoroheptanesulfonate, silver heptadecafluorooctanesulfonate, silver benzenesulfonate, silver p-toluenesulfonate, silver dodecylbenzenesulfonate, pentafluoro Silver benzenesulfonate, silver sulfonate such as silver sulfonate, bis (trifluoromethanesulfonyl) imide silver, bis (pentafluoroethanesulfonyl) imide silver, bis (heptafluoropropanesulfonyl) imide silver, bis (nona Ruolbutanesulfonyl) imide silver, bis (undecafluoropentanesulfonyl) imide silver, bis (tridecafluorohexanesulfonyl) imide silver, bis (pentadecafluoroheptanesulfonyl) imide silver, bis (heptadecafluorooctane) Sulfonyl) imide silver, nonafluoro-N-[(trifluoromethane) sulfonyl] butanesulfonylamidate, bis (sulfonyl) imide silver such as bis (fluorosulfonyl) imide silver, tris (trifluoromethanesulfonyl) methide silver, tris (pentafluoro) And tris (sulfonyl) methide silver such as benzenesulfonyl) methide silver. Preferably, silver trifluoromethanesulfonate, silver pentafluoroethanesulfonate, silver heptafluoropropanesulfonate, silver nonafluorobutanesulfonate, silver p-toluenesulfonate, bis (trifluoromethanesulfonyl) imide silver, bis (pentafluoro) Ethanesulfonyl) imide silver, bis (heptafluoropropanesulfonyl) imide silver, bis (nonafluorobutanesulfonyl) imide silver, particularly preferably silver trifluoromethanesulfonate and bis (trifluoromethanesulfonyl) imide silver.

  The amount of the silver salt (13) used may be adjusted as appropriate, for example, generally 0.1 to 4 mol, preferably 1.8 to 2.2 mol, more preferably, per 1 mol of the transition metal complex (12). 1.9 to 2.1 mol.

  The reaction in step 2 is usually carried out in the presence of a solvent, and the solvent is not particularly limited as long as it does not affect the reaction. Examples of the solvent used include ketone solvents such as acetone and 2-butanone, alcohol solvents such as methanol and ethanol, ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran (THF), and 1,4-dioxane, benzene, and toluene. , Aromatic hydrocarbon solvents such as xylene, aliphatic hydrocarbon solvents such as pentane, hexane, cyclohexane and petroleum ether, ester solvents such as ethyl acetate, halogenated hydrocarbon solvents such as dichloromethane, chloroform and 1,2-dichloroethylene, water Etc., and water is preferable. A solvent can be used individually or in combination of 2 or more types.

  When the solvent is used, the amount of the solvent used may be adjusted as appropriate. For example, the amount is generally 0.1 to 100 L, preferably 10 to 50 L, relative to 1 mol of the transition metal complex (12).

  The reaction in step 2 is preferably performed under light shielding. The light shielding method is not particularly limited as long as the reaction mixture in the reactor is not irradiated with light such as a fluorescent lamp or the sun. The reaction in step 2 can be performed in an atmosphere of an inert gas such as nitrogen or argon.

  The reaction pressure is not particularly limited, and the reaction may be performed at normal pressure or may be performed under pressure.

  Reaction temperature is 0-100 degreeC normally, Preferably it is 10-80 degreeC, More preferably, it is 20-50 degreeC.

  The order of mixing the transition metal complex (12), the silver salt (13) and the solvent is not particularly limited. For example, the transition metal complex (12) and the solvent are charged into a reactor, and the silver salt (13) is charged with stirring. Is mentioned.

  After completion of the reaction, the desired transition metal complex represented by the general formula (1) can be taken out through known purification and isolation processes such as distillation, filtration, and centrifugation.

  In the present invention, the etherification catalyst composition contains the transition metal complex (A) as an active ingredient, and even when used alone, two or more transition metal complexes (A) are used in combination. You can also. In the presence of the etherification catalyst composition of the present invention, an ether compound (hereinafter referred to as ether compound (C)) is produced by reacting two or more alcohol compounds (hereinafter referred to as alcohol compound (B)) with each other. I can do it.

  More preferably, as shown in the following reaction formula 2, the alcohol compound represented by the general formula (6) and the alcohol compound represented by the general formula (7) are reacted in the presence of the etherification catalyst composition of the present invention. By making it, the ether compound represented by General formula (8) can be manufactured.

Reaction formula 2:

（反応式２中、Ｒ^１２〜Ｒ^１５は、前記に同じ。）

(In Reaction Formula 2, R ^{12 to} R ¹⁵ are the same as above.)

  The alcohol compound (B), which is a raw material for producing the ether compound (C), will be described.

  In the present invention, the alcohol compound (B) is not particularly limited as long as it is an organic compound having a hydroxy group, but is preferably a primary alcohol compound or a secondary alcohol compound, more preferably a general formula (6). Or an alcohol compound represented by (7).

In General Formula (6), R ¹² is a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a heterocyclic group having 1 to 20 carbon atoms which may have a substituent, R ^13. Is a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted heterocyclic group having 1 to 20 carbon atoms, and R ¹² and R ¹³ May be bonded to each other to form a ring. In R ¹² and R ¹³ , the optionally substituted hydrocarbon group having 1 to 20 carbon atoms includes an optionally substituted alkyl group having 1 to 20 carbon atoms and a substituent. Examples thereof include an optionally substituted cycloalkyl group having 1 to 20 carbon atoms and an optionally substituted aryl group having 1 to 20 carbon atoms.

In the general formula (7), R ¹⁴ is a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a heterocyclic group having 1 to 20 carbon atoms which may have a substituent, R ^15. Is a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted heterocyclic group having 1 to 20 carbon atoms, and R ¹⁴ and R ^15. May be bonded to each other to form a ring. In R ¹⁴ and R ¹⁵ , the optionally substituted hydrocarbon group having 1 to 20 carbon atoms includes an optionally substituted alkyl group having 1 to 20 carbon atoms and a substituent. Examples thereof include an optionally substituted cycloalkyl group having 3 to 20 carbon atoms and an optionally substituted aryl group having 6 to 20 carbon atoms.

In R ^{12 to} R ¹⁵ , when the hydrocarbon group having 1 to 20 carbon atoms or the heterocyclic group having 1 to 20 carbon atoms has a substituent, the substituent is not limited to this, but a fluorine atom, chlorine Atoms, halogen atoms such as bromine atom, iodine atom, nitro group, cyano group, hydroxy group, amino group, sulfo group, mercapto group, carboxyl group, carbamoyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, vinyl group, allyl group, 3-butenyl group, ethynyl group, 2-propynyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, 4-methyl group Nyl group, 4-methoxyphenyl group, 4- (dimethylamino) phenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4-trifluoromethylphenyl group, benzyl group, trifluoromethyl group, acetyl group, pivaloyl Group, benzoyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, tert-butoxy group, benzyloxy group, acetyloxy group, pivaloyloxy group, benzoyloxy group, dimethylamino group, trifluoromethanesulfonyl group, tri A methoxysilyl group, a triethoxysilyl group, etc. are mentioned.

In R ^{12 to} R ¹⁵ , when the hydrocarbon group having 1 to 20 carbon atoms or the heterocyclic group having 1 to 20 carbon atoms has a substituent, the number of substituents is not particularly limited, but for example 1 to 5, preferably There are 1 to 3 positions, and the positions are not particularly limited as long as they can be substituted.

In R ^{12 to} R ¹⁵ , the optionally substituted alkyl group having 1 to 20 carbon atoms may be linear or branched, preferably alkyl having 1 to 12 carbon atoms. It is a group. Specific examples of the alkyl group having 1 to 20 carbon atoms that may have a substituent include, but are not limited to, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Group, sec-butyl group, isobutyl group, n-pentyl group, isopentyl group, neopentyl group, hexyl group, n-heptyl group, 3-heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group Group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group and the like. Preferably, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, isopentyl group, neopentyl group, hexyl group, n-heptyl group, 3 -Heptyl group, octyl group, nonyl group, decyl group, more preferably methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, hexyl group, n-heptyl group, 3-heptyl group Group, octyl group, nonyl group, decyl group.

Specific examples of the cycloalkyl group having 3 to 20 carbon atoms that may have a substituent in R ^{12 to} R ¹⁵ include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and cyclohexyl. Group, cycloheptyl group, cyclooctyl group and the like. A cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are preferable, and a cyclopentyl group and a cyclohexyl group are more preferable.

The aryl group having 6 to 20 carbon atoms which may have a substituent in R ^{12 to} R ¹⁵ may be a monocyclic aryl group or two or more polycyclic aryl groups. Specific examples of the aryl group having 6 to 20 carbon atoms which may have a substituent include, but are not limited to, a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. Preferably, they are a phenyl group, a naphthyl group, and an anthryl group, More preferably, they are a phenyl group and a naphthyl group, More preferably, it is a phenyl group.

Specific examples of the heterocyclic group having 1 to 20 carbon atoms that may have a substituent in R ^{12 to} R ¹⁵ include, but are not limited to, a furyl group, a thienyl group, a pyrrolinyl group, and a pyridyl group. , Pyrazinyl group, pyradazinyl group, triazinyl group, tetrazinyl group, imidazolyl group, oxazoyl group, thiazoyl group, benzofuryl group, benzoimidazolyl group, benzothienyl group, quinolyl group, isoquinolyl group, quinoxalinyl group, phthalazinyl group, quinazolinyl group, naphthyridinyl group, Examples thereof include a cinnolinyl group, a benzoxazolyl group, a benzothiazolyl group, an indolyl group, and the like. Preferably, it is a furyl group, a thienyl group, a pyrrolinyl group, a benzofuryl group, a benzothienyl group, an indolyl group, more preferably a furyl group, a thienyl group, a benzofuryl group, a benzothienyl group, an indolyl group, and more preferably a furyl group , A thienyl group.

  Specific examples of the alcohol compound (B) include, but are not limited to, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1 -Octanol, 2-ethyl-1-hexanol, 1-nonanol, 1-decanol, 1-undecanol, 2-methoxy-1-ethanol, cyclopentanemethanol, cyclohexanemethanol, benzyl alcohol, 4-methoxybenzyl alcohol, 4-chloro Examples include benzyl alcohol, 1-phenylethyl alcohol, 2-naphthalenemethanol, 2- (hydroxymethyl) furan, 2- (hydroxymethyl) thiophene, cyclopentanol, and cyclohexanol.

  In the present invention, the alcohol compound (B) uses two or more molecules, which may be the same or different. When two or more molecules of alcohol compound (B) are the same, a symmetrical ether compound (C) can be produced, and when two or more molecules of alcohol compound (B) are different, an asymmetric ether compound (C). Can be manufactured. When the ether compound (8) is produced, when the alcohol compounds represented by the general formulas (6) and (7) are the same, the resulting ether compound (8) is a symmetric ether compound (8). However, when the alcohol compound represented by the general formula (6) is different from the alcohol compound represented by (7), an asymmetric ether compound (8) can be produced.

In the present invention, the ether compound (C) is preferably an ether compound represented by the general formula (8). In general formula (8), R < ¹² > -R < ¹⁵ > is the same as the above.

  Specific examples of the ether compound (C) include, but are not limited to, dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, Bis (2-ethylhexyl) ether, didecyl ether, diundecyl ether, bis (2-methoxyethyl) ether, bis (cyclopentylmethyl) ether, bis (cyclohexylmethyl) ether, dibenzyl ether, bis (4-methoxybenzyl) Ether, bis (4-chlorobenzyl) ether, bis (1-phenylethyl) ether, bis (2-naphthalenemethyl) ether, bis (2-furylmethyl) ether, bis (2-thienylmethyl) Ether, dicyclopentyl ether, dicyclohexyl ether,

  Ethyl methyl ether, methyl propyl ether, ethyl propyl ether, isopropyl methyl ether, ethyl isopropyl ether, isopropyl propyl ether, butyl methyl ether, butyl ethyl ether, butyl propyl ether, butyl isopropyl ether, methyl pentyl ether, ethyl pentyl ether, pentyl propyl Ether, isopropyl pentyl ether, butyl pentyl ether, hexyl methyl ether, ethyl hexyl ether, hexyl propyl ether, hexyl isopropyl ether, butyl hexyl ether, hexyl pentyl ether, heptyl methyl ether, ethyl heptyl ether, heptyl propyl ether, heptyl isopropyl ether, butyl Heptyl ether, hep Rupentyl ether, heptyl hexyl ether, octyl methyl ether, ethyl octyl ether, octyl propyl ether, isopropyl octyl ether, butyl octyl ether, octyl pentyl ether, hexyl octyl ether, heptyl octyl ether, (2-ethylhexyl) methyl ether, (2 -Ethylhexyl) ethyl ether, (2-ethylhexyl) propyl ether, (2-ethylhexyl) isopropyl ether, butyl (2-ethylhexyl) ether, (2-ethylhexyl) pentyl ether, (2-ethylhexyl) hexyl ether, (2-ethylhexyl) ) Heptyl ether, (2-ethylhexyl) octyl ether, methyl nonyl ether, ethyl nonyl ether, nonyl pro Ether, isopropyl nonyl ether, butyl nonyl ether, nonyl pentyl ether, hexyl nonyl ether, heptyl nonyl ether, nonyl octyl ether, (2-ethylhexyl) nonyl ether, decyl methyl ether, decyl ethyl ether, decyl propyl ether, decyl isopropyl ether, Butyl decyl ether, decyl pentyl ether, decyl hexyl ether, decyl heptyl ether, decyl octyl ether, decyl (2-ethylhexyl) ether, decyl nonyl ether, methyl undecyl ether, ethyl undecyl ether, propyl undecyl ether, isopropyl undecyl ether Ether, butyl undecyl ether, pentyl undecyl ether, hexyl undecyl ether, Butyl undecyl ether, octyl undecyl ether, (2-ethylhexyl) undecyl ether, nonyl undecyl ether, decyl undecyl ether,

(2-methoxyethyl) methyl ether, ethyl (2-methoxyethyl) ether, (2-methoxyethyl) propyl ether, isopropyl (2-methoxyethyl) ether, butyl (2-methoxyethyl) ether, (2-methoxyethyl ) Pentyl ether, hexyl (2-methoxyethyl) ether, heptyl (2-methoxyethyl) ether, (2-methoxyethyl) octyl ether, (2-ethylhexyl) (2-methoxyethyl) ether, (2-methoxyethyl) Nonyl ether, decyl (2-methoxyethyl) ether, (2-methoxyethyl) undecyl ether, (cyclopentylmethyl) methyl ether, (cyclopentylmethyl) ethyl ether, (cyclopentylmethyl) propyl ether, (cyclopentyl Methyl) isopropyl ether, butyl (cyclopentylmethyl) ether, (cyclopentylmethyl) pentyl ether, (cyclopentylmethyl) hexyl ether, (cyclopentylmethyl) heptyl ether, (cyclopentylmethyl) octyl ether, (cyclopentylmethyl) (2-ethylhexyl) ether , (Cyclopentylmethyl) nonyl ether, (cyclopentylmethyl) decyl ether, (cyclopentylmethyl) undecyl ether, (cyclopentylmethyl) (2-methoxyethyl) ether, (cyclohexylmethyl) methylether, (cyclohexylmethyl) ethylether, (Cyclohexylmethyl) propyl ether, (cyclohexylmethyl) isopropyl ether, butyl (cyclohexyl) Til) ether, (cyclohexylmethyl) pentyl ether, (cyclohexylmethyl) hexyl ether, (cyclohexylmethyl) heptyl ether, (cyclohexylmethyl) octyl ether, (cyclohexylmethyl) (2-ethylhexyl) ether, (cyclohexylmethyl) nonylether, (Cyclohexylmethyl) decyl ether, (cyclohexylmethyl) undecyl ether, (cyclohexylmethyl) (2-methoxyethyl) ether, (cyclohexylmethyl) (cyclopentylmethyl) ether, benzylmethylether, benzylethylether, benzylpropylether, benzyl Isopropyl ether, benzyl butyl ether, benzyl pentyl ether, benzyl hexyl ether, benzyl Heptyl ether, benzyl octyl ether, benzyl (2-ethylhexyl) ether, benzyl nonyl ether, benzyl decyl ether, benzyl undecyl ether, benzyl (2-methoxyethyl) ether, benzyl (cyclopentylmethyl) ether, benzyl (cyclohexyl) ether, (4-methoxybenzyl) methyl ether, ethyl (4-methoxybenzyl) ether, (4-methoxybenzyl) propyl ether, isopropyl (4-methoxybenzyl) ether, butyl (4-methoxybenzyl) ether, (4-methoxybenzyl) ) Pentyl ether, hexyl (4-methoxybenzyl) ether, heptyl (4-methoxybenzyl) ether, (4-methoxybenzyl) octyl ether, (2-ethyl) Xyl) (4-methoxybenzyl) ether, (4-methoxybenzyl) nonyl ether, decyl (4-methoxybenzyl) ether, (4-methoxybenzyl) undecyl ether, (4-methoxybenzyl) (2-methoxyethyl) Ether, (cyclopentylmethyl) (4-methoxybenzyl) ether, (cyclohexylmethyl) (4-methoxybenzyl) ether, benzyl (4-methoxybenzyl) ether, (4-chlorobenzyl) methylether, ethyl (4-chlorobenzyl) ) Ether, (4-chlorobenzyl) propyl ether, (4-chlorobenzyl) isopropyl ether, butyl (4-chlorobenzyl) ether, (4-chlorobenzyl) pentyl ether, (4-chlorobenzyl) hexyl ether, (4 − (Rorobenzyl) heptyl ether, (4-chlorobenzyl) octyl ether, (4-chlorobenzyl) (2-ethylhexyl) ether, (4-chlorobenzyl) nonyl ether, (4-chlorobenzyl) decyl ether, (4-chlorobenzyl) ) Undecyl ether, (4-chlorobenzyl) (2-methoxyethyl) ether, (4-chlorobenzyl) (cyclopentylmethyl) ether, (4-chlorobenzyl) (cyclohexylmethyl) ether, benzyl (4-chlorobenzyl) Ether, (4-chlorobenzyl) (4-methoxybenzyl) ether, (1-phenylethyl) methyl ether, ethyl (1-phenylethyl) ether, (1-phenylethyl) propyl ether, isopropyl (1-phenylethyl) ether, Butyl (1-phenylethyl) ether, pentyl (1-phenylethyl), hexyl (1-phenylethyl) ether, heptyl (1-phenylethyl) ether, (1-phenylethyl) octyl ether, (2-ethylhexyl) ( 1-phenylethyl) ether, nonyl (1-phenylethyl) ether, decyl (1-phenylethyl) ether, (1-phenylethyl) undecylether, (2-methoxyethyl) (1-phenylethyl) ether, Cyclopentylmethyl) (1-phenylethyl) ether, (cyclohexylmethyl) (1-phenylethyl) ether, benzyl (1-phenylethyl) ether, (4-methoxybenzyl) (1-phenylethyl) ether, (4-chloro Benzyl) (1-phenylethyl) Ether, methyl (2-naphthalene methyl) ether, ethyl (2-naphthalene methyl) ether, (2-naphthalene methyl) propyl ether, isopropyl (2-naphthalene methyl ether) ether, butyl (2-naphthalene methyl) ether, (2 -Naphthalenemethyl) pentyl ether, hexyl (2-naphthalenemethyl) ether, heptyl (2-naphthalenemethyl) ether, (2-naphthalenemethyl) octylether, (2-ethylhexyl) (2-naphthalenemethyl) ether, (2- Naphthalenemethyl) nonyl ether, decyl (2-naphthalenemethyl) ether, (2-naphthalenemethyl) undecylether, (2-methoxyethyl) (2-naphthalenemethyl) ether, (cyclopentylmethyl) (2-naphthalene) Ether), (cyclohexylmethyl) (2-naphthalenemethyl) ether, benzyl (2-naphthalenemethyl) ether, (4-methoxybenzyl) (2-naphthalenemethyl) ether, (4-chlorobenzyl) (2-naphthalenemethyl) ) Ether, (1-phenylethyl) (2-naphthalenemethyl) ether, (2-furylmethyl) methylether, ethyl (2-furylmethyl) ether, (2-furylmethyl) propylether, (2-furylmethyl) Isopropyl ether, butyl (2-furylmethyl) ether, (2-furylmethyl) pentyl ether, (2-furylmethyl) hexyl ether, (2-furylmethyl) heptyl ether, (2-furylmethyl) octyl ether, (2 -Ethylhexyl) (2-furylme Til) ether, (2-furylmethyl) nonyl ether, decyl (2-furylmethyl) ether, (2-furylmethyl) undecyl ether, (2-furylmethyl) (2-methoxyethyl) ether, (cyclopentylmethyl) (2-furylmethyl) ether, (cyclohexylmethyl) (2-furylmethyl) ether, benzyl (2-furylmethyl) ether, (2-furylmethyl) (4-methoxybenzyl) ether, (4-chlorobenzyl) ( 2-furylmethyl) ether, (2-furylmethyl) (1-phenylethyl) ether, (2-furylmethyl) (2-naphthalenemethyl) ether, methyl (2-thienylmethyl) ether, ethyl (2-thienylmethyl) ) Ether, propyl (2-thienylmethyl) ether, isopropyl 2-thienylmethyl) ether, butyl (2-thienylmethyl) ether, pentyl (2-thienylmethyl) ether, hexyl (2-thienylmethyl) ether, heptyl (2-thienylmethyl) ether, octyl (2-thienylmethyl) Ether, (2-ethylhexyl) (2-thienylmethyl) ether, nonyl (2-thienylmethyl) ether, decyl (2-thienylmethyl) ether, (2-thienylmethyl) undecyl ether, (2-methoxyethyl) ( 2-thienylmethyl) ether, (cyclopentylmethyl) (2-thienylmethyl) ether, (cyclohexylmethyl) (2-thienylmethyl) ether, benzyl (2-thienylmethyl) ether, (4-methoxybenzyl) (2-thienyl) Methyl) ether, ( -Chlorobenzyl) (2-thienylmethyl) ether, (1-phenylethyl) (2-thienylmethyl) ether, (2-naphthalenemethyl) (2-thienylmethyl) ether, (2-furylmethyl) (2-thienyl) Methyl) ether, (cyclopentyl) methyl ether, (cyclopentyl) ethyl ether, (cyclopentyl), (cyclopentyl) propyl ether, (cyclopentyl) isopropyl ether, butyl (cyclopentyl) ether, (cyclopentyl) pentyl ether, (cyclopentyl) hexyl ether, (Cyclopentyl) heptyl ether, (cyclopentyl) octyl ether, (cyclopentyl) (2-ethylhexyl) ether, (cyclopentyl) nonyl ether, (cyclopentyl) decyl ether Ter, (cyclopentyl) undecyl ether, (cyclopentyl) (2-methoxyethyl) ether, (cyclopentyl) (cyclopentylmethyl) ether, (cyclohexylmethyl) (cyclopentyl) ether, benzyl (cyclopentyl) ether, (cyclopentyl) (4- (Methoxybenzyl) ether, (4-chlorobenzyl) (cyclopentyl) ether, (cyclopentyl) (1-phenylethyl) ether, (cyclopentyl) (2-naphthalenemethyl) ether, (cyclopentyl) (2-furylmethyl) ether, Cyclopentyl) (2-thienylmethyl) ether, (cyclohexyl) methyl ether, (cyclohexyl) ethyl ether, (cyclohexyl) propyl ether, (cyclohexyl) isopro Ether, (cyclohexyl) butyl ether, (cyclohexyl) pentyl ether, (cyclohexyl) hexyl ether, (cyclohexyl) heptyl ether, (cyclohexyl) octyl ether, (cyclohexyl) (2-ethylhexyl) ether, (cyclohexyl) nonyl ether, (cyclohexyl) Decyl ether, (cyclohexyl) undecyl ether, (cyclohexyl) (2-methoxyethyl) ether, (cyclohexyl) (cyclopentylmethyl) ether, (cyclohexyl) (cyclohexylmethyl) ether, benzyl (cyclohexyl) ether, (cyclohexyl) (4 -Methoxybenzyl) ether, (4-chlorobenzyl) (cyclohexyl) ether, (cyclohexyl) (1- Niruechiru) ether, (cyclohexyl) (2-naphthalene) ether, (cyclohexyl) (2-furylmethyl) ether, (cyclohexyl) (2-thienylmethyl) ether, (cyclohexyl) (cyclopentyl) ether.

In the method for producing the ether compound (C) of the present invention, the amount of the etherification catalyst composition used is not particularly limited, but usually the metal element of the transition metal complex (A) (general formula) with respect to 1 mol of the alcohol compound (B). (1) and in general formula (2), ruthenium, rhodium or iridium represented by M ¹ ) on the basis of 0.001 to 50 mol% or more, preferably about 0.01 to 10 mol%, more preferably 0.00. The amount is about 1 to 2 mol%.

Moreover, in the manufacturing method of the ether compound (C) of this invention, in addition to a transition metal complex (A), further general formula (9):
M ² · N (ZSO ₂ ) ₂ (9)
(In the formula, M ² represents an alkali metal atom, and Z represents a fluorine atom or a perfluoroalkyl group having 1 to 20 carbon atoms. Z may be bonded to each other to form a ring.)
In the presence of an alkali metal compound (hereinafter referred to as alkali metal compound (9)), and from the viewpoint of improving the yield of the ether compound (C), in the presence of the alkali metal compound (9). It is preferable to react.

In the general formula (9), M ² is an alkali metal atom, preferably Li, Na, K, and particularly preferably Li. Z is a fluorine atom or a C 1-20 perfluoroalkyl group, preferably a fluorine atom, a C 1-6 perfluoroalkyl group, more preferably a C 1-6 perfluoroalkyl group. Z may be bonded to each other to form a ring.

Specific examples of the alkali metal compound (9) include, but are not limited to, lithium bis (fluorosulfonyl) imide ((FSO ₂ ) ₂ NLi) and sodium bis (fluorosulfonyl) imide ((FSO ₂ ) _2. NNa), bis (fluorosulfonyl) imide salts such as potassium bis (fluorosulfonyl) imide ((FSO ₂ ) ₂ NK), lithium bis (trifluoromethanesulfonyl) imide ((CF ₃ SO ₂ ) ₂ NLi), sodium bis ( Trifluoromethanesulfonyl) imide ((CF ₃ SO ₂ ) ₂ NNa), potassium bis (trifluoromethanesulfonyl) imide ((CF ₃ SO ₂ ) ₂ NK), lithium bis (pentafluoroethanesulfonyl) imide ((C ₂ F ₅ SO _{2) 2} NLi), sodium Bis (pentafluoroethane sulfonyl) imide _{((C 2 F 5 SO 2} ) 2 NNa), potassium bis (pentafluoroethane sulfonyl) imide _{((C 2 F 5 SO 2} ) 2 NK), lithium bis (heptafluoropropanesulfonyl ) Imide ((C ₃ F ₇ SO ₂ ) ₂ NLi), sodium bis (heptafluoropropanesulfonyl) imide ((C ₃ F ₇ SO ₂ ) ₂ NNa), potassium bis (heptafluoropropanesulfonyl) imide ((C _{3 F 7 SO 2) 2 NK)} , lithium bis (nonafluorobutanesulfonyl) imide _{((C 4 F 9 SO 2} ) 2 NLi), sodium bis (nonafluorobutanesulfonyl) imide _{((C 4 F 9 SO 2} ) 2 NNa), potassium bis (nonafluorobutanesulfonyl) i De _{((C 4 F 9 SO 2} ) 2 NK), lithium nonafluoro -N - [(trifluoromethane) sulfonyl] butane sulfonyl amide _{((CF 3 SO 2) (} C 4 F 9 SO 2) NLi), sodium nona Fluoro-N-[(trifluoromethane) sulfonyl] butanesulfonylamide ((CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ) NNa), potassium nonafluoro-N-[(trifluoromethane) sulfonyl] butanesulfonylamide (( _{CF 3 SO 2) (C 4} F 9 SO 2) NK), 1,1,2,2,3,3- hexafluoropropane-1,3-disulfonic imide _{(CF 2 (CF 2 SO 2} ) 2 NLi ), 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonic imide sodium _(CF 2 (C _{2 SO 2) 2 NNa),} 1,1,2,2,3,3- hexafluoropropane-1,3-disulfonic imide potassium _{(CF 2 (CF 2 SO 2} ) 2 NK) such bis (perfluoroalkyl Sulfonyl) imide salts and the like, preferably lithium bis (trifluoromethanesulfonyl) imide ((CF ₃ SO ₂ ) ₂ NLi), sodium bis (trifluoromethanesulfonyl) imide ((CF ₃ SO ₂ ) ₂ NNa), potassium Bis (trifluoromethanesulfonyl) imide ((CF ₃ SO ₂ ) ₂ NK), lithium bis (pentafluoroethanesulfonyl) imide ((C ₂ F ₅ SO ₂ ) ₂ NLi), sodium bis (pentafluoroethanesulfonyl) imide ( (C ₂ F ₅ SO ₂ ) ₂ NNa), potassium bis (pe Ntafluoroethanesulfonyl) imide ((C ₂ F ₅ SO ₂ ) ₂ NK), lithium bis (heptafluoropropanesulfonyl) imide ((C ₃ F ₇ SO ₂ ) ₂ NLi), sodium bis (heptafluoropropanesulfonyl) imide ((C ₃ F ₇ SO ₂ ) ₂ NNa), potassium bis (heptafluoropropanesulfonyl) imide ((C ₃ F ₇ SO ₂ ) ₂ NK), lithium bis (nonafluorobutanesulfonyl) imide ((C ₄ F ₉ SO ₂ ) ₂ NLi), sodium bis (nonafluorobutanesulfonyl) imide ((C ₄ F ₉ SO ₂ ) ₂ NNa), potassium bis (nonafluorobutanesulfonyl) imide ((C ₄ F ₉ SO ₂ ) ₂ NK) , Lithium nonafluoro-N-[(trifluoromethane) sulfonate ] Butane sulfonyl amide _{((CF 3 SO 2) (} C 4 F 9 SO 2) NLi), sodium nonafluoro -N - [(trifluoromethane) sulfonyl] butane sulfonyl amide _{((CF 3 SO 2) (} C 4 F 9 SO ₂₎ NNa), potassium nona fluoro -N - [(trifluoromethane) sulfonyl] butane sulfonyl amide _{((CF 3 SO 2) (} C 4 F 9 SO 2) NK), 1,1,2,2,3, 3-hexafluoropropane-1,3-disulfonimidolithium (CF ₂ (CF ₂ SO ₂ ) ₂ NLi), 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide sodium ( _{CF 2 (CF 2 SO 2)} 2 NNa), 1,1,2,2,3,3- hexafluoropropane-1,3 Jisuruhon'imi Potassium _{(CF 2 (CF 2 SO 2} ) 2 NK).

  In the present invention, the amount of alkali metal compound (9) used is not particularly limited, but is usually 0.001 to 100 mol%, preferably 0.01 to 50 mol%, more preferably 1 mol of alcohol compound (B). Is an amount of 0.1 to 30 mol%.

  The production method of the ether compound (C) of the present invention is carried out in the presence or absence of a solvent, and the reaction is usually carried out in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely affect the present invention. For example, hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, octane, petroleum ether, and aromatics such as toluene, xylene, mesitylene, and chlorobenzene. Group hydrocarbon solvent, dibutyl ether, diisopropyl ether, cyclopentyl methyl ether (CPME), tert-butyl methyl ether (TBME), tetrahydrofuran (THF), 2-methyltetrahydrofuran (MeTHF), 1,4-dioxane, diethylene glycol dimethyl ether, etc. Examples include ether solvents. You may use these in mixture of 2 or more types. Of these, aromatic hydrocarbons such as toluene, xylene, mesitylene and chlorobenzene are preferred, and toluene is particularly preferred from the viewpoint of economy.

  In the method for producing an ether compound of the present invention, an equimolar amount of water is by-produced together with the target ether compound in the reaction. When a large amount of water is present in the system, the ether compound is hydrolyzed. Examples of a method for reducing the influence of water include 1) a method of reacting under a high dilution condition with a solvent, and 2) a method of reacting while discharging water produced as a by-product during the reaction from the reaction system.

  1) When making it react as a high dilution condition with a solvent, the said solvent of a large excess is used with respect to alcohol compound (B). At this time, as the usage-amount of a solvent, it is 10L or more normally with respect to 1 mol of alcohol compounds (B), Preferably it is 10-100L, More preferably, it is 10-50L.

  2) As a method to be carried out while discharging water produced as a by-product during the reaction, for example, a method of removing water by carrying out the reaction in the presence of a dehydrating agent, water removal by azeotropic dehydration, etc. The method of doing is mentioned. Among these methods, a method of removing water by azeotropic dehydration using a reaction apparatus equipped with a Dean-Stark apparatus or the like is preferable. Such a method for removing water can reduce the amount of solvent to be used as compared with a high dilution condition.

  2) When the reaction is performed while discharging water produced as a by-product from the reaction system, the amount of the solvent used may be appropriately adjusted depending on the reaction conditions and the like, and is not particularly limited. For example, 1 mol of the alcohol compound (B) On the other hand, it is less than 10L, preferably 0.01 to 9L, more preferably 0.1 to 1.0L.

  The reaction according to the production method of the present invention can be carried out in an inert gas atmosphere, in an air, or in a hydrogen atmosphere. However, in terms of suppression of byproducts, improvement in yield, etc., a hydrogen atmosphere It is preferable to carry out below.

  The reaction pressure is not particularly limited, and the reaction may be performed at normal pressure or may be performed under pressure.

  Reaction temperature is not specifically limited, It can implement at arbitrary temperature, For example, it is preferable to implement reaction in the range of 20-200 degreeC. More preferably, it is 100-180 degreeC, More preferably, it is 130-160 degreeC.

  You may perform the manufacturing method of this invention in an airtight container. There is no restriction | limiting in particular as the container, A stainless steel airtight container, a pressure-resistant glass airtight container, etc. are mentioned.

  After completion of the reaction, the resulting reaction mixture is subjected to post-treatment operations such as filtration and centrifugation, and, if desired, purification operations such as silica gel column chromatography, distillation and recrystallization according to methods known to those skilled in the art. The ether compound (C) can be taken out.

Next, the present invention will be specifically described based on examples, but the present invention is not limited thereto. In the following examples, the yield of the obtained ether compound was calculated by an internal standard quantitative method based on GC biphenyl or an internal standard quantitative method based on ¹ H-NMR phenanthrene.

Measurement conditions for gas chromatography (hereinafter abbreviated as GC) analysis are as follows.
Apparatus: Gas chromatography manufactured by Shimadzu Corporation (GC-2010)
Column: Made by Agilent Technologies
(Length 60m, inner diameter 0.25mm, membrane pressure 1.00μm)
Carrier gas: Helium linear velocity: 28.5 cm / sec Split ratio: 1: 100
Column temperature: 50 ° C → 10 ° C / min → 300 ° C (10 min hold)
Detection method: FID (hydrogen flame ion detector)
Total analysis time: 35 minutes Detector temperature: 300 ° C
Inlet temperature: 250 ° C
Injection volume: 1.0 μL

¹ H-NMR analysis was performed at 400 MHz using Bruker's nuclear magnetic resonance apparatus AV400 and using CDCl ₃ , CD ₃ OD or D ₂ O as a solvent.

In the examples, lithium bis (trifluoromethanesulfonyl) imide ((CF ₃ SO ₂ ) ₂ NLi) is LiTFSI, bis (trifluoromethanesulfonyl) imide ion is TFSI ⁻ , trifluoromethanesulfonate ion is OTf ⁻ , and bis (trifluoromethanesulfonyl). ) Imido acid is abbreviated as HTFSI, and trifluoromethanesulfonic acid is abbreviated as TfOH.

  The pyridine compound 10a, the iridium complex 12a, the iridium complex 1a, and the iridium complex 1b were synthesized as shown in the following reaction formula.

[Production Example 1] Synthesis of 2-benzyloxy-6- (1-imidazolyl) pyridine 2-Bromo-6-benzyloxypyridine (4.52 g, 17.1 mmol), imidazole (1 .30 g, 19.1 mmol), copper iodide (0.33 g, 1.7 mmol), L-proline (0.39 g, 3.4 mmol), potassium carbonate (3.51 g, 25.4 mmol), dimethyl sulfoxide (30 mL) ) And then reacted at 95 ° C. for 4 hours (deep blue-green suspension). After cooling to 20 ° C., water (90 mL) was added to dissolve the solid, and the mixture was extracted with ethyl acetate (90 mL × 3 times). After filtering the organic layer containing a trace amount of solid, the solvent was distilled off from the obtained filtrate. The crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 1: 1) and then the solvent was distilled off to give 2-benzyloxy-6- (1-imidazolyl) pyridine as a yellow oil (3. 53 g, 14.0 mmol, yield 81.9%). The ¹ H-NMR data of 2-benzyloxy-6- (1-imidazolyl) pyridine is shown below.

¹ H-NMR (400 MHz, CDCl ₃ ) δ = 8.30 (s, 1 H, aromatic), 7.69 (t, J = 8.0 Hz, 1 H, aromatic), 7.57 (s, 1 H, aromatic) 7.47 (m, 2H, aromatic), 7.31-7.41 (m, 3H, aromatic), 7.18 (s, 1H, aromatic), 6.91 (d, J = 7.6 Hz, 1H, aromatic), 6.74 (d, J = 8.4 Hz, 1H, aromatic), 5.43 (s, 2H, CH ₂ ).

[Production Example 2] Synthesis of compound 10a To a nitrogen-substituted three-necked flask, 2-benzyloxy-6- (1-imidazolyl) pyridine (3.48 g, 13.8 mmol) and ethyl acetate (39 mL) were added. added. Subsequently, methyl iodide (19.71 g, 139 mmol) was added, followed by reaction at 20 ° C. for 18 hours (white suspension). The solid obtained by filtering the reaction mixture was washed (toluene 11.5 mL × 3 times) to obtain a white solid. The white solid was vacuum-dried to obtain Compound 10a (5.02 g, 12.8 mmol, yield 92.8%). The ¹ H-NMR data of compound 10a are shown below.

¹ H-NMR (400 MHz, CDCl ₃ ) δ = 11.03 (s, 1 H, aromatic), 8.06 (s, 1 H, aromatic), 7.86 (t, J = 8.4 Hz, 1 H, aromatic) , 7.75 (d, J = 7.6 Hz, 1H, aromatic), 7.61 (s, 1H, aromatic), 7.47 (m, 2H, aromatic), 7.31-7.40 (m, 3H, aromatic), 6.94 (d , J = 8.4Hz, 1H, aromatic), 5.46 (s, 2H, CH 2), 4.30 (s, 3H, CH 3).

[Production Example 3] Synthesis of iridium complex 12a To a nitrogen-substituted three-necked flask, compound 10a (1.00 g, 2.54 mmol) and dichloromethane (26 mL) were added. Silver oxide (289 mg, 1.25 mmol) was added, and the mixture was reacted at 20 ° C. for 4 hours under the light shielding of aluminum foil (white suspension). (Pentamethylcyclopentadienyl) iridium (III) dichloride (dimer) (1.00 g, 1.26 mmol) was added to the resulting reaction solution, and the mixture was reacted at 20 ° C. for 5 hours under light shielding. The yellow suspension was evaporated to remove the solvent to obtain a brown yellow solid. The obtained yellowish solid, 3N hydrochloric acid (30 mL) was added to a nitrogen-substituted three-necked flask, and reacted at 100 ° C. for 26 hours (orange suspension). After cooling to 70 ° C., hot filtration and washing (8 mL of water) were performed to obtain an orange solution. The solvent was distilled off by vacuuming to obtain a yellow orange solid. The yellow orange solid was finely pulverized, chloroform (25 mL) was added thereto, and the mixture was stirred at 20 ° C. for 3 hours. The solid obtained by filtering the suspension was washed (chloroform 1 mL) and vacuum-dried to obtain a yellow solid. Next, methanol (50 mL) was added to dissolve the yellow solid, and a part of the insoluble solid was removed with a syringe filter to obtain a yellow transparent solution. Diethyl ether (165 mL) was added dropwise thereto at 20 ° C. (1 hour), and then kept at 0 ° C. for 2 hours. After the obtained yellow suspension was filtered, the obtained solid was washed (methanol: diethyl ether = 3: 1, 3 mL) and dried in vacuo to obtain iridium complex 12a as a yellow solid (498 mg, 0.868 mmol, yield 34.2%). The ¹ H-NMR data of the iridium complex 12a are shown below.

¹ H-NMR (400 MHz, CD ₃ OD) δ = 8.01 (br, 1H, aromatic), 7.75 (t, J = 8.0 Hz, 1H, aromatic), 7.52 (br, 1H, aromatic) ), 7.13 (d, J = 7.6 Hz, 1H, aromatic), 6.65 (d, J = 8.4 Hz, 1H, aromatic), 4.02 (s, 3H, CH ₃ ), 1. 85 (s, 15H, Cp ^* ).

[Production Example 5] Synthesis of iridium complex 1a Iridium complex 12a (100 mg, 0.174 mmol), water (8 mL), bis (trifluoromethanesulfonyl) imide silver (135 mg, 0.348 mmol) were added to a 30 mL eggplant flask, and light-shielded. The reaction was carried out at 20 ° C. for 4 hours. Water (80 mL) was added to the obtained yellow suspension, and after filtration through Celite, the filtrate was dried under reduced pressure to obtain iridium complex 1a as a yellow solid (180 mg, 0.167 mmol, yield 96.0). %). The obtained iridium complex 1a was stable without being decomposed even in the air. The ¹ H-NMR data of the iridium complex 1a are shown below.

¹ H-NMR (400 MHz, D ₂ O) δ = 7.90 (t, J = 8.0 Hz, 1H, aromatic), 7.86 (d, J = 2.4 Hz, 1H, aromatic), 7.45 (D, J = 2.4 Hz, 1H, aromatic), 7.21 (d, J = 7.6 Hz, 1H, aromatic), 6.86 (d, J = 8.4 Hz, 1H, aromatic), 4. _{07 (s, 3H, CH 3} ), 1.68 (s, 15H, Cp *).

[Production Example 4] Synthesis of iridium complex 1b Iridium complex 12a (101 mg, 0.176 mmol), water (4.9 mL), and silver trifluoromethanesulfonate (86 mg, 0.34 mmol) were added to a nitrogen-substituted eggplant flask. The reaction was carried out at 20 ° C. for 4 hours. The yellow suspension was filtered through Celite and washed (2 mL of water) to obtain a yellow solution. The obtained yellow solution was evaporated under vacuum to obtain iridium complex 1b (132 mg, 0.167 mmol, yield 94.9%). The obtained iridium complex 1b was stable without being decomposed even in the air. The ¹ H-NMR data of the iridium complex 1b is shown below.

¹ H-NMR (400 MHz, D ₂ O) δ = 7.92 (t, J = 8.0 Hz, 1H, aromatic), 7.89 (d, J = 2.0 Hz, 1H, aromatic), 7.48 (D, J = 2.4 Hz, 1H, aromatic), 7.22 (d, J = 7.6 Hz, 1H, aromatic), 6.88 (d, J = 8.4 Hz, 1H, aromatic), 4. _{11 (s, 3H, CH 3} ), 1.71 (s, 15H, Cp *).

  The iridium complex 15 was synthesized as shown in the following reaction formula.

[Production Example 6] Synthesis of Iridium Complex 15 An iridium complex 14 (100 mg, 0.202 mmol) synthesized in accordance with a previously reported production method (J. Organomet. Chem. 2008, 693, 3363-3368) was added to a nitrogen-substituted eggplant flask. (12.5 mL) and silver trifluoromethanesulfonate (105 mg, 0.409 mmol) were added. The reaction was carried out at 20 ° C. for 14 hours in the dark. The yellow suspension was filtered through Celite and washed (dichloromethane 2 mL) to give a yellow solution. The obtained yellow solution was evaporated under vacuum to obtain iridium complex 15 (138 mg, 0.182 mmol, yield 90.0%). The ¹ H-NMR data of the iridium complex 15 are shown below.

¹ H-NMR (400 MHz, D ₂ O) δ = 7.31 (s, 2H, aromatic), 3.76 (s, 6H, CH ₃ ), 1.62 (s, 15H, Cp ^* ).

[Example 1a-1] Synthesis of dioctyl ether using complex 1a (with hydrogenation)
Complex 1a (13.0 mg, 1.2 × 10 ⁻⁵ mol) (2.0 mol%), 1-octanol (78 mg, 0.60 mmol), toluene (10.8 mL) was added to a 30 mL stainless steel sealed container. After purging with hydrogen, the mixture was stirred at 160 ° C. for 20 hours. When the reaction solution was cooled and quantified by GC analysis, it was confirmed that dioctyl ether was produced in a yield of 90%. The results are shown in Table 1.

[Example 1b-1] Synthesis of dioctyl ether using complex 1b (no hydrogenation)
To a 30 mL stainless steel sealed container, complex 1b (9.8 mg, 1.2 × 10 ⁻⁵ mol) (2.0 mol%), 1-octanol (78 mg, 0.60 mmol), and toluene (10.8 mL) were added. After nitrogen substitution, the mixture was stirred at 160 ° C. for 20 hours. When the reaction solution was cooled and quantified by GC analysis, it was confirmed that dioctyl ether was produced in a yield of 35%. The results are shown in Table 1.

[Example 1b-2] Synthesis of dioctyl ether using complex 1b (with hydrogenation)
To a 30 mL stainless steel sealed container, complex 1b (9.8 mg, 1.2 × 10 ⁻⁵ mol) (2.0 mol%), 1-octanol (78 mg, 0.60 mmol), and toluene (10.8 mL) were added. After purging with hydrogen, the mixture was stirred at 160 ° C. for 20 hours. When the reaction solution was cooled and quantified by GC analysis, it was confirmed that dioctyl ether was produced in a yield of 92%. The results are shown in Table 1.

[Example 1b-3] Synthesis of dioctyl ether In a 30 mL stainless steel sealed container, iridium complex 1b (2.5 mg, 3.0 μmol) (0.5 mol%), 1-octanol (78 mg, 0.60 mmol), toluene (10.8 mL) was added, and after replacing with hydrogen, the mixture was stirred at 160 ° C. for 20 hours. When the reaction solution was cooled and quantified by GC analysis, it was confirmed that dioctyl ether was produced in a yield of 94%. The results are shown in Table 2.

Example 1b-4 Synthesis of butyl octyl ether In a 30 mL stainless steel sealed container, iridium complex 1b (4.9 mg, 6.0 μmol) (1.0 mol%), LiTFSI (3.4 mg, 1.2 × 10 ⁻⁵ mol) (2.0 mol%), 1-octanol (78 mg, 0.6 mmol), 1-butanol (133 mg, 1.8 mmol), toluene (10.8 mL) were added, and after hydrogen substitution, 4 ° C. at 160 ° C. Stir for hours. When the reaction solution was cooled and quantified by ¹ H-NMR analysis, it was confirmed that butyl octyl ether was produced in a yield of 82%. The results are shown in Table 2.

[Example 1b-5] Synthesis of butylcyclohexyl ether In Example 1b-4, cyclohexanol (180.3 mg, 1.8 mmol) was used instead of 1-butanol. The reaction was performed. The results are shown in Table 2.

[Example 1b-6] Examination of etherification of asymmetric alcohol The same as Example 1b-4 except that in Example 1b-4, methoxyethanol (228.3 mg, 3.0 mmol) was used instead of 1-butanol. The reaction was carried out. The results are shown in Table 2.

Stainless steel closed container synthesis 30mL of Example 1b-7] dibutyl ether, iridium complex 1b (4.9mg, 6.0μmol) (1.0mol %), LiTFSI (3.4mg, 1.2 × 10 - ⁵ mol) (2.0 mol%), 1-butanol (45 mg, 0.6 mmol) and toluene (10.8 mL) were added, and the mixture was purged with hydrogen and stirred at 160 ° C. for 4 hours. When the reaction solution was cooled and quantified by GC analysis, it was confirmed that dibutyl ether was produced in a yield of 89%.
The results are shown in Table 2.

Example 1b-8 Synthesis of benzylbutyl ether In a 30 mL stainless steel sealed container, iridium complex 1b (4.9 mg, 6.0 μmol) (1.0 mol%), LiTFSI (3.4 mg, 1.2 × 10 ^{− 5} mol) (2.0 mol%), 1-butanol (45 mg, 0.6 mmol), benzyl alcohol (195 mg, 1.8 mmol) and toluene (10.8 mL) were added, and the mixture was replaced with hydrogen and stirred at 160 ° C. for 4 hours. did. When the reaction solution was cooled and quantified by GC analysis, it was confirmed that benzylbutyl ether was produced in a yield of 89%. The results are shown in Table 2.

[Example 1b-9] Synthesis of butyl ethyl ether The reaction was conducted in the same manner as in Example 1b-8 except that ethanol (138.2 mg, 3.0 mmol) was used instead of benzyl alcohol in Example 1b-8. Went. The results are shown in Table 2.

[Example 1b-10] Synthesis of didecyl ether Example 1b-7 except that 1-decyl alcohol (95.0 mg, 0.6 mmol) was used instead of 1-butanol in Example 1b-7. The reaction was carried out in the same manner as above. The results are shown in Table 2.

[Example 1b-11] Synthesis of decylisopropyl ether In Example 1b-4, instead of 1-octanol, 1-decyl alcohol (95.0 mg, 0.6 mmol) was replaced with 1-butanol, and isopropanol ( The reaction was performed in the same manner as in Example 1b-4 except that 108.2 mg, 1.8 mmol) was used. The results are shown in Table 2.

[Example 1b-12] Synthesis of dibenzyl ether In a 30 mL stainless steel sealed container, iridium complex 1b (4.9 mg, 6.0 μmol) (1.0 mol%), benzyl alcohol (65 mg, 0.6 mmol), toluene (10.8 mL) was added and, after purging with hydrogen, the mixture was stirred at 160 ° C. for 4 hours. When the reaction solution was cooled and quantified by GC analysis, it was confirmed that dibenzyl ether was produced in a yield of 68%. The results are shown in Table 2.

[Example 1a-2] Synthesis of dioctyl ether using iridium complex 1a (under drainage condition using Dean-Stark apparatus)
In a 30 mL glass test tube equipped with a Dean-Stark apparatus, iridium complex 1a (24.5 mg, 2.27 × 10 ⁻⁵ mol) (0.1 mol%), 1-octanol (2.95 g, 22.7 mmol), Toluene (6.8 mL) was added, and after purging with nitrogen, the mixture was stirred at 130 ° C. for 4 hours. When the reaction solution was cooled and quantified by GC analysis, it was confirmed that dioctyl ether was produced in a yield of 90%. The results are shown in Table 3.

[Example 1b-13] Synthesis of dioctyl ether using iridium complex 1b (under drainage condition using Dean-Stark apparatus)
In a 30 mL glass test tube equipped with a Dean-Stark apparatus, iridium complex 1b (18.5 mg, 2.27 × 10 ⁻⁵ mol) (0.1 mol%), 1-octanol (2.95 g, 22.7 mmol), Toluene (6.8 mL) was added, and after purging with nitrogen, the mixture was stirred at 130 ° C. for 4 hours. When the reaction solution was cooled and quantified by GC analysis, it was confirmed that dioctyl ether was produced in a yield of 50%. The results are shown in Table 3.

[Example 1b-14] Synthesis of dioctyl ether using complex 1b and LiTFSI (under drainage conditions using a Dean-Stark apparatus)
In a 30 mL glass test tube equipped with a Dean-Stark apparatus, iridium complex 1b (18.5 mg, 2.27 × 10 ⁻⁵ mol) (0.1 mol%), LiTFSI (13.0 mg, 4.5 × 10 ^−5). mol) (0.2 mol%), 1-octanol (2.95 g, 22.7 mmol), and toluene (6.8 mL) were added, and after purging with nitrogen, the mixture was stirred at 130 ° C. for 4 hours. When the reaction solution was cooled and quantified by GC analysis, it was confirmed that dioctyl ether was produced in a yield of 74%. The results are shown in Table 3.

[Comparative Example 1] Synthesis of dioctyl ether using iridium complex 12a Iridium complex 12a (13.0 mg, 2.27 x ^10-5 mol) (0.1 mol%) was placed in a 30 mL glass test tube equipped with a Dean-Stark apparatus. , 1-octanol (2.95 g, 22.7 mmol) and toluene (6.8 mL) were added, and after purging with nitrogen, the mixture was stirred at 130 ° C. for 4 hours. After the reaction solution was cooled and quantified by GC analysis, it was not possible to confirm the formation of dioctyl ether. The results are shown in Table 3.

[Comparative Example 2] Synthesis of dioctyl ether using iridium complex 15 Iridium complex 15 (17.2 mg, 2.27 x 10 ^-5 mol) was added to a 30 mL glass test tube equipped with a Dean-Stark apparatus ( 0.1 mol%), 1-octanol (2.95 g, 22.7 mmol), and toluene (6.8 mL) were added, and after purging with nitrogen, the mixture was stirred at 130 ° C. for 4 hours. When the reaction solution was cooled and quantified by GC analysis, the yield of dioctyl ether was 1.0% or less. The results are shown in Table 3.

Comparative Example 3 Synthesis of Dioctyl Ether Using LiTFSI To a 30 mL glass test tube equipped with a Dean-Stark apparatus, LiTFSI (13.0 mg, 4.5 × 10 ⁻⁵ mol) (0.2 mol%), 1− Octanol (2.95 g, 22.7 mmol) and toluene (6.8 mL) were added, and after purging with nitrogen, the mixture was stirred at 130 ° C. for 4 hours. GC analysis was performed after cooling the reaction solution, but formation of dioctyl ether could not be confirmed. The results are shown in Table 3.

[Comparative Example 4] Synthesis of dioctyl ether using trifluoromethanesulfonic acid A 30 mL glass test tube equipped with a Dean-Stark apparatus was charged with trifluoromethanesulfonic acid (6.8 mg, 4.5 x ^10-5 mol) (0 0.2 mol%), 1-octanol (2.95 g, 22.7 mmol) and toluene (6.8 mL) were added, and the mixture was purged with nitrogen and stirred at 130 ° C. for 4 hours. When the reaction solution was cooled and quantified by GC analysis, the yield of dioctyl ether was 1.0% or less. The results are shown in Table 3.

[Comparative Example 5] Synthesis of dioctyl ether using bis (trifluoromethanesulfonyl) imidic acid To a 30 mL glass test tube equipped with a Dean-Stark apparatus, bis (trifluoromethanesulfonyl) imidic acid (12.7 mg, 4.5 × 10 ⁻⁵ mol) (0.2 mol%), 1-octanol (2.95 g, 22.7 mmol) and toluene (6.8 mL) were added, and after purging with nitrogen, the mixture was stirred at 130 ° C. for 4 hours. When the reaction solution was cooled and quantified by GC analysis, the yield of dioctyl ether was 1.0% or less. The results are shown in Table 3.

Claims (15)

An etherification catalyst composition containing a transition metal complex represented by the general formula (1) or (2).
General formula (1):

General formula (2):

[In the general formulas (1) and (2), Ar is an aromatic compound which may have a substituent or a cyclopentadienyl group which may have a substituent, M ¹ is ruthenium, rhodium or Iridium, R ¹ is an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and R ^{2 to} R ⁷ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, hydroxy group , An amino group, a sulfo group, a mercapto group, a carboxyl group, a carbamoyl group or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. R ² and R ³ , R ³ and R ⁴ , or adjacent R ^{4 to} R ⁷ may be bonded to each other to form a ring. L is a ligand selected from the group consisting of a sulfoxide ligand, an amide ligand, a nitrogen-containing aromatic ring ligand, an amine ligand, an ether ligand, a nitrile ligand, and an aco ligand Indicates. A broken line shows that the single bond or the double bond is formed with the solid line. Y ⁻ represents an anion. ] The etherification catalyst composition according to claim 1, wherein Ar is a 1,2,3,4,5-pentamethylcyclopentadienyl group. The etherification catalyst composition according to claim 1 or 2, wherein M ¹ is iridium. Y ⁻ represents the general formula (3):
R ⁸ SO ₃ ^- ₍₃₎
(In General Formula (3), R ⁸ is an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or (It is a C6-C20 perfluoroaryl group.)
A sulfonate ion represented by the general formula (4):

(In the general formula (4), R ⁹ and R ¹⁰ may be the same or different from each other, and the alkyl group having 1 to 20 carbon atoms, the perfluoroalkyl group having 1 to 20 carbon atoms, and the cycloalkyl having 3 to 20 carbon atoms. A group, an aryl group having 6 to 20 carbon atoms, a perfluoroaryl group having 6 to 20 carbon atoms, or a fluorine atom, and R ⁹ and R ¹⁰ may be bonded to each other to form a ring.)
A bis (sulfonyl) imide ion represented by the general formula (5):
_{^{(R 11 SO 2) 3 C}} - (5)
(In the general formula (5), R ¹¹ is an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or (It is a C6-C20 perfluoroaryl group.)
The etherification catalyst composition according to claim 1, which is a tris (sulfonyl) methide ion represented by the formula: The etherification catalyst composition according to claim 1, wherein Y ⁻ is a bis (sulfonyl) imide ion represented by the general formula (4). L is an acoligand, The etherification catalyst composition in any one of Claims 1-5. Etherification catalyst composition according to any one of claims 1 to 6 R ⁷ is a hydroxy group. R < ² > -R < ⁶ > is a hydrogen atom, The etherification catalyst composition in any one of Claims 1-7. Etherification catalyst composition according to any one of claims 1 to 8 R ¹ is an alkyl group having 1 to 6 carbon atoms. The manufacturing method of the ether compound which makes 2 or more molecules of alcohol compounds react in the presence of the etherification catalyst composition in any one of Claims 1-9. In the presence of the etherification catalyst composition according to any one of claims 1 to 9, the general formula (6):

[In General Formula (6), R ¹² is an optionally substituted hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted heterocyclic group having 1 to 20 carbon atoms, R ¹³ is a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted heterocyclic group having 1 to 20 carbon atoms, and R ¹² and R ¹³ may be bonded to each other to form a ring. ]
An alcohol compound represented by formula (7):

[In General Formula (7), R ¹⁴ is a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a heterocyclic group having 1 to 20 carbon atoms which may have a substituent, R ¹⁵ is a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted heterocyclic group having 1 to 20 carbon atoms, and R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. ]
General formula (8) in which an alcohol compound represented by the formula is reacted:

[In general formula (8), R < ¹² > -R < ¹⁵ > is the same as the above. ]
The manufacturing method of the ether compound represented by these. Furthermore, the general formula (9):
M ² · N (ZSO ₂ ) ₂ (9)
[In General Formula (9), M ² is Li, Na, K, and Z represents a fluorine atom or a C 1-20 perfluoroalkyl group. Z may be bonded to each other to form a ring. ]
The manufacturing method of the ether compound of Claim 10 or 11 made to react in presence of the alkali metal compound represented by these. The method for producing an ether compound according to claim 10, wherein water produced as a by-product during the reaction is discharged out of the reaction system. The method for producing an ether compound according to any one of claims 10 to 13, wherein the reaction is carried out in the presence of a hydrocarbon solvent. The method for producing an ether compound according to any one of claims 10 to 14, wherein the reaction is performed in a hydrogen gas atmosphere.