DE69924077T2 - Process for the preparation of a palladium complex compound - Google Patents

Description

BACKGROUND THE INVENTION

The The present invention relates to a process for the preparation of a Palladium-phosphine complex compound which acts as a catalyst organic Synthesis is suitable.

So far were various transition metal complexes used as catalysts of organic syntheses. Especially noble metal complexes are stable and easy to handle. Thus be widely used as catalysts for organic syntheses, although they are expensive. Of the optically active ligands of transition metal complexes used in asymmetric catalytic reactions is a ligand of 2,2-bis (diphenylphosphino) -1,1-binaphthyl (here as "BINAP") one the best ligand in the ability asymmetric differentiation. It is in J. Am. Chem. Soc. 1991, volume 113, page 1417 and J. Org. Chem. 1989, volume 54, page 4738 reported that a palladium complex with a BINAP ligand in the catalytic activity, especially in the enantioselectivity, for the Heck reaction on a Olefin which is an asymmetric carbon-carbon bond forming reaction is much better. It is believed that in such a reaction an intermediate of [PhPd (I) (BINAP)] is involved, which is characterized by an oxidative addition of benzene iodide to Pd (O) -BINAP formed in the reaction system is formed.

in der Y Fluor, Chlor, Brom oder Iod ist.There are known palladium complex compounds having ligands of trifluoromethylphenyl and tris (trifluoromethyl) phenyl which are represented by the following general formulas:

where Y is fluorine, chlorine, bromine or iodine.

J. Organomet. Chem., 1971, 28, 287 discloses a process for preparing a palladium complex compound represented by the general formula Ar ¹ Pd (PPh ₃ ) ₂ X ¹ in which Ar ^{1 is} an aryl and X ^{1 is} a halogen. In this method, a stable palladium complex Pd ⁰ (PPh ₃ ) _{4 is} reacted with an aryl halide. J. Organometallics, 1996, 15 (17), 3708 discloses a similar process in which a palladium complex Pd ₂ (DBA) ₃ is used.

J. Chem. Commun., 1994, 121 discloses a reaction of a dibromobis (triphenylphosphine) palladium (II) with toluene in the presence of potassium carbonate at 130 ° C during one Hour to small amounts of bromo [methylphenyl] bis (triphenylphosphine) palladium (II).

J. Am. Chem. Soc., Vol. 117, No. 15, 4305 (1995) discloses a process for preparing a palladium complex compound having a benzoato ligand represented by the formula (Ph ₃ P) ₂ PdPh (PhCOO). In this process, (Ph ₃ P) ₂ Pd ₂ Ph ₂ (μ-OH) _{2 is} dispersed in benzene. Benzoic acid is then added to the mixture to give a solution of pale yellow color. Then the solvent is distilled off. Thereafter, n-hexane is added to give (Ph ₃ P) ₂ Pd ₂ Ph ₂ (μ-PhCOO) ₂ in the form of crystals. The resulting crystals are dispersed in benzene. Then triphenylphosphine is added to produce a transparent solution. Then the solvent is distilled off. Thereafter, n-hexane is added to obtain the desired palladium complex compound in the form of crystals.

J. Organomet. Chem. 553 (1998) 83-90 discloses a process for the preparation of trans [Pd (OOC- (C ₆ H ₄ ) -2-SMe-κ ¹ -O) Ph (PPh ₃ ) ₂ ]. In this process, a thallium salt 2-RS-C ₆ H ₄ -COOTl is prepared by reacting 2-RS-C ₆ H ₄ -COOH with thallium carbonate in ethanol. Then the thallium salt is reacted with trans- [PdCl (Ph) (PPh ₃ ) ₂ ] in tetrahydrofuran to give the product with a thallium chloride precipitate.

SUMMARY THE INVENTION

It is an object of the invention, a method for easy production a palladium complex compound useful as a catalyst to disposal to deliver.

It Another object of the present invention is a palladium complex compound available too pose, which in the physical and / or chemical properties is improved.

in der Ar¹, Ar² und L wie oben definiert sind.According to a first aspect of the present invention, there is provided a first process for producing a first palladium complex compound represented by the general formula (4). Thus, it is possible to easily obtain the product through the following reaction steps (a) and (b). The first method comprises (a) reacting an aromatic compound represented by the general formula (1) with a palladium compound and a phosphine derivative in the presence of a first basic substance to give a second palladium complex compound represented by the general formula (2); and (b) reacting said second palladium complex compound with a benzoic acid represented by the general formula (3) in the presence of a second basic substance, wherein the first palladium complex compound Ar ¹ X (1) wherein Ar ^{1 is} an aryl group and X is a halogen, ie, fluorine, chromium, bromine or iodine, a trifluoromethanesulfonate group, an alkylsulfonate group having a number of carbon atoms of 1 to 4, or a substituted or unsubstituted arylsulfonate group Ar ¹ -PdL ₂ X (2) in which each L is independently a phosphine ligand and Ar ¹ X are as defined above, Ar ² -COOH (3) Ar ^{2 is} an aryl group,

wherein Ar ¹ , Ar ² and L are as defined above.

According to one second aspect of the invention is a second method of preparation the first palladium complex compound represented by the general Formula (4) available posed. Compared to the first method, the second method comprises a single reaction step in which an aromatic compound represented by the general formula (1) with a palladium compound, a phosphine derivative and a benzoic acid derivative represented by the general formula (3) in the presence of a basic substance is reacted to obtain the first palladium complex compound becomes.

in der Ar³ und Ar⁴ Arylgruppen sind, dargestellt durch die allgemeinen Formeln (6) bzw. (7) und jedes L unabhängig voneinander ein Phosphinligand ist,

in der R² eine Trifluoromethylgruppe, eine Trifluoromethyloxygruppe, ein Halogen, d.h. Fluor, Chlor, Brom oder Iod, eine Nitrogruppe, Acetylgruppe, Cyanogruppe, eine Alkylgruppe mit einer Anzahl Kohlenstoffatome von 1 bis 4, eine Alkoxylgruppe mit einer Anzahl Kohlenstoffatome von 1 bis 4, oder eine Alkoxycarbonylgruppe mit einer Anzahl Kohlenstoffatome von 2 bis 5 und m eine ganze Zahl von 0 bis 4 ist,

in der R¹ eine Trifluoromethylgruppe ist und n eine ganze Zahl von 1 bis 3 ist.According to a third aspect of the invention, a novel palladium complex compound is provided. This compound, which can be produced by the above-mentioned first or second method, is represented by the general formula (5)

wherein Ar ³ and Ar ^{4 are} aryl groups represented by the general formulas (6) and (7), respectively, and each L is independently a phosphine ligand,

in R ^2, a trifluoromethyl group, a trifluoromethyloxy group, a halogen, ie, fluorine, chlorine, bromine or iodine, a nitro group, acetyl group, cyano group, an alkyl group having a number of carbon atoms of 1 to 4, an alkoxyl group having a number of carbon atoms of 1 to 4 or an alkoxycarbonyl group having a number of carbon atoms of 2 to 5 and m is an integer of 0 to 4,

wherein R ^{1 is} a trifluoromethyl group and n is an integer of 1 to 3.

The following palladium complex compound which can be prepared by step (A) of the above-mentioned first process is represented by the general formula Ar ⁵ -PdL ₂ X in which Ar ^{5 is} a bis (trifluoromethyl) phenyl group, X is a halogen, ie fluorine, Chlorine, bromine or iodine, and each L is independently a phosphine ligand.

DESCRIPTION THE PREFERRED EMBODIMENTS

The mentioned above first and second methods of the present invention described in detail below.

In the aromatic compound Ar ¹ X used in the first and second processes, X is defined as above and is preferably bromine or iodine in practical use.

in der R² ein Halogen, d.h. Fluor, Chlor, Brom oder Iod, oder eine monovalente organische Gruppe ist und m eine ganze Zahl von 0 bis 4 ist. Der Substituent R² ist nicht in besonderer Weise beschränkt, solange er in der Reaktion der Erfindung inert ist.As used in the first and second methods aromatic compound Ar ¹ X Ar ¹ is defined as aryl group, as mentioned above. This aryl group Ar ¹ may be selected from cyclic carbon groups such as phenyl and naphthyl, and heterocyclic groups such as pyridyl and quinolyl. These groups may have substituents. The aryl group Ar ¹ is preferably one represented by the general formula (6)

in which R ^{2 is} a halogen, ie fluorine, chlorine, bromine or iodine, or a monovalent organic group and m is an integer from 0 to 4. The substituent R ² is not particularly limited as long as it is inert in the reaction of the invention.

in der R¹ wie R² der allgemeinen Formel (6) definiert ist und n eine ganze Zahl von 0–3 ist. Der Substituent R¹ ist nicht in besonderer Weise beschränkt, solange er in der Reaktion der vorliegenden Erfindung inert ist.In the benzoic acid Ar ² -COOH used in the first and second methods, Ar ^{2 is} also defined as the aryl group as mentioned above. This aryl group Ar ² can also be selected from the above exemplified groups of the aryl group Ar ¹ . The exemplary groups of the aryl group Ar ² may also have substituents. The aryl group Ar ² is preferably one represented by the general formula (7)

in which R ^{1 is defined} as R ² of general formula (6) and n is an integer of 0-3. The substituent R ¹ is not particularly limited as long as it is inert in the reaction of the present invention.

Examples of the substituents R ¹ and R ² in the general formulas (6) and (7) are trifluoromethyl group, trifluoromethyloxy group, halogens, ie fluorine, chlorine, bromine and iodine, nitro group, acetyl group, cyano group, alkyl groups each having a number of carbon atoms of 1- 4, alkoxyl groups each having a number of carbon atoms of 1-4 and alkoxycarbonyl groups each having a number of carbon atoms of 2 to 5. Examples of the alkyl group are methyl group, ethyl group, n-propyl group and i-propyl group. Examples of the alkoxyl group are methoxy group, ethoxy group, n-propoxy group, and i-propoxy group. Examples of the alkoxycarbonyl group are methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group and i-propoxycarbonyl group. The aryl group Ar ¹ is preferably one in which at least one R ^{2 is} a trifluoromethyl group. The aryl group Ar ² is also preferably one in which at least one of R ^{1 is} a trifluoromethyl group.

Examples of the aryl groups Ar ¹ and Ar ^{2 used} in the first and second methods are (1) aryl groups each having a trifluoromethyl such as 2-trifluoromethylphenyl, 3-trifluoromethylphenyl and 4-trifluoromethylphenyl, (2) aryl groups each having one Trifluoromethoxy such as 2-trifluoromethoxyphenyl, 3-trifluoromethoxyphenyl and 4-trifluoromethoxyphenyl, (3) aryl groups each having a fluorine such as 2-fluorophenyl, 3-fluorophenyl and 4-fluorophenyl, (4) aryl groups each having a chlorine such as 2-chlorophenyl, 3-chlorophenyl and 4-chlorophenyl; (5) aryl groups each having a bromine such as 2-bromo mophenyl, 3-bromophenyl and 4-bromophenyl, (6) aryl groups with one iodine each, such as 2-iodophenyl, 3-iodophenyl and 4-iodophenyl, (7) aryl groups each having a nitro group, such as 2-nitrophenyl, 3 Nitrophenyl and 4-nitrophenyl, (8) aryl groups each having one acetyl, such as 2-acetylphenyl, 3-acetylphenyl and 4-acetylphenyl, (9) aryl groups each containing a cyano group, such as 2-cyanophenyl, 3-cyanophenyl and 4- Cyanophenyl, (11) aryl groups each containing an alkyl, such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl and 4-ethylphenyl, (12) aryl groups each containing an alkoxy, such as Methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl and 4-ethoxyphenyl, and (13) aryl groups each containing an alkoxycarbonyl such as 2-methoxycarbonylphenyl, 3-methoxycarbonylphenyl, 4-methoxycarbonylphenyl, 2-ethoxycarbonylphenyl, 3-ethoxycarbonylphenyl and 4-ethoxycarbonylphenyl. Each of the aryl groups Ar ¹ and Ar ² may have at least two substituents. These at least two substituents may be any combination of different substituents. One of the at least two substituents of the aryl group Ar ¹ or Ar ² is preferably a trifluoromethyl group. Non-limiting examples of such aryl groups are Ar ¹ and Ar ²
Of 2-chloro-3- (trifluoromethyl) phenyl,
2-fluoro-3- (trifluoromethyl) phenyl,
2-fluoro-4- (trifluoromethyl) phenyl,
3-Fluoro-5- (trifluoromethyl) phenyl,
2-Bromo-6- (trifluoromethyl) phenyl,
4-chloro-2- (trifluoromethyl) phenyl,
4-Fluoro-2- (trifluoromethyl) phenyl,
2-chloro-6- (trifluoromethyl) phenyl,
4-fluoro-3- (trifluoromethyl) phenyl,
1-chloro-4- (trifluoromethyl) phenyl,
2-Fluoro-6- (trifluoromethyl) phenyl,
2-Fluoro-5- (trifluoromethyl) phenyl,
Of 2-chloro-4- (trifluoromethyl) phenyl,
4-chloro-3- (trifluoromethyl) phenyl,
4-chloro-2- (trifluoromethyl) phenyl and the like;
2-methyl-3- (trifluoromethyl) phenyl,
3-methyl-5- (trifluoromethyl) phenyl,
2-methyl-4- (trifluoromethyl) phenyl,
4,5-dimethyl-2- (trifluoromethyl) phenyl,
2-methyl-5- (trifluoromethyl) phenyl,
5,6-dimethyl-2- (trifluoromethyl) phenyl,
4-methyl-3- (trifluoromethyl) phenyl, and the like;
2-methoxy-4- (trifluoromethyl) phenyl,
2-ethoxy-4- (trifluoromethyl) phenyl,
4-ethoxy-2- (trifluoromethyl) phenyl,
4-methoxy-2- (trifluoromethyl) phenyl,
2-methoxy-5- (trifluoromethyl) phenyl and the like;
2-Nitro-3- (trifluoromethyl) phenyl,
2-nitro-4- (trifluoromethyl) phenyl,
4-nitro-2- (trifluoromethyl) phenyl,
3-nitro-5- (trifluoromethyl) phenyl,
2-nitro-5- (trifluoromethyl) phenyl,
4-nitro-3- (trifluoromethyl) phenyl and the like;
2-cyano-5- (trifluoromethyl) phenyl,
2-Cyano-4- (trifluoromethyl) phenyl,
4-Fluoro-3-cyano-5- (trifluoromethyl) phenyl,
4-Cyano-3- (trifluoromethyl) phenyl,
2-Chloro-5-cyano-3- (trifluoromethyl) phenyl,
4-cyano-2- (trifluoromethyl) phenyl and the like; and
2-amino-6- (trifluoromethyl) phenyl,
2-amino-5- (trifluoromethyl) phenyl,
2-amino-4- (trifluoromethyl) phenyl,
2-Amino-3- (trifluoromethyl) phenyl,
3-Amino-6- (trifluoromethyl) phenyl,
3-Amino-5- (trifluoromethyl) phenyl,
4-amino-2- (trifluoromethyl) phenyl,
4-amino-3- (trifluoromethyl) phenyl and the like.

Each aryl group Ar ¹ and Ar ² is preferably one having at least two trifluoromethyl groups. Examples of such an aryl group are
2,3-bis (trifluoromethyl) phenyl,
2,4-bis (trifluoromethyl) phenyl,
2,5-bis (trifluoromethyl) phenyl,
2,6-bis (trifluoromethyl) phenyl,
3,4-bis (trifluoromethyl) phenyl, and
3,5-Bis (trifluoromethyl) phenyl.

Other non-limiting examples of such an aryl group are
2,3,4-tris (trifluoromethyl) phenyl,
2,4,5-tris (trifluoromethyl) phenyl,
2,3,5-tris (trifluoromethyl) phenyl,
1,3,5-tris (trifluoromethyl) phenyl,
3,4,5-Tris / trifluoromethyl) phenyl,
2,3,4,6-tetrakis (trifluoromethyl) phenyl,
1-Bromo-2,3,4-tris (trifluoromethyl) phenyl,
2-bromo-4,5,6-tris (trifluoromethyl) phenyl and the like;
3,5-dichloro-4,6-bis (trifluoromethyl) phenyl,
2-dichloro-3,5-bis (trifluoromethyl) phenyl,
2-methoxy-3,5-bis (trifluoromethyl) phenyl,
2-Bromo-3,5-bis (trifluoromethyl) phenyl,
2-nitro-4,6-bis (trifluoromethyl) phenyl,
5,6-dichloro-1,3-bis (trifluoromethyl) phenyl,
4-chloro-3,5-bis (trifluoromethyl) phenyl and the like.

The second palladium complex compound (Ar ¹ -PdL ₂ X) prepared in step (a) of the first process of the invention is preferably one in which at least one of R ^{2 is} a trifluoromethyl group, and more preferably one in which at least two of R ^{2 are} trifluoromethyl groups, since the desired product becomes extremely useful. The benzoic acid (Ar ² -COOH) used in the first and second methods of the invention is preferably one in which at least one of R ^{2 is} a trifluoromethyl group, and more preferably one in which at least two of R ^{2 are} trifluoromethyl groups, because the desired product is extremely useful.

As stated above, the second palladium complex compound represented by the general formula (2), Ar ¹ -PdL ₂ X in which each L is independently a phosphine ligand, is prepared in step (a) of the first method. Furthermore, the phosphine derivative is used in the first and second methods. Such a phosphine (phosphine derivative or phosphine ligand) used in the first and second methods is not particularly limited and may be one represented by the general formula P (R ¹ ) ₃ which is a monodentate ligand in Ar ¹ . PdL ₂ X, wherein each R ^{1 is} independently a first group selected from the group consisting of lower alkyl groups, cycloalkyl groups, phenyl group, naphthyl group, anthryl group, pyridyl group and quinolyl group. The first group optionally has a first substituent R ² selected from the group consisting of nitro group, primary amino group, secondary amino group, tertiary amino group, halogen atoms and a second substituent. The second substituent is selected from the group consisting of lower alkyl groups, cycloalkyl groups, phenyl group, naphthyl group, anthryl group, pyridyl group and quinolyl group. The second substituent optionally has a third substituent R ³ selected from the group consisting of nitro group, primary amino group, secondary amino group, tertiary amino group, halogen atoms, and a substituent selected from the group consisting of lower alkyl groups, lower alkoxy groups, cycloalkyl groups, phenyl group, naphthyl group , Anthryl group, pyridyl group and quinolyl group. The substituent optionally has a substituent.

In the present application, "lower alkyl groups", for example, the above-mentioned phosphine, may be straight chain or branched alkyl groups each having a number of carbon atoms of 1 to 6. Examples of such lower alkyl groups are methyl group (which may be referred to as "Me" hereinafter) , Ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl group. In the present application, "lower alkoxy groups", for example, the above-mentioned phosphine, straight-chain or branched alkoxy groups each having a number of carbon atoms may be from 1 to 6. Examples of such lower alkoxy groups are methoxy group (which may be referred to as "MeO" hereinafter), Ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group and n-hexyloxy group.

in der n eine ganze Zahl von 1 bis 2 ist, eine beliebige Anzahl Wasserstoffatome des kondensierten Rings durch den oben definierten ersten Substituenten R² ersetzt sein kann und jedes R⁴ unabhängig voneinander eine Phenylgruppe, o-Tolylgruppe, m-Tolylgruppe, p-Tolylgruppe, 4-Acynylgruppe oder 3,5-Xylylgruppe ist. Ein solches Phosphin P(R¹)₃ kann ein zweites sein, dargestellt durch die folgende Formel:

in der eine beliebige Zahl Wasserstoffatome des Naphthalin-Rings durch den oben definierten ersten Substituenten R² ersetzt werden kann und jedes R⁴ wie oben definiert ist. Des Weiteren kann das Phosphin P(R¹)₃ ein drittes sein, dargestellt durch die folgende Formel:

in der eine beliebige Anzahl Wasserstoffatome des Naphthalin-Rings mit niedrigen Alkylgruppen oder niedrigen Alkoxygruppen ersetzt sein kann und jedes R⁴ wie oben definiert ist. Des Weiteren kann das Phosphin P(R¹)₃ ein viertes sein, dargestellt durch die folgende Formel:

in der R⁵ eine niedrige Alkylgruppe und jedes R⁴ wie oben definiert ist. Des Weiteren kann das Phosphin P(R¹)₃ ein fünftes sein, dargestellt durch die folgende Formel:

in der jedes R⁴ wie oben definiert ist. Ein bevorzugtes Beispiel der zweiten Palladiumkomplexverbindung enthaltend das obige fünfte Phosphin, welches als Ausgangsmaterial für das dritte Verfahren verwendet werden kann, ist eines, welches durch die folgende Formel dargestellt wird:

in der X ein Halogen, d.h. Fluor, Chlor, Brom oder Jod ist, eine Trifluoromethansulfonatgruppe, eine Alkylsulfonatgruppe mit einer Anzahl Kohlenstoffatome von 1 bis 4 oder eine substituierte oder unsubstituierte Arylsulfonatgruppe ist. In dieser zweiten Palladiumkomplexverbindung ist X vorzugsweise Brom und zwei der Trifluoromethylgruppen sind bevorzugt insbesondere an die 3- und 5-Position gebunden.In the above-mentioned phosphine represented by the general formula P (R ¹ ) ₃ , at least one of R ^{1 is} preferably a phenyl group, o-tolyl group, m-toly group, p-tolyl group, 4-acynyl group or 3,5-xylyl group. Concrete examples of such a phosphine are triphenylphosphine, tris (o-tolyl) phosphine, tris (m-tolyl) phosphine, tris (p-tolyl) phosphine, tris (4-acynyl) phosphine, tris (3,5-xylyl) phosphine and Tris (n-butyl) phosphine. Of these, triphenylphosphine is particularly preferred. The phosphine P (R ¹ ) ₃ may be a first one represented by the following formula:

wherein n is an integer of 1 to 2, any number of hydrogen atoms of the fused ring may be replaced by the above-defined first substituent R ² , and each R ^{4 is} independently a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group , 4-acynyl group or 3,5-xylyl group. Such a phosphine P (R ¹ ) ₃ may be a second represented by the following formula:

in which any number of hydrogen atoms of the naphthalene ring can be replaced by the above-defined first substituent R ² and each R ^{4 is} as defined above. Further, the phosphine P (R ¹ ) _{3 may be} a third represented by the following formula:

wherein any number of hydrogen atoms of the naphthalene ring may be replaced with lower alkyl groups or lower alkoxy groups and each R ^{4 is} as defined above. Furthermore, the phosphine P (R ¹ ) _{3 may be} a fourth represented by the following formula:

R ^{5 is} a lower alkyl group and each R ^{4 is} as defined above. Furthermore, the phosphine P (R ¹ ) _{3 may be} a fifth, represented by the following formula:

where each R ^{4 is} as defined above. A preferable example of the second palladium complex compound containing the above fifth phosphine which can be used as the starting material for the third method is one represented by the following formula:

wherein X is a halogen, ie, fluorine, chlorine, bromine or iodine, a trifluoromethanesulfonate group, an alkylsulfonate group having a number of carbon atoms of 1 to 4, or a substituted or unsubstituted arylsulfonate group. In this second palladium complex compound, X is preferably bromine, and two of the trifluoromethyl groups are preferably bonded to the 3- and 5-positions, in particular.

in der eine beliebige Anzahl Wasserstoffatome jedes aromatischen Rings durch den oben definierten ersten Substituenten R² ersetzt sein kann, R⁴ wie im ersten des Phosphins P(R¹)₃ definiert ist und sowohl m als auch n unabhängig voneinander eine ganze Zahl von 0 bis 2 sind.The phosphine (ie, phosphine derivative or phosphine ligand) used in the first and second methods may be one represented by the general formula (R ¹ ) ₂ PQP (R ¹ ) ₂ , which is a bidentate ligand in Ar ¹ -PdL ₂ X in which each R ^{1 is} as defined in the phosphine P (R ¹ ) ₃ and Q is a divalent group. In the phosphine (R ¹ ) ₂ PQP (R ¹ ) ₂ , at least one of R ^{1 is} preferably a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 4-acynyl group or 3,5-xylyl group. The divalent group Q may be (1) any number of a first divalent group selected from an alkylene group, phenylene group, naphthylene group and anthrylene group, and (2) any number of a linking group selected from the group consisting of a single bond, -O-, -S -, -C (= O) - and -S (= O) -. The first divalent group optionally has any number of a substituent which can be selected from a nitro group, primary amino group, secondary amino group, tertiary amino group, halogen atoms, lower alkyl groups, lower alkoxy groups, cycloalkyl groups, phenyl group, naphthyl group, anthryl group, pyridyl group and quinolyl group. The bivalent group Q may be a preferable one selected from an alkylene group, biphenylene group, binaphthylene group and bianthrylene group. This preferred group optionally has any number of a group selected from a nitro group, primary amino group, secondary amino group, tertiary amino group, halogen atoms, lower alkyl groups, lower alkoxy groups, cycloalkyl groups, phenyl group, naphthyl group, anthryl group, pyridyl group and quinolyl group. The phosphine (R ¹ ) ₂ PQP (R ¹ ) ₂ may be a first one represented by the following general formula:

in which any number of hydrogen atoms of each aromatic ring are defined by the first defined above Substituents R ² may be replaced, R ^{4 is} as defined in the first of the phosphine P (R ¹ ) ₃ and both m and n are independently an integer from 0 to 2.

in der eine beliebige Anzahl Wasserstoffatome jedes aromatischen Rings durch den oben definierten ersten Substituenten R² ersetzt sein kann und R⁴ wie im ersten des Phosphins P(R¹)₃ ist. Des Weiteren kann das Phosphin (R¹)₂P-Q-P(R¹)₂ ein drittes sein, dargestellt durch die folgende allgemeine Formel:

in der eine beliebige Anzahl Wasserstoffatome jedes aromatischen Rings mit einer niedrigen Alkylgruppe oder einer niedrigen Alkoxygruppe ersetzt sein kann. Ein bevorzugtes Beispiel der zweiten Palladiumkomplexverbindung enthaltend das obige Phosphin (R¹)₂P-Q-P(R¹)₂, welches als Ausgangsmaterial des dritten Verfahrens verwendet werden kann, ist eines, welches durch die folgende Formel dargestellt wird:

in der X ein Halogen, d.h. Fluor, Chlor, Brom oder Jod, eine Trifluoromethansulfonatgruppe, eine Alkylsulfonatgruppe mit einer Anzahl Kohlenstoffatome von 1 bis 4 oder eine substituierte oder unsubstituierte Arylsulfonatgruppe ist. In dieser zweiten Palladiumkomplexverbindung ist X vorzugsweise Brom und zwei der Trifluoromethylgruppen sind vorzugsweise insbesondere an die 3- und 5-Position gebunden.Further, the phosphine (R ¹ ) ₂ PQP (R ¹ ) _{2 may be} a second represented by the following general formula:

in which any number of hydrogen atoms of each aromatic ring may be replaced by the above-defined first substituent R ² and R ^{4 is} as in the first of the phosphine P (R ¹ ) ₃ . Furthermore, the phosphine (R ¹ ) ₂ PQP (R ¹ ) _{2 may be} a third, represented by the following general formula:

wherein any number of hydrogen atoms of each aromatic ring may be replaced with a lower alkyl group or a lower alkoxy group. A preferable example of the second palladium complex compound containing the above phosphine (R ¹ ) ₂ PQP (R ¹ ) ₂ which can be used as the starting material of the third method is one represented by the following formula:

wherein X is a halogen, ie, fluorine, chlorine, bromine or iodine, a trifluoromethanesulfonate group, an alkylsulfonate group having a number of carbon atoms of 1 to 4, or a substituted or unsubstituted arylsulfonate group. In this second palladium complex compound, X is preferably bromine, and two of the trifluoromethyl groups are preferably bonded to the 3- and 5-positions, in particular.

The phosphine (ie, the phosphine derivative or the phosphine ligand) may be one represented by the general formula (R ⁴ ) ₂ P- (CH ₂ ) _q -P (R ⁴ ) ₂ wherein R ^{4 is} as defined above and q is an integer Number is from 2 to 8. Furthermore, the phosphine may be one which, by the general formula, is Ph ₂ P- (CH ₂ ) _q -PPh ₂ , in which q is an integer from 2 to 8.

The palladium compound used in the first and second methods is preferably a palladium salt such as palladium acetate, palladium chloride, palladium bromide, palladium iodide or palladium nitrate. Further, the palladium compound may be a palladium complex (II) such as [Pd (NH ₃ ) ₄ ] Y ₂ , Pd (NH ₃ ) ₂ Y ₂ , Pd (NH ₃ ) ₄ or PdY ₄ , in which Y is a halogen ie chlorine, bromine or iodine.

The basic substance used in the first and second methods, including each of the first and second basic substances used in the first method, is not limited to a particular type. Non-limiting examples of the basic substance are (1) ammonium and the like, such as ammonium and hydroxyamine, (2) amines, such as primary amines, seconds such as amines, tertiary amines, alicyclic amines (eg, cyclopropylamine) and aromatic amines, and (3) inorganic bases such as acetate (eg, sodium acetate and potassium acetate), sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. Examples of the primary amine are propylamine, isopropylamine, butylamine, amylamine and hexylamine. Examples of the secondary amine are diethylamine, dipropylamine, diisopropylamine and dibutylamine. Examples of the third amine are triethylamine, tripropylamine and tributylamine. Examples of the aromatic amine are triarylamine, N, N-dimethylaniline, N, N-diethylaniline, pyridine and N-methylmorpholine.

Optionally, a solvent may be used in the first and second methods. Examples of such a solvent are (1) aliphatic hydrocarbons such as pentane, hexane, heptane and octane, (2) aromatic hydrocarbons such as benzene, toluene and xylene, (3) ethers such as diethyl ether, dioxane, tetrahydrofuran (THF) and (4) ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, (5) nitriles such as acetonitrile, (6) tertiary amines such as pyridine, (7) acid amides such as N, N-dimethylformamide (DMF) and ethylene glycol dimethyl ether N, N-dimethylacetamide (DMAc); (8) sulfur containing compounds such as dimethyl sulfoxide (DMSO) and sulforane, and (9) water. In the case where a water-soluble basic substance is used in the reaction, it is preferred to use water optionally together with another solvent. Further, the aromatic compound Ar ¹ X itself used in the first and second methods can be used as a reaction solvent.

According to the second Process of the invention, it is substantially possible, the reaction in a single reaction vessel to perform completely. Therefore, it becomes possible the reaction procedures considerably to simplify. Optionally, the reaction of the second method be modified by providing different reaction steps become.

In the first and second methods of the invention, the respective amounts of the raw materials used in the reaction are not particularly limited. In fact, it is preferable to use at least one mole of the aromatic compound Ar ¹ X and at least two moles of the phosphine derivative relative to 1 mole of palladium of the palladium compound in the reaction step (a) of the first process. Further, it is preferable to use at least one mole of the benzoic acid Ar ² -COOH relative to one mole of palladium of the second palladium complex compound Ar ¹ -PdL ₂ X in the reaction step (b) of the first method. Similarly, it is preferable to use at least one mole of the aromatic compound Ar ¹ X, at least one mole of the benzoic acid Ar ² -COOH, and at least two moles of the phosphine derivative relative to one mole of the palladium of the palladium compound in the second process. In the first and second processes, the respective amounts of the other raw materials such as the basic substance and the solvent are not particularly limited and they can be used in appropriate suitable amounts.

The reaction in both of the first and second methods can be carried out as follows, and the following manner can be suitably modified. First, a reaction vessel containing the raw materials is charged (eg, in the case of step (a) of the first method, the aromatic compound Ar ¹ X, the palladium compound, the phosphine derivative, the basic substance, and optionally the solvent). The reaction vessel may optionally be pressurized and optionally stirred. The charged raw materials may optionally be heated to carry out the reaction and the reaction may be carried out at a temperature of about 0 to 200 ° C, preferably at about 50-150 ° C to accelerate the reaction. After the reaction, the reaction vessel can be cooled and then the contents are removed from the reaction vessel. Then, an extraction solvent can be added to the ingredients to separate the solids. Thereafter, the volatile substances are distilled off from the filtrate, whereby the desired product (eg, the second palladium complex compound in step (a) of the first method) is obtained. If necessary, the aimed product can be purified by recrystallization, silica gel chromatography or the like.

in der Ar³ und Ar⁴ Arylgruppen sind, dargestellt durch die obige allgemeine Formeln (6) bzw. (7), und jedes L unabhängig voneinander ein Phosphinligand ist. In der allgemeinen Formel (6), welche Ar³ darstellt, ist R² eine Trifluoromethylgruppe, eine Trifluoromethyloxygruppe, ein Halogen, d.h. Fluor, Chlor, Brom oder Iod, eine Nitrogruppe, eine Acetylgruppe, eine Cyanogruppe, eine Alkylgruppe mit einer Anzahl Kohlenstoffatomen von 1 bis 4, eine Alkoxylgruppe mit einer Anzahl Kohlenstoffatomen von 1 bis 4 oder eine Alkoxycarbonylgruppe mit einer Anzahl Kohlenstoffatomen von 2 bis 5. Beispiele dieser Alkylgruppe, Alkoxygruppe und Alkoxycarbonylgruppen von Ar³ sind dieselben wie die oben genannten Beispiele jener Gruppen von Ar¹. In der allgemeinen Formel (7), welche Ar⁴ darstellt, ist R¹ eine Trifluoromethylgruppe. Beispiele der Arylgruppe Ar⁴ sind (1) Arylgruppen mit je einem Trifluoromethyl, wie etwa 2-Trifluoromethylphenyl, 3-Trifluoromethylphenyl und 4-Trifluoromethylphenyl, und (2) Arylgruppen mit je zwei Trifluoromethylgruppen, wie etwa 2,3-Bis(trifluoromethyl)phenyl, 2,4-Bis(trifluoromethyl)phenyl, 2,5-Bis(trifluoromethyl)phenyl, 2,6-Bis(trifluoromethyl)phenyl, 3,4-Bis(trifluoromethyl)phenyl und 3,5-Bis(trifluoromethyl)phenyl. Von diesen ist eine Arylgruppe mit zwei Trifluoromethylgruppen bevorzugt und 3,5-Bis(trifluoromethyl)phenyl ist bevorzugter. Somit ist die Palladiumkomplexverbindung, dargestellt durch die allgemeine Formel (5), vorzugsweise eine, die durch die folgende allgemeine Formel dargestellt wird:

in der R², m und L wie oben definiert sind. Des Weiteren ist sie bevorzugt eine durch die folgende allgemeine Formel dargestellte:

in der R², m und L wie oben definiert sind. Ähnlich wie die Arylgruppen Ar¹ und Ar² ist die Arylgruppe Ar³ vorzugsweise eine, in welcher wenigstens eines von R² eine Trifluoromethylgruppe ist. Beispiele der Arylgruppe Ar³ sind dieselben wie jene der Arylgruppen Ar¹ und Ar². Die Arylgruppe Ar³ kann wenigstens zwei Substituenten aufweisen. Diese wenigstens zwei Substituenten kann irgendeine beliebige Kombination von verschiedenen Substituenten sein. Eine der wenigstens zwei Substituenten der Arylgruppe Ar³ ist vorzugsweise eine Trifluoromethylgruppe. Nicht beschränkende Beispiele einer solchen Arylgruppe Ar³ sind dieselben wie jene der Arylgruppen Ar¹ und Ar². Die Arylgruppe Ar³ ist vorzugsweise eine mit wenigstens zwei Trifluoromethylgruppen. Beispiele einer solchen Arylgruppe sind dieselben wie jene der Arylgruppe Ar¹ oder Ar². Weitere nicht beschränkende Beispiele der Arylgruppe der Ar³ sind dieselben wie jene der Arylgruppen Ar¹ oder Ar². Wie oben bemerkt, ist die zweite Palladiumkomplexverbindung, die in Schritt (a) des ersten Verfahrens hergestellt wird, dargestellt durch die allgemeine Formel Ar⁵-PdL₂X, in der Ar⁵ eine Bis(trifluoromethyl)phenylgruppe, X ein Halogen, d.h. Fluor, Chlor, Brom oder Iod, und jedes L unabhängig ein Phosphinligand ist. Beispiele der Arylgruppe Ar⁵ sind 2,3-Bis(trifluoromethyl)phenyl, 2,4-Bis(trifluoromethyl)phenyl, 2,5-Bis(trifluoromethyl)phenyl, 2,6-Bis(trifluoromethyl)phenyl, 3,4-Bis(trifluoromethyl)phenyl und 3,5-Bis(trifluoromethyl)phenyl. Von diesen ist 3,5-Bis(trifluoromethyl)phenyl bevorzugter. Die zweite Palladiumkomplexverbindung kann durch die folgende allgemeine Formel dargestellt werden:

in der Ph eine Phenylgruppe und X ein Halogen, d.h. Fluor, Chlor, Brom oder Iod ist. Bevorzugte Beispiele der zweiten Palladiumkomplexverbindung sind die durch die folgenden allgemeinen Formeln dargestellten:

in denen Ph eine Phenylgruppe, Tolyl eine Tolylgruppe und n-Bu eine n-Butylgruppe ist. Von diesen sind die durch die folgenden Formeln dargestellten bevorzugtere BeispieleThe above-mentioned novel first palladium complex compounds according to the third aspect of the invention will be described below in detail. The first palladium complex compound which can be produced by the first or second method is represented by the general formula (5):

wherein Ar ³ and Ar ^{4 are} aryl groups represented by the above general formulas (6) and (7), respectively, and each L is independently a phosphine ligand. In the general formula (6) which represents Ar ³ , R ^{2 is} a trifluoromethyl group, a trifluoromethyloxy group, a halogen, ie, fluorine, chlorine, bromine or iodine, a nitro group, an acetyl group, a cyano group, an alkyl group having a number of carbon atoms of 1 to 4, an alkoxyl group having a number of carbon atoms of 1 to 4 or an alkoxycarbonyl group having a number of carbon atoms of 2 to 5. Examples of this alkyl group, alkoxy group and alkoxycarbonyl groups of Ar ³ are the same as the above-mentioned examples of those groups of Ar ¹ . In the general formula (7), which represents Ar ⁴ , R ^{1 is} a trifluoromethyl group. Examples of the aryl group Ar ⁴ are (1) aryl groups each having a trifluoromethyl such as 2-trifluoromethylphenyl, 3-trifluoromethylphenyl and 4-trifluoromethylphenyl, and (2) aryl groups each having two trifluoromethyl groups such as 2,3-bis (trifluoromethyl) phenyl , 2,4-bis (trifluoromethyl) phenyl, 2,5-bis (trifluoromethyl) phenyl, 2,6-bis (trifluoromethyl) phenyl, 3,4-bis (trifluoromethyl) phenyl and 3,5-bis (trifluoromethyl) phenyl , Of these, an aryl group having two trifluoromethyl groups is preferable, and 3,5-bis (trifluoromethyl) phenyl is more preferable. Thus, the palladium complex compound represented by the general formula (5) is preferably one represented by the following general formula:

in which R ² , m and L are as defined above. Furthermore, it is preferably one represented by the following general formula:

in which R ² , m and L are as defined above. Similar to the aryl groups Ar ¹ and Ar ² , the aryl group Ar ^{3 is} preferably one in which at least one of R ^{2 is} a trifluoromethyl group. Examples of the aryl group Ar ³ are the same as those of the aryl groups Ar ¹ and Ar ² . The aryl group Ar ³ may have at least two substituents. These at least two substituents may be any combination of different substituents. One of the at least two substituents of the aryl group Ar ³ is preferably a trifluoromethyl group. Non-limiting examples of such an aryl group Ar ³ are the same as those of the aryl groups Ar ¹ and Ar ² . The aryl group Ar ³ is preferably one having at least two trifluoromethyl groups. Examples of such an aryl group are the same as those of the aryl group Ar ¹ or Ar ² . Other non-limiting examples of the aryl group of the Ar ³ are the same as those of the aryl groups Ar ¹ or Ar ² . As noted above, the second palladium complex compound prepared in step (a) of the first process represented by the general formula Ar ⁵ -PdL ₂ X, wherein Ar ^{5 is} a bis (trifluoromethyl) phenyl group, X is a halogen, ie fluorine , Chlorine, bromine or iodine, and each L is independently a phosphine ligand. Examples of the aryl group Ar ⁵ are 2,3-bis (trifluoromethyl) phenyl, 2,4-bis (trifluoromethyl) phenyl, 2,5-bis (trifluoromethyl) phenyl, 2,6-bis (trifluoromethyl) phenyl, 3,4- Bis (trifluoromethyl) phenyl and 3,5-bis (trifluoromethyl) phenyl. Of these, 3,5-bis (trifluoromethyl) phenyl is more preferable. The second palladium complex compound can be represented by the following general formula:

in which Ph is a phenyl group and X is a halogen, ie fluorine, chlorine, bromine or iodine. Preferred examples of the second palladium complex compound are those represented by the following general formulas:

in which Ph is a phenyl group, tolyl is a tolyl group and n-Bu is an n-butyl group. Of these, the more preferred examples represented by the following formulas are

Of the Phosphine ligand of the new first palladium complex compounds not restricted in a special way and is the same as that used in the first and second methods Phosphine. Therefore all of the above descriptions are in the First and second methods used phosphine applicable the new first palladium complex compound.

The The new first palladium complex compound can be crystalline and can in different organic solvents solved which makes them stable. Furthermore, these are compounds stable in the air at room temperature. Due to such physical and chemical properties of these compounds will make it easy to isolate these compounds to produce them in high purity. Furthermore, it is easy to store these compounds, which the Easy handling when used on an industrial scale. The new first palladium complex compound has various Reactions catalytic activity on, such as (1) the carbonylation of an aromatic compound by insertion of monoxide or the like into a halogenated one Aryl and the subsequent reductive release, (2) vinylation by Insertion of an olefin into a halogenated aryl and the following reductive release and (3) the coupling of a halogenated aryl. For example, an example of the new first palladium complex compound [3,5-bis (trifluoromethyl) benzoato] 3 ', 5'-bis (trifluoromethyl) phenylbis (triphenylphosphine) palladium (II) by the following formula, catalytic activity in the vinylation by Insertion of an olefin into a halogenated aryl and the following reductive levy.

The following non-limiting Examples serve to illustrate the present invention. The pressure is expressed as Gaussian pressure, unless otherwise stated.

EXAMPLE 1

Synthesis of bromo [3,5-bis (trifluoromethyl) phenyl] bis (triphenylphosphine) palladium (II)

A stainless steel autoclave was charged with 32.5 g of 3,5-bis (trifluoromethyl) bromobenzene, 25.0 g of palladium acetate, 87.3 g of triphenylphosphine and 75 ml of tetrahydrofuran, followed by stirring. Then the autoclave was further charged with 38.0 g of 25% aqueous ammonia. Then, the atmosphere of the autoclave was replaced twice with nitrogen. Then the nitrogen pressure was adjusted to 3 kg / cm ² and the mixture was started to stir. The internal temperature of the autoclave increased. Then, the autoclave was started to be heated by adjusting an oil bath temperature to 105 ° C. About 1.8 hours later, the internal temperature reached 97 ° C and the oil bath was removed. Then the autoclave was cooled to stop the reaction. Then, 200 ml of toluene was added to the reaction liquid, followed by stirring for a few minutes. The thus treated liquid was subjected to vacuum filtration. Then, the resulting solid material was washed with a small amount of n-hexane and then dried to obtain 72.1 g of pale green crystals. Then, the crystals were subjected to recrystallization using methylene chloride to obtain 48.7 g of crystals. The crystals were identified as bromo [3,5-bis (trifluoromethyl) phenyl] bis (triphenylphosphino) palladium (II) by the following properties: Melting point: (Degradation at a temperature of not lower than 192 ° C); IR (KBr: cm ^-1 ): 3052, 1435, 1443, 1166, 1095, 749, 693 and 517; ¹ H-NMR: (standard substance: TMS, solvent: CDCl ₃ ): δ ppm 6.75 (s, 1H), 7.09 (s, 2H), 7.24-7.37 (m, 18H) and 7 , 50-7.55 (m, 12H) and ³¹ P-NMR: (standard substance: 85% H ₃ PO ₄ , solvent: CDCl ₃ ) δ ppm 27.33 (s).

EXAMPLE 2

Synthesis of iodo [3,5-bis (trifluoromethyl) phenyl)] bis (triphenylphosphine) palladium (II)

In this example, Example 1 was repeated except that the autoclave with 4.00 g of 3,5-bis (trifluoromethyl) iodobenzene, 2.64 g of palladium acetate, 9.29 g of triphenylphosphine, 8.91 g of tetrahydrofuran and 3.45 g of aqueous ammonia was charged and that the reaction was carried out under a condition that the reaction temperature in a range of 60 to 80 ° C and the reaction time was 3 hours. Thus, 8.81 g of crystals were obtained. The crystals were identified as iodo [3,5-bis (trifluoromethyl) phenyl] bis (triphenylphosphine) palladium (II) by the following properties: Melting point: (Degradation at a temperature of not lower than 170 ° C)
¹ H-NMR: (standard substance: TMS, solvent: CDCl ₃ ): δ ppm 6.75 (s, 1H), 7.07 (s, 2H), 7.24-7.37 (m, 18H) and 7 , 48-7.56 (m, 12H).

REFERENCE EXAMPLE 1

Synthesis of 3,5-bis (trifluoromethyl) benzoic acid

A stainless steel autoclave was charged with 400 g of 3,5-bis (trifluoromethyl) bromobenzene, 2.40 g of bromo [3,5-bis (trifluoromethyl) phenyl] bis (triphenylphosphine) palladium (II), followed by mixing. Then the autoclave was further charged with 291.4 g of triethylamine, 0.887 g of triphenylphosphine and 200 g of water. While the autoclave was closed, the mixture was started to stir. Then the atmosphere of the autoclave was replaced three times with nitrogen and then three times with carbon monoxide. The initial carbon monoxide pressure was adjusted to 3 kg / cm ² and the autoclave was started to be heated in an oil bath. When the internal temperature reached 104 to 105 ° C, the internal pressure was adjusted to 8.5 kg / cm ² . Then, the autoclave was maintained at an internal temperature of 105 ° C and an internal pressure of 8.5 kg / cm ² while adjusting the amount of carbon monoxide to be introduced. About 16 hours later, the heating was stopped and then the autoclave was cooled. Then the gas was discharged inside. The reaction liquid was placed in a separatory funnel, followed by the addition of 200 ml of water. The thus treated liquid was added dropwise with a dropping funnel to 370 g of a 6N-HCl aqueous solution contained in a 2 liter beaker while keeping this solution at a temperature of 20 to 30 ° C and stirred. Crystals were precipitated, then separated by vacuum filtration and then washed with 1120 ml of water and then 336 ml of cooled toluene to obtain 279 g of colorless crystals of 3,5-bis (trifluoromethyl) benzoic acid.

EXAMPLE 3

Synthesis of trans- [3,5-bis (trifluoromethyl) benzoato] 3 ', 5'-bis (trifluoromethyl) phenylbis (triphenylphosphine) palladium (II)

First, Example 1 was repeated except that the recrystallization was omitted to obtain pale green crystals of bromo [3,5-bis (trifluoromethyl) phenyl] bis (triphenylphosphine) palladium (II). Then, a stainless steel autoclave was charged with 70.0 g of the obtained bromo [3,5-bis (trifluoromethyl) phenyl] bis (triphenylphosphine) palladium (II), 39.1 g of 3,5-bis (trifluoromethyl) benzoic acid and 150 g ml of tetrahydrofuran, followed by mixing and stirring. The autoclave was further charged with 20.5 g of 25% aqueous ammonia. Then the atmosphere of the autoclave was replaced twice with nitrogen. Then the nitrogen pressure was adjusted to 3 kg / cm ² and the mixture was started to stir. The autoclave was then started to be heated by adjusting the oil bath temperature to 100 ° C. Approximately 2 hours later, the oil bath was removed. Then the autoclave was cooled. Then, 500 ml of toluene and 200 ml of 25% aqueous ammonia were added to the reaction liquid, followed by stirring for several minutes. Then, an upper organic layer (toluene layer) was washed twice with water and then with a saturated brine, then dried with anhydrous magnesium sulfate and concentrated by distilling off volatiles to obtain 75.3 g of pale yellow crystals. The crystals were identified as trans- [3,5-bis (trifluoromethyl) benzoato] 3 ', 5'-bis (trifluoromethyl) phenylbis (triphenylphosphine) palladium (II) by the following properties:
Melting point: 168-170 ° C (degradation); IR (KBr: cm ^-1 ): 3060, 2926, 1637, 1437, 1321, 1277, 1173, 1127, 748, 697 and 518;
¹ H-NMR: (standard substance: TMS, solvent: CDCl ₃ ):
δ ppm 6.97 (s, 1H), 7.09 (s, 2H), 7.20-7.32 (m, 18H), 7.40-7.50 (m, 12H), 7.53 ( s, 2H) and 7.62 (s, 1H) and ³¹ P-NMR: (standard substance: 85% H ₃ PO ₄ , solvent CDCl ₃ ): δ ppm 25.73 (s).

EXAMPLE 4

Synthesis of [3,5-bis (trifluoromethyl) benzoato] 3 ', 5'-bis (trifluoromethyl) phenylbis (triphenylphosphine) palladium (II)

A stainless steel autoclave was charged with 65.3 g of 3,5-bis (trifluoromethyl) bromobenzene, 100 ml of tetrahydrofuran, 50.0 g of palladium acetate, 175.5 g of triphenylphosphine, 57.6 g of 3,5-bis (trifluoromethyl) benzoic acid and 60.8 g of 25% aqueous ammonia. Then the atmosphere of the autoclave was replaced twice with nitrogen. Then the nitrogen pressure was adjusted to 3 kg / cm ² and the mixture was started to stir. The internal temperature of the autoclave increased to about 50 ° C. Then, the autoclave was started to be heated by adjusting the temperature of an oil bath to 120 ° C. About 2 hours later, the internal temperature reached 95.6 ° C and the oil bath was removed. Then the autoclave was cooled. Then, 200 ml of water and 600 ml of toluene were added to the reaction liquid, followed by stirring for several minutes. The thus treated liquid was subjected to vacuum filtration. An organic layer (upper layer) of the obtained filtrate was washed twice with a saturated brine, then dried with anhydrous magnesium sulfate, and then concentrated by distilling off volatile matter. Solid material which precipitated at the beginning of this concentration was separated by filtration. Further, the filtrate was concentrated and then added with n-hexane, followed by cooling. Then, the precipitated solid material was separated by filtration to obtain 187.5 g of a crude product. This crude product was subjected to recrystallization using toluene to obtain 143.0 g of pale yellow crystals. The crystals were identified as [3,5-bis (trifluoromethyl) benzoato] 3 ', 5'-bis (trifluoromethyl) phenylbis (triphenylphosphine) palladium (II) by the following properties:
Melting point: 168-170 ° C (degradation);
IR (KBr: cm ^-1 ): 3060, 2926, 1637, 1437, 1321, 1277, 1173, 1127, 748, 697 and 518;
¹ H-NMR: (standard substance: TMS, solvent: CDCl ₃ ):
δ ppm 6.97 (s, 1H), 7.09 (s, 2H), 7.20-7.32 (m, 18H), 7.40-7.50 (m, 12H), 7.53 ( s, 2H) and 7.62 (s, 1H) and
³¹ P-NMR: (standard substance: 85% H ₃ PO ₄ , solvent: CDCl ₃ ): δ ppm 25.73 (s).

EXAMPLE 5

Synthesis of [3,5-bis (trifluoromethyl) benzoato] 3'-trifluoromethylphenylbis (triphenylphosphine) palladium (II)

A stainless steel autoclave was charged with 25.0 g of 3-trifluoromethylbromobenzene, 75 mL of tetrahydro furan, 25 g of palladium acetate, 87.3 g of triphenylphosphine, 38 g of 25% aqueous ammonia and 57.5 g of 3,5-bis (trifluoromethyl) benzoic acid. Thereafter, the same procedures of Example 4 were repeated to obtain 32.3 g of a reaction product. This reaction product was identified as [3,5-bis (trifluoromethyl) benzoato] 3'-trifluoromethylphenylbis (triphenylphosphine) palladium (II) by the following properties:
¹ H-NMR: (standard substance: TMS, solvent: CDCl ₃ ):
δ ppm 6.47 (dd, J = 7.3, 7.8 Hz, 1H), 6.77 (d, J = 7.3 Hz, 1H), 6.80 (brs, 1H), 6.95 (d, J = 7.8Hz, 1H), 7.24-7.30 (m, 18H) and 7.40-7.46 (m, 12H).

REFERENCE EXAMPLE 2

Synthesis of 3,5-bis (trifluoromethyl) cinnamic acid n-butyl ester

First, 9.02 g of a vacuum dried anhydrous sodium acetate was added to a 200 ml flask. Under a stream of nitrogen, 29.3 g of 3,5-bis (trifluoromethyl) bromobenzene, 15.4 g of n-butyl acrylate, 210 mg of [3,5-bis (trifluoromethyl) benzoato] 3 ', 5'-bis (trifluoromethyl) phenylbis (triphenylphosphine) palladium (II) (the palladium complex compound prepared in Example 4) and 70 ml of N, N-dimethylacetoamide added. Then the flask was heated in an oil bath with stirring. After conducting the reaction for about one hour at 110 ° C, the reaction liquid was cooled to room temperature. Then, the reaction liquid was poured into ice-water. Organic material of the reaction liquid was extracted with ether. The obtained organic layer (ether layer) was separated from the aqueous layer, then washed three times with water and then twice with a saturated brine, and then dried with anhydrous magnesium sulfate. Then the solvent was distilled off under vacuum using an evaporator to give a brown solid as a residue. This solid was subjected to recrystallization using n-hexane to obtain 22.3 g of crystals. The crystals were identified as 3,5-bis (trifluoromethyl) cinnamic acid n-butyl ester by the following properties: Melting point: 47-48 ° C (degradation) and ¹ H-NMR: (standard substance: TMS, solvent: CDCl ₃ ): δ ppm 0.975 (t, J = 7.3 Hz, 3H), 1.38-1.50 (m, 2H), 1.66-1.75 (m, 2H), 4.25 (t, J = 6.6 Hz, 2H), 6.57 (d, J = 16 Hz, 1H), 7.70 (d, J = 16 Hz, 1H), 7.86 (s, 1H) and 7.93 (s , 2H).

EXAMPLE 6

¹H-NMR: (300 MHz, Standardsubstanz: TMS, Lösungsmittel CDCl₃):
δ ppm: 3,35 (s, 6H), 6,48–6,63 (m, 9H), 6,65–6,80 (m, 10H), 6,85–6,95 (m, 4H), 7,04–7,16 (m, 10H), 7,27 (bs, 1H), 7,50–7,60 (m, 7H), 7,95 (d, 2H, J = 8,1 Hz), 8,05 (d, 2H, J = 8,7 Hz) und 8,84–8,95 (m, 2H) und
IR (KBr Pulver: cm^–1): 3060, 1626, 1595, 1512, 1435, 1342, 1276, 1253, 1178, 1127, 1087, 878, 806, 745 und 690.A pressure-tight 100 ml reaction vessel, the atmosphere of which was replaced with argon, was treated with 204 mg (0.91 mmol) of palladium acetate, 1.28 g (2.72 mmol) of (S) -2-methoxy-2 '- (diphenylphosphino) - 1,1'-binaphthyl [(S) -MeO-MOP], 266 mg (0.91 mmol) of 3,5-bis (trifluoromethyl) bromobenzene, and 1 ml of tetrahydrofuran, followed by mixing and stirring. Then, 0.5 ml of 28% aqueous ammonia was added and then the atmosphere of the reaction vessel was replaced again with argon. Thereafter, the reaction vessel was sealed tight without putting pressure on it. Thereafter, the reaction vessel was heated for six hours in an oil bath of 110 ° C, followed by cooling to room temperature. Then, 1 ml of pure water and 3 ml of toluene were added to the reaction liquid, followed by stirring for several minutes. The thus treated liquid was subjected to vacuum filtration. The obtained filtrate was washed with a saturated brine twice, then dried with anhydrous magnesium sulfate and then concentrated to obtain a mixture in the form of a brown syrup. The resulting mixture was subjected to thin layer chromatography using a silica gel neutral column (methylene chloride: hexane = 1: 1). Thus, a product having an Rf value of 0.50 (hexane: ethyl acetate = 2: 1) was obtained in a yield of 22.1. This product was identified as a palladium complex compound [MBT-Pd-Br ((S) -MeO-MOP) having the following formula by the following properties:

¹ H-NMR: (300 MHz, standard substance: TMS, solvent CDCl ₃ ):
δ ppm: 3.35 (s, 6H), 6.48-6.63 (m, 9H), 6.65-6.80 (m, 10H), 6.85-6.95 (m, 4H) , 7.04-7.16 (m, 10H), 7.27 (bs, 1H), 7.50-7.60 (m, 7H), 7.95 (d, 2H, J = 8.1 Hz ), 8.05 (d, 2H, J = 8.7 Hz) and 8.84-8.95 (m, 2H) and
IR (KBr powder: cm ^-1 ): 3060, 1626, 1595, 1512, 1435, 1342, 1276, 1253, 1178, 1127, 1087, 878, 806, 745 and 690.

The Procedures for obtaining the above palladium complex compound was repeated with the exception that (S) -MeO-MOP with (R) -2-methoxy-2 '- (diphenylphosphino-1,1'-binaphthyl [(R) -MeO-MOP] replacing another palladium complex compound [MBT-Pd-Br ((R) -MeO-MOP)] which was a stereoisomer (R configuration) of the above Palladium complex compound is.

EXAMPLE 7

¹H-NMR: (300 MHz, Standardsubstanz: TMS, Lösungsmittel: CDCl₃):
δ ppm: 6,58–6,82 (m, 8H), 6,96–7,16 (m, 9H), 7,33 (d, 1H, 7,5 Hz), 7,38 (d, 1H, 6,3 Hz), 7,40–7,64 (m, 10H), 7,69 (dd, 1H, J = 9,0, 1,8 Hz) und 7,76–7,94 (m, 5H);
³¹P-NMR: (376 MHz, Lösungsmittel: CDCl₃):
δ ppm 14,84 (d, J = 38,1) und 30,51 (d, J = 40,0);
¹⁹F-NMR: (376 MHz, Standardsubstanz: BTF, Lösungsmittel: C₆D₃):
δ ppm –62,98 (s); und
IR (KBr Pulver: cm^–1): 3060, 1607, 1586, 1572, 1557, 1502, 1483, 1437, 1342, 1311, 1276, 1226, 1176, 1098, 1027, 1000, 880, 837, 816, 743 und 692.A pressure-tight 100 ml reaction vessel whose atmosphere had been replaced with argon was treated with 449 mg (2 mmol) of palladium acetate, 1.83 g (3 mmol) of (R) -2,2'-bis (diphenylphosphine) -1,1'- binaphthyl [(R) -BINAP], 586 mg (3 mmol) of 3,5-bis (trifluoromethyl) bromobenzene and 2 ml of tetrahydrofuran, followed by mixing and stirring. Then 1 ml of 28% aqueous ammonia was added thereto and then the atmosphere of the reaction vessel was replaced again with argon. Thereafter, the reaction vessel was sealed tight without putting pressure on it. Then, the reaction vessel was heated for six hours in an oil bath of 110 ° C. Then the reaction vessel was cooled to room temperature. Then, 2 ml of pure water and 6 ml of toluene were added to the reaction liquid, followed by stirring for several minutes. The thus treated liquid was subjected to vacuum filtration. The obtained filtrate was washed twice with a saturated brine, then dried with anhydrous magnesium sulfate and then concentrated to obtain a mixture in the form of a brown syrup. The resulting mixture was subjected to thin layer chromatography using a silica gel neutral column (methylene chloride: hexane = 2: 1). Thereby, a product having an Rf of 0.38 (hexane: ethyl acetate = 2: 1) was obtained in a yield of 38.2%. This product was identified as a palladium complex compound [MBT-Pd-Br ((R) -BINAP) having the following formula by the following properties:

¹ H-NMR: (300 MHz, standard substance: TMS, solvent: CDCl ₃ ):
δ ppm: 6.58-6.82 (m, 8H), 6.96-7.16 (m, 9H), 7.33 (d, 1H, 7.5Hz), 7.38 (d, 1H , 6.3 Hz), 7.40-7.64 (m, 10H), 7.69 (dd, 1H, J = 9.0, 1.8 Hz) and 7.76-7.94 (m, 5H);
³¹ P-NMR: (376 MHz, solvent: CDCl ₃ ):
δ ppm 14.84 (d, J = 38.1) and 30.51 (d, J = 40.0);
¹⁹ F-NMR: (376 MHz, standard substance: BTF, solvent: C ₆ D ₃ ):
δ ppm -62.98 (s); and
IR (KBr powder: cm ^-1 ): 3060, 1607, 1586, 1572, 1557, 1502, 1483, 1437, 1342, 1311, 1276, 1226, 1176, 1098, 1027, 1000, 880, 837, 816, 743 and 692.

Claims (49)

A process for producing a first palladium complex compound represented by the general formula (4), which process comprises: (a) reacting an aromatic compound represented by the general formula (1) with a palladium compound and a phosphine derivative in the presence of a first basic substance, wherein a second palladium complex compound represented by the general formula (2) is obtained; and (b) reacting said second palladium complex compound with a benzoic acid represented by the general formula (3) in the presence of a second basic substance, wherein the first palladium complex compound Ar ¹ X (1) in which Ar ^{1 is} an aryl group; and X is a halogen, that is, fluorine, chlorine, bromine or iodine, trifluoromethanesulfonate group, an alkylsulfonate group having a number of carbon atoms of 1-4 or a substituted or unsubstituted arylsulfonate group, Ar1-PdL ₂ X (2) wherein each L is independently a phosphine ligand and Ar ¹ and X are as defined above, Ar ² -COOH (3) Ar ^{2 is} an aryl group,

wherein Ar ¹ , Ar ² and L are as defined above. A process for producing a palladium complex compound represented by the general formula (4), which process comprises reacting an aromatic compound represented by the general formula (1) with a palladium compound, a phosphine derivative and a benzoic acid derivative represented by the general formula ( 3), in the presence of a basic substance, wherein the palladium complex compound Ar ¹ X (1) in which Ar ^{1 is} an aryl group and X is a halogen, that is, fluorine, chlorine, bromine or iodine, a trifluoromethanesulfonate group, an alkylsulfonate group having a number of carbon atoms of 1-4 or a substituted or unsubstituted arylsulfonate group, Ar ² -COOH (3) Ar ^{2 is} an aryl group,

wherein Ar ¹ , Ar ² and X are as defined above and each L is independently a phosphine ligand. A palladium complex compound represented by the general formula (5)

in which Ar ³ or Ar ^{4 are} aryl groups represented by the general formulas (6) and (7) and each L is independently a phosphine ligand,

in R ^2, a trifluoromethyl group, a trifluoromethyloxy group, a halogen, that is, fluorine, chlorine, bromine or iodine, a nitro group, acetyl group, cyano group, an alkyl group having a number of carbon atoms of 1-4, an alkoxy group having a number of carbon atoms of 1 4, or an alkoxycarbonyl group having a number of carbon atoms of 2-5 and m is an integer of 0-4,

wherein R ^{1 is} a trifluoromethyl group and m is an integer of 1-3. A process according to claim 1, wherein the second palladium complex compound is represented by the general formula Ar ⁵ -PdL ₂ X in which Ar ^{5 is} a bis (trifluoromethyl) phenyl group, X is a halogen, that is, a fluorine, chlorine, bromine or Iodine, is, and each L is independently a phosphine ligand. A method according to claim 1 or 2, wherein the Ar ¹ in the general formula (1) is represented by the general formula (6)

in which R ^{2 is} a halogen, that is to say fluorine, chlorine, bromine or iodine or a monovalent organic group, and m is an integer from 0-4. A method according to claim 5, wherein the monovalent organic group of R ² in the general formula (6) comprises a trifluoromethyl group, trifluoromethyloxy group, nitro group, acetyl group, cyano group, an alkyl group having a number of carbon atoms of 1-4, an alkoxy group having a number of carbon atoms of 1-4 or an alkoxycarbonyl group having a number of carbon atoms of 2-5. A method according to claim 1 or 2, wherein the Ar ¹ in the general formula (1) is a phenyl group having at least one trifluoromethyl group. A method according to claim 1 or 2, wherein the Ar ¹ in the general formula (1) is a phenyl group having at least two trifluoromethyl groups. A method according to claim 1 or 2, in which the aromatic compound 3,5-bis (trifluoromethyl) bromobenzene or 3,5-bis (trifluoromethyl) iodobenzene is. A method according to claim 1 or 2, wherein X in of the general formula (1) is bromine or iodine. A method according to claim 1 or 2, in which the Palladium compound is a palladium salt. A method according to claim 1 or 2, wherein the phosphine derivative represented by the general Formula: P (R ¹ ) ₃ in which R ^{1 is} independently a first group selected from the group consisting of lower alkyl groups, cycloalkyl groups, phenyl group, naphthyl group, anthryl group, pyridyl group and quinolyl group, the first group optionally having a first substituent R ² selected from the group consisting of nitro group, primary amino group, secondary amino group, tertiary amino group, halogen atoms, and may have a second substituent, wherein the second substituent is selected from the group consisting of lower alkyl groups, cycloalkyl groups, phenyl group, naphthyl group, anthryl group, pyridyl group and quinolyl group, wherein the second substituent optionally one third substituent R ³ selected from the group consisting of nitro group, primary amino group, secondary amino group, tertiary amino group, halogen atoms and a substituent selected from the group consisting of lower alkyl groups, lower alkoxy groups, cycloalkyl groups, Ph enyl group, naphthyl group, anthryl group, pyridyl group and quinolyl group, which substituent may optionally have a substituent. A method according to claim 12, wherein at least one of these R ^{1 of} the phosphine derivative is selected from the group consisting of phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 4-acynyl group and 3,5-xylyl group. A method according to claim 12, wherein the phosphine derivative is represented by the following general formula:

wherein any number of hydrogen atoms of the naphthalene ring is optionally replaced with the first substituent R ² , and each R ⁴ is independently selected from the group consisting of phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 4-acynyl group and 3, 5-xylyl group. A method according to claim 1 or 2, in which the phosphine derivative is represented ⁽¹ R) ₂ PQP (R ¹⁾ _2, is represented by the general formula wherein Q is a divalent group, each R ^{1 is} independently a first group selected from the group consisting of lower alkyl groups, cycloalkyl groups, phenyl group, naphthyl group, anthryl group, pyridyl group and quinolyl group, the first group optionally a first substituent R ² selected from the group consisting of nitro group, primary amino group, secondary amino group, tertiary amino group, halogen atoms, and a second Substituents, said second substituent being selected from the group consisting of lower alkyl groups, cycloalkyl groups, phenyl group, naphthyl group, anthryl group, pyridyl group and quinolyl group, said second substituent optionally having a third substituent R ³ selected from the group consisting of nitro group, primary Amino group, secondary amino group, tertiary amino group, halogen atoms and a substituent is selected from the group consisting of lower alkyl groups, lower alkoxy groups, cycloalkyl groups, phenyl group, naphthyl group, anthryl group, pyridyl group, and quinolyl group and the substituent optionally has a substituent. A method according to claim 15, wherein the bivalent Group Q (1) any number of first bivalent ones Group, selected from the group consisting of alkylene group, phenylene group, naphthylene group and anthrylene group and (2) any number of a linking group selected from the group consisting of a single bond -O-, -S-, -C (= O) - and -S (= O) -, where the first bivalent group is optionally a any number of a substituent selected from the group consisting from a nitro group, primary Amino group, secondary Amino group, tertiary Amino group, halogen atoms, lower alkyl groups, lower alkoxy groups, Cycloalkyl groups, phenyl group, naphthyl group, anthryl group, Pyridyl group and quinolyl group. A method according to claim 15, wherein the divalent group Q optionally has a substituent and is selected from the group consisting of alkylene group, biphenylene group, binaphthylene group and bianthrenyl group and the substituent of this divalent group Q is any number of a group selected from the group consisting of Nitro group, primary amino group, secondary amino group, tertiary Amino group, halogen atoms, lower alkyl groups, lower alkoxy groups, cycloalkyl groups, phenyl group, naphthyl group, anthryl group, pyridyl group and quinolyl group. A method according to claim 1 or 2, wherein the Phosphine derivative is a triphenylphosphine. A method according to claim 1 or 2, in which the basic substance selected is from the group consisting of ammonium and amines. A method according to claim 1 or 2, wherein the Reacting this aromatic compound in the presence of a solvent carried out becomes. A method according to claim 1 or 2, wherein the React the aromatic compound in the presence of water as a solvent accomplished becomes. A method according to claim 1 or 2, wherein the Reacting the aromatic compound is carried out in a single reaction vessel. A method according to claim 1 or 2, wherein the Ar ² in the general formula (3) is represented by the general formula (7)

in which R ^{1 is} a halogen, that is to say fluorine, chlorine, bromine or iodine, or a monovalent organic group and n is an integer from 0-3. A process according to claim 23, wherein the monovalent organic group of R ¹ in the general formula (7) has a trifluoromethyl group, a trifluoromethyloxy group, nitro group, acetyl group, cyano group, an alkyl group having a number of carbon atoms of 1-4, an alkoxy group having a number Carbon atoms of 1-4, or an alkoxycarbonyl group having a number of carbon atoms of 2-5. A method according to claim 1 or 2, wherein the Ar ² in the general formula (3) is a phenyl group having at least one trifluoromethyl group. A method according to claim 1 or 2, wherein the Ar ² in the general formula (3) is a phenyl group having at least two trifluoromethyl groups. A method according to claim 1, wherein the reacting the second palladium complex compound in the presence of a solvent is carried out. A method according to claim 1, wherein the reacting the second palladium complex compound in the presence of water as a solvent carried out becomes. A method according to claim 1 or 2, in which the Phosphine ligand selected is selected from the group consisting of triphenylphosphine, tris (o-tolyl) phosphine, tris (m-tolyl) phosphine and tris (n-butyl) phosphine. A method according to claim 1, wherein the phosphine ligand in the general formula (2) is a triphenylphosphine. A palladium complex compound according to claim 3, in which the aryl group represented by the general formula (7) is a bis (trifluoromethyl) phenyl group. A palladium complex compound according to claim 3, in which the aryl group represented by the general formula (7) a 3,5-bis (trifluoromethyl) phenyl group is. A palladium complex compound according to claim 3, wherein at least one of R ² in the general formula (6) is a trifluoromethyl group. A palladium complex compound according to claim 3, in which the aryl group represented by the general formula (6) a phenyl group, trifluoromethylphenyl group or bis (trifluoromethyl) phenyl group is. A palladium complex compound according to claim 3, in which the aryl group represented by the general formula (6) a 3-trifluoromethylphenyl group or 3,5-bis (trifluoromethyl) phenyl group is. A palladium complex compound according to claim 3, in which the aryl group represented by the general formula (6) a phenyl group, 3-trifluoromethylphenyl group or 3,5-bis (trifluoromethyl) phenyl group and the aryl group is represented by the general formula (7) a 3,5-bis (trifluoromethyl) phenyl group. A palladium complex compound according to claim 3, wherein each L in the general formula (5) is represented by the general formula P (R ³ ) ₃ wherein each R ^{3 is} independently (1) a phenyl group optionally having a substituent or (2 ) is an alkyl group having a number of carbon atoms of 1-6. A palladium complex compound according to claim 37, wherein each R ^{3 is} independently selected from the group consisting of a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, methyl group, ethyl group and n-butyl group. A palladium complex compound according to claim 3, wherein each L in the general formula (5) is a triphenylphosphine is. A palladium complex compound according to claim 3, the [3,5-bis (trifluoromethyl) benzoato] 3 ', 5'-bis (trifluoromethyl) phenylbis (triphenylphosphine) palladium (II) is. A palladium complex compound according to claim 3, the [3,5-bis (trifluoromethyl) benzoato] 3'-trifluoromethyl-phenyl-bis (triphenylphosphine) palladium (II) is. A method according to claim 4, wherein the Ar ^{5 is} a 3,5-bis (trifluoromethyl) phenyl group. A process according to claim 4, wherein each L is represented by the general formula P (R ¹ ) ₃ , wherein each R ^{1 is} independently a first group selected from the group consisting of lower alkyl groups, cycloalkyl groups, phenyl group, naphthyl group, anthryl group, pyridyl group and quinolyl group, said first group optionally having a first substituent R ² selected from the group consisting of nitro group, primary amino group, secondary amino group, tertiary amino group, halogen atoms and a second substituent, said second substituent selected from the group consisting of lower alkyl groups , Cycloalkyl groups, phenyl group, naphthyl group, anthryl group, pyridyl group and quinolyl group, the second substituent optionally has a third substituent R ³ selected from the group consisting of nitro group, primary amino group, secondary amino group, tertiary amino group, halogen atoms and a substituent is selected from the group consisting of lower alkyl groups, lower alkoxy groups, cycloalkyl groups, phenyl group, naphthyl group, anthryl group, pyridyl group and quinolyl group, said substituent optionally having a substituent. A method according to claim 43, wherein at least one of these R ¹ of each L is selected from the group consisting of phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 4-acynyl group and 3,5-xylyl group. A method according to claim 43, wherein each L is represented by the following general formula:

wherein any number of hydrogen atoms of the naphthalene ring are optionally replaced by the first substituent R ² and each R ^{4 is} independently selected from the group consisting of phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 4-acynyl group and 3,5-xylylene group. A method according to claim 1 or 2, wherein each L is represented by the general formula (R ¹⁾ ₂ PQP (R ¹⁾ ₂ in which Q is a divalent group and each R ^{1 is} independently a first group selected from the group consisting of lower alkyl groups, cycloalkyl groups, phenyl group, naphthyl group, anthryl group, pyridyl group and quinolyl wherein the first group optionally has a first substituent R ² selected from the group consisting of nitro group, primary amino group, secondary amino group, tertiary amino group, halogen atoms, and a second substituent, the second substituent being selected from the group consisting of lower alkyl groups, Cycloalkyl groups, phenyl group, naphthyl group, anthryl group, pyridyl group and quinolyl group, wherein the second substituent optionally has a third substituent R ³ selected from the group consisting of nitro group, primary amino group, secondary amino group, tertiary amino group, halogen atoms and a substituent selected from the group best consisting of lower alkyl groups, lower alkoxy groups, cycloalkyl groups, phenyl group, naphthyl group, anthryl group, pyridyl group and quinolyl group, said substituent optionally having a substituent. A method according to claim 46, wherein the bivalent Group Q contains (1) any number of a first bivalent group is selected from the group consisting of alkylene group, phenylene group, naphthylene group and anthrylene group, and (2) any number of linking groups selected from the group consisting of a single bond, -O-, -S-, -C (= O) - and -S (= O) -, where the first bivalent group is optionally any one Number of a substituent selected from the group consisting from nitro group, primary Amino group, secondary amino group, tertiary Amino group, halogen atoms, lower alkyl groups, lower alkoxy groups, Cycloalkyl groups, phenyl group, naphthyl group, anthryl group, Pyridyl group and quinolyl group has. A method according to claim 46, wherein the bivalent Group Q optionally has a substituent and is selected from the group consisting of alkylene group, biphenylene group, binaphthylene group and bianthrylene group, and the substituent of this bivalent group Q is any number of groups selected from the group from nitro group, primary Amino group, secondary Amino group, tertiary Amino group, halogen atoms, lower alkyl groups, lower alkoxy groups, Cycloalkyl groups, phenyl group, naphthyl group, anthryl group, Pyridyl group and quinolyl group. A method according to claim 4, wherein each L is one Triphenylphosphine is.