JP2001002692A - Production of palladium complex compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new method for producing a palladium-phosphine complex compound. SOLUTION: This method for producing a palladium-phosphine complex compound expressed by formula II: Ar-PdL2X (L is phosphine ligand, Ar is an aromatic group; X is a halogen (means fluorine, chlorine, bromine or iodine), trifluoromethanesulfonate group, a 1-4C alkylsulfonate group or a (substituted) arylsulfonate group), is provided by mixing and reacting an aromatic compound expressed by formula I: ArX (Ar, X are each the same in the formula II) with a palladium compound and phosphine in the presence of a base substance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel method for producing a palladium-phosphine complex compound.

[0002]

[Prior art]

Ar ¹ -PdL ¹ ₂ X ¹ (wherein, Ar ¹ represents an aryl group, L ¹ represents a phosphine ligand, X ¹ is a halogen) as a method for producing the palladium complex compound represented by the A stable zero-valent palladium complex and an aryl halide (Ar ¹ -X ¹ ) (wherein
Ar ¹ represents an aryl group, and X ¹ represents a halogen). For example, in the literature (J. Organ
Omet. Chem., 1971, 28, 287) includes a stable zero-valent complex Pd.
⁰ (PPh ₃ ) ₄ and an aryl halide) to give Ar ¹
A method for obtaining Pd (PPh ₃ ) ₂ X ¹ is described, and other documents (Organometallics, 1996, 15 (17), 3708)
Describes a method of performing the same reaction using Pd ₂ (dba) ₃ as zero-valent palladium.

Further, when dibromobis (triphenylphosphine) palladium (II) and toluene are reacted at 130 ° C. for 1 hour in the presence of potassium carbonate, a small amount of bromo [methylphenyl] bis (triphenylphosphine) palladium is obtained.
(II) can be obtained (J. Chem. Commun., 1994, 121)
It is described in.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a method of preparing a zero-valent palladium complex and reacting it with an aryl halide as described in the prior art, or a method of preparing a dihalogenphosphine complex once and preparing an aromatic compound. A novel method for producing a palladium complex compound represented by the general formula (2) and Ar-PdL ₂ X (2) without performing a complicated operation such as reacting

[0005]

The above object can be attained by mixing and reacting an aromatic halide, a palladium compound, and phosphine as a ligand in the presence of a basic substance.

That is, the present invention relates to a compound represented by the general formula (1): ArX (1) (wherein, Ar represents an aryl group, X represents halogen (referring to fluorine, chlorine, bromine or iodine), a trifluoromethanesulfonate group, An aromatic compound represented by the following formula (2), which represents an alkylsulfonate group or a substituted or unsubstituted arylsulfonate group of formulas (1) to (4), a palladium compound and phosphine in the presence of a basic substance. This is a method for producing a palladium complex compound represented by Ar-PdL ₂ -X (wherein L represents a phosphine ligand, and Ar and X have the same meanings as in general formula (1)).

According to the method of the present invention, basically, all the reactions can be completed in a single reactor (one pot), and the reaction operation is significantly simplified. Naturally, the processing steps can be divided into a number of processing steps as required, and such a means is also an embodiment of the present invention.

The aromatic group represented by Ar is a carbocyclic group such as a phenyl group or a naphthyl group, or a heterocyclic group such as a pyridyl group or a quinolyl group, which may have a substituent. Ar (aromatic group) is represented by the general formula (3)

[0009]

Embedded image

(Wherein R ¹ is a trifluoromethyl group, a trifluoromethyloxy group, a halogen (fluorine, chlorine,
Bromine or iodine), nitro, acetyl,
Represents a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxycarbonyl group having 2 to 5 carbon atoms, and n represents 0 or an integer of 1 to 5. ) Is preferably a monovalent aryl group. C 1-4
Examples of the alkyl group include a methyl group, an ethyl group,
Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and a 2 to 2 carbon atoms.
Examples of the alkoxycarbonyl group 5 include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, and an i-propoxycarbonyl group.

Further, the aryl group represented by the general formula (3) is preferably an aryl group having at least one trifluoromethyl group.

As an example of the aryl group represented by the general formula (3), a trifluoromethyl group such as a 2-trifluoromethylphenyl group, a 3-trifluoromethylphenyl group or a 4-trifluoromethylphenyl group may be used. Aryl group having one trifluoromethoxy group such as 2-trifluoromethoxyphenyl group, 3-trifluoromethoxyphenyl group, and 4-trifluoromethoxyphenyl group; 2-fluorophenyl group, 3-fluoro Aryl group having one fluorine such as phenyl group and 4-fluorophenyl group; chlorine such as 2-chlorophenyl group, 3-chlorophenyl group and 4-chlorophenyl group
Aryl group having one bromine such as 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group; 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group, etc. An aryl group having one iodine; a nitro group such as a 2-nitrophenyl group, a 3-nitrophenyl group, a 4-nitrophenyl group
Aryl group having one acetyl group such as 2-acetylphenyl group, 3-acetylphenyl group, 4-acetylphenyl group; 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group Aryl groups having one cyano group such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group,
Aryl group having one alkyl group such as 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group; 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-ethoxyphenyl Group having one alkoxy group such as a group, 3-ethoxyphenyl group or 4-ethoxyphenyl group; 2-methoxycarbonylphenyl group, 3-methoxycarbonylphenyl group, 4-methoxycarbonylphenyl group, 2-ethoxycarbonylphenyl And an aryl group having one alkoxycarbonyl group such as a 3-ethoxycarbonylphenyl group or a 4-ethoxycarbonylphenyl group.

The aryl group represented by the general formula (3) can have two or more substituents, and can be in any combination. One of the substituents is trifluoromethyl. An aryl group which is a group is preferable, for example, a 2-chloro-3- (trifluoromethyl) phenyl group, a 2-fluoro-3- (trifluoromethyl) phenyl group, a 2-fluoro-4- (trifluoromethyl) phenyl Group, 3-fluoro-5- (trifluoromethyl) phenyl group, 2-bromo-6- (trifluoromethyl) phenyl group, 4-chloro-2- (trifluoromethyl) phenyl group, 4-fluoro-2- (Trifluoromethyl)
Phenyl group, 2-chloro-6- (trifluoromethyl)
Phenyl group, 4-fluoro-3- (trifluoromethyl) phenyl group, 1-chloro-4- (trifluoromethyl) phenyl group, 2-fluoro-6- (trifluoromethyl) phenyl group, 2-fluoro-5 -(Trifluoromethyl) phenyl group, 2-chloro-4- (trifluoromethyl) phenyl group, 4-chloro-3- (trifluoromethyl) phenyl group, 4-chloro-2- (trifluoromethyl) phenyl group 2-methyl-3- (trifluoromethyl) phenyl group, 3-methyl-5- (trifluoromethyl) phenyl group, 2-methyl-4- (trifluoromethyl) phenyl group, 4,5-dimethyl- 2- (trifluoromethyl) phenyl group, 2-methyl-5- (trifluoromethyl) phenyl group, 5,6-dimethyl-2
-(Trifluoromethyl) phenyl group, 2-methyl-5
-(Trifluoromethyl) phenyl group, 4-methyl-3
-(Trifluoromethyl) phenyl group, etc .; 2-methoxy-4- (trifluoromethyl) phenyl group, 2-ethoxy-4- (trifluoromethyl) phenyl group, 4-ethoxy-2- (trifluoromethyl) phenyl Group, 4-
Methoxy-2- (trifluoromethyl) phenyl group, 2
-Methoxy-5- (trifluoromethyl) phenyl group; 2-nitro-3- (trifluoromethyl) phenyl group, 2-nitro-4- (trifluoromethyl) phenyl group, 4-nitro-2- (tri A fluoromethyl) phenyl group, a 3-nitro-5- (trifluoromethyl) phenyl group, a 2-nitro-5- (trifluoromethyl) phenyl group, a 4-nitro-3- (trifluoromethyl) phenyl group, and the like; 2 -Cyano-5- (trifluoromethyl) phenyl group, 2-cyano-4- (trifluoromethyl) phenyl group, 4-fluoro-3-cyano-5- (trifluoromethyl) phenyl group, 4-cyano-3 -(Trifluoromethyl) phenyl group, 2-chloro-5-cyano-3-
(Trifluoromethyl) phenyl group, 4-cyano-2-
(Trifluoromethyl) phenyl group and the like; (2-amino-6- (trifluoromethyl) phenyl group, 2-amino-5- (trifluoromethyl) phenyl group, 2-amino-4- (trifluoromethyl) phenyl Group, 2-amino-3- (trifluoromethyl) phenyl group, 3-amino-6- (trifluoromethyl) phenyl group, 3-amino-5- (trifluoromethyl) phenyl group, 4-amino-2- (Trifluoromethyl) phenyl group, 4-amino-3- (trifluoromethyl) phenyl group, 4-amino-2- (trifluoromethyl) phenyl group, 3-amino-5- (trifluoromethyl) phenyl group And the like, but are not limited thereto.

The aryl group represented by the general formula (3) is more preferably an aryl group having two or more trifluoromethyl groups.

The aryl group having only two trifluoromethyl groups includes 2,3-bis (trifluoromethyl) phenyl group and 2,4-bis (trifluoromethyl)
Phenyl group, 2,5-bis (trifluoromethyl) phenyl group, 2,6-bis (trifluoromethyl) phenyl group, 3,4-bis (trifluoromethyl) phenyl group,
3,5-bis (trifluoromethyl) phenyl group and the like.

Further, the aryl group having a substituent described above includes a 2,3,4-tris (trifluoromethyl) phenyl group, a 2,4,5-tris (trifluoromethyl) phenyl group, a 2,3 , 5-tris (trifluoromethyl) phenyl group, 1,3,5-tris (trifluoromethyl) phenyl group, 3,4,5-tris (trifluoromethyl) phenyl group, 2,3,4,6- Tetrakis (trifluoromethyl) phenyl group, 1-bromo-
2,3,4-tris (trifluoromethyl) phenyl group, 2-bromo-4,5,6-tris (trifluoromethyl) phenyl group and the like; 3,5-dichloro-4,6-bis (trifluoromethyl ) Phenyl group, 2-chloro-
3,5-bis (trifluoromethyl) phenyl group, 2-
Methoxy-3,5-bis (trifluoromethyl) phenyl group, 2-bromo-3,5-bis (trifluoromethyl) phenyl group, 2-nitro-4,6-bis (trifluoromethyl) phenyl group, 5 , 6-Dichloro-1,3-
Bis (trifluoromethyl) phenyl group, 4-chloro-
Examples thereof include a 3,5-bis (trifluoromethyl) phenyl group, but are not limited thereto.

As the aromatic compound represented by the general formula (1), among the compounds exemplified above, at least one of R ¹ is a trifluoromethyl group because of the remarkable usefulness of the product. Group compounds are preferred, and aromatic compounds in which at least two of R ¹ are trifluoromethyl groups are more preferred.

Further, 3,5-bis (trifluoromethyl) bromobenzene or 3,5-bis (trifluoromethyl) iodobenzene is more preferable because the usefulness of the product is remarkable.

The phosphine used in the method of the present invention is not particularly limited, but is a phosphine represented by the general formula (4) and P (R ³ ) ₃ (4). Here, R ³ is each independently unsubstituted or a phenyl group substituted by an alkyl group having 1 to 6 carbon atoms, or an alkyl group having a branched chain having 1 to 6 carbon atoms. Specifically, it is preferably a group selected from a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a methyl group, an ethyl group, an n-butyl group and the like. The phosphine ligand represented by L is, for example, triphenylphosphine, tris (o-tolyl) phosphine, tris (m-tolyl) phosphine, tris (p-tolyl) phosphine, or tris (n-butyl) phosphine. Preferably, triphenylphosphine is particularly preferred.

In the method of the present invention, the raw material compound represented by the general formula (1) itself can be used as a reaction solvent, and various solvents can also be used. Examples of such a solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene; diethyl ether, dioxane, tetrahydrofuran (THF), and ethylene glycol dimethyl ether. Ethers such as
Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile,
Tertiary amines such as pyridine, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (D
Acid amides such as MAc), dimethyl sulfoxide (D
(MSO), sulfur-containing compounds such as sulfolane, water, and the like. When using a water-soluble basic substance, it is preferable to use water at least in part.

The reaction according to the present invention requires the presence of a basic substance, but the type thereof is not particularly limited. As the basic substance, ammonias, amines and inorganic bases can be used. Ammonia as ammonia, hydroxyamine and the like; primary amine as propylamine, isopropylamine, butylamine, amylamine, hexylamine and the like; secondary amine as diethylamine,
Dipropylamine, diisopropylamine, dibutylamine, etc .; tertiary amines, such as triethylamine, tripropylamine, tributylamine, etc .; alicyclic amines, such as cyclopropylamine; aromatic amines, triallylamine, N, N-dimethyl Aniline,
N, N-diethylaniline, pyridine, N-methylmorpholine and the like; and inorganic bases such as acetates such as sodium acetate and potassium acetate, and sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. Can be mentioned.

As the palladium compound, palladium salts such as palladium acetate, palladium chloride, palladium bromide, palladium iodide and palladium nitrate are preferred. Further, a divalent palladium complex compound, for example, [P
d (NH ₃ ) ₄ ] Y ₂ , Pd (NH ₃ ) ₂ Y ₂ , [Pd (NH
₃ ) ₄ ] [PdY ₄ ] and the like can also be suitably used. Here, Y is a halogen (chlorine, bromine and iodine).

The ratio of each raw material used is not particularly limited. However, in order to effectively use palladium, the palladium compound is used in an amount of 1 mol or more, and the aromatic compound represented by the general formula (1) is used in an amount of 1 mol or more per mol of palladium. The phosphine used is preferably used in an amount of 2 mol or more. Other basic substances, solvents and the like may be used in appropriate amounts.

The method for producing the complex compound of the present invention may be generally carried out as follows, but is not necessarily required to be as described above, and can be appropriately changed. A container is charged with an aromatic compound represented by the general formula (1), a palladium compound, a phosphine serving as a phosphine ligand, a basic substance, and if necessary, a solvent. The container may or may not be pressurized and may or may not be agitated. Raw materials charged are about 0-200 ° C,
Usually, the reaction is accelerated by heating to about 50 to 150 ° C. After a predetermined time has elapsed, the container is cooled and the contents are taken out. An extraction solvent is appropriately added to the contents to separate a solid content, and a volatile component is distilled off to obtain a target palladium complex compound represented by the general formula (2). If necessary, it can be purified by recrystallization or silica gel chromatography.

The palladium complex compound represented by the general formula (2) produced by the method of the present invention may be crystalline, is soluble in many organic solvents, and is stable. Also,
Stable in air at room temperature.

Because of these physical and chemical properties, the isolation operation is easy, so that a high-purity substance is easily obtained, and storage is easy, so that it is easy to handle even in industrial use. is there.

The palladium complex compound represented by the general formula (2) produced by the method of the present invention can be used as an intermediate for the preparation of a palladium complex compound having a different ligand, and can be subjected to various reactions, for example, , Carbon monoxide insertion reaction into aryl halide, followed by reductive elimination carbonylation of aromatic compounds, olefins into aryl halide insertion reaction, followed by reductive elimination vinylation reaction, It has catalytic activity for the coupling reaction of aryl halide and the like. For example, bromo [3,5-bis (trifluoromethyl) phenyl] bis (triphenylphosphine) palladium (II) represented by the following formula:

[0028]

Embedded image

Carbonylation of an aromatic compound by insertion reaction of carbon monoxide into aryl halide and subsequent reductive elimination, vinyl reaction by insertion reaction of olefin into aryl halide and subsequent reductive elimination Chemical reaction,
Shows catalytic activity in aryl halide coupling reactions and the like.

[0030]

Next, the present invention will be described in detail with reference to examples of the production method, but the present invention is not limited to these examples. Unless otherwise noted, pressures indicate gauge pressure. Example 1 Synthesis of bromo [3,5-bis (trifluoromethyl) phenyl] bis (triphenylphosphine) palladium (II) 32.5 g of 3,5-bis (trifluoromethyl) bromobenzene in a stainless steel autoclave. , Palladium acetate 25.0 g, triphenylphosphine 87.3 g, and tetrahydrofuran 75 ml were mixed and stirred. 2 more
After charging 38.0 g of 5% aqueous ammonia, nitrogen replacement was performed twice, and the internal temperature was increased when stirring was started at a nitrogen pressure of 3 kg / cm ² . Thereafter, the oil bath temperature was set at 105 ° C., and heating was started. After about 1.8 hours, when the internal temperature reached 97 ° C., the oil bath was removed and the reaction was stopped by cooling. 200 ml of toluene was added to the reaction solution, and the mixture was stirred for several minutes. The obtained treatment liquid was subjected to suction filtration, washed with a small amount of n-hexane, and then dried to obtain 72.1 g of pale green crystals. This was recrystallized and purified from methylene chloride to obtain 48.7 g of bromo [3,5-bis (trifluoromethyl) phenyl] bis (triphenylphosphine) palladium (II). Physical properties: Melting point: (decomposed at 192 ° C or higher) IR (KBr: cm-1): 3052,1435,1443,1166,1095,749,693,5
17 ¹ H-NMR: (Reference substance: TMS solvent: CDCl ₃ ) δ ppm 6.75 (s, 1H), 7.09 (s, 2H), 7.24-7.37 (m, 18H), 7.50-
7.55 (m, 12H) ³¹ P-NMR: (Reference substance: 85% H ₃ PO ₄ solvent: CDCl ₃ ) δ ppm 27.33 (s) [Example 2] Iodo [3,5-bis (trifluoromethyl) phenyl] Synthesis of bis (triphenylphosphine) palladium (II) 3,5-bis (trifluoromethyl) bromobenzene of Example 1 was changed to 4.00 g of 3,5-bis (trifluoromethyl) iodobenzene, and palladium acetate 2 .64
g, 9.29 g of triphenylphosphine, 8.91 g of tetrahydrofuran, 3.45 g of 29% aqueous ammonia, a reaction temperature of 60 to 80 ° C., and a reaction time of 3 hours.
The reaction was carried out in the same manner as As a result, the target iodo [3,5-bis (trifluoromethyl) phenyl] bis (triphenylphosphine) palladium (II) was 8.81.
g were obtained. Physical properties: melting point: (decomposed at 170 ° C. or higher) ¹ H-NMR: (reference substance: TMS solvent: CDCl ₃ ) δ ppm 6.75 (s, 1H), 7.07 (s, 2H), 7.24-7.37 (m, 18H), 7.48-
7.56 (m, 12H) [Reference Example] Synthesis of 3,5-bis (trifluoromethyl) benzoic acid 400 g of 3,5-bis (trifluoromethyl) bromobenzene and bromo [3,5] were placed in a stainless steel autoclave.
-Bis (trifluoromethyl) phenyl] bis (triphenylphosphine) palladium (II) 2.40 g, and triethylamine 291.4 g, triphenylphosphine 0.887 g and water 200 g were further added.
After the autoclave was closed, stirring was started, nitrogen replacement and carbon monoxide replacement were performed three times, the initial pressure of carbon monoxide was set to 3 kg / cm ² , and heating was started in an oil bath. 7. When the internal temperature reaches 104 to 105 ° C., the internal pressure is set to 8.
It was adjusted to 5 kg / cm ² . Then, the internal temperature was adjusted to 105 ° C. and the internal pressure was adjusted to 8.5 kg / cm while adjusting the amount of carbon monoxide introduced.
Kept ^two .

After about 16 hours, the heating was stopped, the autoclave was cooled, and the internal gas was purged. The reaction solution was taken out into a separating funnel and 200 ml of water was added. This treatment solution was added to a 6N-HCl aqueous solution 370 prepared in a 2 liter beaker.
g was added dropwise from a dropping funnel while stirring at 20 to 30 ° C. The precipitated crystals were separated by suction filtration and washed with 1120 ml of water and subsequently with 336 ml of cooled toluene to obtain 279 g of colorless crystals of 3,5-bis (trifluoromethyl) benzoic acid.

[0032]

According to the process for producing a palladium complex compound of the present invention, a palladium complex compound useful as a catalyst for various reactions can be produced by a simple one-pot operation using a readily available stable chemical substance. This has the effect.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Makoto Koide 2805 Imafukunakadai, Kawagoe-shi, Saitama F-Term in Chemical Research Laboratory, Central Glass Co., Ltd. 4G069 AA08 BB13A BC72A BE26A 4H039 CA65 CD20 4H050 AA02 BB11 BB15 BB16 BB20 BB21 BB24 BB25 BB31 BD60 BE60 WB11 WB15 WB16 WB17 WB21

Claims (10)

[Claims] (1) ArX (1) wherein Ar represents an aromatic group, X represents a halogen (fluorine, chlorine, bromine or iodine), a trifluoromethanesulfonate group, and a compound having 1 to 1 carbon atoms. (P. 4 represents an alkylsulfonate group or a substituted or unsubstituted arylsulfonate group), a palladium compound and a phosphine in the presence of a basic substance and mixing and reacting them. ₂ X (2) (wherein L represents a phosphine ligand, and Ar and X have the same meanings as in general formula (1)). 2. Ar is a compound represented by the general formula (3): (Wherein, R ¹ is a trifluoromethyl group, a trifluoromethyloxy group, a halogen (fluorine, chlorine, bromine or iodine), a nitro group, an acetyl group, a cyano group, a carbon number of 1 to
4 represents an alkyl group, an alkoxy group having 1 to 4 carbon atoms, or an alkoxycarbonyl group having 2 to 5 carbon atoms, and n represents 0 or an integer of 1 to 5. The method for producing a palladium complex compound according to claim 1, which is a monovalent aryl group represented by the formula: 3. The method according to claim 1, wherein the aromatic group represented by Ar is a phenyl group having at least one trifluoromethyl group. 4. The method according to claim 1, wherein the aromatic group represented by Ar is a phenyl group having at least two trifluoromethyl groups. 5. The method according to claim 1, wherein the palladium compound is a palladium salt. 6. The method according to claim 1, wherein the basic substance is an ammonia or an amine. 7. A phosphine represented by the general formula (4): P (R ³ ) ₃ (4) (wherein, R ³ is independently a phenyl group which may have a substituent, alkyl having 1 to 6 carbon atoms) The method for producing a palladium complex compound according to claim 1, which is a phosphine represented by the following formula: 8. The method according to claim 1, wherein a solvent is further present in the reaction system.
The method for producing the palladium complex compound according to the above. 9. The method according to claim 7, wherein the solvent is water. 10. The method for producing a palladium complex compound according to claim 1, wherein the reaction is carried out in a single reactor.