JP2012188370A - Phosphine compound, organic inorganic composite material containing phosphine, and utilization of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phosphine compound utilizable as a silane coupling agent usable as a precursor for forming a covalent bond with an inorganic oxide by introducing a silyl group having a leaving substituent to the phosphine compound.SOLUTION: The phosphine compound is represented by formula (1), wherein Rand Rare each independently an aryl group or an alkyl group; Y is an aryl group or an alkyl group; X, when Y is an aryl group, is one group selected from the group consisting of a halogen atom, an alkoxy group, a hydroxy group and an amino group, and when Y is an alkyl group, is one group selected from the group consisting of an alkoxy group, a hydroxy group and an amino group; and n is an integer of 1 to 3.

Description

  The present invention relates to a novel phosphine compound and an organic-inorganic composite material containing phosphine, and more specifically, for organic synthesis reactions such as cross-coupling comprising the phosphine compound or organic-inorganic composite material containing phosphine and a transition metal. It relates to a catalyst.

Conventionally, phosphine compounds have been used as ligands for transition metal complexes such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, and gold, and can change the substituents on the phosphorus atom in various ways. Therefore, attempts have been made to improve the performance when a transition metal complex is used as a homogeneous catalyst. For example, in cross-coupling reactions represented by Suzuki-Miyaura coupling reaction, Heck reaction, Buchwald-Hartig reaction and the like using a palladium phosphine complex, by introducing a sterically bulky substituent on the phosphorus atom, It is known that the catalyst performance can be improved.
On the other hand, a reactive silyl group site is introduced into the phosphine site of a transition metal complex containing a phosphine compound or phosphine as a ligand via an alkylene chain or a paraphenylene chain to form a so-called silane coupling agent. Attempts have also been made to obtain organic-inorganic composite materials to which phosphine or transition metal complexes are bonded by reacting and covalently bonding hydroxyl groups of inorganic oxides such as silica gel and zeolite.
Organic-inorganic composite materials obtained in this way include industrial materials such as various adsorbents, column fillers, surfactants, drug delivery systems, biocompatible materials, pharmaceutical materials such as test chips, sensors, organic EL, In addition to applications such as electronic materials such as liquid crystals, they are used as heterogeneous catalysts that can facilitate the separation and recovery of catalyst components.
For example, in Non-Patent Document 1, an organic-inorganic composite material in which a palladium complex containing a diphenylphosphino group as a ligand is bonded to a silica gel surface via an alkylene chain is used for Suzuki-Miyaura coupling reaction and Heck reaction. Use for heterogeneous catalysts is disclosed.
Non-Patent Document 2 discloses the synthesis by a sol-gel method of an organic-inorganic composite material in which a palladium complex and a platinum complex having a diphenylphosphino group as a ligand are bonded to a silica surface via a paraphenylene chain. ing.
On the other hand, as a phosphine compound having a silyl group, in addition to those having a silyl group via the above-described alkylene chain, non-patent document 3 describes one phenyl group in a triphenylphosphine molecule as viewed from a phosphorus atom. There are only a few known synthesis examples of phosphine compounds in which a dialkylchlorosilyl group is introduced at the ortho position.

Top. Catal. 53 (2010), 1059. J. et al. Organomet. Chem. 643-644 (2002) 453. Synthesis (2002) 905.

However, in the phosphine compound used in the organic-inorganic composite material of the above-described conventional example, the silyl group site is bonded to the phosphine via an alkylene chain or a paraphenylene chain, and exists in a spatially distant position in the molecule. Therefore, the functions are separated, and the silyl group serves only as a bonding point for forming a covalent bond with the inorganic oxide, and the silyl group site is a three-dimensional structure around the phosphorus atom of the phosphine. The bulkiness was not affected. Therefore, it is necessary for the phosphine compound to have a molecular design for independently imparting bulkiness for improving the catalyst performance and the ability to form a covalent bond to the inorganic oxide, which is inefficient in synthesizing the compound. There were drawbacks.
The object of the first invention according to the present application is to introduce a silyl group having a detachable substituent into a phosphine compound, thereby providing bulkiness around the phosphine and simultaneously forming a covalent bond with an inorganic oxide. The object is to provide a phosphine compound that can be used as a precursor and to provide an organic-inorganic composite material containing this phosphine.
The object of the second invention according to the present application is to provide a transition metal complex having the phosphine compound as a ligand and a transition metal-containing organic-inorganic composite material in which a transition metal is supported on the phosphine-containing organic-inorganic composite material. is there.
The object of the third invention according to the present application is to provide a homogeneous catalyst and an immobilization catalyst useful for various synthesis reactions using the transition metal complex and the transition metal-containing organic-inorganic composite material, particularly for cross-coupling reactions. Is to provide.

Means for achieving the object is as follows.
<1> A phosphine compound represented by the following general formula (1).
(In formula (1), R ¹ and R ² are each independently an aryl group or an alkyl group, Y is an aryl group or an alkyl group, and X is a halogen atom or an alkoxy group when Y is an aryl group. , Any group selected from the group of hydroxyl group and amino group, and when Y is an alkyl group, any group selected from the group of alkoxy group, hydroxyl group and amino group, and n is an integer of 1 to 3. )
<2> A phosphine-containing organic-inorganic composite material obtained by reacting the phosphine compound according to <1> with an inorganic oxide to covalently bond a silicon atom of the phosphine compound to an oxygen atom on the surface of the inorganic oxide.
<3> A transition metal complex containing the phosphine compound according to <1> as a ligand.
<4> A transition metal-containing organic-inorganic composite material in which a transition metal is supported on the phosphine-containing organic-inorganic composite material according to <2>.
<5> A transition metal-containing organic-inorganic composite material obtained by reacting the transition metal complex according to <3> with an inorganic oxide to covalently bond a silicon atom of the phosphine compound to an oxygen atom on the surface of the inorganic oxide.
<6> A homogeneous catalyst comprising the transition metal complex according to <3>.
<7> An immobilized catalyst comprising the transition metal-containing organic-inorganic composite material according to <4> or <5>.
<8> The homogeneous catalyst according to <6>, which is a homogeneous catalyst for cross-coupling reaction.
<9> The immobilized catalyst according to <7>, which is an immobilized catalyst for cross-coupling reaction.

As described above, the phosphine compound according to the present invention introduces a silyl group having a detachable substituent at the ortho position of the benzene ring to which the phosphorus atom is bonded, so that a bulkiness is imparted around the phosphorus atom of the phosphine. At the same time, it can be used as a precursor for forming a covalent bond with an inorganic oxide.
By imparting bulkiness, in the catalytic reaction using the transition metal complex having the phosphine compound of the present invention as a ligand, it is possible to provide a homogeneous catalyst having higher activity than when a conventional phosphine compound is used.
Moreover, even when the transition metal complex-containing organic-inorganic composite material of the present invention is used as an immobilization catalyst, the bulkiness around the phosphine works effectively, and the immobilization has higher activity than the conventional immobilization catalyst having phosphine. A catalyst can be provided.

The present invention relates to a phosphine compound represented by the following general formula (1).
(In formula (1), R ¹ and R ² are each independently an aryl group or an alkyl group, Y is an aryl group or an alkyl group, and X is a halogen atom or an alkoxy group when Y is an aryl group. , Any group selected from the group of hydroxyl group and amino group, and when Y is an alkyl group, any group selected from the group of alkoxy group, hydroxyl group and amino group, and n is an integer of 1 to 3. )
Since the phosphine compound of the present invention introduces a silyl group having a detachable substituent at the ortho position of the benzene ring to which the phosphorus atom is bonded, the bulk of the phosphine around the phosphorus atom gives the transition metal catalyst. When used as a ligand, a highly active homogeneous catalyst can be obtained, and at the same time, a silyl group site can be reacted with an inorganic oxide to form an organic-inorganic composite material. It can be used as a stable immobilized catalyst.

Below, general formula (1) is demonstrated.
In the formula, R ¹ and R ² are each independently an aryl group or an alkyl group. Specific examples of the aryl group include a phenyl group, an orthotolyl group, a paratolyl group, and a naphthyl group, and a phenyl group is preferable from the viewpoint of ease of synthesis. Examples of the alkyl group include a linear or branched alkyl group having 1 to 6 carbon atoms and a cycloalkyl group. From the viewpoint of catalytic activity, an isopropyl group, a tertiary butyl group, and a cyclohexyl group are preferable. R ¹ and R ² may be the same or different, but are preferably the same from the viewpoint of ease of synthesis.
Y is an aryl group or an alkyl group. Specific examples of the aryl group include a phenyl group, an orthotolyl group, a paratolyl group, and a naphthyl group, and a phenyl group is preferable from the viewpoint of ease of synthesis. Examples of the alkyl group include a linear or branched alkyl group having 1 to 6 carbon atoms and a cycloalkyl group, and a methyl group and an isopropyl group are preferable from the viewpoint of ease of synthesis.
X is a group having a leaving ability for reacting a phosphine compound with an inorganic oxide to synthesize an organic-inorganic composite material. When Y is an aryl group, X is a group of a halogen atom, an alkoxy group, a hydroxyl group, and an amino group. Although it is any group selected, a chlorine atom and a methoxy group are preferable from the viewpoint of achieving both improvement in the amount of organic group immobilized on the inorganic oxide and stability of the compound.
In addition, when Y is an alkyl group, the hydrolyzability of the silicon part tends to be high, and the handleability tends to be difficult. For example, in Non-Patent Document 3, two methyl groups are formed on silicon introduced at the ortho position of phosphine. As it is disclosed that a compound having a chlorine atom is easily hydrolyzed / condensed, when X is a halogen atom, it is particularly unstable. Any group selected from the group consisting of an alkoxy group, a hydroxyl group, and an amino group having the ability to leave is preferable, and an isopropoxy group is more preferable.
n is an integer of 1 to 3.

In the synthesis of the phosphine compound of the present invention, ortho-halogenated phenylphosphine is synthesized by introducing phosphine as a first step using ortho-dihalogenated benzene having two halogen atoms in the ortho position of the benzene ring as a starting material. For the introduction of phosphine, a phosphation reaction using a palladium catalyst or a method in which an organolithium reagent or a Grignard reagent is prepared from orthodihalobenzene and then reacted with a halogenated phosphine can be used.
As the second step, an organolithium reagent or a Grignard reagent is prepared using the remaining halogen atom site, and a silyl group is introduced into the ortho position of the phosphine by reaction with the halogenated silane.
The phosphine compound of the present invention can also be synthesized by introducing a silyl group as the first step and introducing phosphine in the second step, contrary to the above order. Also in this case, as the reaction for introducing each of them, preparation of the above-mentioned organolithium reagent or Grignard reagent, phosphination reaction with a palladium catalyst, and the like can be used.

The phosphine-containing organic-inorganic composite material of the present invention can be synthesized by reacting the above phosphine compound with any inorganic oxide material.
Although there is no restriction | limiting in particular in an inorganic oxide, Single oxides, such as silicon, titanium, aluminum, zirconium, magnesium, or the complex oxide containing them can be used. Among them, silica or silicon which is an oxide of silicon is included from the viewpoint that the surface has many silanol groups as hydroxyl groups and can form a strong covalent bond between the organic group to be immobilized and the inorganic oxide. It is preferable to use a composite oxide, and it is more preferable to use regular mesoporous silica or regular mesoporous metallosilicate because a larger surface area can be used to increase the amount of organic groups introduced per unit weight.
Specifically, as a method for obtaining a phosphine-containing organic-inorganic composite material, for example, if the phosphine compound is liquid, it is a raw solution or a solution in which it is dissolved in aliphatic hydrocarbons, aromatic hydrocarbons, ethers, alcohols, etc. The inorganic oxide is suspended in and stirred while heating. Thereafter, the phosphine-containing organic-inorganic composite material can be obtained by collecting solids by filtration, washing and drying.
In the phosphine-containing organic-inorganic composite material thus obtained, at least one of Y on silicon represented by the general formula (1) is eliminated, so that an oxygen atom on the inorganic oxide and a phosphine compound can be obtained. A covalent bond is formed with the silicon atom.

The transition metal complex of the present invention can contain, for example, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, gold, etc. as a metal, but from the viewpoint of catalytic performance for the cross-coupling reaction. It is preferable to contain platinum, palladium, and nickel.
The transition metal complex of the present invention is prepared by mixing an arbitrary transition metal complex such as palladium acetate or bis (benzonitrile) palladium dichloride with the phosphine compound of the present invention in a suitable solvent such as toluene or tetrahydrofuran. Can be prepared.
When the transition metal complex of the present invention thus obtained is used as a homogeneous catalyst due to the effect of a bulky phosphine ligand, high catalytic performance is realized.

  The transition metal-containing organic-inorganic composite material of the present invention is obtained by suspending the phosphine-containing organic-inorganic composite material of the present invention in a suitable solvent such as toluene and tetrahydrofuran, and any transition metal complex such as palladium acetate or bis (benzonitrile). ) It may be prepared by mixing palladium dichloride, or a transition metal complex having the phosphine of the present invention as a ligand is prepared in advance, and this is reacted with an inorganic oxide to form a transition metal complex You may prepare by forming a covalent bond between inorganic oxides.

The phosphine-containing organic-inorganic composite material and transition metal-containing organic-inorganic composite material of the present invention described so far are used for various adsorbents, column fillers, surfactants and other industrial materials, drug delivery systems, biocompatible materials, test chips. It is useful for applications such as pharmaceutical materials such as sensors, electronic materials such as sensors, organic EL and liquid crystal, etc., but separation and recovery of catalyst components that take advantage of the reactivity of transition metal sites and the insolubility of inorganic oxides in particular. It is preferable to use it as an easy immobilized catalyst.
Even when the transition metal-containing organic-inorganic composite material of the present invention is used as an immobilization catalyst, the steric bulk effect of the phosphine compound of the present invention improves the catalyst performance over the conventional immobilization catalyst. The

The homogeneous catalyst and the immobilization catalyst of the present invention can be used as catalysts for various synthesis reactions, but for coupling reactions such as homo-coupling and cross-coupling reactions, hydrosilylation, carbonylation, hydroformyl It is effective as a catalyst for addition reactions such as hydrogenation, Michael addition, and hydrogenation (including asymmetric hydrogenation), and is particularly effective as a catalyst for cross-coupling reactions.
Among the above reactions, the cross-coupling reaction is a reaction that selectively binds two different chemical species, unlike a homo-coupling reaction that binds two identical chemical species, and uses a transition metal as a catalyst. It is a reaction characterized by proceeding with. When the catalyst is used for the cross-coupling reaction, the transition metal or a compound thereof is preferably platinum, palladium, or nickel.

Typical examples of the cross-coupling reaction include the following, but the catalyst of the present invention is effective for any of these cross-coupling reactions (1) Suzuki coupling reaction Reactions in which organoboron compounds and organic halides are cross-coupled under basic conditions using transition metals such as palladium as catalysts (2) Mizorogi-Heck coupling reaction Basic using transition metals such as palladium as catalysts Reaction to synthesize alkenyl aryl compounds by cross-coupling terminal alkene and aryl halide under conditions (3) Negishi coupling reaction Organo zinc compounds and organic halides using transition metals such as palladium and nickel as catalysts (4) Stille coupling reaction Transition of palladium, etc. Reaction that cross-couples organotin compounds and organic halides using transfer metals as catalysts (5) 辻 -Trost coupling reaction Allyl esters, etc. under basic conditions using transition metals such as palladium as catalysts Reaction of cross-coupling organic nucleophiles to synthesize allylic alkylation products (6) Sonogashira coupling reaction Terminal alkynes and aryl halides are converted under basic conditions using transition metals such as palladium as catalysts. Reaction for synthesizing alkynylaryl compounds by cross-coupling (7) Kumada-Tamao coupling reaction Reaction for cross-coupling Grignard reagents with organic halides using transition metals such as nickel and palladium as catalysts (8) Buchwald-Hartwick coupling reaction Using transition metals such as palladium as catalysts Reaction to synthesize arylamine or aryl ether by cross-coupling aryl halide and amine or alcohol under basic conditions

Hereinafter, a preferred embodiment of the cross coupling reaction using the catalyst of the present invention will be described by taking the Suzuki coupling reaction as an example. Examples of raw materials used for the synthesis of biaryl compounds by the Suzuki coupling reaction include aryl halides and aryl boronic acids. Each raw material may be substituted with various substituents on the aryl group. Moreover, as a transition metal compound of this invention catalyst used by this reaction, what contains platinum, palladium, and nickel is used preferably.
Examples of the base coexisting in the cross-coupling reaction system include both organic bases and inorganic bases, but inorganic bases are preferred. Specific examples of the inorganic base include sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium phosphate, potassium phosphate, sodium acetate and the like.
When carrying out the cross-coupling reaction, a solvent is not always necessary, but various solvents may be used alone or in combination. Solvents include organic solvents such as aromatic hydrocarbons such as toluene and xylene, ethers such as diethyl ether, dibutyl ether and tetrahydrofuran, aliphatic saturated hydrocarbons such as pentane and hexane, and alcohols such as methanol and ethanol. Or water etc. are mentioned.

  The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

Example 1. Synthesis of compound 2:
First stage: Pd (PPh ₃ ) ₄ (0.463 g, 0.400 mmol) was placed in a 100 ml two-necked eggplant type flask, and after nitrogen atmosphere, 60 ml of acetonitrile, diphenylphosphine (7.11 g, 38.2 mmol), triethylamine (4.69 g, 46.4 mmol) and 2-bromoiodobenzene (12.0 g, 42.3 mmol) were sequentially added, and the mixture was reacted for 6 hours under heating and refluxing conditions. Water was added to the reaction solution, and the organic phase was extracted with dichloromethane and dried over anhydrous magnesium sulfate. After distilling off the organic solvent under reduced pressure, Compound 1 was isolated by silica gel column chromatography. Yield 12.3 g, 97% yield.
Second Step Subsequently, Compound 1 (0.500 g, 1.47 mmol) was placed in a 100 ml two-necked eggplant type flask, 7.5 ml of diethyl ether was added under a nitrogen atmosphere, and the mixture was cooled to −50 ° C. Furthermore, 1.0 ml (1.55 M, 1.55 mmol) of n-BuLi hexane solution was added dropwise and stirred for 3 hours. Thereafter, diphenyldichlorosilane (4.51 g, 17.8 mmol) was added, and the temperature was raised to room temperature while stirring. After the reaction, the solution was diluted with hexane, and by-product salts were removed by filtration.
The solvent was distilled off under reduced pressure, and then recrystallized from a hexane solvent to isolate Compound 2. Yield 0.204 g, yield 29%.
NMR data of Compound 2:
¹ H NMR (CD ₂ Cl ₂ , δ) 7.51-6.92 (m, 24H).
¹³ C NMR (CD ₂ Cl ₂ , δ) 137.62 (d, J = 16.4 Hz), 137.11 (d, J = 10.4 Hz), 136.17, 135.41 (d, J = 2.55 Hz), 135.13, 134.76 (d, J = 3.71 Hz), 133.19 (d, J = 18.31 Hz), 131.39, 130.39, 129.33, 128.40 (2C), 128.33 (d, J = 6.65 Hz), 128.00.
³¹ P NMR (CD ₂ Cl ₂ , δ) -12.31.
²⁹ Si NMR (CD ₂ Cl ₂ , δ) -0.22 (d, J = 14.7 Hz),

Example 2 Synthesis of compound 3:
Compound 2 (2.18 g, 4.56 mmol) synthesized as in Example 1 was placed in a 100 ml two-necked eggplant-shaped flask, and 40 ml of diethyl ether was added under a nitrogen atmosphere and cooled with ice. Thereafter, methanol (2.37 g, 74.0 mmol) and triethylamine (0.653 g, 6.46 mmol) were added, and the temperature was raised to room temperature while stirring. After the reaction, by-product salt was removed by suction filtration using a Kiriyama funnel. After filtration, the solvent was distilled off under reduced pressure, and then Compound 3 was isolated by silica gel column chromatography. Yield 0.773 g, yield 36%.
NMR data of compound 3:
¹ H NMR (CD ₂ Cl ₂ , δ) 7.92-6.93 (m, 24H), 3.50 (s, 3H).
¹³ C NMR (CD ₂ Cl ₂ , δ) 144.03 (d, J = 12.5 Hz), 142.6, 137.96 (d, J = 11.8 Hz), 137.06 (d, J = 16.5 Hz), 135.83 (d, J = 2.95 Hz), 135.75 (d, J = 1.47 Hz), 135.13 (d, J = 2.99 Hz), 133.24 (d, J = 18.39 Hz), 130.45, 129.77, 128.82, 128.25 (d, J = 6.61 Hz), 128.17 , 127.75, 51.61 (d, J = 2.19 Hz).
³¹ P NMR (CD ₂ Cl ₂ , δ) -11.19.
²⁹ Si NMR (CD ₂ Cl ₂ , δ) -13.10 (d, J = 11.0 Hz).

Example 3 Synthesis of compound 5:
Compound 1 (1.02 g, 2.98 mmol) was placed in a 100 ml two-necked eggplant type flask, 30 ml of diethyl ether was added under a nitrogen atmosphere, and the mixture was cooled to -78 ° C. To this, 2 ml (1.55 M, 3.10 mmol) of n-butyllithium in hexane was added dropwise and stirred for 3 hours. Thereafter, dimethyldichlorosilane (4.26 g, 33.0 mmol) was added, and the temperature was raised to room temperature. After completion of the reaction, the solvent and excess dimethyldichlorosilane were distilled off under reduced pressure.
30 ml of diethyl ether was added to the reaction system and cooled to 0 ° C. 2-Propanol (1.56 g, 26.0 mmol) and triethylamine (0.426 g, 4.31 mmol) were added, stirred for 30 minutes, and then warmed to room temperature. The salt formed as a by-product was removed by filtration, and then the solvent was distilled off under reduced pressure. Compound X was isolated by silica gel column chromatography. Yield 0.784 g, yield 70%.
NMR data of compound 5:
¹ H NMR (CD ₂ Cl ₂ , δ) 7.40-7.15 (m, 14H), 4.12 (sept, J = 5.99 Hz, 1H), 1.12 (d, J = 6.04 Hz, 6H), 0.47 (d, J = 2.03 Hz, 6H).
¹³ C NMR (CD ₂ Cl ₂ , δ) 147.22 (d, J = 46.9 Hz), 142.49 (d, J = 12.5 Hz), 138.47 (d, J = 11.7 Hz), 135.43, 135.27, 133.44 (d, J = 18.8 Hz), 129.63 (s, 2C), 128.51 (d, J = 6.59 Hz), 128.38, 65.48, 25.72, 1.74 (d, J = 10.4 Hz).
³¹ P NMR (CD ₂ Cl ₂ , δ) -10.33.
²⁹ Si NMR (CD ₂ Cl ₂ , δ) 3.24 (d, J = 8.81 Hz).

Example 4 Synthesis of organic-inorganic composite material 1:
First, J.H. Chem. Soc. Chem. Commun. (1993) 680. The mesoporous silica FSM-22 (BET surface area: 1039 m ² / g, average pore diameter by BJH method: 4 nm) was prepared according to the method described in 1).
FSM-22 (0.506 g) was placed in a 100 ml two-necked eggplant type flask and dried at 80 ° C. under reduced pressure for 3 hours. After drying under reduced pressure, the temperature was returned to room temperature, Compound 2 (98.1 mg, 0.205 mmol) was added, 12 ml of heptane was added under a nitrogen atmosphere, and the mixture was reacted under reflux conditions for 20 hours. Then, the silica which fixed the phosphine was collect | recovered by filtration using the Kiriyama funnel. After washing with hexane, ethyl acetate, and dichloromethane, drying was performed at 80 ° C. under reduced pressure for 3 hours to obtain the target organic-inorganic composite material 1.
The content of organic groups was determined to be 0.265 mmol / g by elemental analysis of carbon.
Solid-state NMR (CP / MAS method) data of organic-inorganic composite material 1:
¹³ C
NMR (δ) 136.5-129.3.
³¹ P
NMR (δ) -8.0.
²⁹ Si
NMR (δ) -16.9 (Ph ₂ Si-O), -89.5 to -115.0 (SiO ₂ ).

Example 5 FIG. Synthesis of organic-inorganic composite material 2:
Organic-inorganic composite material 2 was obtained in the same manner as in Example 4, except that Compound 2 in Example 4 was changed to Compound 3 (94.9 mg, 0.205 mmol).
The content of organic groups was determined to be 0.161 mmol / g by elemental analysis of carbon.
Solid-state NMR (CP / MAS method) data of organic-inorganic composite material 2:
¹³ C
NMR (δ) 136.5-129.3.
³¹ P
NMR (δ) -8.0.
²⁹ Si NMR (δ) -16.9 (Ph ₂ Si-O), -89.5 to -115.0 (SiO ₂ ).

Example 6 Synthesis of organic-inorganic composite material 3:
Organic-inorganic composite material 3 was obtained in the same manner as in Example 4, except that Compound 2 in Example 4 was changed to Compound 5 (138 mg, 0.366 mmol).
The organic group content was determined to be 0.172 mmol / g by elemental analysis of carbon.
Solid-state NMR (CP / MAS method) data of organic-inorganic composite material 3:
¹³ C
NMR (δ) 135.2-129.7.
³¹ P
NMR (δ) -7.5.
²⁹ Si NMR (δ) 6.3 (Me ₂ Si-O), -89.5 to -115.0 (SiO ₂ ).

Example 7 Preparation of transition metal complex 1:
Compound 3 (7.12 mg, 0.015 mmol) and (PhCN) ₂ PdCl ₂ (5.75 mg, 0.015 mmol) were placed in a 50 ml two-necked eggplant type flask, and 5.0 ml of toluene was added under a nitrogen atmosphere. The mixture was stirred at room temperature for 4 hours to prepare transition metal complex 1 having compound 3 as a ligand.
NMR data of transition metal complex 1:
¹ H NMR (toluene-d ₈ , δ) 8.13-6.70 (m, 29H), 3.31 (s, 3H).
³¹ P NMR (toluene-d ₈ , δ) 18.30.

Example 8 FIG. Synthesis of transition metal complex 2:
A transition metal complex 2 having Compound 5 as a ligand was prepared in the same manner as in Example 7, except that Compound 3 in Example 7 was changed to Compound 5 (5.68 mg, 0.015 mmol). .
NMR data of transition metal complex 2:
¹ H NMR (toluene-d ₈ , δ) 8.02 to 6.71 (m, 19H), 3.72 (sept, J = 5.99 Hz, 1H), 0.99 (d, J = 6.04 Hz, 6H), 0.35.
³¹ P NMR (toluene-d ₈ , δ) 22.20.
²⁹ Si NMR (CD ₂ Cl ₂ , δ) 0.31 (d, J = 3.01 Hz).

Example 9 Synthesis of transition metal-containing organic-inorganic composite material 1:
Into a 50 ml Schlenk flask, the organic-inorganic composite material 1 (200 mg) was placed, dried under reduced pressure at 80 ° C. for 3 hours, returned to room temperature, added with Pd (OAc) ₂ (2.20 mg), and added with THF solvent 4 under nitrogen atmosphere. 0.0 ml was added and stirred for 20 hours. Thereafter, the organic-inorganic composite material supporting palladium was collected by filtration. After washing with hexane, ethyl acetate, and dichloromethane, drying under reduced pressure was performed at 80 ° C. for 3 hours to obtain a transition metal-containing organic-inorganic composite material 1.
Solid state NMR (CP / MAS method) data of transition metal-containing organic-inorganic composite material 1:
¹³ C
NMR (δ) 136.5-129.3.
³¹ P
NMR (δ) 28.2 (Pd-P), -8.0.
²⁹ Si NMR (δ) -16.9 (Ph ₂ Si-O), -89.5 to -115.0 (SiO ₂ ).

Example 10 Synthesis of transition metal-containing organic-inorganic composite material 2:
The same operation as in Example 9 except that the organic-inorganic composite material 1 in Example 9 was changed to the organic-inorganic composite material 2 (100 mg), and Pd (OAc) ₂ was changed to (PhCN) ₂ PdCl ₂ (3.39 mg). Thus, a transition metal-containing organic-inorganic composite material 2 was obtained.
Solid state NMR (CP / MAS method) data of transition metal-containing organic-inorganic composite material 2:
¹³ C
NMR (δ) 136.5-129.3.
³¹ P
NMR (δ) 28.2 (Pd-P), -8.0.
²⁹ Si NMR (δ) -16.9 (Ph ₂ Si-O), -89.5 to -115.0 (SiO ₂ ).

Example 11 Synthesis of transition metal-containing organic-inorganic composite material 3:
The same operation as in Example 9 except that the organic-inorganic composite material 1 in Example 9 was changed to the organic-inorganic composite material 3 (634 mg), and Pd (OAc) ₂ was changed to (PhCN) ₂ PdCl ₂ (13.9 mg). Thus, a transition metal-containing organic-inorganic composite material 3 was obtained.
Solid state NMR (CP / MAS method) data of transition metal-containing organic-inorganic composite material 3:
¹³ C
NMR (δ) 135.2-129.7.
³¹ P
NMR (δ) 28.0 (Pd-P), -7.5.
²⁹ Si NMR (δ) 6.3 (Me ₂ Si-O), -89.5 to -115.0 (SiO ₂ ).

Example 12 Suzuki coupling reaction with homogeneous catalyst 1:
Potassium carbonate (1.66 g, 12 mmol) and phenylboronic acid (768 mg, 6.3 mmol) were placed in a 100 ml Schlenk flask. Under a nitrogen atmosphere, 5.0 ml of toluene, pt-butyltoluene 1 as an internal standard for gas chromatographic analysis 1.0 ml, a toluene solution (1.0 ml) of transition metal complex 1 (1.2 μmol) and p-bromoanisole (1.12 g, 6.0 mmol) were sequentially added. The mixture was heated and stirred at 100 ° C. for reaction. The yield of 4-methoxybiphenyl as a coupling product was calculated by gas chromatographic analysis (GC14-B, manufactured by Shimadzu Corporation). The results are shown in Table 1.

Example 13 Suzuki coupling reaction with homogeneous catalyst 2:
A Suzuki coupling reaction was performed in the same manner as in Example 12 except that the transition metal complex 1 in Example 12 was changed to the transition metal complex 2 (1.2 μmol). The results are shown in Table 1.

Example 14 Suzuki coupling reaction with immobilized catalyst 1:
A transition metal-containing organic-inorganic composite material 1 (1.2 μmol of palladium), potassium carbonate (1.66 g, 12 mmol), phenylboronic acid (768 mg, 6.3 mmol) was placed in a 100 ml Schlenk flask, and toluene was added under a nitrogen atmosphere. 5.0 ml of pt-butyltoluene 1.0 ml and p-bromoanisole (1.12 g, 6.0 mmol) were sequentially added as an internal standard for gas chromatographic analysis. The mixture was heated and stirred at 100 ° C. for reaction. The yield of 4-methoxybiphenyl as a coupling product was calculated by gas chromatographic analysis (GC14-B, manufactured by Shimadzu Corporation). The results are shown in Table 2.

Example 15. Suzuki coupling reaction with immobilized catalyst 2:
The Suzuki coupling reaction was carried out in the same manner as in Example 14 except that the transition metal-containing organic-inorganic composite material 1 in Example 14 was changed to the transition metal-containing organic-inorganic composite material 2 (palladium amount: 1.2 μmol). It was. The results are shown in Table 2.

Example 16 Suzuki coupling reaction with immobilized catalyst 3:
The Suzuki coupling reaction was carried out in the same manner as in Example 14 except that the transition metal-containing organic-inorganic composite material 1 in Example 14 was changed to the transition metal-containing organic-inorganic composite material 3 (palladium amount 1.2 μmol). It was. The results are shown in Table 2.

Comparative Example 1
Into a 50 ml two-necked eggplant type flask, the above compound 6 (5.68 mg, 0.015 mmol) and (PhCN) ₂ PdCl ₂ (5.75 mg, 0.015 mmol) were placed, and 5.0 ml of toluene was added under a nitrogen atmosphere. The mixture was stirred at room temperature for 4 hours to prepare transition metal complex 3 having compound 6 as a ligand. Then, Suzuki coupling reaction was performed by the same operation as Example 12 except having changed the transition metal complex 1 in Example 12 into the transition metal complex 3. The results are shown in Table 1.

Comparative Example 2
Into a 50 ml two-necked eggplant type flask, put the above compound 7 (4.75 mg, 0.015 mmol) and (PhCN) ₂ PdCl ₂ (5.75 mg, 0.015 mmol), and add 5.0 ml of toluene under a nitrogen atmosphere. The mixture was stirred at room temperature for 4 hours to prepare transition metal complex 4 having compound 7 as a ligand. Then, Suzuki coupling reaction was performed by the same operation as Example 12 except having changed the transition metal complex 1 in Example 12 into the transition metal complex 4. The results are shown in Table 1.

Comparative Example 3
Triphenylphosphine (3.93 mg, 0.015 mmol) and (PhCN) ₂ PdCl ₂ (5.75 mg, 0.015 mmol) were placed in a 50 ml two-necked eggplant type flask, and 5.0 ml of toluene was added under a nitrogen atmosphere. The mixture was stirred at room temperature for 4 hours to prepare transition metal complex 5 having triphenylphosphine as a ligand. Then, Suzuki coupling reaction was performed by the same operation as Example 12 except having changed the transition metal complex 1 in Example 12 into the transition metal complex 5. The results are shown in Table 1.

Comparative Example 4
Into a 50 ml Schlenk flask, the above organic-inorganic composite material 4 (200 mg) having an organic group of 0.147 mmol / g immobilized on FSM-22 was placed, dried at 80 ° C. under reduced pressure for 3 hours, and then returned to room temperature. (PhCN) ₂ PdCl ₂ (4.10 mg, 0.0105 mmol) was added, and 4.0 ml of a THF solvent was added under a nitrogen atmosphere, followed by stirring for 20 hours. Thereafter, the organic-inorganic composite material supporting palladium was collected by filtration. After washing with hexane, ethyl acetate, and dichloromethane, drying under reduced pressure at 80 ° C. for 3 hours was performed to obtain a transition metal-containing organic-inorganic composite material 4. The Suzuki coupling reaction was carried out in the same manner as in Example 14 except that the transition metal-containing organic-inorganic composite material 1 in Example 14 was changed to the transition metal-containing organic-inorganic composite material 4 (palladium amount 1.2 μmol). It was. The results are shown in Table 2.

Comparative Example 5
Into a 50 ml Schlenk flask, the above-mentioned organic-inorganic composite material 5 (200 mg) having organic group 0.313 mmol / g immobilized on FSM-22 was placed, dried at 80 ° C. under reduced pressure for 3 hours, and then returned to room temperature. (PhCN) ₂ PdCl ₂ (8.72 mg, 0.0224 mmol) was added, and 4.0 ml of a THF solvent was added under a nitrogen atmosphere, followed by stirring for 20 hours. Thereafter, the organic-inorganic composite material supporting palladium was collected by filtration. After washing with hexane, ethyl acetate, and dichloromethane, drying under reduced pressure at 80 ° C. for 3 hours was performed to obtain a transition metal-containing organic-inorganic composite material 5. The Suzuki coupling reaction was carried out in the same manner as in Example 14, except that the transition metal-containing organic-inorganic composite material 1 in Example 14 was changed to the transition metal-containing organic-inorganic composite material 5 (1.2 μmol as the amount of palladium). It was. The results are shown in Table 2.

  The phosphine compound of the present invention is useful as a ligand of a metal complex used as a homogeneous catalyst and as a silane coupling agent serving as a precursor of an organic-inorganic composite material. In addition, the phosphine-containing organic-inorganic composite material and transition metal-containing organic-inorganic composite material of the present invention include an immobilization catalyst and various adsorbents, column fillers, surfactants and other industrial materials, drug delivery systems, biocompatible materials, and inspections. It is useful for uses such as medical materials such as chips, sensors, electronic materials such as organic EL and liquid crystals.

Claims (9)

A phosphine compound represented by the following general formula (1).
(In formula (1), R ¹ and R ² are each independently an aryl group or an alkyl group, Y is an aryl group or an alkyl group, and X is a halogen atom or an alkoxy group when Y is an aryl group. , Any group selected from the group of hydroxyl group and amino group, and when Y is an alkyl group, any group selected from the group of alkoxy group, hydroxyl group and amino group, and n is an integer of 1 to 3. )   A phosphine-containing organic-inorganic composite material obtained by reacting the phosphine compound according to claim 1 and an inorganic oxide to covalently bond a silicon atom of the phosphine compound to an oxygen atom on the surface of the inorganic oxide.   A transition metal complex containing the phosphine compound according to claim 1 as a ligand.   A transition metal-containing organic-inorganic composite material obtained by supporting a transition metal on the phosphine-containing organic-inorganic composite material according to claim 2.   A transition metal-containing organic-inorganic composite material obtained by reacting the transition metal complex according to claim 3 and an inorganic oxide to covalently bond a silicon atom of the phosphine compound to an oxygen atom on the surface of the inorganic oxide.   A homogeneous catalyst comprising the transition metal complex according to claim 3.   An immobilized catalyst comprising the transition metal-containing organic-inorganic composite material according to claim 4 or 5.   The homogeneous catalyst according to claim 6, which is a homogeneous catalyst for cross-coupling reaction.   The immobilized catalyst according to claim 7, which is an immobilized catalyst for cross-coupling reaction.