JP5577687B2 - Polysubstituted phosphine compound and catalyst containing the phosphine compound - Google Patents

Description

  The present invention relates to a phosphine compound and a palladium-phosphine complex obtained by allowing a palladium compound to act on the phosphine compound. The palladium-phosphine complex according to the present invention is useful as a catalyst for the synthesis of arylamines or biaryls used in electronic materials and intermediates thereof.

  Currently, many transition metal complexes such as palladium are used as catalysts for organic synthesis reactions (eg, Shinjiro, Palladium Reagents and Catalysts, 1995). It is well known that a ligand plays an important role in addition to the transition metal species as the central metal as a factor for expressing the performance or activity of these catalysts. For example, many phosphine compounds have been developed as ligands and play such an important role.

  As ligands reported so far in carbon-carbon (or heteroelement) bonding reactions, tri (tert-butyl) phosphine (see, for example, Patent Document 1 and Non-Patent Document 1) and dialkylphosphine substituted. Ferrocene derivatives (for example, see Patent Document 2), 2-dicyclohexylphosphino-1,1′-biphenyl derivatives (for example, see Patent Document 3), 1,3-bis (2,6-diisopropylphenyl) imidazolinium salt (For example, see Non-Patent Document 2) carbene ligands are known.

  On the other hand, there are 2,2′-bis (diphenylphosphino) -1,1′-binaphthyl (commonly known as BINAP) and 6,6′-positions in reactions other than carbon-carbon (or heteroelement) bonding reactions. A bidentate ligand having a 1,1′-biphenyl structure bonded through a linking group has been reported as a ligand for asymmetric synthesis reaction (particularly asymmetric hydrogenation) (for example, Patent Documents 4 and 5). reference).

JP 10-139742 A JP 2000-247990 A US Published Patent No. 2002/156295 Japanese Patent No. 4167899 JP 2000-154156 A

Journal of American Chemical Society, 122 (17), 4020-4028 (2000) Angew. Chem. Int. Ed. , 46, 2768-2813 (2007)

  Although transition metal complexes having tri (tert-butyl) phosphine as a ligand are known to be extremely highly active, tri (tert-butyl) phosphine itself has a feature that it is easily oxidized with oxygen. It has a drawback that is difficult to handle. On the other hand, although other ligands are relatively stable to oxygen, they have a defect that they are less active than a transition metal catalyst having tri (tert-butyl) phosphine as a ligand. In particular, for the synthesis of triarylamines and biaryls, development of oxygen-stable and highly active catalysts has been desired.

  In addition, in the fields of electronic materials, intermediates thereof, pharmaceuticals, and the like, there is a strong demand for a production method that suppresses the incorporation of harmful metals into products, and a solution for removing metal catalysts has been desired.

  In order to achieve the above object, the present inventors have intensively studied, and as a result, phosphine compounds represented by the following general formula (1):

［式中、Ｒ^１およびＲ^２は各々独立して、炭素数１〜１０のアルキル基、または炭素数６〜１２のアリール基を示し、Ｘは水素または下記一般式（２）

[Wherein, R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and X represents hydrogen or the following general formula (2)

（式中、Ｙは水素、炭素数１〜３のアルキル基、またはＰＲ^１Ｒ^２基を示す。）
で表される置換フェニル基を示す。］
を配位子として有する金属錯体が、芳香族アミン誘導体やビアリール誘導体の合成に有用な触媒となることを見出した。

(In the formula, Y represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or a PR ¹ R ² group.)
The substituted phenyl group represented by these is shown. ]
It has been found that a metal complex having a ligand as a useful catalyst for the synthesis of aromatic amine derivatives and biaryl derivatives.

  Hereinafter, the present invention will be described in more detail.

R ¹ and R ² in the phosphine compound represented by the general formula (1) each independently represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and X represents hydrogen or the general formula The substituted phenyl group represented by (2) is shown. Here, the alkyl group having 1 to 10 carbon atoms of R ¹ and R ² is not particularly limited. For example, cyclohexyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec -Butyl group, tert-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, adamantyl group and the like can be mentioned. Examples of the aryl group having 6 to 12 carbon atoms of R ¹ and R ² include a phenyl group, an o-tolyl group, a 2,6-dimethylphenyl group, and a 2,4,6-trimethylphenyl group. Among them, bulky and electron-donating substituents such as a tert-butyl group, a cyclohexyl group, and an adamantyl group are preferable from the viewpoint of high catalytic activity, and a cyclohexyl group is more preferable from the viewpoint of oxidation resistance.

  X is hydrogen or the following general formula (2)

（式中、Ｙは水素、炭素数１〜３のアルキル基、またはＰＲ^１Ｒ^２基を示す。）
で表される置換フェニル基を示す。また、上記式中Ｙは、水素、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ＰＲ^１Ｒ^２基（Ｒ^１およびＲ^２は、前記した置換基を例示することができる）を示し、合成の容易さの点から、水素またはＰＲ^１Ｒ^２基が好ましい。

(In the formula, Y represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or a PR ¹ R ² group.)
The substituted phenyl group represented by these is shown. In the above formula, Y represents hydrogen, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a PR ¹ R ² group (R ¹ and R ² can exemplify the above-described substituents). From the viewpoint of ease of synthesis, hydrogen or a PR ¹ R ² group is preferable.

  Although it does not specifically limit, the following phosphine compound is mentioned as an example of a particularly preferable phosphine compound (A-1 to A-20).

（式中、Ｃｙはシクロヘキシル基を示す。）
一般式（１）で表されるホスフィン化合物は、配位子として遷移金属化合物と組み合わせることにより各種反応の触媒となる。特に限定されるものではないが、例えば、ハロゲン化アリールとアミンとの反応によるアリールアミンの合成、ハロゲン化アリールとアリールボロン酸試薬等とのカップリングによるビアリールの合成、およびハロゲン化アリールとオレフィン類との反応による置換スチレンの合成等の反応を挙げることができる。これらの反応において、ハロゲン化アリールの代わりにアリールスルホネートを用いることもできる。

(In the formula, Cy represents a cyclohexyl group.)
The phosphine compound represented by the general formula (1) becomes a catalyst for various reactions by combining with a transition metal compound as a ligand. Although not particularly limited, for example, synthesis of arylamines by reaction of aryl halides with amines, synthesis of biaryls by coupling of aryl halides with arylboronic acid reagents, etc., and aryl halides and olefins Reactions such as synthesis of substituted styrene by reaction with In these reactions, an aryl sulfonate can be used in place of the aryl halide.

  The conditions for these catalytic reactions are not particularly limited. For example, the amount of the transition metal compound used is in the range of 0.001 to 10 mol% with respect to the substrate such as aryl halide, and the ligand. The use amount of is in the range of 0.8 to 5.0 mol% in terms of a molar ratio with respect to the transition metal compound. The solvent used for the reaction is preferably inert to the substrate, for example, an aromatic solvent such as toluene and xylene, an ether solvent such as tetrahydrofuran, dimethoxyethane, 1,4-dioxane, and cyclopentylmethyl ether, Nonpolar solvents such as dimethyl sulfoxide, dimethylformamide and the like can be mentioned. The reaction temperature is 20 to 160 ° C., the reaction time is 0.5 to 72 hours, and the reaction is usually carried out under an inert gas atmosphere such as nitrogen or argon.

  Regarding the metal complex of the present invention, the ligand can form a complex with various transition metal compounds such as a palladium compound and a nickel compound. For example, although not particularly limited, hexachloropalladium (IV ) Sodium tetrahydrate, tetravalent palladium compounds such as potassium hexachloropalladium (IV), palladium (II) chloride, palladium (II) bromide, palladium (II) acetate, palladium (II) acetylacetonate, Dichlorobis (benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorotetraamminepalladium (II), dichloro (cycloocta-1,5-diene) palladium (II) ), Divalent palladium compounds such as radium (II) trifluoroacetate, tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform complex, tetrakis (triphenylphosphine) palladium (0 ) And other zero-valent palladium compounds.

  Since the metal complex of the present invention is insoluble in water, methanol, ethanol, n-hexane and the like at room temperature, it can be easily recovered by mixing the reaction liquid and these solvents and filtering. It is presumed that the polysubstituted phosphine ligand forms an insoluble polymer complex via the metal. By this operation, the metal concentration in the reaction solution can be reduced.

  According to the present invention, arylamines can be produced with high selectivity. In particular, it is suitable for the production of electronic component materials that require high purity in products. A phosphine compound that is easy to handle and a palladium-phosphine complex obtained by allowing a palladium compound to act on the phosphine compound are useful as catalyst components for producing arylamines and biaryls.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these Examples. The following equipment was used for product analysis.

Nuclear magnetic resonance analyzer: Gemini200 manufactured by Varian
Mass spectrometer: M-80B manufactured by Hitachi, Ltd. (measurement method: FD-MS analysis)
Gas chromatograph: Using a GC-17A manufactured by Shimadzu Corporation equipped with a capillary column (DB-5 manufactured by J & WS Science), the temperature was raised from 100 ° C. to 300 ° C. at 10 ° C./min and detected by FID.

  Liquid chromatography: Tosoh column (ODS-80Ts, 4.6 mm ID × 250 mm), methanol / tetrahydrofuran = 9/1 (v / v) as elution solvent, flow rate 1.0 mL / min, column temperature 40 ° C. The solution was passed through and detected with a UV-visible detector (UV-8020) manufactured by Tosoh Corporation.

Element analyzer: Perkin Elmer fully automatic element analyzer 2400II: Oxygen flask combustion-IC measurement method: Tosoh ion chromatograph IC-2001
Example 1
Synthesis of 4,4 "-bis (dicyclohexylphosphino) -m-terphenyl
Intermediate synthesis 1
Synthesis of 4,4 "-dibromo-m-terphenyl

ｍ−ジヨードベンゼン １．００ｇ（３．０３ｍｍｏｌ）、４−ブロモフェニルボロン酸 １．４６ｇ（７．２７ｍｍｏｌ）、トルエン ３０ｍＬ、２．０Ｍ炭酸ナトリウム水溶液 １５ｍＬ、テトラキストリフェニルフォスフィンパラジウム ０．１４ｇ（０．１３ｍｍｏｌ）を窒素雰囲気下、還流下で１６時間攪拌した。水５０ ｍＬを加え、トルエン １００ｍＬで抽出し、飽和塩化ナトリウム水溶液で洗浄した。無水硫酸マグネシウムで乾燥し、有機溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィーにより分離精製し、さらにクーゲルロールにて蒸留して表題化合物０．６７ｇ（２．４２ｍｍｏｌ、収率８０％）を得た。

m-diiodobenzene 1.00 g (3.03 mmol), 4-bromophenylboronic acid 1.46 g (7.27 mmol), toluene 30 mL, 2.0 M aqueous sodium carbonate solution 15 mL, tetrakistriphenylphosphine palladium 0.14 g ( 0.13 mmol) was stirred at reflux under a nitrogen atmosphere for 16 hours. 50 mL of water was added, extracted with 100 mL of toluene, and washed with a saturated aqueous sodium chloride solution. It dried with anhydrous magnesium sulfate and the organic solvent was distilled off. The obtained residue was separated and purified by silica gel column chromatography, and further distilled by Kugelrohr to obtain 0.67 g (2.42 mmol, yield 80%) of the title compound.

¹ H-NMR (CDCl ₃ ): 7.46-7.69 (12H)
¹³ C-NMR (CDCl ₃ ): 121.66, 125.47, 126.08, 128.64, 129.32, 131.77, 139.66, 140.56
Synthesis of 4,4 "-bis (dicyclohexylphosphino) -m-terphenyl

４，４”−ジブロモ−ｍ−ターフェニル ０．８６ｇ（２．２２ｍｍｏｌ）、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン ０．５４ｇ（４．６４ｍｍｏｌ）をＴＨＦ １００ｍＬに加え、窒素雰囲気下、−８０℃に冷却した。これにｎ−ブチルリチウム（１．６Ｍ−ヘキサン溶液） ２．９３ｍＬ（４．８７ｍｍｏｌ）を滴下し、−８０℃で１時間攪拌した。次いで、この反応液にジシクロヘキシルクロロホスフィン １．１９ｇ（５．１０ｍｍｏｌ）をＴＨＦ ５ｍＬに溶解させた溶液を滴下し、−８０℃で１時間攪拌した後、室温まで昇温させ、さらに１６時間攪拌した。

0.84 g (2.22 mmol) of 4,4 ″ -dibromo-m-terphenyl and 0.54 g (4.64 mmol) of N, N, N ′, N′-tetramethylethylenediamine were added to 100 mL of THF, and a nitrogen atmosphere was added. The solution was cooled to −80 ° C. 2.93 mL (4.87 mmol) of n-butyllithium (1.6M hexane solution) was added dropwise thereto and stirred for 1 hour at −80 ° C. Then, dicyclohexyl was added to the reaction solution. A solution prepared by dissolving 1.19 g (5.10 mmol) of chlorophosphine in 5 mL of THF was added dropwise, stirred at −80 ° C. for 1 hour, then warmed to room temperature, and further stirred for 16 hours.

100 mL of saturated aqueous ammonium chloride solution was added, and extracted with 100 mL of CH ₂ Cl ₂ . The extract was washed with 50 mL of a saturated aqueous sodium chloride solution and then dried over anhydrous magnesium sulfate. The organic solvent was distilled off under reduced pressure, and the resulting residue was separated and purified by silica gel column chromatography to obtain 0.39 g (0.60 mmol, yield 27%) of the title compound.

¹ H-NMR (CDCl ₃ ): 1.23-2.09 (44H), 7.57-7.88 (12H)
FD-MS: 623 (M ^{+ 1} )
Example 2
Synthesis of 1,3,5-tris (4-dicyclohexylphosphinophenyl) benzene

１，３，５−トリス（４−ブロモフェニル）ベンゼン １．００ｇ（１．７９ｍｍｏｌ）、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン ０．６６ｇ（５．６４ｍｍｏｌ）をＴＨＦ １００ｍＬに加え、窒素雰囲気下、−８０℃に冷却した。これにｎ−ブチルリチウム（１．６Ｍ−ヘキサン溶液） ３．４０ｍＬ（５．６４ｍｍｏｌ）を滴下し、−８０℃で１時間攪拌した。次いで、この反応液にジシクロヘキシルクロロホスフィン １．３７ｇ（５．９１ｍｍｏｌ）をＴＨＦ ５ｍＬに溶解させた溶液を滴下し、−８０℃で１時間攪拌した後、室温まで昇温させ、さらに１６時間攪拌した。

1.00 g (1.79 mmol) of 1,3,5-tris (4-bromophenyl) benzene and 0.66 g (5.64 mmol) of N, N, N ′, N′-tetramethylethylenediamine were added to 100 mL of THF, It cooled to -80 degreeC under nitrogen atmosphere. To this was added dropwise 3.40 mL (5.64 mmol) of n-butyllithium (1.6 M hexane solution), and the mixture was stirred at −80 ° C. for 1 hour. Next, a solution of 1.37 g (5.91 mmol) of dicyclohexylchlorophosphine dissolved in 5 mL of THF was added dropwise to the reaction solution, stirred at −80 ° C. for 1 hour, then warmed to room temperature, and further stirred for 16 hours. .

100 mL of saturated aqueous ammonium chloride solution was added, and extracted with 100 mL of CH ₂ Cl ₂ . The extract was washed with 50 mL of a saturated aqueous sodium chloride solution and then dried over anhydrous magnesium sulfate. The organic solvent was distilled off under reduced pressure, and the resulting residue was separated and purified by silica gel column chromatography to obtain 0.10 g (0.11 mmol, yield 6%) of the title compound.

¹ H-NMR (CDCl ₃ ): 0.85-2.02 (66H), 7.53-7.83 (15H)
FD-MS: 895 (M ^{+ 1} )
Example 3
Application of 4,4 ″ -bis (dicyclohexylphosphino) -m-terphenyl to an arylamination reaction catalyst In a 300 mL four-necked flask purged with nitrogen gas, 6.24 g (40 mmol) of bromobenzene, 3- Methyldiphenylamine 7.32 g (40 mmol), sodium tertiary butoxide 4.99 g (52 mmol), palladium acetate 9.0 mg (0.040 mmol), 4,4 ″ -bis (dicyclohexylphosphino) -m-terphenyl 24.9 mg (0.040 mmol) and 90 mL of toluene were added, and the mixture was stirred at 100 ° C. for 3 hours. After completion of the reaction, 70 g of pure water was added, and the organic layer obtained by the liquid separation operation was further washed with a saturated aqueous sodium chloride solution. As a result of analyzing the 3-methyltriphenylamine in the obtained organic layer by gas chromatography quantitative analysis using n-eicosane as an internal standard substance, the yield of 3-methyltriphenylamine was 34% (3- (Based on methyldiphenylamine). The results are shown in Table 1.

Example 4, Comparative Example 1
The reaction was performed in accordance with Example 3 except that the phosphine compound shown in Table 1 was used as the ligand. The results are shown in Table 1.

実施例５
４，４”−ビス（ジシクロヘキシルホスフィノ）−ｍ−ターフェニルの鈴木−宮浦カップリング反応触媒への適用
窒素ガスで置換された１００ｍＬのフラスコに、酢酸パラジウム ６．７ｍｇ（０．０３０ｍｍｏｌ）、４，４”−ビス（ジシクロヘキシルホスフィノ）−ｍ−ターフェニル １８．７ｍｇ（０．０３０ｍｍｏｌ）、フェニルボロン酸（ＰｈＢ（ＯＨ）_２） ０．４０ｇ（３．３ｍｍｏｌ）、ｐ−クロロトルエン ０．３８ｇ（３．０ｍｍｏｌ）、テトラヒドロフラン １１．０ｍＬ、炭酸カリウム １．２４ｇ（９．０ｍｍｏｌ）、水 ９．０ｍＬを加えて、溶媒還流温度にて１２時間攪拌した。反応終了後、５％ＨＣｌ水溶液を加えて後処理し、分液操作にて得られた有機層をさらに飽和塩化ナトリウム水溶液で洗浄した。得られた有機層を、ｎ−ドデカンを内部標準物質とするガスクロマトグラフィー定量分析にて分析した結果、目的物である４−メチルビフェニルが、収率８１％（ｐ−クロロトルエン基準）の割合で生成していた。有機層にｎ−ヘキサンを６０ｍＬ加え、析出する成分を濾過し、回収率５５％で１４ｍｇの触媒を回収した。

Example 5
Application of 4,4 ″ -bis (dicyclohexylphosphino) -m-terphenyl to Suzuki-Miyaura coupling reaction catalyst In a 100 mL flask purged with nitrogen gas, 6.7 mg (0.030 mmol) of palladium acetate, 4 , 4 ″ -bis (dicyclohexylphosphino) -m-terphenyl 18.7 mg (0.030 mmol), phenylboronic acid (PhB (OH) ₂ ) 0.40 g (3.3 mmol), p-chlorotoluene 0.38 g (3.0 mmol), 11.0 mL of tetrahydrofuran, 1.24 g (9.0 mmol) of potassium carbonate, and 9.0 mL of water were added, and the mixture was stirred at a solvent reflux temperature for 12 hours. After completion of the reaction, 5% aqueous HCl solution was added for post-treatment, and the organic layer obtained by the liquid separation operation was further washed with saturated aqueous sodium chloride solution. As a result of analyzing the obtained organic layer by gas chromatography quantitative analysis using n-dodecane as an internal standard substance, the target product, 4-methylbiphenyl, had a yield of 81% (p-chlorotoluene standard). It was generated with. 60 mL of n-hexane was added to the organic layer, the precipitated component was filtered, and 14 mg of catalyst was recovered at a recovery rate of 55%.

Claims (4)

The following general formula (1)

[Wherein, R ¹ and R ² both represent a cyclohexyl group , X is hydrogen or the following general formula (2)

(In the formula, Y represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or a PR ¹ R ² group.)
The substituted phenyl group represented by these is shown. ]
The phosphine compound represented by these. A metal complex having the phosphine compound according to claim 1 as a ligand. The metal complex according to claim 2 , wherein the metal is palladium. A catalyst for synthesizing an aromatic amine derivative or biaryl derivative comprising the metal complex according to claim 2 or 3 .