JP2011126803A - Multiply substituted phosphine compound and catalyst containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for producing arylamines or biaryls in high selectivity. <P>SOLUTION: The metal complex includes a compound represented by formula (1) (R<SP>1</SP>and R<SP>2</SP>are each independently alkyl; X is hydrogen or a phosphorus-containing substituent; l, m and n are each independently an integer of 0-2) as a ligand. <P>COPYRIGHT: (C)2011,JPO&INPIT

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. In addition, the palladium-phosphine complex according to the present invention is useful as a catalyst for 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), 6,6′-position 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及びＲ^２は各々独立して、炭素数１〜１０のアルキル基、又は炭素数６〜１２のアリール基を示し、Ｘは水素、炭素数１〜３のアルキル基、又はＰＲ^１Ｒ^２基を示し、ｌ、ｍ、ｎはそれぞれ独立して０〜２の整数を示す。）
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。

(Wherein R ¹ and R ² each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, X is hydrogen, an alkyl group having 1 to 3 carbon atoms, or Represents a PR ¹ R ² group, and l, m and n each independently represent an integer of 0 to 2.)
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 carbon number. 1 to 3 alkyl groups or PR ¹ R ² groups, l, m and n each independently represent an integer of 0 to 2. Here, although not particularly limited as alkyl group having 1 to 10 carbon atoms of ^{R 1} and ^{R 2,} for example, a cyclohexyl group, a methyl group, an ethyl group, n- propyl group, an 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 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), and ease of synthesis From this point, 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、及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 the arylamination reaction.

  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 [4- (dicyclohexylphosphino) phenyl] -4 "-phenyltriphenylamine

４，４’−ジブロモ−４”−フェニルトリフェニルアミン １．００ｇ（２．０９ｍｍｏｌ）、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン ０．５３ｇ（４．５９ｍｍｏｌ）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） ２．６４ｍＬ（４．３９ｍｍｏｌ）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 １．０７ｇ（４．５９ｍｍｏｌ）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 (2.09 mmol) of 4,4′-dibromo-4 ″ -phenyltriphenylamine and 0.53 g (4.59 mmol) of N, N, N ′, N′-tetramethylethylenediamine were added to 100 mL of THF, Under nitrogen atmosphere, the mixture was cooled to −80 ° C. 2.64 mL (4.39 mmol) of n-butyllithium (1.6M hexane solution) was added dropwise thereto, and the mixture was stirred at −80 ° C. for 1 hour. A solution prepared by dissolving 1.07 g (4.59 mmol) of dicyclohexylchlorophosphine in 5 mL of THF was added dropwise to the solution, and the mixture was 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 0.18 g (0.25 mmol, yield 12%) of the title compound.

¹ H-NMR (200 MHz, CDCl ₃ ): 0.90-1.87 (44H), 7.05-7.63 (17H)
FD-MS: 714 (M ^{+ 1} )
Example 2
Synthesis of tris [4- [2- (dicyclohexylphosphino) phenyl] phenyl] amine
Intermediate synthesis 1
Synthesis of tris [4- (4,4,5,5-tetramethyl- [1,3,2] dioxaborolan-2-yl) phenyl] amine

トリス（４−ブロモフェニル）アミン ４．００ｇ（８．３３ｍｍｏｌ）、１，１’−ビス（ジフェニルフォスフィノ）−フェロセンジクロロパラジウム（ＩＩ）ジクロロメタン錯体 ０．３４ｇ（０．４２ｍｍｏｌ）、酢酸カリウム ７．４８ｇ（７６．２ｍｍｏｌ）、ビス（ピナコレート）ジボロン ６．７６ｇ（２６．６ｍｍｏｌ）のＤＭＦ ８０ｍＬ懸濁液を８０℃で１５時間攪拌した。水 ９０ｍＬを加え、トルエン １００ｍＬで３回抽出した。抽出したトルエン層を合わせ、さらに水 ５０ｍＬで１回、飽和塩化ナトリウム水溶液 ５０ｍＬで２回洗浄後、無水硫酸マグネシウムで乾燥し、有機溶媒を留去した。得られた残渣をエタノールで洗浄し、表題化合物１．６８ｇ（２．７０ｍｍｏｌ、収率３２％）を得た。

6. Tris (4-bromophenyl) amine 4.00 g (8.33 mmol), 1,1′-bis (diphenylphosphino) -ferrocenedichloropalladium (II) dichloromethane complex 0.34 g (0.42 mmol), potassium acetate A suspension of 48 g (76.2 mmol) and 6.76 g (26.6 mmol) of bis (pinacolato) diboron in 80 mL of DMF was stirred at 80 ° C. for 15 hours. 90 mL of water was added and extracted three times with 100 mL of toluene. The extracted toluene layers were combined, further washed once with 50 mL of water and twice with 50 mL of a saturated aqueous sodium chloride solution, and then dried over anhydrous magnesium sulfate, and the organic solvent was distilled off. The obtained residue was washed with ethanol to obtain 1.68 g (2.70 mmol, yield 32%) of the title compound.

¹ H-NMR (200 MHz, CDCl ₃ ): 1.34 (d, 36H), 7.07 (d, 6H), 7.68 (s, 6H)
Intermediate synthesis 2
Synthesis of tris [4- (2-bromophenyl) phenyl] amine

トリス［４−（４，４，５，５−テトラメチル−［１，３，２］ジオキサボロラン−２−イル）フェニル］アミン １．６７ｇ（２．６８ｍｍｏｌ）、２−ブロモヨードベンゼン ３．３１ｇ（１１．８ｍｍｏｌ）、２１％炭酸水素ナトリウム水溶液 ２０．０ｇ（３９．６ｍｍｏｌ）、テトラキストリフェニルフォスフィンパラジウム ０．２４ｇ（０．２２ｍｍｏｌ）、１，２−ジメトキシエタン ４５ｍＬを窒素雰囲気下、還流下で５日間攪拌した。水 ６０ｍＬを加え、トルエン ６０ｍＬ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。得られた残渣にヘキサンとトルエンの混合溶媒を１０ｍＬ加え、析出物として淡黄色粉末の表題化合物１．３７ｇ（２．０２ｍｍｏｌ、収率７５％）を得た。

Tris [4- (4,4,5,5-tetramethyl- [1,3,2] dioxaborolan-2-yl) phenyl] amine 1.67 g (2.68 mmol), 2-bromoiodobenzene 3.31 g ( 11.8 mmol), 21% aqueous sodium hydrogen carbonate solution 20.0 g (39.6 mmol), tetrakistriphenylphosphine palladium 0.24 g (0.22 mmol), 1,2-dimethoxyethane 45 mL under a nitrogen atmosphere under reflux Stir for 5 days. 60 mL of water was added, extracted with 60 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. 10 mL of a mixed solvent of hexane and toluene was added to the resulting residue to obtain 1.37 g (2.02 mmol, yield 75%) of the title compound as a pale yellow powder as a precipitate.

Synthesis of tris [4- [2- (dicyclohexylphosphino) phenyl] phenyl] amine

トリス［４−（２−ブロモフェニル）フェニル］アミン １．３０ｇ（１．８４ｍｍｏｌ）をＴＨＦ １３ｍＬ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） ４．４ｍＬ（７．０ｍｍｏｌ）を滴下し、−８０℃で２．５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 １．６７ｇ（７．２ｍｍｏｌ）のＴＨＦ溶液 １４ｍＬ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１９時間攪拌した。

Tris [4- (2-bromophenyl) phenyl] amine 1.30 g (1.84 mmol) was added to 13 mL of THF, and cooled to −80 ° C. in a nitrogen atmosphere. To this, 4.4 mL (7.0 mmol) of n-butyllithium (1.6 M-hexane solution) was added dropwise and stirred at −80 ° C. for 2.5 hours. Next, 14 mL of a THF solution of 1.67 g (7.2 mmol) of dicyclohexylchlorophosphine was added dropwise to the reaction solution, and the mixture was stirred at −80 ° C. for 1 hour, then warmed to room temperature, and further stirred for 19 hours.

After adding and stirring 10 mL of saturated ammonium chloride aqueous solution, only the organic layer was filtered. The obtained pale yellow powder was washed twice with 10 mL of methanol and once with 5 mL of hexane and dried in vacuo to give 1.34 g (1.26 mmol, 69% yield) of the title compound.
FD-MS: 1062 (M ^{+ 1} )
Elemental analysis (calculated values): C = 81.4, H = 8.5, N = 1.3
Elemental analysis (actual measurement): C = 81.4, H = 8.6, N = 1.2
Example 3
Application of 4,4′-bis [4- (dicyclohexylphosphino) phenyl] -4 ″ -phenyltriphenylamine to an arylamination reaction catalyst In a 300 mL four-necked flask substituted with nitrogen gas, bromobenzene 6 .24 g (40 mmol), 7.32 g (40 mmol) of 3-methyldiphenylamine, 4.99 g (52 mmol) of sodium tertiary butoxide, 9.0 mg (0.040 mmol) of palladium acetate, 4,4′-bis [4- (dicyclohexyl) Phosphino) phenyl] -4 ″ -phenyltriphenylamine 28.6 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 30% (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［４−（ジシクロヘキシルホスフィノ）フェニル］−４”−フェニルトリフェニルアミンの鈴木−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［４−（ジシクロヘキシルホスフィノ）フェニル］−４”−フェニルトリフェニルアミン ２１．４ｍｇ（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８５％（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４０ｍＬ加え、析出する成分を濾過し、回収率４３％で１２ｍｇの触媒を回収した。

Example 5
4. Application of 4,4′-bis [4- (dicyclohexylphosphino) phenyl] -4 ″ -phenyltriphenylamine to the Suzuki-Miyaura coupling reaction catalyst Palladium acetate in a 100 mL flask purged with nitrogen gas. 7 mg (0.030 mmol), 4,4′-bis [4- (dicyclohexylphosphino) phenyl] -4 ″ -phenyltriphenylamine 21.4 mg (0.030 mmol), phenylboronic acid (PhB (OH) ₂ ) 0.40 g (3.3 mmol), p-chlorotoluene 0.38 g (3.0 mmol), tetrahydrofuran 11.0 mL, potassium carbonate 1.24 g (9.0 mmol), and water 9.0 mL were added to the solvent reflux temperature. And stirred 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 85% (p-chlorotoluene standard). It was generated with. 40 mL of n-hexane was added to the organic layer, the precipitated component was filtered, and 12 mg of catalyst was recovered at a recovery rate of 43%.

Claims (6)

The following general formula (1)

(Wherein R ¹ and R ² each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, X is hydrogen, an alkyl group having 1 to 3 carbon atoms, or Represents a PR ¹ R ² group, and l, m and n each independently represent an integer of 0 to 2.)
The phosphine compound represented by these. In general formula (1), R ¹ and R ² are all cyclohexyl, tert-butyl, 1-adamantyl, phenyl, o-tolyl, 2,6-dimethylphenyl, and 2,4,6. The phosphine compound according to claim 1, wherein the phosphine compound is a substituent selected from trimethylphenyl groups. In general formula (1), R < ¹ > and R < ² > are both cyclohexyl groups, The phosphine compound of Claim 1 characterized by the above-mentioned. A metal complex having the phosphine compound according to claim 1 as a ligand. The metal complex according to claim 4, wherein the metal is palladium. A catalyst for synthesizing an aromatic amine derivative or biaryl derivative comprising the metal complex according to claim 4 or 5.