JP2009023925A - Method for producing amide compound and catalyst used for the method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new catalyst for producing an amide compound through a hydration reaction of a nitrile compound under a mild condition in good efficiency, and to provide a method for efficiently producing the amide compound by using the catalyst. <P>SOLUTION: An amide compound can be synthesized by efficiently hydrating the nitrile compound under a mild condition, by using the catalytic action caused by combining an iridium complex with an organic phosphine having an electron-attracting organic group such as a pyridylphosphine derivative. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is a method for synthesizing an amide compound by hydrating a nitrile compound using a catalytic action of a combination of an iridium complex and an organic phosphine having an electron-withdrawing organic group such as a pyridylphosphine derivative, and the method used in the method. Relates to the catalyst.

  Catalytic synthesis methods of amide compounds by adding water to nitriles are known, and those using solid catalysts and biocatalysts are known. Although these catalysts exhibit a relatively high activity, development of catalysts with higher activity and higher selectivity is desired. Although a method using a complex catalyst is also known, a catalyst that has sufficient activity and can be easily prepared industrially is desired. The ruthenium complex reported by Murahashi et al. Has triphenylphosphine that can be easily obtained as a ligand, and therefore can be prepared relatively easily, but its activity is not high (Non-patent Document 1). The platinum complex of Parkins et al. Is known as a highly active catalyst, but the preparation of the ligand and the catalyst is complicated (Non-patent Document 2).

Further ruthenium - complex acetylacetonato ligand unit (Ru (acac) ₂₎ in diphenyl-2-pyridyl phosphine (= PPh ₂ py) (Chemical Formula 1) is coordinated (Formula 2), a nitrile hydration Reported that Oshiki et al. Have high catalytic activity (Non-patent Document 3). This complex activates the nitrile at the ruthenium center, and the nitrogen atom of the ligand pyridylphosphine functions as a bifunctional catalyst that assists the nucleophilic attack of water by hydrogen bonding, and thus exhibits high catalytic activity. A patent application has been filed for producing such an ruthenium complex and an amide using the same (Patent Document 1).

  However, the complexes described in Non-Patent Document 3 and Patent Document 1 cannot catalyze the hydration reaction unless the high-temperature conditions are around 180 ° C. The acetylacetonate ligand (acac), which is tightly bound to ruthenium, dissociates and vacancies are formed, and nitrile coordinates there. However, since this dissociation does not occur unless the temperature is high, a high temperature is required for the hydration reaction by this complex catalyst.

JP 2004-269522 A Murahashi S. -I. Et al. J. Org. Chem. 1992, 57, 2521 Ghaffar, T .; Parkins, A. M. J. Mol. Cat. A 2000, 160, 249 Oshiki, T. Et al. Organometallics 2005, 24, 6287

  Therefore, by developing a new catalyst that is completely different from the ruthenium complex having such drawbacks, there has been a demand for a means for efficiently generating a amide compound by catalyzing the hydration reaction of a nitrile compound at a low temperature. . Therefore, an object of the present invention is to provide a novel catalyst having such advantages and an efficient method for synthesizing an amide compound using the catalyst.

Therefore, in order to achieve the above object, a novel iridium catalyst is provided by the present invention. Therefore, the present invention provides the invention consisting of the following (1) to (46).
(1) A method of synthesizing an amide compound by hydrating a nitrile compound using a catalytic action of a combination of an iridium complex represented by X-Ir-L ₂ and an organic phosphine having an electron-withdrawing organic group, X is a group 15 element capable of coordinating with iridium, and a bidentate ligand in which a negatively charged oxygen atom is bonded to iridium, and L is neutral and the electron-withdrawing organic A method for synthesizing an amide compound, which is a ligand that can be substituted with an organic phosphine having a group, or an organic phosphine having an electron-withdrawing organic group.
(2) The method according to (1) above, wherein the organic phosphine having an electron-withdrawing organic group is a pyridylphosphine derivative.
(3) The method according to (1) or (2) above, wherein the Group 15 element is nitrogen.
(4) When L is neutral and can be substituted with an organic phosphine having an electron-withdrawing organic group, L is an electron-donating group of 14, 15, or 16. The method according to any one of (1) to (3) above, wherein the method is a neutral ligand.
(5) When L is neutral and can be substituted with an organic phosphine having an electron-withdrawing organic group, the L is alkene, alkyne, nitrogen compound, phosphorus compound, ethers and thioethers. The method according to any one of (1) to (4) above, wherein the method is selected from the group consisting of:
(6) When L is a ligand that can be substituted with an organic phosphine having an electron-withdrawing organic group, L is ethylene, propylene, isoprene, butadiene, 2,3-dimethyl- 1,3-butadiene, cyclohexene, cyclooctene, acetylene, propyne, phenylacetylene, trimethylsilylpropyne, phenylpropyne, diphenylacetylene, ammonia, trimethylamine, triethylamine, pyridine, 4,4-dimethylaminopyridine, imidazole, acetonitrile, benzonitrile , Trimethylphosphine, triphenylphosphine, tricyclohexylphosphine, diphenylpentafluorophenylphosphine, diphenyl-2-pyridylphosphine, 2-phosphanyl-4-pyridyl (dimethyl) amine, tris (3-sulfonatofe Le) phosphine sodium salt, diethyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, dimethyl sulfide, is selected from the group consisting of tetrahydrothiophene and thiophene, or L ₂ which the L is to form a ring with each other cyclooctadiene Alternatively, the method according to any one of (1) to (5) above, wherein the method is norbornadiene.
(7) The method according to any one of (1) to (6) above, wherein L ₂ in which L forms a ring with each other is cyclooctadiene.
(8) The iridium complex is 2-N-phenyliminophenoxyiridium cyclooctadiene, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine or 2-diphenylphosphanyl-4-pyridyl ( The method according to any one of (1) to (7) above, which is (dimethyl) amine.
(9) The iridium complex is 2-N-phenylimino-3-tbutylphenoxyiridium cyclooctadiene, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine or 2-diphenylphosphanyl. The method according to any one of (1) to (7) above, which is -4-pyridyl (dimethyl) amine.

(I)
(上記一般式(I)中、Yは炭素又は窒素上に陰電荷を持つ多座配位子であり、上記Zは陰電荷を持つ単座配位子であり、上記Lは中性であり且つ電子吸引性の有機基をもつ有機ホスフィンと置換しうる配位子、又は電子吸引性の有機基をもつ有機ホスフィンである。)
（１１）前記電子吸引性の有機基をもつ有機ホスフィンがピリジルホスフィン誘導体であることを特徴とする上記（１０）記載の方法。
（１２）前記Yがシクロペンタジエニル誘導体、ピロリル誘導体、及びインドリル誘導体からなる群から選択されたものであることを特徴とする上記（１０）又は（１１）に記載の方法。
（１３）前記Yがシクロペンタジエニル、メチルシクロペンタジエニル、ペンタメチルシクロペンタジエニル、インデニル、及びフルオレニルからなる群から選択されたものであることを特徴とする上記（１０）から（１２）のいずれか１に記載の方法。
（１４）上記Yがピロリル、インドリルからなる群から選択されたものであることを特徴とする上記（１０）から（１３）のいずれか１に記載の方法。
（１５）前記Zが、ハロゲン又は下記一般式(II)で表される陰電荷をもつ配位子、又はヒドロキシ基若しくは水素であることを特徴とする上記（１０）から（１４）のいずれか１に記載の方法。

(II)
(上記一般式(II)中、Rは水素、飽和または不飽和の炭化水素基、飽和または不飽和の環状炭化水素基、芳香族化合物残基、アルコキシ基、アリールオキシ基、及び有機金属化合物残基からなる群から選択された基を表す。)
（１６）前記Rは飽和炭化水素基または芳香族化合物残基である上記（１５）に記載の方法。
（１７）前記Rはメチル基である上記（１５）又は（１６）に記載の方法。
（１８）前記Lが中性であり且つ該電子吸引性の有機基をもつ有機ホスフィンと置換しうる配位子である場合、前記Lは電子供与性の14族、15族、又は16族の中性の配位子であることを特徴とする上記（１０）から（１７）のいずれか１に記載の方法。
（１９）前記Lが中性であり且つ該電子吸引性の有機基をもつ有機ホスフィンと置換しうる配位子である場合、前記Lはアルケン、アルキン、窒素化合物、リン化合物、エーテル類及びチオエーテル類からなる群から選択されたもの、又はそれらが相互に環を形成したものであることを特徴とする上記（１０）から（１８）のいずれか１に記載の方法。
（２０）前記Lが中性であり且つ該電子吸引性の有機基をもつ有機ホスフィンと置換しうる配位子である場合、前記Lはエチレン、プロピレン、イソプレン、ブタジエン、2,3-ジメチル-1,3-ブタジエン、シクロヘキセン、シクロオクテン、アセチレン、プロピン、フェニルアセチレン、トリメチルシリルプロピン、フェニルプロピン、ジフェニルアセチレン、アンモニア、トリメチルアミン、トリエチルアミン、ピリジン、4,4-ジメチルアミノピリジン、イミダゾール、アセトニトリル、ベンゾニトリル、トリメチルホスフィン、トリフェニルホスフィン、トリシクロヘキシルホスフィン、ジフェニルペンタフルオロフェニルホスフィン、ジフェニル-2-ピリジルホスフィン、２ーホスファニルー４ーピリジル（ジメチル）アミン、トリス(3-スルホナトフェニル)ホスフィンナトリウム塩、ジエチルエーテル、テトラヒドロフラン、テトラヒドロピラン、1,4-ジオキサン、ジメチルスルフィド、テトラヒドロチオフェン及びチオフェンからなる群から選択され、又は上記Lが相互に環を形成したL₂がシクロオクタジエン若しくはノルボルナジエンであることを特徴とする上記（１０）から（１９）のいずれか１に記載の方法。
（２１）前記Lが相互に環を形成したL₂がシクロオクタジエンであることを特徴とする上記（１０）から（２０）のいずれか１に記載の方法。
（２２）前記イリジウム錯体はジヒドロキソ(ペンタメチルシクロペンタジエニル)イリジウムであり、前記電子吸引性の有機基をもつ有機ホスフィンがジフェニル-2-ピリジルホスフィン又は２−ジフェニルホスファニル−４−ピリジル（ジメチル）アミンであることを特徴とする上記（１０）から（２０）のいずれか１に記載の方法。
（２３）前記イリジウム錯体はジアセタト(ペンタメチルシクロペンタジエニル)(ジフェニル-2-ピリジルホスフィン)イリジウムであり、前記電子吸引性の有機基をもつ有機ホスフィンがジフェニル-2-ピリジルホスフィンであることを特徴とする上記（１０）から（２０）のいずれか１に記載の方法。
（２４）前記イリジウム錯体はビストリフルオロスルホナト(ペンタメチルシクロペンタジエニル)(ジフェニル-2-ピリジルホスフィン)イリジウムであり、前記電子吸引性の有機基をもつ有機ホスフィンがジフェニル-2-ピリジルホスフィンであることを特徴とする上記（１０）から（２１）のいずれか１に記載の方法。 (10) A method of synthesizing an amide compound by hydrating a nitrile compound using a catalytic action of a combination of an iridium complex represented by the following general formula (I) and an organic phosphine having an electron-withdrawing organic group.

(I)
(In the above general formula (I), Y is a polydentate ligand having a negative charge on carbon or nitrogen, Z is a monodentate ligand having a negative charge, L is neutral and (It is a ligand that can be substituted with an organic phosphine having an electron-withdrawing organic group, or an organic phosphine with an electron-withdrawing organic group.)
(11) The method according to (10) above, wherein the organic phosphine having an electron-withdrawing organic group is a pyridylphosphine derivative.
(12) The method according to (10) or (11) above, wherein Y is selected from the group consisting of a cyclopentadienyl derivative, a pyrrolyl derivative, and an indolyl derivative.
(13) The above (10) to (12), wherein Y is selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, pentamethylcyclopentadienyl, indenyl, and fluorenyl. ) Any one of the methods.
(14) The method according to any one of (10) to (13) above, wherein Y is selected from the group consisting of pyrrolyl and indolyl.
(15) Any one of (10) to (14) above, wherein Z is a halogen, a negatively charged ligand represented by the following general formula (II), a hydroxy group or hydrogen The method according to 1.

(II)
(In the general formula (II), R represents hydrogen, a saturated or unsaturated hydrocarbon group, a saturated or unsaturated cyclic hydrocarbon group, an aromatic compound residue, an alkoxy group, an aryloxy group, and an organometallic compound residue. Represents a group selected from the group consisting of groups.)
(16) The method according to (15) above, wherein R is a saturated hydrocarbon group or an aromatic compound residue.
(17) The method according to (15) or (16) above, wherein R is a methyl group.
(18) When L is a ligand that can be substituted with an organic phosphine having a neutral and electron-withdrawing organic group, the L is an electron-donating group of 14, 15, or 16. The method according to any one of (10) to (17) above, wherein the method is a neutral ligand.
(19) When L is a ligand that can be substituted with an organic phosphine having a neutral and electron-withdrawing organic group, the L is an alkene, alkyne, nitrogen compound, phosphorus compound, ether, and thioether. The method according to any one of the above (10) to (18), wherein the method is selected from the group consisting of a group, or they form a ring with each other.
(20) When L is a ligand that can be substituted with an organic phosphine having an electron-withdrawing organic group, L is ethylene, propylene, isoprene, butadiene, 2,3-dimethyl- 1,3-butadiene, cyclohexene, cyclooctene, acetylene, propyne, phenylacetylene, trimethylsilylpropyne, phenylpropyne, diphenylacetylene, ammonia, trimethylamine, triethylamine, pyridine, 4,4-dimethylaminopyridine, imidazole, acetonitrile, benzonitrile , Trimethylphosphine, triphenylphosphine, tricyclohexylphosphine, diphenylpentafluorophenylphosphine, diphenyl-2-pyridylphosphine, 2-phosphanyl-4-pyridyl (dimethyl) amine, tris (3-sulfona Phenyl) phosphine sodium salt, diethyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, dimethyl sulfide, is selected from the group consisting of tetrahydrothiophene and thiophene, or L ₂ which the L is to form a ring with each other cyclooctadiene Alternatively, the method according to any one of (10) to (19) above, wherein the method is norbornadiene.
(21) The method according to any one of (10) to (20) above, wherein L ₂ in which L forms a ring with each other is cyclooctadiene.
(22) The iridium complex is dihydroxo (pentamethylcyclopentadienyl) iridium, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine or 2-diphenylphosphanyl-4-pyridyl (dimethyl). The method according to any one of (10) to (20) above, which is an amine.
(23) The iridium complex is diacetato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine. The method according to any one of (10) to (20) above,
(24) The iridium complex is bistrifluorosulfonate (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine. The method according to any one of (10) to (21) above, wherein

(III)
(上記一般式(III)中、Rは水素、飽和または不飽和の炭化水素基、飽和または不飽和の環状炭化水素基、芳香族化合物残基、アルコキシ基、アリールオキシ基、及び有機金属化合物残基からなる群から選択された基を表す。)
（３１）前記Rは飽和炭化水素基または芳香族化合物残基である上記（３０）に記載の方法。
（３２）前記Rはメチル基である上記（３０）又は（３１）に記載の方法。
（３３）前記Zが塩素である上記（３０）に記載の方法。 (25) Hydrating a nitrile compound using a catalytic action of a combination of an iridium complex represented by Y-Ir-Z ₂ or (Y-Ir-Z) ₂ and an organic phosphine having an electron-withdrawing organic group. A method of synthesizing a compound, wherein Y is a polydentate ligand having a negative charge on carbon or nitrogen, and Z is a monodentate ligand having a negative charge. How to synthesize.
(26) The method according to (25) above, wherein the organic phosphine having an electron-withdrawing organic group is a pyridylphosphine derivative.
(27) The method according to (25) or (26) above, wherein Y is a cyclopentadienyl derivative or a pyrrolyl derivative.
(28) The above (25) to (27), wherein Y is selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, pentamethylcyclopentadienyl, indenyl, and fluorenyl. ) Any one of the methods.
(29) The method according to any one of (25) to (28) above, wherein Y is selected from the group consisting of pyrrolyl and indolyl.
(30) Any of the above (25) to (29), wherein Z is a halogen, a negatively charged ligand represented by the following general formula (III), a hydroxy group or hydrogen The method according to 1.

(III)
(In the above general formula (III), R represents hydrogen, a saturated or unsaturated hydrocarbon group, a saturated or unsaturated cyclic hydrocarbon group, an aromatic compound residue, an alkoxy group, an aryloxy group, and an organometallic compound residue. Represents a group selected from the group consisting of groups.)
(31) The method according to (30) above, wherein R is a saturated hydrocarbon group or an aromatic compound residue.
(32) The method according to (30) or (31) above, wherein R is a methyl group.
(33) The method according to (30) above, wherein Z is chlorine.

(34) The iridium complex is di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl) iridium], and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine, 2- It is selected from the group consisting of diphenylphosphanyl-4-pyridyl (dimethyl) amine, triphenylphosphine, tris (3-sulfonatophenyl) phosphine sodium salt), and diphenylpentafluorophenylphosphine The method according to any one of (25) to (30) above.
(35) The iridium complex is diacetato (pentamethylcyclopentadienyl) iridium, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine, 2-diphenylphosphanyl-4-pyridyl (dimethyl). The method according to any one of (25) to (30) above, wherein the method is selected from the group consisting of amine, triphenylphosphine, and tris (3-sulfonatophenyl) phosphine sodium salt.

(36) An iridium complex which is 2-N-phenyliminophenoxyiridium cyclooctadiene.
(37) An iridium complex which is 2-N-phenylimino-3-tbutylphenoxyiridium cyclooctadiene.
(38) An iridium complex which is diacetato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium.
(39) An iridium complex which is bistrifluorosulfonate (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium.

(IV)
ここで上記一般式(IV)中、Yは炭素又は窒素上に陰電荷を持つ多座配位子であり、上記Zは陰電荷を持つ単座配位子であり、上記Lは中性であり且つ該電子吸引性の有機基をもつ有機ホスフィンと置換しうる配位子、又は電子吸引性の有機基をもつ有機ホスフィンであることを特徴とする触媒。
（４５）前記電子吸引性の有機基をもつ有機ホスフィンがピリジルホスフィン誘導体であることを特徴とする上記（４４）に記載の触媒。
（４６）前記イリジウム錯体はジヒドロキソ(ペンタメチルシクロペンタジエニル)イリジウムであり、前記電子吸引性の有機基をもつ有機ホスフィンがジフェニル-2-ピリジルホスフィン又は２−ジフェニルホスファニル−４−ピリジル（ジメチル）アミンであることを特徴とする上記（４４）に記載の触媒。
（４７）前記イリジウム錯体はジアセタト(ペンタメチルシクロペンタジエニル)(ジフェニル-2-ピリジルホスフィン)イリジウムであり、前記電子吸引性の有機基をもつ有機ホスフィンがジフェニル-2-ピリジルホスフィンであることを特徴とする上記（４４）に記載の触媒。
（４８）前記イリジウム錯体はビストリフルオロスルホナト(ペンタメチルシクロペンタジエニル)(ジフェニル-2-ピリジルホスフィン)イリジウムであり、前記電子吸引性の有機基をもつ有機ホスフィンがジフェニル-2-ピリジルホスフィンであることを特徴とする上記（４４）に記載の触媒。
（４９）Y-Ir-Z₂又は(Y-Ir-Z)₂で示されるイリジウム錯体と電子吸引性の有機基をもつ有機ホスフィンを組み合わせた触媒であって、ここで上記Yは炭素又は窒素上に陰電荷を持つ多座配位子であり、上記Zは陰電荷を持つ単座配位子であることを特徴とする触媒。
（５０）前記電子吸引性の有機基をもつ有機ホスフィンがピリジルホスフィン誘導体であることを特徴とする上記（４９）に記載の触媒。
（５１）前記イリジウム錯体はジ-μ-クロロ-ビス［クロロ(ペンタメチルシクロペンタジエニル)イリジウム］であり、前記電子吸引性の有機基をもつ有機ホスフィンがジフェニル-2-ピリジルホスフィン、２−ジフェニルホスファニル−４−ピリジル（ジメチル）アミン、トリフェニルホスフィン、トリス(3-スルホナトフェニル)ホスフィンナトリウム塩、およびジフェニルペンタフルオロフェニルホスフィンからなる群から選択されたものであることを特徴とする上記（４９）に記載の触媒。
（５２）前記イリジウム錯体はジアセタト(ペンタメチルシクロペンタジエニル)イリジウムであり、前記電子吸引性の有機基をもつ有機ホスフィンがジフェニル-2-ピリジルホスフィン、２−ジフェニルホスファニル−４−ピリジル（ジメチル）アミン、トリフェニルホスフィン、トリス(3-スルホナトフェニル)ホスフィンナトリウム塩からなる群から選択されたものであることを特徴とする上記（４９）に記載の触媒。 (40) A catalyst comprising a combination of an iridium complex represented by X-Ir-L ₂ and an organic phosphine having an electron-withdrawing organic group, wherein X is a group 15 element capable of coordinating with iridium, and A bidentate ligand in which an oxygen atom having a negative charge is bonded to iridium, and the L is neutral and can be substituted with an organic phosphine having the electron-withdrawing organic group, or an electron A catalyst characterized by being an organic phosphine having an attractive organic group.
(41) The catalyst according to (40) above, wherein the organic phosphine having an electron-withdrawing organic group is a pyridylphosphine derivative.
(42) The iridium complex is 2-N-phenyliminophenoxyiridium cyclooctadiene, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine or 2-diphenylphosphanyl-4-pyridyl ( 41. The catalyst as described in 40 above, which is dimethyl) amine.
(43) The iridium complex is 2-N-phenylimino-3-tbutylphenoxyiridium cyclooctadiene, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine or 2-diphenylphosphanyl. 41. The catalyst as described in 40 above, which is -4-pyridyl (dimethyl) amine.
(44) A catalyst comprising a combination of an iridium complex represented by the following general formula (IV) and an organic phosphine having an electron-withdrawing organic group:

(IV)
In the general formula (IV), Y is a polydentate ligand having a negative charge on carbon or nitrogen, Z is a monodentate ligand having a negative charge, and L is neutral. And a catalyst capable of substituting with an organic phosphine having an electron-withdrawing organic group, or an organic phosphine with an electron-withdrawing organic group.
(45) The catalyst as described in (44) above, wherein the organic phosphine having an electron-withdrawing organic group is a pyridylphosphine derivative.
(46) The iridium complex is dihydroxo (pentamethylcyclopentadienyl) iridium, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine or 2-diphenylphosphanyl-4-pyridyl (dimethyl). The catalyst according to (44) above, which is an amine.
(47) The iridium complex is diacetato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine. The catalyst according to (44) above, which is characterized by
(48) The iridium complex is bistrifluorosulfonato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine. The catalyst according to (44), which is characterized in that it exists.
(49) A catalyst comprising a combination of an iridium complex represented by Y-Ir-Z ₂ or (Y-Ir-Z) ₂ and an organic phosphine having an electron-withdrawing organic group, wherein Y is carbon or nitrogen A catalyst, which is a multidentate ligand having a negative charge on the top, and Z is a monodentate ligand having a negative charge.
(50) The catalyst according to (49) above, wherein the organic phosphine having an electron-withdrawing organic group is a pyridylphosphine derivative.
(51) The iridium complex is di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl) iridium], and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine, 2- The above, which is selected from the group consisting of diphenylphosphanyl-4-pyridyl (dimethyl) amine, triphenylphosphine, tris (3-sulfonatophenyl) phosphine sodium salt, and diphenylpentafluorophenylphosphine The catalyst according to (49).
(52) The iridium complex is diacetato (pentamethylcyclopentadienyl) iridium, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine, 2-diphenylphosphanyl-4-pyridyl (dimethyl) ) The catalyst according to (49) above, which is selected from the group consisting of amine, triphenylphosphine, and tris (3-sulfonatophenyl) phosphine sodium salt.

  By using the novel iridium catalyst provided by the present invention, the nitrile compound can be hydrated to easily synthesize the amide compound under mild conditions.

  The present invention is described in further detail below. Based on the knowledge of Non-Patent Document 3 and Patent Document 1 that ruthenium complexes exhibit high catalytic activity for nitrile hydration, using ruthenium complexes having anionic ligands that are more easily dissociated, and The inventors have found that a bifunctional catalyst with easy coordination of nitriles can be obtained by combining pyridylphosphine derivatives.

  Based on the above findings, the present inventors conducted a nitrile hydration reaction at a lower temperature in order to promote the coordination unsaturated 16-electron having an acetylacetonato ligand (acac) and diphenyl-2-pyridylphosphine. Further study was conducted considering the use of the complex. That is, since the iridium complex has a planar 4-coordinate 16-electron structure, nitrile can be coordinated without dissociating acac and giving an empty coordination site. It is generally known that complexes with a 16-electron structure tend to receive 2 electrons and easily become 18 electrons. In the case of this iridium complex, it is required by a nitrile compound that is a raw material for amide compound synthesis. 2 electrons are donated.

An outline of the action mechanism of the catalyst when iridium complex and pyridylphosphine are used as the catalyst is as follows. That is, pyridylphosphine (PPh ₂ py) acts on the iridium complex, and a complex in which pyridylphosphine is bonded to the iridium complex is generated. Benzonitrile is coordinated to the pyridylphosphine-bound complex, and water is activated by forming a hydrogen bond with a nitrogen atom contained in PPh ₂ py. In this mechanism of action, water is activated by forming hydrogen bonds with nitrogen atoms. And hydration reaction advances when activated water attacks the benzonitrile coordinated to the complex.

The present inventors further investigated the combination of such an iridium complex and pyridylphosphine as a catalyst, and not only a complex having an acetylacetonato ligand (acac) but also a group 15 element capable of coordinating with iridium and a negative charge. It has been found that the nitrile can be hydrated under mild conditions by using a complex having a ligand in which an oxygen atom having a hydrogen atom is bonded to iridium, and the present invention has been completed. It is considered that the effect of the present invention can be achieved because the electronic state on iridium becomes appropriate for the hydration reaction of nitrile by coordinating an oxygen atom to iridium by a covalent bond. On the other hand, it is considered that the cyclooctadiene ligand undergoes an exchange reaction with pyridylphosphine (PPh ₂ py), which is an effective ligand, in the catalytic reaction system.

Therefore, in the present invention, a covalent bond is formed between iridium and a Group 16 element such as oxygen having negative charge, and in addition, a coordination bond is also formed between a Group 15 element such as nitrogen and iridium. An iridium complex which is a bidentate ligand is used as a catalyst. The iridium complex of the present invention also requires a ligand that easily undergoes an exchange reaction with a neutral ligand such as PPh ₂ py, such as cyclooctadiene.

Based on this technical idea, the present invention synthesizes an amide compound by hydrating a nitrile compound using a catalytic action of a combination of an iridium complex represented by X-Ir-L ₂ and an organic phosphine having an electron-withdrawing organic group. Provide a way to do it. In the present invention, the organic phosphine having an electron-withdrawing organic group is preferably a pyridylphosphine derivative, and the X is a group 15 element capable of coordinating with iridium, and an oxygen atom having a negative charge is bonded to iridium. L is a ligand which can be substituted for the organic phosphine having an electron-withdrawing organic group or an organic phosphine having an electron-withdrawing organic group. In the present specification, “organic phosphine having an electron-withdrawing organic group” is an organic compound having a structure represented by RR′R ″ P, and R, R ′, R ″ therein It means that at least one is an electron-withdrawing organic group. Examples of such electron-withdrawing organic groups include pyridine derivatives such as pyridine having a nitrogen atom. Therefore, L may be a ligand that can be substituted with an organic phosphine having an electron-withdrawing organic group, such as a neutral and pyridylphosphine derivative, or instead of iridium, an electron such as a pyridylphosphine derivative. An organic phosphine having an attractive organic group may be bonded. It is known that pyridine derivatives such as pyridine having a nitrogen atom exhibit an electron withdrawing property as an organic group. For example, Imamoto et al. Described in J. Am. Chem. Soc., 127, 11934 (2005) that the quinoxaline group, which is a pyridine derivative, is electron withdrawing.

  In the present specification, the term “ligand” has a meaning usually used in this technical field, and means a molecule or ion bonded to a central atom by a coordinate bond in a complex. . The atom directly involved in this coordination bond is the coordination atom, and a ligand having two or more coordination atoms is said to be a multidentate ligand. It is called a child or a tridentate ligand. Therefore, in the present specification, the “bidentate ligand” means a ligand having two coordination atoms.

  As described above, X is a group 15 element capable of coordinating with iridium and a bidentate ligand in which an oxygen atom is bonded to the iridium, and has a negative charge on the oxygen atom. The Group 15 element is preferably nitrogen, and more specifically, X is most preferably 2-N-phenyliminophenoxy group or 2-N-phenylimino-3-tbutylphenoxy group. preferable.

  The fact that L is a neutral ligand indicates that L binds to iridium with a weak coordination bond, that is, L can be substituted with another ligand, such as a pyridylphosphine derivative. Will have. There are many compounds for neutral ligands. Among them, the neutral ligands of the 14-group, 15-group, or 16-group exemplified above are easily dissociated from iridium. It is a compound suitable for substitution with a phosphine derivative.

  Accordingly, L is preferably an electron-donating group 14, 15 or 16 neutral ligand. The L is preferably selected from the group consisting of alkenes, alkynes, nitrogen compounds, phosphorus compounds, ethers and thioethers, or those in which they form a ring.

More specifically, L is preferably ethylene, propylene, isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, cyclohexene, cyclooctene, acetylene, propyne, phenylacetylene, trimethylsilylpropyne, phenylpropyne. , Diphenylacetylene, ammonia, trimethylamine, triethylamine, pyridine, 4,4-dimethylaminopyridine, imidazole, acetonitrile, benzonitrile, trimethylphosphine, triphenylphosphine, tricyclohexylphosphine, diphenylpentafluorophenylphosphine, diphenyl-2-pyridylphosphine 2-phosphanyl-4-pyridyl (dimethyl) amine, diethyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, dimethylsulfur De is selected from the group consisting of tetrahydrothiophene and thiophene. Alternatively, L ₂ in which L forms a ring with each other is preferably cyclooctadiene or norbornadiene. It is particularly preferable in the present invention that L ₂ in which L forms a ring with each other is cyclooctadiene.

  Specific examples of the iridium complex include 2-N-phenyliminophenoxyiridium cyclooctadiene, 2-N-phenylimino-3-tbutylphenoxyiridium cyclooctadiene, and 2-N-phenylimino-3-methyl. Phenoxyiridium cyclooctadiene, 2-N-iminophenoxyiridium cyclooctadiene 2-N-methyliminophenoxyiridium cyclooctadiene, 2-N-methylimino-3-tbutylphenoxyiridium cyclooctadiene, 2-Ntbutyliminophenoxy Mention may be made of iridium cyclooctadiene.

  Further, as pyridylphosphine derivatives which are organic phosphines having an electron-withdrawing organic group, specifically, 2-pyridylphosphine, 3-pyridylphosphine, 4-pyridylphosphine, diphenyl-2-pyridylphosphine, diphenyl-3-pyridylphosphine , Diphenyl-4-pyridylphosphine, 2-diphenylphosphanyl 4-pyridyl (dimethyl) amine, phenylmethyl-2-pyridylphosphine, ditolyl-2-pyridylphosphine, bis (methoxyphenyl) -2-pyridylphosphine, diphenoxy-2- Pyridylphosphine, phenoxyphenyl-2-pyridylphosphine, phenoxymethyl-2-pyridylphosphine, phenoxytertiarybutyl-2-pyridylphosphine, dimethoxy-2-pyridylphosphine, Methyl-2-pyridylphosphine, diisopropyl-2-pyridylphosphine, ditertiarybutyl-2-pyridylphosphine, didecyl-2-pyridylphosphine, dinonyl-2-pyridylphosphine, dioctyl-2-pyridylphosphine, diheptyl-2-pyridylphosphine , Dihexyl-2-pyridylphosphine, dipentyl-2-pyridylphosphine, dinormalbutyl-2-pyridylphosphine, diisobutyl-2-pyridylphosphine, dinormalpropyl-2-pyridylphosphine, diethyl-2-pyridylphosphine, octylmethyl- 2-pyridylphosphine, methylheptyl-2-pyridylphosphine, methylhexyl-2-pyridylphosphine, methylpentyl-2-pyridylphosphine, dimethylbutyl- -Pyridylphosphine, normal butylmethyl-2-pyridylphosphine, tertiary butylmethyl-2-pyridylphosphine, isopropylmethyl-2-pyridylphosphine, dicyclohexyl-2-pyridylphosphine, dibenzyl-2-pyridylphosphine, methylcyclohexyl-2- Pyridylphosphine, difuryl-2-pyridylphosphine, bispentafluorophenyl-2-pyridylphosphine, phenylpentafluorophenyl-2-pyridylphosphine, pentafluorophenylmethyl-2-pyridylphosphine, diphenylphosphino 6-methylpyridine, diphenylphosphite No 6-ethylpyridine, diphenylphosphino 6-tertiary butyl pyridine, 2-phosphanyl-4-pyridyl (dimethyl) a 2-dimethylphosphanyl-4-pyridyl (dimethyl) amine, 2-diethylphosphanyl-4-pyridyl (dimethyl) amine, 2-dipropylphosphanyl-4-pyridyl (dimethyl) amine, 2-diisopropylphosphanyl 4-Pyridyl (dimethyl) amine, 2-dibutylphosphanyl-4-pyridyl (dimethyl) amine, 2-diphenylphosphanyl-4-pyridyl (diethyl) amine, 2-diphenylphosphanyl-4-pyrrolidinopyridine, 2-phenylphosphani Examples thereof include organic phosphines such as ru 4-methoxypyridine, 2-phenylphosphanyl-4-ethoxypyridine, 2-phenylphosphanyl-4-phenoxypyridine, 2-phenylphosphanyl-4-thiomethylpyridine. Preferably, 2-pyridylphosphine, 3-pyridylphosphine, 4-pyridylphosphine, diphenyl-2-pyridylphosphine, diphenyl-3-pyridylphosphine, diphenyl-4-pyridylphosphine, 2-diphenylphosphanyl-4-pyridyl (dimethyl) Amine, ditolyl-2-pyridylphosphine, bis (methoxyphenyl) -2-pyridylphosphine, diphenoxy-2-pyridylphosphine, phenoxyphenyl-2-pyridylphosphine, phenoxymethyl-2-pyridylphosphine, phenoxytertiarybutyl-2- Pyridylphosphine, dimethoxy-2-pyridylphosphine, tris (3-sulfonatophenyl) phosphine sodium salt, 2-t-butylmethylphosphinoquinoxaline, 2-diphenylphosphinoquinoxa Phosphorus, 2-methylphenylphosphinoquinoxaline, 2-dimethylphosphinoquinoxaline, 2-diethylphosphinoquinoxaline, 2-dipropylphosphinoquinoxaline, 2-diisopropylphosphinoquinoxaline, 2-dibutylphosphinoquinoxaline, 2-di- t-Butylphosphinoquinoxaline, 2-dicyclohexylphosphinoquinoxaline, 2-t-butylmethylphosphinoquinoline, 2-diphenylphosphinoquinoline, 2-methylphenylphosphinoquinoline, 2-dimethylphosphinoquinoline, 2-diethylphos Phinoquinoline, 2-dipropylphosphinoquinoline, 2-diisopropylphosphinoquinoline, dibutylphosphinoquinoline, 2-di-t-butylphosphinoquinoline, 2-dicyclohexylphosphinoquinoline, 2-t-butylmethylphosphinopyrazine 2-diphenyl Sufinopyrazine, 2-methylphenylphosphinopyrazine, 2-dimethylphosphinopyrazine, 2-diethylphosphinopyrazine, 2-dipropylphosphinopyrazine, 2-diisopropylphosphinopyrazine, 2-dibutylphosphinopyrazine, 2- Examples thereof include di-t-butylphosphinopyrazine and 2-dicyclohexylphosphinopyrazine. Among them, diphenyl-2-pyridylphosphine and 2-diphenylphosphanyl-4-pyridyl (dimethyl) amine are particularly preferable.

  Specific examples of the iridium complex include 2-N-phenyliminophenoxyiridium cyclooctadiene (Chemical Formula 7: Complex 1 of Example) or 2-N-phenylimino-3-tbutylphenoxyiridium cyclooctadiene (Chemical Formula 8). : The complex 3) of the example is diphenyl-2-pyridylphosphine (chemical formula 9: ligand 1 of the example) or 2-diphenylphosphanyl-4-pyridyl (dimethyl) amine (chemical formula 10: The specific example which synthesize | combined the amide compound from the nitrile compound using the ligand 2) of an Example is shown in an Example. Although not within the scope of the iridium complex of the present invention, an example in which an amide compound was synthesized from a nitrile compound using di-μ-acetato-bis (cyclooctadiene) diiridium (Chemical Formula 11) and pyridylphosphine was also carried out. Shown in the example. 2-N-phenyliminophenoxyiridium cyclooctadiene and 2-N-phenylimino-3-tbutylphenoxyiridium cyclooctadiene are novel compounds.

(I) Furthermore, the present inventors have found that a complex in which a cyclopentadienyl derivative is coordinated to iridium is also effective and can be used to achieve the intended effect in the present invention. Therefore, the present invention also provides a method for synthesizing an amide compound by hydrating a nitrile compound using a catalytic action of a combination of an iridium complex represented by the following general formula (I) and an organic phosphine having an electron-withdrawing organic group. provide. Cyclopentadienyl derivatives are generally known to be coordinated to iridium in the η5 type, but in the catalytic reaction system, they change to the η3 type, etc., by opening a coordination site on iridium. It is considered that the coordination of nitrile is promoted. As a result, it is believed that the nitrile can be hydrated under mild conditions.

(I)

  In the general formula (I), Y is a polydentate ligand having a negative charge on carbon or nitrogen, the Z is a monodentate ligand having a negative charge, the L is neutral, and A ligand that can be substituted for the organic phosphine having an electron-withdrawing organic group, or a water-soluble organic phosphine. Therefore, L may be a ligand that can be substituted with an organic phosphine having an electron-withdrawing organic group, such as a neutral and pyridylphosphine derivative, or instead of iridium, an electron such as a pyridylphosphine derivative. An organic phosphine having an attractive organic group may be bonded. In the present specification, “monodentate ligand” means a ligand coordinated to iridium by one coordination atom.

  In the present invention, the organic phosphine having an electron-withdrawing organic group is preferably a pyridylphosphine derivative, and the Y is preferably selected from the group consisting of a cyclopentadienyl derivative, a pyrrolyl derivative, and an indolyl derivative. And more preferably selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, pentamethylcyclopentadienyl, indenyl, and fluorenyl.

(II) Z is preferably a halogen, a ligand having a negative charge represented by the following general formula (II), or hydrogen.

(II)

  In the general formula (II), R is hydrogen, a saturated or unsaturated hydrocarbon group, a saturated or unsaturated cyclic hydrocarbon group, an aromatic compound residue, an alkoxy group, an aryloxy group, and an organometallic compound residue. Represents a group selected from the group consisting of groups.

  In the general formula (II), R is preferably a saturated hydrocarbon group or an aromatic compound residue, and more preferably, R is a methyl group.

  The fact that L is a neutral ligand indicates that L binds to iridium with a weak coordination bond, that is, L can be substituted with another ligand, such as a pyridylphosphine derivative. Will have. There are many compounds for neutral ligands. Among them, the neutral ligands of the 14-group, 15-group, or 16-group exemplified above are easily dissociated from iridium. It is a compound suitable for substitution with a phosphine derivative.

  Accordingly, L is preferably an electron-donating group 14, 15 or 16 neutral ligand. The L is preferably selected from the group consisting of alkenes, alkynes, nitrogen compounds, phosphorus compounds, ethers and thioethers, or those in which they form a ring.

More specifically, L is preferably ethylene, propylene, isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, cyclohexene, cyclooctene, acetylene, propyne, phenylacetylene, trimethylsilylpropyne, phenylpropyne. , Diphenylacetylene, ammonia, trimethylamine, triethylamine, pyridine, 4,4-dimethylaminopyridine, imidazole, acetonitrile, benzonitrile, trimethylphosphine, triphenylphosphine, tricyclohexylphosphine, diphenylpentafluorophenylphosphine, diphenyl-2-pyridylphosphine 2-phosphanyl-4-pyridyl (dimethyl) amine, tris (3-sulfonatophenyl) phosphine sodium salt, diethyl ether, tetrahydrofuran Tetrahydropyran, 1,4-dioxane, dimethyl sulfide, is selected from the group consisting of tetrahydrothiophene and thiophene. Alternatively, L ₂ in which L forms a ring with each other is preferably cyclooctadiene or norbornadiene. It is particularly preferable in the present invention that L ₂ in which L forms a ring with each other is cyclooctadiene.

  Specific examples of the iridium complex include diacetato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium, diacetato (cyclopentadienyldiphenyl-2-pyridylphosphine) iridium, and diacetato (methylcyclopentadiene). Enyl) (diphenyl-2-pyridylphosphine) iridium, diacetato (dimethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium, diacetato (indenyl) (diphenyl-2-pyridylphosphine) iridium, diacetate (pyrrolyl) (diphenyl) -2-pyridylphosphine) iridium, diacetato (indolyl) (diphenyl-2-pyridylphosphine) iridium, diacetato (pentamethylcyclopentadienyl) (2-diphenylphosphanyl-4-pyridyl (dimethyl) amine) iridium Diacetato (cyclopentadienyl) (2-diphenylphosphanyl-4-pyridyl (dimethyl) amine) iridium, diacetato (methylcyclopentadienyl) (2-diphenylphosphanyl-4-pyridyl (dimethyl) amine) iridium, diacetato (Dimethylcyclopentadienyl) (2-diphenylphosphanyl-4-pyridyl (dimethyl) amine) iridium, diacetatoindenyl (2-diphenylphosphanyl-4-pyridyl (dimethyl) amine) iridium, diacetato (pyrrolyl) Mention may be made of (2-diphenylphosphanyl-4-pyridyl (dimethyl) amine) iridium, diacetato (indolyl) (2-diphenylphosphanyl-4-pyridyl (dimethyl) amine) iridium.

  Further, as pyridylphosphine derivatives which are organic phosphines having an electron-withdrawing organic group, specifically, 2-pyridylphosphine, 3-pyridylphosphine, 4-pyridylphosphine, diphenyl-2-pyridylphosphine, diphenyl-3-pyridylphosphine , Diphenyl-4-pyridylphosphine, 2-diphenylphosphanyl 4-pyridyl (dimethyl) amine, phenylmethyl-2-pyridylphosphine, ditolyl-2-pyridylphosphine, bis (methoxyphenyl) -2-pyridylphosphine, diphenoxy-2- Pyridylphosphine, phenoxyphenyl-2-pyridylphosphine, phenoxymethyl-2-pyridylphosphine, phenoxytertiarybutyl-2-pyridylphosphine, dimethoxy-2-pyridylphosphine, Methyl-2-pyridylphosphine, diisopropyl-2-pyridylphosphine, ditertiarybutyl-2-pyridylphosphine, didecyl-2-pyridylphosphine, dinonyl-2-pyridylphosphine, dioctyl-2-pyridylphosphine, diheptyl-2-pyridylphosphine , Dihexyl-2-pyridylphosphine, dipentyl-2-pyridylphosphine, dinormalbutyl-2-pyridylphosphine, diisobutyl-2-pyridylphosphine, dinormalpropyl-2-pyridylphosphine, diethyl-2-pyridylphosphine, octylmethyl- 2-pyridylphosphine, methylheptyl-2-pyridylphosphine, methylhexyl-2-pyridylphosphine, methylpentyl-2-pyridylphosphine, dimethylbutyl- -Pyridylphosphine, normal butylmethyl-2-pyridylphosphine, tertiary butylmethyl-2-pyridylphosphine, isopropylmethyl-2-pyridylphosphine, dicyclohexyl-2-pyridylphosphine, dibenzyl-2-pyridylphosphine, methylcyclohexyl-2- Pyridylphosphine, difuryl-2-pyridylphosphine, bispentafluorophenyl-2-pyridylphosphine, phenylpentafluorophenyl-2-pyridylphosphine, pentafluorophenylmethyl-2-pyridylphosphine, diphenylphosphino 6-methylpyridine, diphenylphosphite No 6-ethylpyridine, diphenylphosphino 6-tertiary butyl pyridine, 2-phosphanyl-4-pyridyl (dimethyl) a 2-dimethylphosphanyl-4-pyridyl (dimethyl) amine, 2-diethylphosphanyl-4-pyridyl (dimethyl) amine, 2-dipropylphosphanyl-4-pyridyl (dimethyl) amine, 2-diisopropylphosphanyl 4-Pyridyl (dimethyl) amine, 2-dibutylphosphanyl-4-pyridyl (dimethyl) amine, 2-diphenylphosphanyl-4-pyridyl (diethyl) amine, 2-diphenylphosphanyl-4-pyrrolidinopyridine, 2-phenylphosphani Roux 4-methoxypyridine, 2-phenylphosphanyl-4-ethoxypyridine, 2-phenylphosphanyl-4-phenoxypyridine, 2-phenylphosphanyl-4-thiomethylpyridine, 2-t-butylmethylphosphinoquinoxaline, 2-diphenylphosphino Quinoxaline, 2-methylphenylphosphinoquinoxaline, 2-dimethylphosphinoquinoxaline, 2-diethylphosphinoquinoxaline, 2-dipropylphosphinoquinoxaline, 2-diisopropylphosphinoquinoxaline, 2-dibutylphosphinoquinoxaline, 2-di- t-Butylphosphinoquinoxaline, 2-dicyclohexylphosphinoquinoxaline, 2-t-butylmethylphosphinoquinoline, 2-diphenylphosphinoquinoline, 2-methylphenylphosphinoquinoline, 2-dimethylphosphinoquinoline, 2-diethylphos Phinoquinoline, 2-dipropylphosphinoquinoline, 2-diisopropylphosphinoquinoline, dibutylphosphinoquinoline, 2-di-t-butylphosphinoquinoline, 2-dicyclohexylphosphinoquinoline, 2-t-butylmethylphosphinopyrazine , 2-di Enylphosphinopyrazine, 2-methylphenylphosphinopyrazine, 2-dimethylphosphinopyrazine, 2-diethylphosphinopyrazine, 2-dipropylphosphinopyrazine, 2-diisopropylphosphinopyrazine, 2-dibutylphosphinopyrazine, 2 And organic phosphines such as -di-t-butylphosphinopyrazine and 2-dicyclohexylphosphinopyrazine. Preferably, 2-pyridylphosphine, 3-pyridylphosphine, 4-pyridylphosphine, diphenyl-2-pyridylphosphine, diphenyl-3-pyridylphosphine, diphenyl-4-pyridylphosphine, 2-diphenylphosphanyl-4-pyridyl (dimethyl) Amine, ditolyl-2-pyridylphosphine, bis (methoxyphenyl) -2-pyridylphosphine, diphenoxy-2-pyridylphosphine, phenoxyphenyl-2-pyridylphosphine, phenoxymethyl-2-pyridylphosphine, phenoxytertiarybutyl-2- Examples include pyridylphosphine, dimethoxy-2-pyridylphosphine, and tris (3-sulfonatophenyl) phosphine sodium salt. Among them, diphenyl-2-pyridylphosphine and 2-diphenylphosphine Suphanyl-4-pyridyl (dimethyl) amine is particularly preferred.

  Specific examples of the iridium complex include diacetato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium (Chemical Formula 14: Complex 3 of Example) or bistrifluorosulfonate (pentamethylcyclopentadienyl). Nitrile compound using (diphenyl-2-pyridylphosphine) iridium (Chemical Formula 15: Complex 4 of Example) and diphenyl-2-pyridylphosphine (Chemical Formula 16: Ligand 1 of Example) as the pyridylphosphine derivative Specific examples of synthesizing amide compounds from the above are shown in the Examples. Diacetato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium and bistrifluorosulfonato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium are novel compounds.

Furthermore, the present invention hydrates a nitrile compound using a catalytic action of a combination of an iridium complex represented by Y-Ir-Z ₂ or (Y-Ir-Z) ₂ and an organic phosphine having an electron-withdrawing organic group. A method of synthesizing an amide compound is also provided, wherein Y is a polydentate ligand having a negative charge on carbon or nitrogen, and Z is a monodentate ligand having a negative charge.

  In the present invention, the organic phosphine having an electron-withdrawing organic group is preferably a pyridylphosphine derivative, and the Y is preferably a cyclopentadienyl derivative or a pyrrolyl derivative, and more preferably cyclopentadienyl. , Methylcyclopentadienyl, pentamethylcyclopentadienyl, indenyl, fluorenyl.

(III) Z is preferably a halogen, a ligand having a negative charge represented by the following general formula (III), or hydrogen.

(III)

  In the general formula (III), R represents hydrogen, a saturated or unsaturated hydrocarbon group, a saturated or unsaturated cyclic hydrocarbon group, an aromatic compound residue, an alkoxy group, an aryloxy group, and an organometallic compound residue. Represents a group selected from the group consisting of groups.

  In the general formula (III), R is preferably a saturated hydrocarbon group or an aromatic compound residue, and more preferably, R is a methyl group.

  Z is preferably chlorine.

  As the iridium complex, specifically, di-μ-chloro-bis [chloro (cyclopentadienyl) iridium], di-μ-bromo-bis [bromo (cyclopentadienyl) iridium], di-μ- Iodo-bis [iodo (cyclopentadienyl) iridium], di-μ-chloro-bis [chloro (methylcyclopentadienyl) iridium], di-μ-bromo-bis [bromo (methylcyclopentadienyl) iridium ], Di-μ-iodo-bis [iodo (methylcyclopentadienyl) iridium], di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl) iridium], di-μ-bromo-bis [bromo (Pentamethylcyclopentadienyl) iridium], di-μ-iodo-bis [iodo (pentamethylcyclopentadienyl) iridium], di-μ-chloro-bis [chloro (indenyl) iridium] Di-μ-bromo-bis [bromo (indenyl) iridium], di-μ-iodo-bis [iodo (indenyl) iridium], diacetato (cyclopentadienyl) iridium, diacetato (methylcyclopentadienyl) iridium, Diacetato (pentamethylcyclopentadienyl) iridium, diacetato (indenyl) iridium, dihydroxo (cyclopentadienyl) iridium, dihydroxo (methylcyclopentadienyl) iridium, dihydroxo (pentamethylcyclopentadienyl) iridium, dihydroxo (indenyl) ) Iridium, di-μ-hydrido-bis [cyclopentadienyl] iridium hydride, di-μ-hydrido-bis [methylcyclopentadienyl] iridium hydride, di-μ-hydrido-bis [chloropentamethylcyclopentadi] Enil] Irijiu Hydride, di -μ- hydride - bis [indenyl] can be mentioned iridium complex is an iridium hydride.

  Further, as pyridylphosphine derivatives which are organic phosphines having an electron-withdrawing organic group, specifically, 2-pyridylphosphine, 3-pyridylphosphine, 4-pyridylphosphine, diphenyl-2-pyridylphosphine, diphenyl-3-pyridylphosphine , Diphenyl-4-pyridylphosphine, 2-diphenylphosphanyl 4-pyridyl (dimethyl) amine, phenylmethyl-2-pyridylphosphine, ditolyl-2-pyridylphosphine, bis (methoxyphenyl) -2-pyridylphosphine, diphenoxy-2- Pyridylphosphine, phenoxyphenyl-2-pyridylphosphine, phenoxymethyl-2-pyridylphosphine, phenoxytertiarybutyl-2-pyridylphosphine, dimethoxy-2-pyridylphosphine, Methyl-2-pyridylphosphine, diisopropyl-2-pyridylphosphine, ditertiarybutyl-2-pyridylphosphine, didecyl-2-pyridylphosphine, dinonyl-2-pyridylphosphine, dioctyl-2-pyridylphosphine, diheptyl-2-pyridylphosphine , Dihexyl-2-pyridylphosphine, dipentyl-2-pyridylphosphine, dinormalbutyl-2-pyridylphosphine, diisobutyl-2-pyridylphosphine, dinormalpropyl-2-pyridylphosphine, diethyl-2-pyridylphosphine, octylmethyl- 2-pyridylphosphine, methylheptyl-2-pyridylphosphine, methylhexyl-2-pyridylphosphine, methylpentyl-2-pyridylphosphine, dimethylbutyl- -Pyridylphosphine, normal butylmethyl-2-pyridylphosphine, tertiary butylmethyl-2-pyridylphosphine, isopropylmethyl-2-pyridylphosphine, dicyclohexyl-2-pyridylphosphine, dibenzyl-2-pyridylphosphine, methylcyclohexyl-2- Pyridylphosphine, difuryl-2-pyridylphosphine, bispentafluorophenyl-2-pyridylphosphine, phenylpentafluorophenyl-2-pyridylphosphine, pentafluorophenylmethyl-2-pyridylphosphine, diphenylphosphino 6-methylpyridine, diphenylphosphite No 6-ethylpyridine, diphenylphosphino 6-tertiary butyl pyridine, 2-phosphanyl-4-pyridyl (dimethyl) a 2-dimethylphosphanyl-4-pyridyl (dimethyl) amine, 2-diethylphosphanyl-4-pyridyl (dimethyl) amine, 2-dipropylphosphanyl-4-pyridyl (dimethyl) amine, 2-diisopropylphosphanyl 4-Pyridyl (dimethyl) amine, 2-dibutylphosphanyl-4-pyridyl (dimethyl) amine, 2-diphenylphosphanyl-4-pyridyl (diethyl) amine, 2-diphenylphosphanyl-4-pyrrolidinopyridine, 2-phenylphosphani Roux 4-methoxypyridine, 2-phenylphosphanyl-4-ethoxypyridine, 2-phenylphosphanyl-4-phenoxypyridine, 2-phenylphosphanyl-4-thiomethylpyridine, 2-t-butylmethylphosphinoquinoxaline, 2-diphenylphosphino Quinoxaline, 2-methylphenylphosphinoquinoxaline, 2-dimethylphosphinoquinoxaline, 2-diethylphosphinoquinoxaline, 2-dipropylphosphinoquinoxaline, 2-diisopropylphosphinoquinoxaline, 2-dibutylphosphinoquinoxaline, 2-di- t-Butylphosphinoquinoxaline, 2-dicyclohexylphosphinoquinoxaline, 2-t-butylmethylphosphinoquinoline, 2-diphenylphosphinoquinoline, 2-methylphenylphosphinoquinoline, 2-dimethylphosphinoquinoline, 2-diethylphos Phinoquinoline, 2-dipropylphosphinoquinoline, 2-diisopropylphosphinoquinoline, dibutylphosphinoquinoline, 2-di-t-butylphosphinoquinoline, 2-dicyclohexylphosphinoquinoline, 2-t-butylmethylphosphinopyrazine , 2-di Enylphosphinopyrazine, 2-methylphenylphosphinopyrazine, 2-dimethylphosphinopyrazine, 2-diethylphosphinopyrazine, 2-dipropylphosphinopyrazine, 2-diisopropylphosphinopyrazine, 2-dibutylphosphinopyrazine, 2 And organic phosphines such as -di-t-butylphosphinopyrazine and 2-dicyclohexylphosphinopyrazine. Preferably, 2-pyridylphosphine, 3-pyridylphosphine, 4-pyridylphosphine, diphenyl-2-pyridylphosphine, diphenyl-3-pyridylphosphine, diphenyl-4-pyridylphosphine, 2-diphenylphosphanyl-4-pyridyl (dimethyl) Amine, ditolyl-2-pyridylphosphine, bis (methoxyphenyl) -2-pyridylphosphine, diphenoxy-2-pyridylphosphine, phenoxyphenyl-2-pyridylphosphine, phenoxymethyl-2-pyridylphosphine, phenoxytertiarybutyl-2- Examples include pyridylphosphine and dimethoxy-2-pyridylphosphine. Among them, diphenyl-2-pyridylphosphine and 2-diphenylphosphanyl-4-pyridyl (dimethyl) amine are particularly preferred. Arbitrariness.

  In addition, di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl) iridium] (Chemical Formula 18: Complex 5 of Example) or diacetato (pentamethylcyclopentadienyl) iridium (Chemical Formula 19: Example) As a pyridylphosphine derivative, diphenyl-2-pyridylphosphine (Chemical Formula 20: Ligand 1 of the Example), 2-diphenylphosphanyl-4-pyridyl (dimethyl) amine (Chemical Formula 21: of the Example) Ligand 2), triphenylphosphine (Chemical formula 22: Ligand 3 of Example), tris (3-sulfonatophenyl) phosphine sodium salt (Chemical formula 23: Ligand 4 of Example), diphenylpentafluorophenyl A amide compound synthesized from a nitrile compound using phosphine (Chemical Formula 24: Ligand 5 of the Example) Examples are shown in the examples.

  The method using the iridium complex catalyst of the present invention is preferable as a catalyst for hydrating a nitrile compound and synthesizing an amide compound. The nitrile compound used for such hydration reaction is not particularly limited, but specific examples include monovalent aliphatic nitriles such as acetonitrile, propionitrile, butyronitrile, malononitrile, succinonitrile, adiponitrile, etc. And unsaturated aliphatic nitriles such as polyhydric aliphatic nitriles, acrylonitrile and methacrylonitrile, and aromatic nitriles such as benzonitrile, 3-cyanopyridine and phthalonitrile. The catalyst of the present invention is particularly suitable for the production of benzamide from benzonitrile, as will be shown later in Examples.

  The amount of water used in the nitrile hydration reaction of the present invention is usually 0.1 or more, preferably 0.5 or more, more preferably 1 or more in terms of a water / nitrile group molar ratio to the nitrile group. In general, it is 1000 or less, preferably 100 or less, more preferably 10 or less. If the amount of water used is too small, the yield of the amide is greatly reduced. If it is too large, the contact of the raw material such as nitrile with the catalyst is suppressed, thereby reducing the yield of the amide.

  The ratio of the nitrile compound to the complex is usually 0.00001 mol or more, preferably 0.001 mol or more, and usually 1 mol or less, preferably 0.5 mol or less as a complex with respect to 1 mol of the nitrile. It may be present in the reaction system. When the amount of the complex is too small relative to the nitrile, the reaction rate is lowered and industrially disadvantageous, and when it is too large, the amount of the complex used is increased and the economy is lowered.

  The ratio of the complex to the ligand is usually such that the ligand is 0.01 mol or more, preferably 0.1 mol or more, and usually 10 mol or less, preferably 5 mol or less with respect to 1 mol of the complex. In the reaction system. If the amount of ligand is too small relative to the complex, the production concentration of catalytically active species will decrease, leading to a decrease in reaction rate, which will be industrially disadvantageous. If it is too large, nitrile coordination to the complex will be difficult and catalytic activity will decrease. To do.

  Examples of the solvent used for the hydration reaction of the nitrile compound of the present invention include water; ethers such as dimethoxyethane, diethyl ether, anisole, tetrahydrofuran, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dioxane; Alcohols such as ethanol, n-butanol, benzyl alcohol, ethylene glycol and diethylene glycol; phenols such as phenol; carboxylic acids such as formic acid, acetic acid, propionic acid and toluic acid; methyl acetate, butyl acetate, benzyl benzoate, etc. Esters; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and tetralin; aliphatic hydrocarbons such as n-hexane, n-octane, and cyclohexane; Halogenated hydrocarbons such as rhomethane, trichloroethane and chlorobenzene; nitro compounds such as nitromethane and nitrobenzene; carboxylic acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; hexamethylphosphoric triamide and the like Other amide compounds; urea such as N, N-dimethylimidazolidinone; sulfones such as dimethyl sulfone; sulfoxides such as dimethyl sulfoxide; lactones such as gamma butyrolactone and caprolactone; carbonates such as dimethyl carbonate and ethylene carbonate And polyethers such as triglyme and tetraglyme. Further, nitrile compounds themselves such as acrylonitrile, acetonitrile, benzonitrile, 3-cyanopyridine, etc., which are raw materials, can also be used as a solvent.

  The reaction temperature is usually 0 ° C. or higher, preferably 10 ° C. or higher, more preferably 20 ° C. or higher, and is usually 350 ° C. or lower, preferably 250 ° C. or lower, more preferably 220 ° C. or lower. If the reaction temperature is too low, the reaction rate decreases, which is industrially disadvantageous. If it is too high, the reaction activity decreases due to decomposition of the catalyst component.

  The complex concentration may be an industrially desired level, but is usually 0.0001 mol / L or more, preferably 0.001 mol / L or more as a metal atom such as iridium with respect to the reaction solution, Usually, it may be present in the reaction system so as to be 100 mol / L or less, preferably 10 mol / L or less. If the complex concentration is too low, the reaction rate decreases and industrially advantageous productivity cannot be obtained, and if it is too high, the catalyst cost increases and the practical value is lost. The reaction usually proceeds as a homogeneous catalytic reaction.

  The reaction pressure is arbitrary as long as the reaction system can be kept in a liquid phase, but a reaction vessel does not need a pressure vessel because the reaction proceeds at a temperature below the boiling point of water. When carried out in a closed system, the atmosphere is preferably an inert gas such as nitrogen, argon, helium or carbon dioxide. The reaction can be carried out either batchwise or continuously. From the reaction product liquid, the product amide compound can be recovered by methods such as distillation and crystallization. Further, since the catalyst is dissolved in the residual liquid after the product is recovered, it can be directly or indirectly circulated and used again for the reaction.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

  Di-μ-acetato-bis (cyclooctadiene) diiridium (Ir (OAc) (cod)) can be found in Haszeldine, RN; Lunt, RJ; Parish, RVJ Chem. Soc. (A), 3696 (1971). Synthesized by the method described.

Synthesis of 2-N-phenyliminophenoxyiridium cyclooctadiene (complex 1: Ir (Phenoxyimine) (cod)) 2-N-phenyliminophenol (39.4 mg, 0.2 mmol) was placed in a Schlenk tube and THF (2 ml) Dissolved in. The Schlenk tube was cooled in an ice bath and NaH (content 60%, 10 mg, 0.2 mmol) was added. The yellow reaction was stirred at room temperature for 25 minutes. Again, the Schlenk tube was cooled in an ice bath, [IrCl (cod)] 2 (67.1 mg, 0.1 mmol) was added, and the mixture was stirred overnight at room temperature. The reaction solution was centrifuged, and the solution was transferred to a Schlenk tube with a syringe and concentrated to obtain 102.4 mg (0.2 mmol, yield 100%) of 2-N-phenyliminophenoxyiridium cyclooctadiene.
¹ H NMR (C ₆ D ₆ ): δ1.55-1.75 (m, 4H), 2.10-2.15 (m, 4H), 3.19 (m, 2H), 4.94 (m, 2H), 6.58 (m, 1H) , 6.71 (d, J = 7.2Hz, 2H), 6.90 (d, J = 7.8Hz, 2H), 7.01 (t, J = 8.1Hz, 2H), 7.40 (m, 2H), 7.97 (s, 1H) .

Synthesis of 2-N-phenylimino-3-tbutylphenoxyiridium cyclooctadiene (complex 2: Ir ( ¹ Bu-Phenoxyimine) (cod)) In a Schlenk tube, 2-N-phenylimino-3-tbutylphenol (50.7 mg , 0.2 mmol) and dissolved in THF (2 ml). The Schlenk tube was cooled in an ice bath and NaH (content 60%, 10 mg, 0.2 mmol) was added. The yellow reaction was stirred at room temperature for 25 minutes. Again, the Schlenk tube was cooled in an ice bath, [IrCl (cod)] ₂ (67.1 mg, 0.1 mmol) was added, and the mixture was stirred overnight at room temperature. The reaction solution was centrifuged, and the solution was transferred to a Schlenk tube with a syringe and concentrated to obtain 110.4 mg (0.2 mmol, yield 100%) of 2-N-phenylimino-3-tbutylphenoxyiridium cyclooctadiene. .

White, A.; Yates, A.; Maitrlis, P. M. Inorg. Synth.1992, 29, 230に記載の方法に従い、以下の方法で合成した。シュレンク管にIrCl₃・3H₂O(2.00g,5.68mmol)を入れ、メタノール37.2 mlとCp*H（ペンタメチルシクロペンタジエン） 1.15 ml（7.35 mmol）を加えた。オイルバスで加熱還流すると反応液は最初は黒緑色の懸濁液だったが、次第にオレンジ色の粉末が析出してきた。48時間加熱還流を続けた後、反応液を20 mlまで濃縮し、析出したオレンジ色の粉末を濾取した。濾取した粉末をジエチルエーテルで洗浄後、減圧下で乾燥し、目的生成物を収率79%(文献値85%)で単離した(2.52g,3.16mmol)。 Synthesis of di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl) iridium] (complex 5: [Cp * IrCl (μ-Cl)] ₂ )

According to the method described in White, A .; Yates, A .; Maitrlis, PM Inorg. Synth. 1992, 29, 230, it was synthesized by the following method. IrCl ₃ · 3H ₂ O (2.00 g, 5.68 mmol) was placed in a Schlenk tube, and 37.2 ml of methanol and 1.15 ml (7.35 mmol) of Cp * H (pentamethylcyclopentadiene) were added. When heated and refluxed in an oil bath, the reaction liquid was initially a black-green suspension, but gradually an orange powder precipitated. After continuing to reflux for 48 hours, the reaction mixture was concentrated to 20 ml, and the precipitated orange powder was collected by filtration. The powder collected by filtration was washed with diethyl ether and then dried under reduced pressure, and the target product was isolated in a yield of 79% (literature value 85%) (2.52 g, 3.16 mmol).

Kang, J, W.; Maitlis, P. M. J. Organomet.Chem. 1971, 30, 127を参考にして、以下の方法で合成した。シュレンク管に[Cp*IrCl(μ-Cl)]₂(500mg,0.628mmol)とAgOAc(酢酸銀)(450mg,2.7mmol)を入れ、トルエンを25ml加え、室温で23時間攪拌した。遠心分離により塩を除き、減圧下で乾燥した。シュレンク管に黄色粉末の生成物を収率96%で単離した(498mg,1.205mmol)。
¹H NMR(C₆D₆)：δ1.28(s,15H),2.06(s,6H). Diacetato (pentamethylcyclopentadienyl) iridium (complex 6: synthesis of Cp * Ir (OAc) ₂ )

Synthesized by the following method with reference to Kang, J, W .; Maitlis, PMJ Organomet. Chem. 1971, 30, 127. [Cp * IrCl (μ-Cl)] ₂ (500 mg, 0.628 mmol) and AgOAc (silver acetate) (450 mg, 2.7 mmol) were placed in a Schlenk tube, 25 ml of toluene was added, and the mixture was stirred at room temperature for 23 hours. The salt was removed by centrifugation and dried under reduced pressure. A yellow powder product was isolated in a Schlenk tube with a yield of 96% (498 mg, 1.205 mmol).
¹ H NMR (C ₆ D ₆ ): δ 1.28 (s, 15H), 2.06 (s, 6H).

シュレンク管に [Cp*IrCl(μ-Cl)]₂ (854.7mg,1.072mmol)を入れ、ピリジルホスフィン2当量を加え、アルゴンで置換してエタノールを45ml加え、加熱還流を行った。2時間還流した後、エタノールとジエチルエーテルでそれぞれ洗浄し、減圧乾燥してオレンジ色の生成物を収率85%で単離した(1.2046g,1.821mmol)。
¹H NMR(C₆D₆)：δ1.2(d,15H),6.5(m,1H)6.8(m,1H),7.0(m,7H), 8.3(m,6H),
³¹P{¹H} NMR(C₆D₆)：δ-0.7(s) Synthesis of Cp * IrCl ₂ (PPh ₂ py)

[Cp * IrCl (μ-Cl)] ₂ (854.7 mg, 1.072 mmol) was placed in a Schlenk tube, 2 equivalents of pyridylphosphine were added, and the mixture was replaced with argon, and 45 ml of ethanol was added, followed by heating under reflux. After refluxing for 2 hours, each was washed with ethanol and diethyl ether and dried under reduced pressure to isolate an orange product in a yield of 85% (1.2046 g, 1.821 mmol).
¹ H NMR (C ₆ D ₆ ): δ 1.2 (d, 15H), 6.5 (m, 1H) 6.8 (m, 1H), 7.0 (m, 7H), 8.3 (m, 6H),
³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ-0.7 (s)

シュレンク管にCp*IrCl₂(PPh₂py)を502.2mg(0.759mmol)、AgOAc(酢酸銀) 2当量(253.4mg)を入れ、アルゴンで置換してCH₂Cl₂ 30mlを加え、室温で1時間攪拌した。生成した塩を遠心分離により除き、溶媒を留去して減圧乾燥後、淡黄色の生成物を収率85%で単離した(478.3mg,0.648mmol)。得られた錯体の¹H NMR、³¹P｛¹H｝NHRスペクトルデータは以下の通りである。
¹H NMR(C₆D₆)：δ1.5(d,15H),2.1(s, 6H),6.6(m,1H)6.9(m,1H),7.1(m,7H), 8.1(t,4H),
8.5(d,1H)
³¹P{¹H}NMR(C₆D₆)：δ 14.2(s) Synthesis of diacetato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium (complex 3: Cp * Ir (OAc) ₂ (PPh ₂ py))

A Schlenk tube was charged with 502.2 mg (0.759 mmol) of Cp * IrCl ₂ (PPh ₂ py) and 2 equivalents (253.4 mg) of AgOAc (silver acetate) .Substituted with argon, 30 ml of CH ₂ Cl ₂ was added. Stir for hours. The formed salt was removed by centrifugation, the solvent was distilled off, and after drying under reduced pressure, the pale yellow product was isolated in a yield of 85% (478.3 mg, 0.648 mmol). ¹ H NMR and ³¹ P { ¹ H} NHR spectrum data of the obtained complex are as follows.
¹ H NMR (C ₆ D ₆ ): δ 1.5 (d, 15H), 2.1 (s, 6H), 6.6 (m, 1H) 6.9 (m, 1H), 7.1 (m, 7H), 8.1 (t, 4H),
8.5 (d, 1H)
³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ 14.2 (s)

シュレンク管に Cp*IrCl₂(PPh₂py) (58.1mg,0.0878mmol)を入れ、AgOTf（トリフルオロメタンスルホン酸銀）を5当量加えアルゴンで置換した。CH₂Cl₂ 15mlを加え、室温で40分間攪拌した。生成した塩を遠心分離により除き、溶媒を留去してトルエン、ヘキサン、ジエチルエーテルでそれぞれ洗浄し、減圧乾燥して淡黄色の生成物を収率96%で単離した(62.3mg,0.0842mmol)。得た錯体の¹H NMR、³¹P｛¹H｝NHRスペクトルデータは以下の通りである。
¹H NMR(CD₂Cl₂)：δ1.7(d,15H), 7.2(m,1H), 7.6(m,5H) 7.7(m,5H) 7.9(t,1H), 8.3(t,1H),
8.9(d,1H)
³¹P{¹H}NMR(CD₂Cl₂)：δ-21.7(s) Synthesis of bistrifluorosulfonato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium (complex 4: Cp * Ir (OTf) ₂ (PPh ₂ py))

Cp * IrCl ₂ (PPh ₂ py) (58.1 mg, 0.0878 mmol) was placed in a Schlenk tube, and 5 equivalents of AgOTf (silver trifluoromethanesulfonate) was added and replaced with argon. 15 ml of CH ₂ Cl ₂ was added and stirred at room temperature for 40 minutes. The formed salt was removed by centrifugation, the solvent was distilled off, washed with toluene, hexane and diethyl ether, and dried under reduced pressure to isolate a pale yellow product in 96% yield (62.3 mg, 0.0842 mmol). ). ¹ H NMR and ³¹ P { ¹ H} NHR spectrum data of the obtained complex are as follows.
¹ H NMR (CD ₂ Cl ₂ ): δ1.7 (d, 15H), 7.2 (m, 1H), 7.6 (m, 5H) 7.7 (m, 5H) 7.9 (t, 1H), 8.3 (t, 1H ),
8.9 (d, 1H)
³¹ P { ¹ H} NMR (CD ₂ Cl ₂ ): δ-21.7 (s)

Dihydroxo (pentamethylcyclopentadienyl) iridium (complex 5: synthesis of Cp * Ir (OH) ₂ )
Synthesized according to Kang, J, W .; Maitlis, PMJ Organomet. Chem. 1971, 30, 127.

For diphenyl-2-pyridylphosphine (PPh ₂ py: ligand 1), a commercially available product from Aldrich was used as it was.

For 2-diphenylphosphanyl-4-pyridyl (dimethyl) amine (PPh ₂ (dmap): ligand 2), see Coppery, D. et al. Gros, P; Fort, Y .; J. 0rg. Chem. 2002, 67, 238. It was synthesized by the method described in 1.

For triphenylphosphine (PPh ₃ : ligand 3), a commercially available product from Aldrich was used as it was.

As for tris (3-sulfonatophenyl) phosphine sodium salt (P [C ₆ H ₄ (m-SO ₃ Na)]: ligand 4), a commercially available product of Strem was used as it was.

As for diphenylpentafluorophenylphosphine (PPh ₂ (C ₆ F ₅ ): ligand 5), a commercially available product of Aldrich was used as it was.

The reaction formula for the hydration reaction of benzonitrile with an iridium complex is as follows.

The hydration reaction of benzonitrile with an iridium complex was performed as follows. Under argon atmosphere, in a screw-type small glass test tube, 0.5 mL of 1,2-dimethoxyethane, 0.005 mmol of complex, benzonitrile (102 μL, 1 mmol), water (72 μL, 4 mmol), ligand and addition A predetermined amount of the product was added and sealed. And it heated at 80 degreeC with the oil bath for 3.5 hours. The progress of the reaction was confirmed by gas chromatography, and the product yield (benzamide yield) was calculated. The results are shown in Table 1.

From Table 1, it was confirmed that the hydration reaction of benzonitrile proceeds at a low temperature of 80 ° C. by using the combination of the iridium complex of the present invention and the pyridylphosphine derivative as a catalyst. More specifically, 2-N-phenyliminophenoxyiridium cyclooctadiene (Ir (Phenoxyimine) (cod): complex 1) and 2-N-phenylimino-3-tbutylphenoxyiridium cyclooctadiene (Ir ( ^t Bu-Phenoxyimine) (cod): The progress of the reaction was observed in the absence of additives by the combination of the complex 2) and the pyridylphosphine derivative (Examples 1 to 4).

  As shown in Example 1, when an iridium complex which is 2-N-phenyliminophenoxyiridium cyclooctadiene and a diphenyl-2-pyridylphosphine ligand were used, benzamide was obtained in a yield of 13%. As shown in Comparative Example 1, benzamide could not be obtained only with 2-N-phenyliminophenoxyiridium cyclooctadiene.

  As shown in Example 2, when an iridium complex which is 2-N-phenyliminophenoxyiridium cyclooctadiene and 2-diphenylphosphanyl-4-pyridyl (dimethyl) amine ligand are used, the yield of benzamide is 7%. Was obtained. As shown in Comparative Example 1, benzamide could not be obtained only with 2-N-phenyliminophenoxyiridium cyclooctadiene.

  As shown in Examples 3, 4, and 5, an iridium complex that is 2-N-phenylimino-3-tbutylphenoxyiridium cyclooctadiene and a diphenyl-2-pyridylphosphine ligand are mixed into a ligand / complex mole. When the ratio was used at 2, 3 and 4, benzamide was obtained in 3%, 7% and 12% yields, respectively. As shown in Comparative Example 2, benzamide could not be obtained only with 2-N-phenylimino-3-tbutylphenoxyiridium cyclooctadiene.

  As shown in Example 6, using an iridium complex that is 2-N-phenylimino-3-tbutylphenoxyiridium cyclooctadiene and a 2-diphenylphosphanyl-4-pyridyl (dimethyl) amine ligand, Was obtained in 11% yield. As shown in Comparative Example 2, benzamide could not be obtained only with 2-N-phenylimino-3-tbutylphenoxyiridium cyclooctadiene.

  As shown in Example 8, using an iridium complex which is di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl) iridium] and a diphenyl-2-pyridylphosphine ligand, silver acetate was used as an additive. When used, benzamide was obtained in 70% yield. As shown in Comparative Example 3, benzamide could not be obtained only with di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl) iridium]. As shown in Comparative Example 9, benzamide could not be obtained with silver acetate alone.

  That is, silver acetate alone does not catalyze the hydration reaction of benzonitrile. As shown in Comparative Example 10, benzamide could not be obtained using silver acetate and diphenyl-2-pyridylphosphine. By adding silver acetate, the chlorine atom of di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl) iridium] is exchanged for an acetate group (acetate ion). It is thought that methylcyclopentadienyl) iridium is formed, and diphenyl-2-pyridylphosphine is further coordinated to form diacetato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium. It is considered that the produced diacetato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium catalyzes the hydration reaction of benzonitrile.

  Diacetato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium was formed by diphenyl-bis- [chloro (pentamethylcyclopentadienyl) iridium] and diphenyl- A process in which 2-pyridylphosphine is coordinated and then a chlorine atom on iridium is exchanged for an acetate group (acetate ion) by silver acetate is also considered. As shown in Comparative Example 12, benzamide was not obtained with di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl] iridium] and diphenyl-2-pyridylphosphine ligand alone. It is clear from the fact of 12 that the introduction of an acetate group on iridium with silver acetate is a requirement for advancing the hydration reaction, In Example 8, silver acetate is used as an additive. However, it is not limited to a silver salt, and a metal salt of acetic acid is suitable as an additive.

  As shown in Example 10, an iridium complex which is di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl) iridium] and a diphenyl-2-pyridylphosphine ligand are used, and potassium hydroxide is used as an additive. Benzamide was obtained in a yield of 23%. As shown in Comparative Example 11, benzamide could not be obtained using only potassium hydroxide. Further, as shown in Comparative Example 12, benzamide could not be obtained even when there was no additive.

  That is, potassium hydroxide alone does not catalyze the hydration reaction of benzonitrile. As shown in Comparative Example 12, benzamide could not be obtained using di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl) iridium] and diphenyl-2-pyridylphosphine. By adding potassium hydroxide, the chlorine atom of di-μ-chloro-bis [chloropentamethylcyclopentadienyliridium] is exchanged with a hydroxyl group (hydroxy group), thereby dihydroxo (pentamethylcyclohexane) in the reaction system. It is thought that dihydroxo (pentamethylcyclopentadienyl) diphenyl-2-pyridylphosphine iridium is formed by the formation of pentadienyl) iridium and the coordination of diphenyl-2-pyridylphosphine. The resulting dihydroxo (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium is thought to catalyze the hydration reaction of benzonitrile.

  Dihydroxo (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium was formed by di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl) iridium] and diphenyl- A process in which 2-pyridylphosphine is coordinated and then a chlorine atom on iridium is exchanged with a hydroxyl group (hydroxy group) by potassium hydroxide is also conceivable. As shown in Comparative Example 12, benzamide was not obtained with di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl) iridium] and diphenyl-2-pyridylphosphine ligand alone. From the fact of Comparative Example 12, it is clear that introduction of an acetate group on iridium with potassium hydroxide is a requirement for the hydration reaction to proceed. In Example 10, potassium hydroxide is used as an additive, but is not limited to a potassium salt, and a metal element hydroxide is suitable as an additive.

  As shown in Example 11, using an iridium complex that is di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl) iridium] and a 2-diphenylphosphanyl-4-pyridyl (dimethyl) amine ligand When silver acetate was used as an additive, benzamide was obtained in a yield of 8%.

  As shown in Example 12, using an iridium complex that is di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl) iridium] and a triphenylphosphine ligand, and using silver acetate as an additive, Benzamide was obtained with a yield of 4%.

  As shown in Example 13, an iridium complex which is di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl) iridium] and a diphenylpentafluorophenylphosphine ligand are used, and silver acetate is used as an additive. Benzamide was obtained in a yield of 4%.

  As shown in Example 14, using an iridium complex which is di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl) iridium] and a tris (3-sulfonatophenyl) phosphine sodium salt ligand, When silver acetate was used as the product, benzamide was obtained in a yield of 5%.

  As shown in Example 15, when an iridium complex that is dihydroxo (pentamethylcyclopentadienyl) iridium and a diphenyl-2-pyridylphosphine ligand were used, benzamide was obtained in a yield of 20%. As shown in Comparative Example 4, benzamide could not be obtained only with dihydroxo (pentamethylcyclopentadienyl) iridium.

  That is, dihydroxo (pentamethylcyclopentadienyl) iridium alone does not catalyze the hydration reaction of benzonitrile. When the diphenyl-2-pyridylphosphine ligand shown in Example 15 was added, diphenyl-2-pyridylphosphine coordinated on iridium, and dihydroxo (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium was It is thought to generate. The resulting dihydroxo (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium is thought to catalyze the hydration reaction of benzonitrile.

  As shown in Example 16, when an iridium complex that is dihydroxo (pentamethylcyclopentadienyl) iridium and a 2-diphenylphosphanyl-4-pyridyl (dimethyl) amine ligand are used, the benzamide is obtained in a yield of 20%. Obtained. As shown in Comparative Example 4, benzamide could not be obtained only with dihydroxo (pentamethylcyclopentadienyl) iridium.

  That is, dihydroxo (pentamethylcyclopentadienyl) iridium alone does not catalyze the hydration reaction of benzonitrile. When the 2-diphenylphosphanyl-4-pyridyl (dimethyl) amine ligand shown in Example 16 was added, 2-diphenylphosphanyl-4-pyridyl (dimethyl) amine was coordinated on iridium to form dihydroxo (pentamethylcyclohexane). It is believed that pentadienyl) (2-diphenylphosphanyl-4-pyridyl (dimethyl) amine) iridium is formed. The resulting dihydroxo (pentamethylcyclopentadienyl) (2-diphenylphosphanyl-4-pyridyl (dimethyl) amine) iridium is considered to catalyze the hydration reaction of benzonitrile.

  As shown in Example 17, using an iridium complex which is diacetato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium and a diphenyl-2-pyridylphosphine ligand, the yield of benzamide is 64%. Was obtained.

  As shown in Example 18, using an iridium complex that is diacetato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium and a 2-diphenylphosphanyl-4-pyridyl (dimethyl) amine ligand Benzamide was obtained in a yield of 21%.

  As shown in Example 19, using an iridium complex that is diacetato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium and a triphenylphosphine ligand, benzamide is obtained in a yield of 8%. It was.

  As shown in Example 20, using an iridium complex that is diacetato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium and a tris (3-sulfonatophenyl) phosphine sodium salt ligand, Was obtained in a yield of 4%.

  As shown in Example 21, when an iridium complex that was diacetato (pentamethylcyclopentadienyl) iridium was used, benzamide was obtained in a yield of 56%.

  As shown in Examples 22 and 23, when an iridium complex which is diacetate (pentamethylcyclopentadienyl) iridium and a diphenyl-2-pyridylphosphine ligand are used at a ligand / complex molar ratio of 1 and 2, And benzamide were obtained in 51% and 9% yields, respectively.

  As shown in Example 24, when an iridium complex which is bistrifluorosulfonate (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium was used, benzamide was obtained in a yield of 8%.

  As shown in Comparative Example 5, Cp * Ir (cod) alone does not catalyze the benzonitrile hydration reaction. As shown in Comparative Example 6, benzamide could not be obtained using Cp * Ir (cod) and diphenyl-2-pyridylphosphine. As shown in Comparative Example 7, benzamide could not be obtained using Cp * Ir (cod) and 2-diphenylphosphanyl-4-pyridyl (dimethyl) amine. As shown in Comparative Example 8, benzamide could not be obtained using Cp * Ir (cod) and triphenylphosphine.

  That is, in addition to the pentamethylcyclopentadienyl group on iridium, introduction of a hydroxyl group (hydroxy group), an acetate group (acetate ion) or a trifluorosulfonate group is suitable for advancing the hydration reaction. It is recognized that there is.

To summarize the above results, a combination of diacetato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium (Cp * Ir (OAc) ₂ (PPh ₂ py): complex 3) and a pyridylphosphine derivative is catalyzed. As a result, the progress of the reaction was observed in the absence of additives. Especially when Cp * Ir (OAc) ₂ (PPh ₂ py) is used alone and when Cp * Ir (OAc) ₂ (PPh ₂ py) and PPh ₂ py are used in combination, 50% or more The reaction proceeded with high yield. Bistrifluorosulfonato (pentamethylcyclopentadienyl) diphenyl-2-pyridylphosphine iridium (Cp * Ir (OTf) ₂ (PPh ₂ py): complex 4) alone, although the yield is low, Progress of the reaction was observed in the absence.

Furthermore, a combination of di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl) iridium] ([Cp * IrCl (μ-Cl)] ₂ : complex 5) and an organic phosphine having an electron-withdrawing organic group When used as a catalyst, the progress of the reaction was observed in the presence of additives. When a combination of diacetapentamethylcyclopentadienyliridium (Cp * Ir (OAc) ₂ : complex 6) and an organic phosphine having an electron-withdrawing organic group is used as a catalyst, Progress of the reaction was observed in the presence. Especially when [Cp * IrCl (μ-Cl)] ₂ and PPh ₂ py are used in combination, and when Cp * Ir (OAc) ₂ (PPh ₂ py) and PPh ₂ py are used in combination, 60 The reaction proceeded with a very high yield of 70% to 70%. Therefore, these combinations are considered to be most suitable in the present invention.

  According to the present invention, a method for synthesizing an amide compound by hydrating a nitrile compound using a catalytic action of a combination of an iridium complex and an organic phosphine having an electron-withdrawing organic group such as a pyridylphosphine derivative is provided. According to the method of the present invention, since the hydration reaction proceeds at a temperature below the boiling point of water of about 80 ° C., less energy is required to heat the reaction vessel. Since the hydration reaction proceeds, there is an advantage that it is not necessary to use a pressure vessel for the reaction. Therefore, according to the method using the catalyst of the present invention, industrially useful nicotinamides can be easily synthesized in high yield.

Claims (52)

A method of synthesizing an amide compound by hydrating a nitrile compound using a catalytic action of a combination of an iridium complex represented by X-Ir-L ₂ and an organic phosphine having an electron-withdrawing organic group, wherein X is A group 15 element capable of coordinating with iridium and a bidentate ligand in which a negatively charged oxygen atom is bonded to iridium, and L is neutral and has the electron-withdrawing organic group A method for synthesizing an amide compound, which is an organic phosphine having an organic phosphine or an organic phosphine having an electron-withdrawing organic group.   The method according to claim 1, wherein the organic phosphine having an electron-withdrawing organic group is a pyridylphosphine derivative.   The method according to claim 1 or 2, wherein the Group 15 element is nitrogen.   When L is a ligand that can be substituted with an organic phosphine having a neutral and electron-withdrawing organic group, L is an electron-donating group 14, 15, or 16 neutral group. The method according to any one of claims 1 to 3, wherein the method is a ligand.   When L is neutral and can be substituted with an organic phosphine having an electron-withdrawing organic group, the L is a group consisting of alkene, alkyne, nitrogen compound, phosphorus compound, ethers and thioethers. The method according to any one of claims 1 to 4, wherein the method is selected from the group consisting of the above-mentioned ones, or they form a ring with each other. When L is a ligand that can be substituted with an organic phosphine having a neutral and electron-withdrawing organic group, L is ethylene, propylene, isoprene, butadiene, 2,3-dimethyl-1,3 -Butadiene, cyclohexene, cyclooctene, acetylene, propyne, phenylacetylene, trimethylsilylpropyne, phenylpropyne, diphenylacetylene, ammonia, trimethylamine, triethylamine, pyridine, 4,4-dimethylaminopyridine, imidazole, acetonitrile, benzonitrile, trimethylphosphine , Triphenylphosphine, tricyclohexylphosphine, diphenylpentafluorophenylphosphine, diphenyl-2-pyridylphosphine, 2-phosphanyl-4-pyridyl (dimethyl) amine, tris (3-sulfonatophenyl) phospho L2 is selected from the group consisting of sphin sodium salt, diethyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, dimethyl sulfide, tetrahydrothiophene, and thiophene, or L ₂ is a cyclooctadiene or norbornadiene. The method according to any one of claims 1 to 5, wherein: The method according to any one of claims 1 to 6, wherein L ₂ in which L forms a ring with each other is cyclooctadiene.   The iridium complex is 2-N-phenyliminophenoxyiridium cyclooctadiene, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine or 2-diphenylphosphanyl-4-pyridyl (dimethyl) amine The method according to any one of claims 1 to 7, characterized in that:   The iridium complex is 2-N-phenylimino-3-tbutylphenoxyiridium cyclooctadiene, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine or 2-diphenylphosphanyl-4- The method according to claim 1, wherein the method is pyridyl (dimethyl) amine. A method of synthesizing an amide compound by hydrating a nitrile compound using a catalytic action of a combination of an iridium complex represented by the following general formula (I) and an organic phosphine having an electron-withdrawing organic group.

(I)
(In the above general formula (I), Y is a polydentate ligand having a negative charge on carbon or nitrogen, Z is a monodentate ligand having a negative charge, L is neutral and (It is a ligand that can be substituted with an organic phosphine having an electron-withdrawing organic group, or an organic phosphine with an electron-withdrawing organic group.)   The method according to claim 10, wherein the organic phosphine having an electron-withdrawing organic group is a pyridylphosphine derivative.   12. The method according to claim 10 or 11, wherein Y is selected from the group consisting of a cyclopentadienyl derivative, a pyrrolyl derivative, and an indolyl derivative.   13. The method according to claim 10, wherein Y is selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, pentamethylcyclopentadienyl, indenyl, and fluorenyl. The method described in the paragraph.   The method according to any one of claims 10 to 13, wherein Y is selected from the group consisting of pyrrolyl and indolyl. 15. The Z according to any one of claims 10 to 14, wherein Z is a halogen, a ligand having a negative charge represented by the following general formula (II), a hydroxy group, or hydrogen. Method.

(II)
(In the general formula (II), R represents hydrogen, a saturated or unsaturated hydrocarbon group, a saturated or unsaturated cyclic hydrocarbon group, an aromatic compound residue, an alkoxy group, an aryloxy group, and an organometallic compound residue. Represents a group selected from the group consisting of groups.)   The method according to claim 15, wherein R is a saturated hydrocarbon group or an aromatic compound residue.   The method according to claim 15 or 16, wherein R is a methyl group.   When L is a ligand that can be substituted with an organic phosphine having a neutral and electron-withdrawing organic group, L is an electron-donating group 14, 15, or 16 neutral group. The method according to any one of claims 10 to 17, wherein the method is a ligand.   When L is neutral and can be substituted with an organic phosphine having an electron-withdrawing organic group, L is composed of alkene, alkyne, nitrogen compound, phosphorus compound, ethers and thioethers. 19. A method according to any one of claims 10 to 18, characterized in that they are selected from the group or they form a ring with one another. When L is a ligand that can be substituted with an organic phosphine having a neutral and electron-withdrawing organic group, L is ethylene, propylene, isoprene, butadiene, 2,3-dimethyl-1,3 -Butadiene, cyclohexene, cyclooctene, acetylene, propyne, phenylacetylene, trimethylsilylpropyne, phenylpropyne, diphenylacetylene, ammonia, trimethylamine, triethylamine, pyridine, 4,4-dimethylaminopyridine, imidazole, acetonitrile, benzonitrile, trimethylphosphine , Triphenylphosphine, tricyclohexylphosphine, diphenylpentafluorophenylphosphine, diphenyl-2-pyridylphosphine, 2-phosphanyl-4-pyridyl (dimethyl) amine, tris (3-sulfonatopheny ) Phosphine sodium salt, diethyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, dimethyl sulfide, is selected from the group consisting of tetrahydrothiophene and thiophene, or L ₂ which the L is to form a ring with each other cyclooctadiene or 20. The method according to any one of claims 10 to 19, wherein the method is norbornadiene. 21. The method according to any one of claims 10 to 20, wherein L ₂ in which L forms a ring with each other is cyclooctadiene.   The iridium complex is dihydroxo (pentamethylcyclopentadienyl) iridium, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine or 2-diphenylphosphanyl-4-pyridyl (dimethyl) amine. 21. The method according to any one of claims 10 to 20, wherein:   The iridium complex is diacetato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine 21. A method according to any one of claims 10 to 20.   The iridium complex is bistrifluorosulfonato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine. 22. A method according to any one of claims 10 to 21 characterized in that: Synthesis of amide compounds by hydration of nitrile compounds using catalysis by the combination of iridium complexes represented by Y-Ir-Z ₂ or (Y-Ir-Z) ₂ and organic phosphines with electron-withdrawing organic groups Wherein Y is a polydentate ligand having a negative charge on carbon or nitrogen, and Z is a monodentate ligand having a negative charge .   The method according to claim 25, wherein the organic phosphine having an electron-withdrawing organic group is a pyridylphosphine derivative.   27. The method according to claim 25 or 26, wherein Y is a cyclopentadienyl derivative or a pyrrolyl derivative.   28. Any one of claims 25 to 27, wherein Y is selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, pentamethylcyclopentadienyl, indenyl, and fluorenyl. The method described in the paragraph.   29. The method according to any one of claims 25 to 28, wherein Y is selected from the group consisting of pyrrolyl and indolyl. 30. The method according to any one of claims 25 to 29, wherein Z is halogen, a ligand having a negative charge represented by the following general formula (III), a hydroxy group, or hydrogen. Method.

(III)
(In the above general formula (III), R represents hydrogen, a saturated or unsaturated hydrocarbon group, a saturated or unsaturated cyclic hydrocarbon group, an aromatic compound residue, an alkoxy group, an aryloxy group, and an organometallic compound residue. Represents a group selected from the group consisting of groups.)   The method according to claim 30, wherein R is a saturated hydrocarbon group or an aromatic compound residue.   32. A method according to claim 30 or claim 31, wherein R is a methyl group.   32. The method of claim 30, wherein Z is chlorine.   The iridium complex is di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl) iridium], and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine or 2-diphenylphosphanyl. 26. It is selected from the group consisting of -4-pyridyl (dimethyl) amine, triphenylphosphine, tris (3-sulfonatophenyl) phosphine sodium salt, and diphenylpentafluorophenylphosphine 31. A method according to any one of claims 30.   The iridium complex is diacetato (pentamethylcyclopentadienyl) iridium, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine, 2-diphenylphosphanyl-4-pyridyl (dimethyl) amine, 31. The method according to any one of claims 25 to 30, wherein the method is selected from the group consisting of triphenylphosphine and tris (3-sulfonatophenyl) phosphine sodium salt.   An iridium complex that is 2-N-phenyliminophenoxyiridium cyclooctadiene.   An iridium complex which is 2-N-phenylimino-3-tbutylphenoxyiridium cyclooctadiene.   An iridium complex that is diacetato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium.   An iridium complex that is bistrifluorosulfonato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium. A catalyst comprising a combination of an iridium complex represented by X-Ir-L ₂ and an organic phosphine having an electron-withdrawing organic group, wherein X is a group 15 element capable of coordinating with iridium, and a negative charge. A bidentate ligand having an oxygen atom bonded to iridium, and L is neutral and can be substituted with an organic phosphine having an electron-withdrawing organic group, or a water-soluble electron A catalyst characterized by being an organic phosphine having an attractive organic group.   41. The catalyst according to claim 40, wherein the organic phosphine having an electron-withdrawing organic group is a pyridylphosphine derivative.   The iridium complex is 2-N-phenyliminophenoxyiridium cyclooctadiene, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine or 2-diphenylphosphanyl-4-pyridyl (dimethyl) amine 41. The catalyst according to claim 40, wherein:   The iridium complex is 2-N-phenylimino-3-tbutylphenoxyiridium cyclooctadiene, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine or 2-diphenylphosphanyl-4- 41. The catalyst according to claim 40, which is pyridyl (dimethyl) amine. A catalyst combining an iridium complex represented by the following general formula (IV) and an organic phosphine having an electron-withdrawing organic group.

(IV)
In the general formula (IV), Y is a polydentate ligand having a negative charge on carbon or nitrogen, Z is a monodentate ligand having a negative charge, and L is neutral. And a catalyst capable of substituting with an organic phosphine having an electron-withdrawing organic group, or an organic phosphine with an electron-withdrawing organic group.   45. The catalyst according to claim 44, wherein the organic phosphine having an electron-withdrawing organic group is a pyridylphosphine derivative.   The iridium complex is dihydroxo (pentamethylcyclopentadienyl) iridium, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine or 2-diphenylphosphanyl-4-pyridyl (dimethyl) amine. 45. The catalyst of claim 44, wherein:   The iridium complex is diacetato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine 45. The catalyst of claim 44.   The iridium complex is bistrifluorosulfonato (pentamethylcyclopentadienyl) (diphenyl-2-pyridylphosphine) iridium, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine. 45. A catalyst according to claim 44, characterized in that: A catalyst comprising a combination of an iridium complex represented by Y-Ir-Z ₂ or (Y-Ir-Z) ₂ and an organic phosphine having an electron-withdrawing organic group, wherein Y is an anion on carbon or nitrogen. A catalyst, which is a multidentate ligand having a charge, wherein Z is a monodentate ligand having a negative charge.   50. The catalyst according to claim 49, wherein the organic phosphine having an electron-withdrawing organic group is a pyridylphosphine derivative.   The iridium complex is di-μ-chloro-bis [chloro (pentamethylcyclopentadienyl) iridium], and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine or 2-diphenylphosphanyl. 50. 49. A compound selected from the group consisting of -4-pyridyl (dimethyl) amine, triphenylphosphine, tris (3-sulfonatophenyl) phosphine sodium salt, and diphenylpentafluorophenylphosphine. Catalyst.   The iridium complex is diacetato (pentamethylcyclopentadienyl) iridium, and the organic phosphine having an electron-withdrawing organic group is diphenyl-2-pyridylphosphine, 2-diphenylphosphanyl-4-pyridyl (dimethyl) amine, 50. The catalyst according to claim 49, wherein the catalyst is selected from the group consisting of triphenylphosphine and tris (3-sulfonatophenyl) phosphine sodium salt.