JP4538638B2 - Selenophosphate chloride and method for producing the same - Google Patents

Description

  The present invention relates to novel selenophosphinic acid amides, selenophosphoric acid amides, selenophosphoric acid chlorides and methods for producing them.

Conventionally, in selenophosphinic acid and selenophosphoric acid in which a selenium atom is bonded to a phosphorus atom, in addition to the selenium atom, an aryl group such as a hydrogen atom, a phenyl group, an alkyl group such as a methyl group, or an alkoxy group such as a methoxy group It binds to a phosphorus atom and is used, for example, as a selenium sensitizer for increasing the spectral sensitivity of a silver halide photographic material (see, for example, Patent Documents 1 to 7).
JP-A-5-40324 Japanese Patent Laid-Open No. 5-224332 JP-A-5-224333 JP-A-6-43576 Japanese Patent Laid-Open No. 11-24195 Japanese Patent Laid-Open No. 2002-214736 JP-A-6-258758

  The inventors of the present invention have discovered selenophosphinic acid amides, selenophosphoric acid amides, and selenophosphoric acid chlorides that are new and stable in air by intensive research. Furthermore, the present inventors have found that selenophosphinic acid amides and selenophosphoric acid amides are useful as selenium sensitizers that increase the spectral sensitivity of silver halide photographic light-sensitive materials, for example, and selenophosphoric acid chlorides are optically active compounds from, for example, racemates. It was found to be useful as a chiral discriminating agent for separating. The present invention is based on the knowledge thus obtained, and provides selenophosphinic amides, selenophosphoric acid amides, selenophosphoric acid chlorides which are stable in air, and methods for producing them.

In one embodiment of the present invention, there is provided a selenophosphate chloride having a structure represented by the following general formula (7) and being an (R) isomer or an (S) isomer. This selenophosphate chloride is stable in air and exhibits optical activity.

（式中、Ｒ^８は水素原子、ハロゲン原子、アルキル基、アリール基、アルコキシ基又はシリル基を示す。）
本発明の別の態様では、前記一般式（７）で示される構造を有し、（Ｒ）体又は（Ｓ）体であるセレノリン酸塩化物の製造方法であって、三塩化リン、トリエチルアミン、下記一般式（８）で示される構造を有し（Ｒ）体又は（Ｓ）体であるビナフトール誘導体、及びセレンを相互に反応させるセレノリン酸塩化物の製造方法が提供される。このセレノリン酸塩化物の製造方法によれば、空気中で安定で、光学活性を発揮するセレノリン酸塩化物の製造が容易である。

(In the formula, R ⁸ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or a silyl group.)
In another aspect of the present invention, there is provided a process for producing a selenophosphate acid chloride having the structure represented by the general formula (7), which is an (R) isomer or an (S) isomer, comprising phosphorus trichloride, triethylamine, A binaphthol derivative which has a structure represented by the following general formula (8) and is an (R) isomer or (S) isomer, and a method for producing a selenophosphate chloride by reacting selenium with each other are provided. According to this method for producing a selenophosphate, it is easy to produce a selenophosphate that is stable in air and exhibits optical activity.

（式中、Ｒ^８は水素原子、ハロゲン原子、アルキル基、アリール基、アルコキシ基又はシリル基を示す。）

(In the formula, R ⁸ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or a silyl group.)

  The selenophosphinic acid amide according to this embodiment is a compound having a structure represented by the following general formula (1).

（式中、Ｐｈはフェニル基を示し、Ｒ¹及びＲ²はそれぞれアルキル基を示し、Ｒ³は水素原子又はアルキル基を示し、Ｒ²及びＲ³から選ばれる少なくとも一方がキラルなアルキル基を示す。）
前記Ｒ^１からＲ^３において、アルキル基としてはメチル基、１−フェニルエチル基、１−（１−ナフチル）エチル基、１−シクロヘキシルエチル等のエチル基、イソプロピル基等のプロピル基又はｔｅｒｔ−ブチル基等のブチル基が挙げられる。ここで、アルキル基には、シクロヘキシル基等のシクロアルキル基が含まれる。

(In the formula, Ph represents a phenyl group, R ¹ and R ² each represents an alkyl group, R ³ represents a hydrogen atom or an alkyl group, and at least one selected from R ² and R ³ represents a chiral alkyl group. Show.)
In R ¹ to R ³ , the alkyl group is a methyl group, 1-phenylethyl group, 1- (1-naphthyl) ethyl group, ethyl group such as 1-cyclohexylethyl, propyl group such as isopropyl group, or tert-butyl. And a butyl group such as a group. Here, the alkyl group includes a cycloalkyl group such as a cyclohexyl group.

This selenophosphinic acid amide is stable in the air, and is used as a selenium sensitizer for enhancing the spectral sensitivity of silver halide photographic light-sensitive materials and as a ligand and a ligand source in various reactions such as asymmetric synthesis reactions. Useful. Further, the selenophosphinic acid amide contains two or more asymmetric centers due to at least one chiral alkyl group selected from R ² and R ³ in the general formula (1), and exhibits optical activity. . Here, the chiral alkyl group is an alkyl group having an (R) configuration and an (S) configuration. Examples of the chiral alkyl group include a 1-phenylethyl group, a 1- (1-naphthyl) ethyl group, and a 1-cyclohexylethyl group. Accordingly, selenophosphinic acid amide is also useful as a raw material for optically active compounds having trivalent phosphorus (P).

  For example, as shown in the following reaction formula (9), by reacting a selenophosphinic acid amide with a reducing agent such as tributylphosphine, an aminophosphine used for the synthesis of a pharmaceutical intermediate can be obtained. This aminophosphine exhibits optical activity, is used as an optically active ligand supply source in asymmetric synthesis, and forms a metal complex by coordination with a metal atom. This metal complex is easily used as a catalyst for the synthesis reaction of a compound having an enantiomer, thereby easily enhancing the selectivity of the configuration of the synthesized compound.

セレノホスフィン酸アミドは、前記一般式（１）中のＲ¹がイソプロピル基、ｔｅｒｔ−ブチル基又はシクロヘキシル基を示し、Ｒ²が１−フェニルエチル基、１−（１−ナフチル）エチル基又は１−シクロヘキシルエチル基を示し、Ｒ³が水素原子を示す構造を有することが、空気中での安定性が特に高いために好ましい。

In the selenophosphinic acid amide, R ¹ in the general formula (1) represents an isopropyl group, a tert-butyl group or a cyclohexyl group, and R ² represents a 1-phenylethyl group, a 1- (1-naphthyl) ethyl group or 1 - indicates cyclohexylethyl group, have a structure in which R ³ represents a hydrogen atom is preferred for especially high stability in air.

  A selenophosphinic acid amide is produced by reacting a selenophosphinic acid chloride having a structure represented by the following general formula (2) with a lithium salt of an amine having a structure represented by the following general formula (3). (See the following reaction formula (10)). Here, the selenophosphinic chloride and the lithium salt of amine may be optically active or racemic.

（式中、Ｐｈはフェニル基を示し、Ｒ¹はアルキル基を示す。）

(In the formula, Ph represents a phenyl group, and R ¹ represents an alkyl group.)

（式中、Ｒ²はアルキル基を示し、Ｒ³は水素原子又はアルキル基を示し、Ｒ²及びＲ³から選ばれる少なくとも一方がキラルなアルキル基を示す。）

(In the formula, R ² represents an alkyl group, R ³ represents a hydrogen atom or an alkyl group, and at least one selected from R ² and R ³ represents a chiral alkyl group.)

このセレノホスフィン酸アミドの製造方法では、セレノホスフィン酸塩化物の溶液及びアミンのリチウム塩の溶液を０℃程度の低温で混合して反応溶液を調製した後、該反応溶液を加熱することが好ましい。このとき、各溶液を低温で混合することにより各溶液中の成分の分解を防止し、反応溶液を加熱することにより前記反応式（１０）の反応が促進されるという利点がある。ここで、セレノホスフィン酸塩化物及びアミンのリチウム塩の反応割合は当量比で１：１であることが好ましい。またこのとき、塩化リチウムが副生成物として生成される。反応に用いられる溶媒は各成分を溶解させるものであれば特に限定されないが、テトラヒドロフラン（ＴＨＦ）等のエーテル系溶媒が前記反応式（１０）の反応を阻害しないとともに各成分の溶解性が高いために好ましい。前記反応式（１０）の反応温度の下限は０℃が好ましく、上限は溶媒の沸点が好ましい。反応温度が０℃未満ではセレノホスフィン酸アミドの製造効率が低下し、逆に溶媒の沸点を超えると反応溶液の溶媒が揮発しやすくなる。前記反応溶液の加熱時間、即ち前記反応式（１０）の反応時間は１〜３時間が好ましい。反応時間が１時間未満では前記反応式（１０）の反応を十分に進行させることができず、逆に３時間を超えるとセレノホスフィン酸アミドの製造効率が低下しやすい。

In this method for producing selenophosphinic acid amide, it is preferable to prepare a reaction solution by mixing a solution of selenophosphinic acid chloride and a lithium salt of amine at a low temperature of about 0 ° C., and then heating the reaction solution. . At this time, there is an advantage that the components in each solution are prevented from being decomposed by mixing each solution at a low temperature, and the reaction of the reaction formula (10) is promoted by heating the reaction solution. Here, the reaction ratio of the selenophosphinic chloride and the lithium salt of amine is preferably 1: 1 in terms of an equivalent ratio. At this time, lithium chloride is produced as a by-product. The solvent used in the reaction is not particularly limited as long as it dissolves each component, but an ether solvent such as tetrahydrofuran (THF) does not inhibit the reaction of the reaction formula (10) and the solubility of each component is high. Is preferred. The lower limit of the reaction temperature in the reaction formula (10) is preferably 0 ° C., and the upper limit is preferably the boiling point of the solvent. When the reaction temperature is lower than 0 ° C., the production efficiency of selenophosphinic acid amide is lowered. Conversely, when the boiling point of the solvent is exceeded, the solvent of the reaction solution is easily volatilized. The heating time of the reaction solution, that is, the reaction time of the reaction formula (10) is preferably 1 to 3 hours. When the reaction time is less than 1 hour, the reaction of the reaction formula (10) cannot be sufficiently progressed. Conversely, when the reaction time exceeds 3 hours, the production efficiency of selenophosphinic acid amide tends to decrease.

In this method for producing selenophosphinic acid amide, selenophosphinic acid amide is obtained as a diastereomer which is a mixture of two stereoisomers. For this reason, after manufacturing selenophosphinic acid amide, it is preferable to perform the refinement | purification operation which isolate | separates each stereoisomer by separation using recrystallization or chromatography.
The selenophosphoric acid amide according to the present embodiment is a compound having a structure represented by the following general formula (4).

（式中、Ｒ⁴は水素原子、ハロゲン原子、アルキル基、アリール基、アルコキシ基又はシリル基を示し、Ｒ⁵は−ＮＲ⁶Ｒ⁷又はアルキルピペリジル基を示す。Ｒ⁶は水素原子又はアルキル基を示し、Ｒ⁷はアルキル基を示す。）

(Wherein R ⁴ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or a silyl group, R ⁵ represents —NR ⁶ R ⁷ or an alkylpiperidyl group. R ⁶ represents a hydrogen atom or an alkyl group. And R ⁷ represents an alkyl group.)

In R ⁴ and R ⁵ , the halogen atom includes a chlorine atom, and the alkyl group includes an ethyl group such as a methyl group, a 1-phenylethyl group, a 1- (1-naphthyl) ethyl group, and a 1-cyclohexylethyl group. , A propyl group such as a 1-methylpropyl group or a 1,2-dimethylpropyl group. The aryl group includes a phenyl group, the alkoxy group includes a menthyloxy group, and the silyl group includes a trimethylsilyl group. Examples of the alkyl piperidyl group include a 2-methyl piperidyl group. Selenophosphoric acid amide is stable in the air, and, like selenophosphinic acid amide, synthesis of ligands and ligand sources in various reactions such as the selenium sensitizer, asymmetric synthesis reaction, and intermediates of pharmaceuticals It is useful as a raw material for aminophosphines used in Here, aminophosphine derived from selenophosphoric acid amide can be obtained by reacting selenophosphoric acid amide with a reducing agent such as tributylphosphine. The selenophosphoric acid amide preferably has a structure in which R ⁵ in the general formula (4) represents a 2-methylpiperidyl group. In the selenophosphoric acid amide, R ⁵ in the general formula (4) represents —NR ⁶ R ⁷ , R ⁶ represents a hydrogen atom or a 1-phenylethyl group, R ⁷ represents a 1-phenylethyl group, 1- It preferably has a structure showing a (1-naphthyl) ethyl group, 1-methylpropyl or 1,2-dimethylpropyl group. These selenophosphoric acid amides have particularly high stability in air.

The selenophosphoric acid amide preferably has a structure in which R ⁵ in the general formula (4) represents a chiral alkylpiperidyl group. Here, the chiral alkylpiperidyl group is a piperidyl group having a chiral alkyl group. Further, the selenophosphoric acid amide preferably has a structure in which R ⁵ in the general formula (4) represents —NR ⁶ R ⁷ and at least one selected from R ⁶ and R ⁷ represents a chiral alkyl group. These selenophosphoric acid amides contain one or more asymmetric centers due to a chiral alkylpiperidyl group or a chiral alkyl group, and each exhibit optical activity. Examples of the chiral alkylpiperidyl group include a 2-methylpiperidyl group. On the other hand, examples of the chiral alkyl group include a 1-phenylethyl group, a 1- (1-naphthyl) ethyl group, a 1-methylpropyl group, and a 1,2-dimethylpropyl group. A selenophosphoric acid amide exhibiting optical activity (hereinafter referred to as an optically active selenophosphoric acid amide) is useful as a raw material for the optically active compound, like the selenophosphinic acid amide. Aminophosphine obtained from optically active selenophosphoric acid amide can be used as an optically active ligand source in the same manner as aminophosphine obtained from selenophosphinic acid amide. It is used as a catalyst for a synthesis reaction of a compound having

  A selenophosphoric acid amide is produced by reacting a selenophosphoric acid chloride having a structure represented by the following general formula (5) with an amine having a structure represented by the following general formula (6) (the following reaction formula ( 11)).

（式中、Ｒ⁴は水素原子、ハロゲン原子、アルキル基、アリール基、アルコキシ基又はシリル基を示す。）
Ｒ⁵−Ｍ …（６）
（式中、Ｒ⁵は−ＮＲ⁶Ｒ⁷又はアルキルピペリジル基を示し、Ｍは水素原子又はリチウム原子を示す。Ｒ⁶は水素原子又はアルキル基を示し、Ｒ⁷はアルキル基を示す。）

(In the formula, R ⁴ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or a silyl group.)
R ⁵ -M (6)
(In the formula, R ⁵ represents —NR ⁶ R ⁷ or an alkylpiperidyl group, M represents a hydrogen atom or a lithium atom, R ⁶ represents a hydrogen atom or an alkyl group, and R ⁷ represents an alkyl group.)

このセレノリン酸アミドの製造方法では、０℃や２５℃程度の低温でセレノリン酸塩化物及びアミンを同じ溶媒に溶解させて反応溶液を調製した後、該反応溶液を加熱することが好ましい。このとき、低温でセレノリン酸塩化物及びアミンを溶解させることによりこれらの分解を抑制し、反応溶液を加熱することにより前記反応式（１１）の反応が促進されるという利点がある。ここで、セレノリン酸塩化物及びアミンの反応割合は当量比で１：２であり、塩化水素又は塩化リチウムが副生成物として生成される。反応に用いられる溶媒は各成分を溶解させるものであれば特に限定されないが、トルエン等のベンゼン系溶媒やＴＨＦ等のエーテル系溶媒が前記反応式（１１）の反応を阻害しないとともに各成分の溶解性が高いために好ましい。前記反応溶液の加熱温度、即ち前記反応式（１１）の反応温度は６５〜１１０℃が好ましい。反応温度が６５℃未満ではセレノリン酸アミドの製造効率が低下し、逆に１１０℃を超えるとセレノリン酸アミドが分解しやすくなる。前記反応溶液の加熱時間、即ち前記反応式（１１）の反応時間は２〜４時間が好ましい。反応時間が２時間未満では前記反応式（１１）の反応を十分に進行させることができず、逆に４時間を超えるとセレノリン酸アミドの製造効率が低下しやすい。

In this method for producing selenophosphoric acid amide, it is preferable to prepare a reaction solution by dissolving selenophosphoric acid chloride and amine in the same solvent at a low temperature of about 0 ° C. or 25 ° C., and then heating the reaction solution. At this time, there is an advantage that the decomposition of selenophosphate and amine is suppressed at a low temperature to suppress the decomposition thereof, and the reaction solution (11) is promoted by heating the reaction solution. Here, the reaction ratio of selenophosphate and amine is 1: 2, and hydrogen chloride or lithium chloride is produced as a by-product. The solvent used in the reaction is not particularly limited as long as it dissolves each component, but a benzene solvent such as toluene or an ether solvent such as THF does not inhibit the reaction of the reaction formula (11) and dissolves each component. It is preferable because of its high properties. The heating temperature of the reaction solution, that is, the reaction temperature of the reaction formula (11) is preferably 65 to 110 ° C. When the reaction temperature is less than 65 ° C., the production efficiency of selenophosphoric acid amide is lowered. The heating time of the reaction solution, that is, the reaction time of the reaction formula (11) is preferably 2 to 4 hours. When the reaction time is less than 2 hours, the reaction of the reaction formula (11) cannot be sufficiently progressed. Conversely, when the reaction time exceeds 4 hours, the production efficiency of selenophosphoric acid amide tends to decrease.

The optically active selenophosphoric acid amide is produced by reacting a selenophosphoric acid chloride with an amine in which R ⁵ in the general formula (6) represents a chiral alkylpiperidyl group in the same manner as the selenophosphoric acid amide. The optically active selenophosphoric acid amide includes selenophosphoric acid chloride, R ⁵ in the general formula (6) represents —NR ⁶ R ⁷ , and at least one selected from R ⁶ and R ⁷ has a chiral alkyl group. It is produced by reacting the amine shown in the same manner as the selenophosphoric acid amide. Here, the amine may be an optically active substance or a racemate. In these cases, since the optically active selenophosphoric acid amide is obtained as a diastereomer, it is preferable to perform the same purification operation as that of the selenophosphinic acid amide.
The selenophosphate chloride according to the present embodiment has a structure represented by the following general formula (7), and is a (R) -form or (S) -form compound.

（式中、Ｒ^８は水素原子、ハロゲン原子、アルキル基、アリール基、アルコキシ基又はシリル基を示す。）

(In the formula, R ⁸ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or a silyl group.)

In R ⁸ , the halogen atom may be a chlorine atom, the alkyl group may be an ethyl group such as a methyl group, 1-phenylethyl group, 1- (1-naphthyl) ethyl group, 1-cyclohexylethyl group, 1- Examples thereof include a propyl group such as a methylpropyl group or a 1,2-dimethylpropyl group. The aryl group includes a phenyl group, the alkoxy group includes a menthyloxy group, and the silyl group includes a trimethylsilyl group. This selenophosphate is stable in air and stable in water. Furthermore, the selenophosphate chloride exhibits optical activity due to the (R) isomer or the (S) isomer. The selenophosphate chloride is useful as a chiral discriminating agent for separating an optically active compound from a racemate and a raw material for the optically active selenophosphoric acid amide. It is preferable that the selenophosphate chloride has a structure in which R ⁸ represents a hydrogen atom because the stability in air and water is particularly high.

Selenophosphate chloride is produced by reacting phosphorus trichloride, triethylamine, a binaphthol derivative having a structure represented by the following general formula (8), which is (R) or (S), and selenium. (See the following reaction formula (12)). Here, when producing the (R) selenophosphate chloride, the (R) binaphthol derivative is used as a raw material, and when producing the (S) selenophosphate chloride, the (S) binaphthol derivative is Used as a raw material. The binaphthol derivative, ^{R 8} represents a hydrogen atom 1,1'-bi-2-naphthol (aka: beta-binaphthol), 3,3'-dichloro-1,1'-bi ^{R 8} represents a chlorine atom -2-naphthol.

（式中、Ｒ^８は水素原子、ハロゲン原子、アルキル基、アリール基、アルコキシ基又はシリル基を示す。）

(In the formula, R ⁸ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or a silyl group.)

このセレノリン酸塩化物の製造方法では、三塩化リン及びトリエチルアミンの溶液と、ビナフトール誘導体の溶液とを０℃程度の低温で混合し、さらにセレンを加えて反応溶液を調製した後、該反応溶液を加熱することが好ましい。このとき、各溶液を低温で混合することにより各溶液中の成分の分解を防止し、反応溶液を加熱することにより前記反応式（１２）の反応が促進されるという利点がある。ここで、三塩化リン、トリエチルアミン、ビナフトール誘導体及びセレンの反応割合は当量比で１：２：１：１であり、ホスホン酸エステルが副生成物として生成される。反応に用いられる溶媒は各成分を溶解させるものであれば特に限定されないが、トルエン等のベンゼン系溶媒が前記反応式（１２）の反応を阻害しないとともに各成分の溶解性が高いために好ましい。前記反応式（１２）の反応温度の下限は０℃が好ましく、上限は溶媒の沸点が好ましい。反応温度が０℃未満ではセレノリン酸塩化物の反応効率が低下し、逆に溶媒の沸点を超えると反応溶液の溶媒が揮発しやすい。前記反応式反応溶液の加熱時間、即ち前記反応式（１２）の反応時間は３〜９時間が好ましい。反応時間が３時間未満では前記反応式（１２）の反応を十分に進行させることができず、逆に９時間を超えるとセレノリン酸塩化物の製造効率が低下しやすい。

In this method for producing a selenophosphate, a solution of phosphorus trichloride and triethylamine and a solution of a binaphthol derivative are mixed at a low temperature of about 0 ° C., and further a selenium is added to prepare a reaction solution. It is preferable to heat. At this time, there is an advantage that the components in each solution are prevented from being decomposed by mixing each solution at a low temperature, and the reaction of the reaction formula (12) is promoted by heating the reaction solution. Here, the reaction ratio of phosphorus trichloride, triethylamine, a binaphthol derivative and selenium is 1: 2: 1: 1 in an equivalent ratio, and a phosphonic acid ester is produced as a by-product. The solvent used in the reaction is not particularly limited as long as it dissolves each component, but a benzene solvent such as toluene is preferable because it does not inhibit the reaction of the reaction formula (12) and the solubility of each component is high. The lower limit of the reaction temperature in the reaction formula (12) is preferably 0 ° C., and the upper limit is preferably the boiling point of the solvent. When the reaction temperature is less than 0 ° C., the reaction efficiency of the selenophosphate chloride is lowered, and conversely, when the boiling point of the solvent is exceeded, the solvent in the reaction solution tends to volatilize. The heating time of the reaction formula reaction solution, that is, the reaction time of the reaction formula (12) is preferably 3 to 9 hours. If the reaction time is less than 3 hours, the reaction of the reaction formula (12) cannot be sufficiently progressed. Conversely, if the reaction time exceeds 9 hours, the production efficiency of selenophosphate is likely to be lowered.

  Therefore, the selenophosphinic acid amide according to the present embodiment is a novel compound having the structure represented by the general formula (1), and the selenophosphoric acid amide according to the present embodiment has the structure represented by the general formula (4). It is a new compound. These selenophosphinic acid amides and selenophosphoric acid amides are stable in the air and are useful, for example, as the selenium sensitizer. In addition, the selenophosphate chloride according to the present embodiment has a structure represented by the general formula (7), is a novel compound of (R) form or (S) form, and is stable in air and water. Selenophosphates are useful, for example, as the chiral discriminating agent.

  Furthermore, since the reactivity of the selenophosphinic chloride and the lithium salt of the amine is high, the reaction of the reaction formula (10) proceeds without using a catalyst. For this reason, according to this method for producing selenophosphinic acid amide, it is easy to produce selenophosphinic acid amide that is stable in air and exhibits optical activity. In addition, since the reactivity between the selenophosphate and the amine is high, the reaction of the reaction formula (11) proceeds without using a catalyst. For this reason, according to this method for producing selenophosphoric acid amide, it is easy to produce selenophosphoric acid amide that is stable in the air. In addition, since the phosphorus trichloride, triethylamine, binaphthol derivative, and selenium have high reactivity, the reaction of the reaction formula (12) proceeds without using a catalyst. For this reason, according to the manufacturing method of a selenophosphate compound, the manufacture of the selenophosphate compound which is stable in the air and water and exhibits optical activity is easy.

Hereinafter, the present invention will be described more specifically with reference to examples. In the following description, Ph represents a phenyl group.
Example 1 At 0 ° C., 0.28 mL (2.2 mmol) of (S) -1-phenylethylamine was dissolved in 5 mL of THF. Next, 1.25 mL (1.6 Msolution in hexane; 2.0 mmol) of butyl lithium was added to the THF, and then the THF was stirred for 10 minutes to obtain a lithium salt of (S) -1-phenylethylamine. Here, the lithium salt of (S) -1-phenylethylamine is the lithium salt of the amine and was obtained in a state dissolved in THF. This THF solution is designated as Solution A. On the other hand, P-1,1-dimethylethyl-P-phenylselenophosphinic chloride 0.560 g (2.00 mmol) as selenophosphinic acid chloride was dissolved in 5 mL of THF. This THF solution is designated as Solution B. Subsequently, the solution A was added to the solution B at 0 ° C. to prepare a reaction solution, and then the reaction solution was heated to 25 ° C. and then stirred for 2 hours. Next, the reaction solution was extracted with dichloromethane to obtain an extract composed of a dichloromethane layer. Subsequently, the extract was washed with water, water was removed from the extract using magnesium sulfate, the extract was filtered, and the filtrate was concentrated, and then the solvent was distilled off from the concentrated filtrate to obtain a residue. Subsequently, the residue was purified by silica gel column chromatography (hexane: dichloromethane = 1: 1) to obtain a colorless solid compound 1a (Rf = 0.40) and a colorless solid compound 1b (Rf = 0.30). The structures of these compounds 1a and 1b were analyzed. The results are described below.

(Compound 1a)
<Infrared absorption spectrum (KBr tablet)> 3287, 3086, 3066, 3045, 3029, 2968, 2952, 2943, 2925, 2899, 2863, 1493, 1472, 1453, 1435, 1411, 1390, 1373,1362, 1312, 1282,1205, 1115, 1100, 1061, 1034, 1012, 1000, 972, 940, 842, 809,783, 745, 699, 627cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ1.11 (d, ³ J _HP = 17.1 Hz, 9 H, CCH ₃ ), 1.32 (d, J = 6.8 Hz , 3H, CH ₃ in _{CHCH 3), 2.40 (s,} broad, 1H, NH), 4.78-4.87 (m, 1H, CH in _{CHCH 3), 7.26-7.53 (m,} 8H, Ar), 8.06- . 8.11 (m, 2H, Ar ), 13 C-NMR (CDCl 3): δ24.5 (CH 3 in CHCH _3), (CH ₃ in _{CCH 3) 25.0, 35.6 (d} , 1 J CP = 56.2 Hz, C bonded to CH ₃ in CCH ₃ ), 52.5 (CH in CHCH ₃ ), 126.6 (Ar), 127.3 (Ar), 127.7 (d, J _CP = 11.6 Hz, Ar), 128.7 (Ar), 131.5 (d, ⁴ J _CP = 3.3Hz, Ar), 132.4 (d, ¹ J _CP = 78.6Hz, Ar), 133.3 (d, J _CP = 9.9Hz, Ar), 145.3 (d, J _CP = 7.4Hz , Ar)., ³¹ P-NMR (CDCl ₃ ): δ 79.0 ( ¹ J _P-Se = 750.2 Hz)., ⁷⁷ Se-NMR (CDCl ₃ ): δ-369.2 (d, ¹ J _Se-P = 750.2Hz).
<Mass spectrometry> MS (EI) m / z 365 (M ⁺ ).
<Elemental Analysis> Anal. Calcd for C ₁₈ H ₂₄ NPSe (364.32): C, 59.34; H, 6.64; N, 3.84. Found: C, 59.23; H, 6.49; N, 3.71.
(Compound 1b)
<Infrared absorption spectrum (KBr tablet)> 3346, 3078, 3060, 3020, 2999,2973, 2961, 2946, 2922, 2905, 2866, 1603, 1493, 1472, 1448, 1436, 1405, 1391,1367, 1343, 1308, 1293, 1276, 1203, 1189, 1102, 1082, 1070, 1022, 1011, 999,957, 907, 848, 809, 763, 750, 696, 627cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ 1.19 (d, ³ J _HP = 17.1 Hz, 9 H, CCH ₃ ), 1.61 (d, J = 6.3 Hz , 3H, CH ₃ in _{CHCH 3), 2.29 (s,} broad, 1H, NH), 4.40-4.50 (m, 1H, CH in _{CHCH 3), 7.19-7.38 (m,} 8H, Ar), 7.47- . 7.73 (m, 2H, Ar ), 13 C-NMR (CDCl 3): δ25.0 (CH 3 in _{CCH 3), 25.8 (d,} 2 J CP = 3.3Hz, CH 3 in CHCH _3), 35.2 (d, ¹ J _CP = 56.2 Hz, C binding to CH ₃ in CCH ₃ ), 52.3 (CH in CHCH ₃ ), 126.2 (Ar), 126.9 (Ar), 127.3 (d, J _CP = 12.4 Hz , Ar), 128.4 (Ar), 130.2 (d, ¹ J _CP = 81.1Hz, Ar), 131.3 (d, J _CP = 2.5Hz, Ar), 133.8 (d, J _CP = 10.8Hz, Ar), 145.1 (d, J _CP = 5.8 Hz, Ar)., ³¹ P-NMR (CDCl ₃ ): δ 81.3 ( ¹ J _P-Se = 741.1 Hz)., ⁷⁷ Se-NMR (CDCl ₃ ): δ-335.4 ( d, ¹ J _Se-P = 741.1Hz).
<Mass spectrometry> MS (EI) m / z 365 (M ⁺ ).
<Elemental Analysis> Anal. Calcd for C ₁₈ H ₂₄ NPSe (364.32): C, 59.34; H, 6.64; N, 3.84. Found: C, 59.23; H, 6.49; N, 3.71.

From the above results, compound 1a has the structure represented by the following formula (13), and (R _P , S) -P-1,1-dimethylethyl-P-phenyl-N-1-phenylethylseleno Identified as phosphinic acid amide. The yield of this selenophosphinic acid amide is 34% (yield: 0.251 g, 0.69 mmol), the melting point is 128 to 130 ° C., and the optical rotation [α] _D ²⁰ (c 1.00, CH ₂ Cl ₂ ) is − It was 40 °.

一方、化合物1bは下記式（14）に示した構造を有しており、(S_P,S)-P-1,1-ジメチルエチル-P-フェニル-N-1-フェニルエチルセレノホスフィン酸アミドであると同定した。このセレノホスフィン酸アミドの収率は51%（収量：0.370g,1.02mmol）であり、融点は104〜106℃であり、旋光度[α]_D ²⁰（c 1.00, CH₂Cl₂）は-62°であった。これらセレノホスフィン酸アミドは新規化合物であり、空気中で安定であった。

On the other hand, Compound 1b has a structure represented by the following formula (14), and (S _P , S) -P-1,1-dimethylethyl-P-phenyl-N-1-phenylethylselenophosphinic acid amide Identified. The yield of this selenophosphinic acid amide is 51% (yield: 0.370 g, 1.02 mmol), the melting point is 104 to 106 ° C., and the optical rotation [α] _D ²⁰ (c 1.00, CH ₂ Cl ₂ ) is − It was 62 °. These selenophosphinic acid amides are novel compounds and were stable in air.

（実施例２） セレノホスフィン酸塩化物としてのP-1-メチルエチル-P-フェニルセレノホスフィン酸クロリド0.531g（2.00mmol）を5mLのTHFに溶解させた。このTHF溶液を溶液Cとする。次いで、0℃で試験例1の溶液Aを溶液Cに加えて反応溶液を調製した後、試験例１と同様にして無色固体の化合物2a（Rf=0.40）及び無色固体の化合物2b（Rf=0.30）を得た。これら化合物2a及び2bの構造解析を行った。結果を以下に記載する。

Example 2 P31-methylethyl-P-phenylselenophosphinic chloride 0.531 g (2.00 mmol) as selenophosphinic acid chloride was dissolved in 5 mL of THF. This THF solution is designated as Solution C. Next, after adding Solution A of Test Example 1 to Solution C at 0 ° C. to prepare a reaction solution, colorless solid compound 2a (Rf = 0.40) and colorless solid compound 2b (Rf = 0.30) was obtained. The structures of these compounds 2a and 2b were analyzed. The results are described below.

(Compound 2a)
<Infrared absorption spectrum (KBr tablet)> 3248, 3058, 3022, 2969, 2927, 2869, 1493, 1466, 1454, 1435, 1418, 1383, 1365, 1314, 1294, 1277, 1254, 1208,1183, 1160, 1119, 1100, 1083, 1065, 1026, 997, 959, 910, 886, 833, 752, 697,674cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ 0.86 (dd, J = 7.0 Hz, ³ J _P-Se = 20.3 Hz, 3H, CH in PCHCH _{3 3), 1.13 (dd, J} = 6.8Hz, 3 J P-Se = 19.5Hz, 3H, CH 3 in _{PCHCH 3), 1.29 (d,} J = 6.3Hz, 3H, CH 3 in NCHCH _3), 1.99 (s, broad, 1H, NH), 2.18-2.31 (m, 1H, PCH), 4.64-4.72 (m, 1H, NCH), 7.24-7.54 (m, 8H, Ar), 8.02-8.07 (m, ^{. 2H, Ar), 13 C} -NMR (CDCl 3): δ16.5 (PCHCH 3 CH 3 in), 16.6 (CH ₃ in _{PCHCH 3), 24.8 (d,} 3 J CP = 3.3Hz, NCHCH 3 CH ₃ ), 32.6 (d, ¹ J _CP = 61.2Hz, PCH), 52.3 (NCH), 126.5 (Ar), 127.3 (Ar), 128.2 (d, J _CP = 11.6Hz, Ar), 128.6 ( Ar), 131.7 (d, ⁴ J _CP = 2.5Hz, Ar), 132.2 (d, J _CP = 10.8Hz, Ar), 133.1 (Ar; One half of the signal isoverlapping with another signal), 145.0 (d, J _CP = 7.4 Hz, Ar)., ³¹ P-NMR (CDCl ₃ ): δ 74.1 ( ¹ J _P-Se = 745.6 Hz)., ⁷⁷ Se-NMR (CDCl ₃ ): δ-386.8 (d, ¹ J _(Se-P = 745.6Hz).
<Mass spectrometry> MS (EI) m / z 351 (M ⁺ ).
(Compound 2b)
<Infrared absorption spectrum (KBr tablet)> 3291, 3079, 3060, 3023, 2976,2927, 2881, 2871, 1491, 1452, 1438, 1412, 1387, 1365, 1308, 1298, 1278, 1243,1204, 1119, 1103, 1085, 1067, 1021, 999, 962, 929, 886, 849, 764, 748, 696,671, 600cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ 0.93 (dd, J = 6.8 Hz, ³ J _P-Se = 20.5 Hz, 3H, CH in PCHCH _{3 3), 1.22 (dd, J} = 6.8Hz, 3 J P-Se = 19.0Hz, 3H, CH 3 in _{PCHCH 3), 1.53 (d,} J = 6.8Hz, 3H, CH 3 in NCHCH _3), 2.22-2.33 (m, 1H, PCH), 2.35 (s, broad, 1H, NH), 4.29-4.37 (m, 1H, NCH), 7.12-7.23 (m, 5H, Ar), 7.26-7.31 (m, . 2H, Ar), 7.37-7.41 ( m, 1H, Ar), 7.74-7.80 (m, 2H, Ar), 13 C-NMR (CDCl 3): δ16.5 (CH 3 in PCHCH _3), 25.5 (d, ³ J _CP = 4.1Hz, CH _{3 in} NCHCH ₃ ), 32.0 (d, ¹ J _CP = 61.2Hz, PCH), 52.3 (NCH), 126.3 (Ar), 127.0 (Ar), 127.9 (d , J _CP = 12.4Hz, Ar), 128.3 (Ar), 131.0 (d, ¹ J _CP = 82.7Hz, Ar), 131.5 (d, ⁴ J _CP = 3.3Hz, Ar), 132.5 (d, J _CP = 10.8 Hz, Ar), 144.7 (d, J _CP = 5.8 Hz, Ar)., ³¹ P-NMR (CDCl ₃ ): δ 75.0 ( ¹ J _P-Se = 744.2 Hz)., ⁷⁷ Se-NMR (CDCl ₃ ): δ-368.0 (d, ¹ J _Se-P = 744.2Hz).
<Mass Spectrometry> MS (EI) m / z 351 (M ⁺ ).

From the above results, compound 2a has the structure represented by the following formula (15), and (R _P , S) -P-1-methylethyl-P-phenyl-N-1-phenylethylselenophosphinic acid Identified as an amide. The yield of this selenophosphinic acid amide is 36% (yield: 0.252 g, 0.72 mmol), the melting point is 65 to 67 ° C., and the optical rotation [α] _D ²⁰ (c 1.00, CH ₂ Cl ₂ ) is − It was 44 °.

一方、化合物2bは下記式（16）に示した構造を有しており、(S_P,S)-P-1-メチルエチル-P-フェニル-N-1-フェニルエチルセレノホスフィン酸アミドであると同定した。このセレノホスフィン酸アミドの収率は46%（収量：0.323g,0.92mmol）であり、融点は89〜91℃であり、旋光度[α]_D ²⁰（c 1.00, CH₂Cl₂）は-55°であった。これらセレノホスフィン酸アミドは新規化合物であり、空気中で安定であった。

On the other hand, compound 2b has the structure shown in the following formula (16) and is (S _P , S) -P-1-methylethyl-P-phenyl-N-1-phenylethylselenophosphinic acid amide. Was identified. The yield of this selenophosphinic acid amide is 46% (yield: 0.323 g, 0.92 mmol), the melting point is 89-91 ° C., and the optical rotation [α] _D ²⁰ (c 1.00, CH ₂ Cl ₂ ) is − It was 55 °. These selenophosphinic acid amides are novel compounds and were stable in air.

（実施例３） セレノホスフィン酸塩化物としてのP-シクロヘキシル-P-フェニルセレノホスフィン酸クロリド0.611g（2.00mmol）を5mLのTHFに溶解させた。このTHF溶液を溶液Dとする。次いで、0℃で試験例1の溶液Aを溶液Dに加えて反応溶液を調製した後、試験例１と同様にして無色固体の化合物3a（Rf=0.40）及び無色固体の化合物3b（Rf=0.30）を得た。これら化合物3a及び3bの構造解析を行った。結果を以下に記載する。

Example 3 0.611 g (2.00 mmol) of P-cyclohexyl-P-phenylselenophosphinic chloride as selenophosphinic acid chloride was dissolved in 5 mL of THF. This THF solution is designated as Solution D. Next, a solution of Test Example 1 was added to Solution D at 0 ° C. to prepare a reaction solution, and then colorless solid compound 3a (Rf = 0.40) and colorless solid compound 3b (Rf = 0.30) was obtained. The structures of these compounds 3a and 3b were analyzed. The results are described below.

(Compound 3a)
<Infrared absorption spectrum (KBr tablet)> 3291, 3068, 3051, 3026, 2966,2925, 2852, 1493, 1450, 1436, 1410, 1371, 1341, 1310, 1297, 1269, 1201, 1176,1101, 1083, 1064, 1029, 1020, 1000, 956, 888, 853, 838, 822, 751, 737, 697,603cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ 0.89-1.85 (m, 11 H, CH ₂ , CH), 1.21 (d, J = 6.8 Hz, 3H, CH ₃ in _{NCHCH 3), 2.25 (s,} broad, 1H, NH), 4.57-4.65 (m, 1H, NCH), 7.16-7.20 (m, 1H, Ar), 7.26 (t, J = 7.8Hz, 2H, Ar), 7.33-7.44 (m, 5H, Ar), 7.94-7.98 (m, 2H, Ar)., ¹³ C-NMR (CDCl ₃ ): δ24.6 (d, ³ J _CP = 3.3 Hz, CH _{3 in} NCHCH ₃ ), 25.5 (CH ₂ ), 25.9 (d, J _CP = 14.9Hz, CH ₂ ), 26.0 (d, J _CP = 14.9Hz, CH ₂ ), 26.1 (CH ₂ ), 26.3 ( CH ₂ ), 42.4 (d, ¹ J _CP = 59.5Hz, CH), 52.0 (NCH), 126.6 (Ar), 127.3 (Ar), 128.0 (d, J _CP = 12.4Hz, Ar), 128.5 (Ar) , 131.6 (d, ⁴ J _CP = 2.5Hz, Ar), 132.3 (d, J _CP = 9.9Hz, Ar), 132.6 (d, ¹ J _CP = 81.9Hz, Ar), 145.0 (d, J _CP = 6.6 Hz, Ar)., ³¹ P-NMR (CDCl ₃ ): δ 70.2 ( ¹ J _P-Se = 739.6 Hz). ⁷⁷ Se-NMR (CDCl ₃ ): δ-363.5 (d, ¹ J _Se-P = 739.6Hz).
<Mass Spectrometry> MS (EI) m / z 391 (M ⁺ ).
(Compound 3b)
<Infrared absorption spectrum (KBr tablet)> 3263, 3060, 3049, 3029, 2980, 2959, 2928, 2854, 1491, 1446, 1435, 1411, 1374, 1311, 1279, 1204, 1177, 1122,1102, 1086, 1032, 998, 960, 917, 889, 855, 834, 822, 755, 739, 695, 602cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ1.06-1.95 (m, 11H, CH ₂ , CH), 1.47 (d, J = 6.8 Hz, 3H, CH ₃ in _{NCHCH 3), 2.37 (s,} broad, 1H, NH), 4.21-4.31 (m, 1H, NCH), 7.06-7.41 (m, 8H, Ar), 7.65-7.70 (m, 2H, Ar ^{), 13 C-NMR (CDCl} 3):. δ25.5 (d, 2 J CP = 4.1Hz, CH 3 in _{NCHCH 3), 25.6 (CH 2} ), 25.9 (d, J CP = 15.7Hz, CH ₂ ), 26.0 (CH ₂ ), 26.0 (d, J _CP = 14.9Hz, CH ₂ ), 26.2 (CH ₂ ), 42.1 (d, ¹ J _CP = 60.4Hz, CH), 52.1 (NCH), 126.2 ( Ar), 126.9 (Ar), 127.7 (d, J _CP = 12.4Hz, Ar), 128.3 (Ar), 130.5 (Ar; One half of the signal is overlapping with another signal), 131.4 (d, J _CP = 2.5 . Hz, Ar), 132.6 ( d, J CP = 10.8Hz, Ar), 144.7 (d, J CP = 5.8Hz, Ar), 31 P-NMR (CDCl 3): δ70.8 (1 J P-Se = 739.6 Hz)., ⁷⁷ Se-NMR (CDCl ₃ ): δ-342.9 (d, ¹ J _Se-P = 739.6 Hz).
<Mass Spectrometry> MS (EI) m / z 391 (M ⁺ ).

From the above results, compound 3a has the structure represented by the following formula (17), and is (R _P , S) _-P- cyclohexyl- _P -phenyl-N-1-phenylethylselenophosphinic acid amide. Was identified. The yield of this selenophosphinic acid amide is 37% (yield: 0.286 g, 0.73 mmol), the melting point is 75-77 ° C., and the optical rotation [α] _D ²⁰ (c 1.00, CH ₂ Cl ₂ ) is − It was 40 °.

一方、化合物3bは下記式（18）に示した構造を有しており、(S_P,S)-P-シクロヘキシル-P-フェニル-N-1-フェニルエチルセレノホスフィン酸アミドであると同定した。このセレノホスフィン酸アミドの収率は50%（収量：0.387g,0.99mmol）であり、融点は82〜84℃であり、旋光度[α]_D ²⁰（c 1.00, CH₂Cl₂）は-37°であった。これらセレノホスフィン酸アミドは新規化合物であり、空気中で安定であった。

On the other hand, compound 3b has the structure shown in the following formula (18) and was identified as (S _P , S) _-P- cyclohexyl- _P -phenyl-N-1-phenylethylselenophosphinic acid amide. . The yield of this selenophosphinic acid amide is 50% (yield: 0.387 g, 0.99 mmol), the melting point is 82 to 84 ° C., and the optical rotation [α] _D ²⁰ (c 1.00, CH ₂ Cl ₂ ) is − It was 37 °. These selenophosphinic acid amides are novel compounds and were stable in air.

（実施例４） 0℃で、(S)-1-(1-ナフチル)エチルアミン0.35mL（2.2mmol）を5mLのTHFに溶解させた。次いで、該THFにブチルリチウム1.25mL（1.6Msolution in hexane；2.0mmol）を加えた後、THFを10分間撹拌して(S)-1-(1-ナフチル)エチルアミンのリチウム塩を得た。ここで、(S)-1-(1-ナフチル)エチルアミンのリチウム塩は前記アミンのリチウム塩であり、THFに溶解した状態で得られた。このTHF溶液を溶液Eとする。続いて、0℃で溶液Eを試験例1の溶液Bに加えて反応溶液を調製した後、試験例１と同様にして淡黄色固体の化合物4a（Rf=0.30）及び淡黄色固体の化合物4b（Rf=0.20）を得た。これら化合物4a及び4bの構造解析を行った。結果を以下に記載する。

(Example 4) At 0 ° C, 0.35 mL (2.2 mmol) of (S) -1- (1-naphthyl) ethylamine was dissolved in 5 mL of THF. Next, 1.25 mL (1.6 Msolution in hexane; 2.0 mmol) of butyl lithium was added to the THF, and then the THF was stirred for 10 minutes to obtain a lithium salt of (S) -1- (1-naphthyl) ethylamine. Here, the lithium salt of (S) -1- (1-naphthyl) ethylamine is the lithium salt of the amine, and was obtained in a state dissolved in THF. This THF solution is designated as Solution E. Subsequently, after preparing a reaction solution by adding Solution E to Solution B of Test Example 1 at 0 ° C., a light yellow solid compound 4a (Rf = 0.30) and a light yellow solid compound 4b were prepared in the same manner as Test Example 1. (Rf = 0.20) was obtained. The structures of these compounds 4a and 4b were analyzed. The results are described below.

(Compound 4a)
<Infrared absorption spectrum (KBr tablet)> 3334, 3276, 3048, 2968, 2946, 2924, 2900, 2865, 1596, 1508, 1472, 1456, 1433, 1390, 1370, 1362, 1326, 1277,1233, 1190, 1170, 1119, 1106, 1098, 1081, 1030, 1016, 999, 969, 947, 939, 856,827, 797, 774, 752, 745, 721, 700, 645, 627, 609cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ1.06 (d, ³ J _HP = 17.1 Hz, 9 H, CCH ₃ ), 1.40 (d, J = 6.8 Hz , 3H, CH ₃ in _{CHCH 3), 2.50 (s,} broad, 1H, NH), 5.61-5.69 (m, 1H, CH in _{CHCH 3), 7.48-7.59 (m,} 6H, Ar), 7.68 ( d, J = 6.8Hz, 1H, Ar), 7.81 (d, J = 8.3Hz, 1H, Ar), 7.87 (d, J = 8.3Hz, 1H, Ar), 8.08-8.13 (m, 2H, Ar) , 8.46 (d, J = 8.3Hz , 1H, Ar), 13 C-NMR (CDCl 3):. δ23.1 (CH 3 in CHCH _3), (CH ₃ in CCH ₃₎ 24.9, 35.7 (d , ¹ J _CP = 56.2Hz, C binding to CH ₃ in CCH ₃ ), 48.6 (CH in CHCH ₃ ), 123.2 (Ar), 124.3 (Ar), 125.3 (Ar), 125.9 (Ar), 126.5 ( Ar), 127.6 (d, J _CP = 11.6Hz, Ar), 128.2 (Ar), 128.7 (Ar), 130.7 (Ar), 131.5 (d, ⁴ J _CP = 2.5Hz, Ar), 132.7 (d, ¹ J _CP = 78.6 Hz, Ar), 133.2 (d, J _CP = 9.9 Hz, Ar), 134.0 (Ar), 140.4 (d, J _CP = 9.1 Hz, Ar)., ³¹ P-NMR (CDCl ₃ ): δ 78.3 ( ¹ J _P-Se = 745.6 Hz). ⁷⁷ Se-NMR (CDCl ₃ ): δ-388.5 (d, ¹ J _Se-P = 745.6 Hz).
<Mass spectrometry> MS (EI) m / z 415 (M ⁺ ).
<Elemental analysis> Anal. Calcd for C ₂₂ H ₂₆ NPSe (414.38): C, 63.77; H, 6.32; N, 7.47. Found: C, 63.50; H, 6.30; N, 3.35.
(Compound 4b)
<Infrared absorption spectrum (KBr tablet)> 3384, 3050, 2968, 2956, 2922, 2898, 2864, 1596, 1509, 1472, 1459, 1433, 1368, 1360, 1331, 1308, 1270, 1253,1236, 1191, 1167, 1098, 1076, 1022, 998, 948, 848, 832, 801, 781, 746, 718,692, 645, 627, 606cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ1.22 (d, ³ J _HP = 17.0 Hz, 9 H, CCH ₃ ), 1.74 (d, J = 6.8 Hz , 3H, CH ₃ in _{CHCH 3), 2.49 (s,} broad, 1H, NH), 5.19-5.30 (m, 1H, CH in _{CHCH 3), 7.03 (dt,} J = 3.4,7.8Hz, 2H, Ar), 7.18-7.27 (m, 2H, Ar), 7.37 (t, J = 7.3Hz, 1H, Ar), 7.48 (t, J = 7.8Hz, 1H, Ar), 7.63-7.83 (m, 6H, ^{. Ar), 13 C-NMR} (CDCl 3): δ25.0 (d, 2 J CP = 1.7Hz, CH 3 in _{CCH 3), 26.1 (d,} 3 J CP = 1.7Hz, CH in CHCH _{3 3} ), 35.3 (d, ¹ J _CP = 56.2Hz, C bonded to CH ₃ in CCH ₃ ), 48.7 (CH in CHCH ₃ ), 122.7 (Ar), 123.3 (Ar), 125.3 (Ar), 125.5 (Ar), 125.8 (Ar), 127.2 (d, J _CP = 12.4Hz, Ar), 127.5 (Ar), 128.5 (Ar), 129.9 (Ar), 130.2 (d, ¹ J _CP = 81.9Hz, Ar) , 131.2 (d, ⁴ J _CP = 2.5Hz, Ar), 133.5 (d, J _CP = 10.8Hz, Ar), 133.7 (Ar), 141.3 (d, J _CP = 5.8Hz, Ar)., ³¹ P- NMR (CDCl ₃ ): δ 82.0 ( ¹ J _P-Se = 744.2 Hz). ⁷⁷ Se-NMR (CDCl ₃ ): δ-336.9 (d, ¹ J _Se-P = 744.2 Hz).
<Mass spectrometry> MS (EI) m / z 415 (M ⁺ ).
<Elemental analysis> Anal. Calcd for C ₂₂ H ₂₆ NPSe (414.38): C, 63.77; H, 6.32; N, 7.47. Found: C, 63.50; H, 6.30; N, 3.35.

From the above results, compound 4a has the structure represented by the following formula (19), and (R _P , S) -P-1,1-dimethylethyl-N-1- (1-naphthyl) ethyl- It was identified as P-phenylselenophosphinic acid amide. The yield of this selenophosphinic acid amide is 36% (yield: 0.296 g, 0.71 mmol), the melting point is 155-157 ° C., and the optical rotation [α] _D ²⁰ (c 1.00, CH ₂ Cl ₂ ) is −13 °. Met.

一方、化合物4bは下記式（20）に示した構造を有しており、(S_P,S)-P-1,1-ジメチルエチル-N-1-(1-ナフチル)エチル-P-フェニルセレノホスフィン酸アミドであると同定した。このセレノホスフィン酸アミドの収率は56%（収量：0.467g,1.13mmol）であり、融点は145〜147℃であり、旋光度[α]_D ²⁰（c 1.00, CH₂Cl₂）は-18°であった。これらセレノホスフィン酸アミドは新規化合物であり、空気中で安定であった。

On the other hand, compound 4b has the structure shown in the following formula (20), and (S _P , S) -P-1,1-dimethylethyl-N-1- (1-naphthyl) ethyl-P-phenyl It was identified as selenophosphinic acid amide. The yield of this selenophosphinic acid amide is 56% (yield: 0.467 g, 1.13 mmol), the melting point is 145 to 147 ° C., and the optical rotation [α] _D ²⁰ (c 1.00, CH ₂ Cl ₂ ) is − It was 18 °. These selenophosphinic acid amides are novel compounds and were stable in air.

（実施例５） 0℃で試験例4の溶液Eを試験例2の溶液Cに加えて反応溶液を調製した後、試験例1と同様にして淡黄色固体の化合物5a（Rf=0.30）及び淡黄色固体の化合物5b（Rf=0.20）を得た。これら化合物5a及び5bの構造解析を行った。結果を以下に記載する。

Example 5 After preparing a reaction solution by adding the solution E of Test Example 4 to the solution C of Test Example 2 at 0 ° C., a light yellow solid compound 5a (Rf = 0.30) and A pale yellow solid compound 5b (Rf = 0.20) was obtained. The structures of these compounds 5a and 5b were analyzed. The results are described below.

(Compound 5a)
<Infrared absorption spectrum (KBr tablet)> 3243, 3046, 2979, 2962, 2928,2871, 1680, 1598, 1508, 1463, 1449, 1434, 1397, 1372, 1331, 1305, 1278, 1242,1171, 1115, 1098, 1081, 1031, 1022, 1001, 948, 883, 848, 824, 798, 779, 743,721, 705, 690, 675, 645, 612cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ 0.82 (dd, J = 6.8 Hz, ³ J _P-Se = 20.0 Hz, 3H, CH in PCHCH _{3 3), 1.07 (dd, J} = 6.8Hz, 3 J P-Se = 19.0Hz, 3H, CH 3 in _{PCHCH 3), 1.37 (d,} J = 6.3Hz, 3H, CH 3 in NCHCH _3), 2.12-2.25 (m, 1H, PCH), 2.55 (s, broad, 1H, NH), 5.49-5.58 (m, 1H, NCH), 7.43-7.62 (m, 7H, Ar), 7.77 (d, J = 8.3Hz, 1H, Ar), 7.85 (d, J = 7.8Hz, 1H, Ar), 8.03-8.09 (m, 2H, Ar), 8.38 (d, J = 8.3Hz, 1H, Ar), ¹³ C _{-NMR (CDCl 3): δ16.4 (} CH 3 in PCHCH _3), 16.5 (CH ₃ in PCHCH _3), 23.5 (CH ₃ in _{NCHCH 3), 32.5 (d,} 1 J CP = 61.2Hz, PCH), 48.2 (NCH), 123.2 (Ar), 123.9 (Ar), 125.3 (Ar), 125.8 (Ar), 126.4 (Ar), 128.1 (Ar), 128.1 (d, J _CP = 12.4Hz, Ar) , 128.7 (Ar), 130.5 (Ar), 131.6 (d, ⁴ J _CP = 2.5Hz, Ar), 131.9 (d, J _CP = 10.8Hz, Ar), 133.4 (d, ¹ J _CP = 80.2Hz, Ar ), 133.9 (Ar), 140.3 (d, J _CP = 8.3 Hz, Ar)., ³¹ P-NMR (CDCl ₃ ): δ73.8 ( ¹ J _P-Se = 745.6 Hz)., ⁷⁷ Se-NMR ( CDCl ₃ ): δ-414.3 (d, ¹ J _Se-P = 745.6 Hz).
<Mass Spectrometry> MS (EI) m / z 401 (M ⁺ ).
(Compound 5b)
<Infrared absorption spectrum (KBr tablet)> 3307, 3061, 3047, 2976, 2959, 2928, 2871, 1597, 1510, 1464, 1447, 1437, 1385, 1363, 1310, 1282, 1241, 1173,1121, 1102, 1076, 1027, 1015, 951, 883, 860, 828, 795, 777, 754, 721, 705, 696,667, 617cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ 0.95 (dd, J = 6.8 Hz, ³ J _P-Se = 20.0 Hz, 3H, CH in PCHCH _{3 3), 1.26 (dd, J} = 6.8Hz, 3 J P-Se = 19.0Hz, 3H, CH 3 in _{PCHCH 3), 1.67 (d,} J = 6.3Hz, 3H, CH 3 in NCHCH _3), 2.25-2.38 (m, 1H, PCH), 2.57 (s, broad, 1H, NH), 5.10-5.21 (m, 1H, NCH), 7.10-7.15 (m, 2H, Ar), 7.23-7.28 (m, 1H, Ar), 7.29-7.34 (m, 1H, Ar), 7.37-7.42 (m, 2H, Ar), 7.55 (d, J = 6.9Hz, 1H, Ar), 7.67-7.72 (m, 3H, Ar .), 7.77-7.84 (m, 2H , Ar), 13 C-NMR (CDCl 3): δ16.5 (CH 3 in PCHCH _3), 16.6 (CH ₃ in _{PCHCH 3), 25.9 (d,} 3 J _CP = 3.3Hz, CH _{3 in} NCHCH ₃ ), 32.2 (d, ¹ J _CP = 61.2Hz, PCH), 48.7 (NCH), 123.1 (Ar), 123.2 (Ar), 125.3 (Ar), 125.5 ( Ar), 125.8 (Ar), 127.6 (Ar), 127.8 (d, J _CP = 12.4Hz, Ar), 128.7 (Ar), 130.0 (Ar), 130.9 (d, ¹ J _CP = 82.7Hz, Ar), 131.4 (d, ⁴ J _CP = 2.5Hz, Ar), 132.3 (d, J _CP = 10.8Hz, Ar), 133.7 (Ar), 140.9 (d, J _CP = 5.0Hz, Ar)., ³¹ P-NMR (CDCl ₃ ): δ 75.5 ( ¹ J _P-Se = 744.2 Hz). ⁷⁷ Se-NMR (CDCl ₃ ): δ-371.2 (d, ¹ J _Se-P = 744.2 Hz).
<Mass Spectrometry> MS (EI) m / z 401 (M ⁺ ).

From the above results, compound 5a has the structure represented by the following formula (21), and (R _P , S) -P-1-methylethyl-N-1- (1-naphthyl) ethyl-P— It was identified as phenylselenophosphinic acid amide. The yield of this selenophosphinic acid amide is 38% (yield: 0.301 g, 0.76 mmol), the melting point is 109-111 ° C., and the optical rotation [α] _D ²⁰ (c 1.00, CH ₂ Cl ₂ ) is − It was 28 °.

一方、化合物5bは下記式（22）に示した構造を有しており、(S_P,S)-P-1-メチルエチル-N-1-(1-ナフチル)エチル-P-フェニルセレノホスフィン酸アミドであると同定した。このセレノホスフィン酸アミドの収率は53%（収量：0.422g,1.05mmol）であり、融点は82〜84℃であり、旋光度[α]_D ²⁰（c 1.00, CH₂Cl₂）は+15°であった。これらセレノホスフィン酸アミドは新規化合物であり、空気中で安定であった。

On the other hand, compound 5b has the structure shown in the following formula (22), and (S _P , S) -P-1-methylethyl-N-1- (1-naphthyl) ethyl-P-phenylselenophosphine Identified as acid amide. The yield of this selenophosphinic acid amide is 53% (yield: 0.422 g, 1.05 mmol), the melting point is 82-84 ° C., and the optical rotation [α] _D ²⁰ (c 1.00, CH ₂ Cl ₂ ) is + It was 15 °. These selenophosphinic acid amides are novel compounds and were stable in air.

（実施例６） 0℃で試験例4の溶液Eを試験例3の溶液Dに加えて反応溶液を調製した後、試験例1と同様にして淡黄色固体の化合物6a（Rf=0.30）及び淡黄色固体の化合物6b（Rf=0.20）を得た。これら化合物6a及び6bの構造解析を行った。結果を以下に記載する。

Example 6 After preparing a reaction solution by adding the solution E of Test Example 4 to the solution D of Test Example 3 at 0 ° C., a light yellow solid compound 6a (Rf = 0.30) and A pale yellow solid compound 6b (Rf = 0.20) was obtained. Structural analysis of these compounds 6a and 6b was performed. The results are described below.

(Compound 6a)
<Infrared absorption spectrum (KBr tablet)> 3049, 2928, 2851, 1597, 1510,1435, 1371, 1173, 1098, 1021, 1000, 949, 888, 853, 827, 798, 776, 740, 692,647, 635, 612cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ0.92-1.94 (m, 11H, CH ₂ , CH), 1.37 (d, J = 6.3 Hz, 3H, CH _{3 in} NCHCH ₃ ), 2.52 (s, broad, 1H, NH), 5.49-5.58 (m, 1H, NCH), 7.45-7.60 (m, 6H, Ar), 7.63 (d, J = 7.3Hz, 1H, Ar), 7.79 (d, J = 8.3Hz, 1H, Ar), 7.87 (d, J = 7.3Hz, 1H, Ar), 8.04-8.09 (m, 2H, Ar), 8.41 (d, J = . 8.8Hz, 1H, Ar), 13 C-NMR (CDCl 3): δ23.5 (CH 3 in _{NCHCH 3), 25.5 (CH 2} ), 25.9 (d, J CP = 14.9Hz, CH 2), 25.9 (CH ₂ ), 26.0 (d, J _CP = 15.7 Hz, CH ₂ ), 26.2 (CH ₂ ), 42.4 (d, ¹ J _CP = 60.4 Hz, CH), 48.2 (NCH), 123.4 (Ar), 123.9 (Ar), 125.3 (Ar), 125.9 (Ar), 126.4 (Ar), 128.1 (d, J _CP = 12.4Hz, Ar), 128.2 (Ar), 128.7 (Ar), 130.6 (Ar), 131.6 ( d, ⁴ J _CP = 2.5Hz, Ar), 132.2 (d, J _CP = 9.9Hz, Ar), 133.4 (d, ¹ J _CP = 81.9Hz, Ar), 134.0 (Ar), 140.4 (d, J _CP = 8.3 Hz, Ar)., ³¹ P-NMR (CDCl ₃ ): δ 69.8 ( ¹ J _P-Se = 744.2 Hz)., ⁷⁷ Se-NMR (CDCl ₃ ): δ-390.6 (d, ¹ J _{Se -P} = 744.2Hz).
<Mass spectrometry> MS (EI) m / z 441 (M ⁺ ).
(Compound 6b)
<Infrared absorption spectrum (KBr tablet)> 3297, 3049, 2926, 2851, 1597, 1510, 1436, 1369, 1308, 1255, 1235, 1172, 1100, 1075, 1021, 1000, 945, 887,851, 824, 797, 776, 740, 691, 648, 619cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ 1.10-1.70 (m, 8H, CH ₂ ), 1.68 (d, J = 6.7Hz, 3H, NCHCH ₃ CH ₃ ), 1.83-1.86 (m, 1H, CH ₂ ), 1.99-2.07 (m, 2H, CH ₂ , CH), 2.59 (s, broad, 1H, NH), 5.12-5.22 (m, 1H , NCH), 7.04-7.11 (m, 2H, Ar), 7.20-7.42 (m, 4H, Ar), 7.56 (d, J = 7.3Hz, 1H, Ar), 7.68 (dt, J = 2.9,7.3Hz , 3H, Ar), 7.77 (d, J = 7.8 Hz, 1H, Ar), 7.83 (d, J = 8.3 Hz, 1H, Ar)., ¹³ C-NMR (CDCl ₃ ): δ25.6 (CH ₃ ), 25.8 (CH ₂ ), 25.88 (d, J _CP = 12.4Hz, CH ₂ ), 25.92 (d, J _CP = 12.4Hz, CH ₂ ), 26.0 (CH ₂ ), 26.3 (CH ₂ ), 42.3 ( d, ¹ J _CP = 60.4Hz, CH), 48.4 (NCH), 123.1 (Ar), 123.2 (Ar), 125.2 (Ar), 125.4 (Ar), 125.8 (Ar), 127.5 (Ar), 127.6 (d , J _CP = 12.4Hz, Ar), 128.6 (Ar), 129.9 (Ar), 130.2 (Ar; One half of the signal is overlapping with another signal), 131.2 (Ar), 132.4 (d, J _CP = 10.8Hz, Ar), 133.6 (Ar), 140.9 (d, J _CP = 5.0 Hz, Ar)., ³¹ P-NMR (CDCl ₃ ): δ71.4 ( ¹ J _P-Se = 738.1 Hz)., ⁷⁷ Se-NMR (CDCl ₃ ): δ-346.3 (d, ¹ J _Se-P = 738.1 Hz).
<Mass spectrometry> MS (EI) m / z 441 (M ⁺ ).

From the above results, compound 6a has the structure shown in the following formula (23), and (R _P , S) _-P -cyclohexyl-N-1- (1-naphthyl) ethyl- _P -phenylselenophosphine Identified as acid amide. The yield of this selenophosphinic acid amide is 34% (yield: 0.298 g, 0.68 mmol), the melting point is 52-54 ° C., and the optical rotation [α] _D ²⁰ (c 1.00, CH ₂ Cl ₂ ) is − It was 13 °.

一方、化合物6bは下記式（24）に示した構造を有しており、(S_P,S)-P-シクロヘキシル-N-1-(1-ナフチル)エチル-P-フェニルセレノホスフィン酸アミドであると同定した。このセレノホスフィン酸アミドの収率は41%（収量：0.361g,0.82mmol）であり、融点は48〜50℃であり、旋光度[α]_D ²⁰（c 1.00, CH₂Cl₂）は+27°であった。これらセレノホスフィン酸アミドは新規化合物であり、空気中で安定であった。

On the other hand, compound 6b has a structure represented by the following formula (24), and is (S _P , S) _-P -cyclohexyl-N-1- (1-naphthyl) ethyl- _P -phenylselenophosphinic acid amide. Identified. The yield of this selenophosphinic acid amide is 41% (yield: 0.361 g, 0.82 mmol), the melting point is 48-50 ° C., and the optical rotation [α] _D ²⁰ (c 1.00, CH ₂ Cl ₂ ) is + It was 27 °. These selenophosphinic acid amides are novel compounds and were stable in air.

（実施例７） 0℃で、(S)-1-シクロヘキシルエチルアミン0.33mL（2.2mmol）を5mLのTHFに溶解させた。次いで、該THFにブチルリチウム1.25mL（1.6Msolution in hexane；2.0mmol）を加えた後、THFを10分間撹拌して(S)-1-シクロヘキシルエチルアミンのリチウム塩を得た。ここで、(S)-1-シクロヘキシルエチルアミンのリチウム塩は前記アミンのリチウム塩であり、THFに溶解した状態で得られた。このTHF溶液を溶液Fとする。続いて、0℃で溶液Fを試験例1の溶液Bに加えて反応溶液を調製し、試験例1と同様にジクロロメタン抽出及びシリカゲルカラムクロマトグラフィを用いた精製を行った後、さらに高速液体クロマトグラフィ（HPLC）を用いた精製を行い無色固体の化合物7a（Rf=0.40）及び無色固体の化合物7b（Rf=0.30）を得た。これら化合物7a及び7bの構造解析を行った。結果を以下に記載する。

Example 7 At 0 ° C., 0.33 mL (2.2 mmol) of (S) -1-cyclohexylethylamine was dissolved in 5 mL of THF. Next, 1.25 mL of butyl lithium (1.6 Msolution in hexane; 2.0 mmol) was added to the THF, and then the THF was stirred for 10 minutes to obtain a lithium salt of (S) -1-cyclohexylethylamine. Here, the lithium salt of (S) -1-cyclohexylethylamine is the lithium salt of the amine, and was obtained in a state dissolved in THF. This THF solution is designated as Solution F. Subsequently, the solution F was added at 0 ° C. to the solution B of Test Example 1 to prepare a reaction solution. After performing purification using dichloromethane extraction and silica gel column chromatography in the same manner as in Test Example 1, high-performance liquid chromatography ( Purification using HPLC) gave colorless solid compound 7a (Rf = 0.40) and colorless solid compound 7b (Rf = 0.30). The structures of these compounds 7a and 7b were analyzed. The results are described below.

(Compound 7a)
<Infrared absorption spectrum (KBr tablet)> 3311, 2965, 2923, 2851, 1474,1465, 1447, 1434, 1404, 1389, 1376, 1362, 1310, 1275, 1187, 1130, 1099, 1073,1046, 1016, 997, 969, 943, 911, 890, 847, 826, 813, 747, 696, 629, 607cm ^-1
<Nuclear magnetic resonance spectrum (CDCl _3, TMS internal ^{standard)> 1 H-NMR (CDCl} 3): δ0.90 (d, J = 6.3Hz, 3H, CH 3 in NCHCH _3), 0.97-1.29 (m, 5H, CH ₂ ), 1.11 (d, ³ J = 16.6Hz, 9H, CCH ₃ ), 1.53-1.73 (m, 6H, CH ₂ , CH), 2.18 (s, broad, 1H, NH), 3.37-3.48 (m, 1H, NCH), 7.35-7.42 (m, 3H, Ar), 7.90-7.94 (m, 2H, Ar)., ¹³ C-NMR (CDCl ₃ ): δ 19.1 (d, ³ J _CP = 1.7 Hz, CH ₃ in _{CHCH 3), 24.9 (d,} J CP = 1.6Hz, CH 3 in _{CCH 3), 26.26 (CH 2} ), 26.34 (CH 2), 26.5 (CH 2), 28.0 (CH ₂ ), 29.5 (CH ₂ ), 35.2 (d, ¹ J _CP = 57.9 Hz, C coupled to CH ₃ in CCH ₃ ), 44.3 (d, J _CP = 6.6 Hz, CH), 52.7 (d, ² J _CP = 2.5Hz, NCH), 127.4 (d, J _CP = 12.4Hz, Ar), 131.1 (d, ⁴ J _CP = 2.5Hz, Ar), 132.4 (Ar; One half of the signal is overlapping with another signal) , 133.2 (d, J _CP = 10.8 Hz, Ar). ³¹ P-NMR (CDCl ₃ ): δ 77.4 ( ¹ J _P-Se = 745.6 Hz). ⁷⁷ Se-NMR (CDCl ₃ ): δ- 367.0 (d, ¹ J _Se-P = 745.6Hz).
<Mass Spectrometry> MS (EI) m / z 371 (M ⁺ ).
(Compound 7b)
<Infrared absorption spectrum (KBr tablet)> 3353, 3076, 3055, 2970, 2922,2850, 1638, 1572, 1473, 1447, 1436, 1410, 1391, 1378, 1362, 1308, 1292, 1186,1155, 1140, 1101, 1085, 1072, 1060, 1011, 967, 908, 892, 873, 846, 831, 811,752, 699, 636, 607cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ0.87-1.34 (m, 5H, CH ₂ ), 1.13 (d, ³ J = 17.1Hz, 9H, CCH _{3), 1.18 (d, J} = 6.8Hz, 3H, CH 3 in _{NCHCH 3), 1.54-1.91 (m,} 7H, CH 2, CH, NH), 3.32-3.39 (m, 1H, NCH), 7.38 . -7.47 (m, 3H, Ar ), 7.95-8.01 (m, 2H, Ar), 13 C-NMR (CDCl 3): δ18.5 (d, 3 J CP = 3.3Hz, CH 3 in CHCH ₃ ), 24.9 (CH _{3 in} CCH ₃ ), 26.2 (CH ₂ ), 26.3 (CH ₂ ), 26.4 (CH ₂ ), 27.2 (CH ₂ ), 29.7 (CH ₂ ), 35.2 (d, ¹ J _CP = 57.1Hz, C bonded to CH ₃ in CCH ₃ ), 44.2 (d, J _CP = 5.0Hz, CH), 52.9 (d, ² J _CP = 1.7Hz, NCH), 127.3 (d, J _CP = 11.6Hz , Ar), 131.2 (d, ⁴ J _CP = 2.5 Hz, Ar), 131.6 (d, ¹ J _CP = 81.1 Hz, Ar), 133.3 (d, J _CP = 9.9 Hz, Ar)., ³¹ P-NMR (CDCl ₃ ): δ 78.4 ( ¹ J _P-Se = 741.1 Hz). ⁷⁷ Se-NMR (CDCl ₃ ): δ-353.6 (d, ¹ J _Se-P = 741.1 Hz).
<Mass Spectrometry> MS (EI) m / z 371 (M ⁺ ).
From the above results, Compound 7a has the structure shown in the following formula (25), and (R _P , S) -N-1-cyclohexylethyl-P-1,1-dimethylethyl-P-phenylseleno Identified as phosphinic acid amide. The yield of this selenophosphinic acid amide is 42% (yield: 0.309 g, 0.83 mmol), the melting point is 106-108 ° C., and the optical rotation [α] _D ²⁰ (c 1.00, CH ₂ Cl ₂ ) is − It was 32 °.

一方、化合物7bは下記式（26）に示した構造を有しており、(S_P,S)-N-1-シクロヘキシルエチル-P-1,1-ジメチルエチル-P-フェニルセレノホスフィン酸アミドであると同定した。このセレノホスフィン酸アミドの収率は43%（収量：0.318g,0.86mmol）、融点は91〜93℃であり、旋光度[α]_D ²⁰（c 1.00, CH₂Cl₂）は+18°であった。これらセレノホスフィン酸アミドは新規化合物であり、空気中で安定であった。

On the other hand, Compound 7b has a structure represented by the following formula (26), and (S _P , S) -N-1-cyclohexylethyl-P-1,1-dimethylethyl-P-phenylselenophosphinic acid amide Identified. The yield of this selenophosphinic acid amide is 43% (yield: 0.318 g, 0.86 mmol), the melting point is 91-93 ° C., and the optical rotation [α] _D ²⁰ (c 1.00, CH ₂ Cl ₂ ) is + 18 °. Met. These selenophosphinic acid amides are novel compounds and were stable in air.

（実施例８） 0℃で試験例7の溶液Fを試験例2の溶液Cに加えて反応溶液を調製した後、試験例7と同様にして無色固体の化合物8a（Rf=0.40）及び無色オイルの化合物8b（Rf=0.30）を得た。これら化合物8a及び8bの構造解析を行った。結果を以下に記載する。

Example 8 After preparing a reaction solution by adding Solution F of Test Example 7 to Solution C of Test Example 2 at 0 ° C., colorless solid compound 8a (Rf = 0.40) and colorless were prepared in the same manner as Test Example 7. Oil compound 8b (Rf = 0.30) was obtained. Structural analysis of these compounds 8a and 8b was performed. The results are described below.

(Compound 8a)
<Infrared absorption spectrum (KBr tablet)> 3298, 3262, 3069, 3050, 2968,2921, 2871, 2851, 1573, 1476, 1463, 1446, 1433, 1410, 1379, 1351, 1308, 1285,1258, 1238, 1189, 1154, 1097, 1073, 1049, 1037, 1028, 1013, 967, 930, 913, 887,873, 843, 824, 770, 749, 703, 695, 676, 627, 615cm ^-1
<Nuclear magnetic resonance spectrum (CDCl _3, TMS internal ^{standard)> 1 H-NMR (CDCl} 3): δ0.82 (d, J = 5.4Hz, 3H, CH 3 in _{NCHCH 3), 0.83 (dd,} J = _{^{6.8Hz, 3 J HP = 20.5Hz,}} 3H, CH 3 in _{PCHCH 3), 0.90-1.13 (m,} 5H, CH 2), 1.17 (dd, J = 6.8Hz, 3 J HP = 18.5Hz, 3H, CH ₃ in _{PCHCH 3), 1.33-1.40 (m,} 1H, CH 2), 1.59-1.69 (m, 5H, CH 2, CH), 2.16 (s, broad, 1H, NH), 2.20-2.30 (m , 1H, PCH), 3.19-3.28 (m, 1H, NCH), 7.34-7.42 (m, 3H, Ar), 7.89-7.94 (m, 2H, Ar)., ¹³ C-NMR (CDCl ₃ ): δ16 .4 (CHCH CH ₃ in _3), 16.6 (CH ₃ in _{CHCH 3), 19.2 (d,} 3 J CP = 2.5Hz, CH 3 in _{CHCH 3), 26.1 (CH 2} ), 26.2 (CH 2 _{), 26.4 (CH 2),} 27.8 (CH 2), 29.3 (CH 2), 32.0 (d, 1 J CP = 62.0Hz, CH of binding to CH ₃ in _{CHCH 3), 44.3 (d,} J CP = 5.8 Hz, CH), 52.4 (d, ² J _CP = 2.3Hz, NCH), 127.9 (d, J _CP = 12.4Hz, Ar), 131.3 (d, ⁴ J _CP = 2.5Hz, Ar), 131.9 (d, J _CP = 9.9 Hz, Ar), 133.4 (d, ¹ J _CP = 79.4 Hz, Ar)., ³¹ P-NMR (CDCl ₃ ): δ72.7 ( ¹ J _P-Se = 741.1 Hz)., ⁷⁷ Se -NMR (CDCl ₃ ): δ-391.3 (d, ¹ J _Se-P = 741.1 Hz).
<Mass Spectrometry> MS (EI) m / z 357 (M ⁺ ).
(Compound 8b)
<Infrared absorption spectrum (KBr tablet)> 3288, 3053, 2963, 2926, 2851,1573, 1462, 1448, 1436, 1408, 1383, 1308, 1287, 1249, 1187, 1154, 1142, 1101,1072, 1028, 968, 930, 912, 888, 844, 825, 748, 705, 694, 673, 622, 614cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ 0.73-1.30 (m, 6H, CH ₂ ), 0.82 (dd, J = 6.8 Hz, ³ J _HP = 20.5Hz, 3H, CH ₃ in _{PCHCH 3), 1.05 (d,} J = 6.8Hz, 3H, CH 3 in _{NCHCH 3), 1.15 (dd,} J = 6.8Hz, 3 J HP = 19.0Hz, 3H, CH _{3 in} PCHCH ₃ ), 1.44-1.56 (m, 5H, CH ₂ , CH), 1.95 (s, broad, 1H, NH), 2.20-2.34 (m, 1H, PCH), 3.02-3.13 (m, . 1H, NCH), 7.34-7.41 ( m, 3H, Ar), 7.90-7.95 (m, 2H, Ar), 13 C-NMR (CDCl 3): δ16.3 (CH 3 in CHCH _3), 16.4 (CH ₃ in _{CHCH 3), 18.8 (d,} 3 J CP = 3.3Hz, CH 3 in _{CHCH 3), 26.0 (CH 2} ), 26.2 (CH 2), 26.3 (CH 2), 27.5 (CH 2 _{), 29.3 (CH 2),} 31.8 (d, 1 J CP = 62.0Hz, CH of binding to CH ₃ in _{CHCH 3), 44.1 (d,} J CP = 5.0Hz, CH), 52.9 (d, 2 J CP = 2.5Hz, NCH), 127.8 (d, J _CP = 12.4Hz, Ar), 131.3 (d, ⁴ J _CP = 2.5Hz, Ar), 132.1 (d, J _CP = 10.8Hz, Ar), 132.3 (d , ¹ J _CP = 82.7 Hz, Ar)., ³¹ P-NMR (CDCl ₃ ): δ 73.4 ( ¹ J _P-Se = 742.7 Hz)., ⁷⁷ Se-NMR (CDCl ₃ ): δ-382.2 (d , ¹ J _Se-P = 742.7Hz).
<Mass Spectrometry> MS (EI) m / z 357 (M ⁺ ).

From the above results, compound 8a has the structure shown in the following formula (27), and (R _P , S) -N-1-cyclohexylethyl-P-1-methylethyl-P-phenylselenophosphinic acid Identified as an amide. The yield of this selenophosphinic acid amide is 40% (yield: 0.285 g, 0.80 mmol), the melting point is 105 to 107 ° C., and the optical rotation [α] _D ²⁰ (c 1.00, CH ₂ Cl ₂ ) is − It was 33 °.

一方、化合物8bは下記式（28）に示した構造を有しており、(S_P,S)-N-1-シクロヘキシルエチル-P-1-メチルエチル-P-フェニルセレノホスフィン酸アミドであると同定した。このセレノホスフィン酸アミドの収率は41%（0.290g,0.81mmol）であり、旋光度[α]_D ²⁰（c 1.00, CH₂Cl₂）は+25°であった。これらセレノホスフィン酸アミドは新規化合物であり、空気中で安定であった。

On the other hand, Compound 8b has a structure represented by the following formula (28) and is (S _P , S) -N-1-cyclohexylethyl-P-1-methylethyl-P-phenylselenophosphinic acid amide. Was identified. The yield of this selenophosphinic acid amide was 41% (0.290 g, 0.81 mmol), and the optical rotation [α] _D ²⁰ (c 1.00, CH ₂ Cl ₂ ) was + 25 °. These selenophosphinic acid amides are novel compounds and were stable in air.

（実施例９） 0℃で試験例7の溶液Fを試験例3の溶液Dに加えて反応溶液を調製した後、試験例7と同様にして無色固体の化合物9a（Rf=0.40）及び無色固体の化合物9b（Rf=0.30）を得た。これら化合物9a及び9bの構造解析を行った。結果を以下に記載する。

Example 9 After preparing a reaction solution by adding Solution F of Test Example 7 to Solution D of Test Example 3 at 0 ° C., colorless solid compound 9a (Rf = 0.40) and colorless were prepared in the same manner as Test Example 7. Solid compound 9b (Rf = 0.30) was obtained. The structures of these compounds 9a and 9b were analyzed. The results are described below.

(Compound 9a)
<Infrared absorption spectrum (KBr tablet)> 3320, 3068, 3045, 2927, 2849,1572, 1479, 1448, 1435, 1400, 1374, 1327, 1309, 1294, 1280, 1235, 1200, 1144,1100, 1061, 1026, 1004, 969, 919, 892, 853, 843, 824, 769, 739, 705, 691, 624cm ^-1
<Nuclear magnetic resonance spectrum (CDCl _3, TMS internal ^{standard)> 1 H-NMR (CDCl} 3): δ0.82 (d, J = 6.8Hz, 3H, CH 3 in NCHCH _3), 0.85-1.28 (m, 9H, CH ₂ ), 1.37-1.48 (m, 3H, CH ₂ ), 1.59-1.66 (m, 7H, CH ₂ ), 1.77-1.80 (m, 1H, CH ₂ ), 1.89-1.98 (m, 2H, CH), 2.14 (s, broad, 1H, NH), 3.18-3.29 (m, 1H, NCH), 7.34-7.42 (m, 3H, Ar), 7.88-7.93 (m, 2H, Ar), ¹³ C _{-NMR (CDCl 3): δ19.1 (} d, 3 J CP = 2.5Hz, CH 3 in _{NCHCH 3), 25.6 (CH 2} ), 25.8 (CH 2), 25.9 (CH 2), 26.1 (CH 2 ), 26.2 (CH ₂ ), 26.26 (CH ₂ ), 26.30 (CH ₂ ), 26.4 (CH ₂ ), 27.9 (CH ₂ ), 29.4 (CH ₂ ), 42.1 (d, ¹ J _CP = 61.2 Hz, CH ), 44.3 (d, J _CP = 6.6Hz, CH), 52.2 (d, ² J _CP = 1.7Hz, NCH), 127.8 (d, J _CP = 11.6Hz, Ar), 131.2 (d, J _CP = 2.5 Hz, Ar), 132.1 (d, ⁴ J _CP = 10.8 Hz, Ar), 133.4 (d, ¹ J _CP = 80.2 Hz, Ar)., ³¹ P-NMR (CDCl ₃ ): δ 68.6 ( ¹ J _{P -Se} = 739.6 Hz), ⁷⁷ Se-NMR (CDCl ₃ ): δ-368.1 (d, ¹ J _Se-P = 739.6 Hz).
<Mass Spectrometry> MS (EI) m / z 397 (M ⁺ ).
(Compound 9b)
<Infrared absorption spectrum (KBr tablet)> 3263, 3071, 3050, 2937, 2851,1574, 1483, 1447, 1435, 1407, 1383, 1334, 1311, 1284, 1268, 1238, 1202, 1178,1152, 1146, 1116, 1100, 1087, 1074, 1014, 1000, 968, 909, 891, 868, 852, 840,822, 774, 753, 740, 703, 694, 614cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ 0.77-2.02 (m, 23 H, CH ₂ , CH, NH), 1.17 (d, J = 6.8 Hz, 3H, CH ₃ in _{NCHCH 3), 3.08-3.17 (m,} 1H, NCH), 7.40-7.48 (m, 3H, Ar), 7.93-7.99 (m, 2H, Ar)., 13 C-NMR (CDCl ₃ ): δ18.8 (d, ³ J _CP = 2.5Hz, CH _{3 in} CHCH ₃ ), 25.5 (CH ₂ ), 25.7 (CH ₂ ), 25.8 (CH ₂ ), 26.0 (CH ₂ ), 26.06 ( CH ₂ ), 26.12 (CH ₂ ), 26.2 (CH ₂ ), 26.4 (CH ₂ ), 27.4 (CH ₂ ), 29.4 (CH ₂ ), 42.0 (d, ¹ J _CP = 61.2 Hz, CH), 44.1 ( d, J _CP = 5.8Hz, CH), 52.2 (NCH), 127.8 (d, J _CP = 12.4Hz, Ar), 131.3 (Ar), 132.3 (d, ¹ J _CP = 82.7Hz, Ar), 133.0 ( d, J _CP = 9.9 Hz, Ar)., ³¹ P-NMR (CDCl ₃ ): δ69.1 ( ¹ J _P-Se = 738.1 Hz)., ⁷⁷ Se-NMR (CDCl ₃ ): δ-358.3 (d , ¹ J _Se-P = 738.1Hz).
<Mass Spectrometry> MS (EI) m / z 397 (M ⁺ ).

From the above results, compound 9a has the structure shown in the following formula (29), and is (R _P , S) _-P -cyclohexyl-N-1-cyclohexylethyl- _P -phenylselenophosphinic acid amide. Was identified. The yield of this selenophosphinic acid amide is 44% (yield: 0.351 g, 0.89 mmol), the melting point is 92-94 ° C., and the optical rotation [α] _D ²⁰ (c 1.00, CH ₂ Cl ₂ ) is − It was 33 °.

一方、化合物9bは下記式（30）に示した構造を有しており、(S_P,S)-P-シクロヘキシル-N-1-シクロヘキシルエチル-P-フェニルセレノホスフィン酸アミドであると同定した。このセレノホスフィン酸アミドの収率は46%（収量：0.366g,0.92mmol）であり、融点は118〜120℃であり、旋光度[α]_D ²⁰（c 1.00, CH₂Cl₂）は+31°であった。これらセレノホスフィン酸アミドは新規化合物であり、空気中で安定であった。

On the other hand, compound 9b has the structure shown in the following formula (30) and was identified as (S _P , S) _-P -cyclohexyl-N-1-cyclohexylethyl- _P -phenylselenophosphinic acid amide. . The yield of this selenophosphinic acid amide is 46% (yield: 0.366 g, 0.92 mmol), the melting point is 118 to 120 ° C., and the optical rotation [α] _D ²⁰ (c 1.00, CH ₂ Cl ₂ ) is + It was 31 °. These selenophosphinic acid amides are novel compounds and were stable in air.

（実施例１０） 25℃で前記セレノリン酸塩化物としての(R)-ビナフチルセレノリン酸クロリド1.290g（3.00mmol）を10mLのトルエンに溶解させた後、該トルエンに前記アミンとしてのフェニルエチルアミン0.786mL（6.10mmol）を加えて反応溶液を調製した。次いで、反応溶液を2時間還流した。続いて、試験例1と同様にして残渣を得た後、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：ジクロロメタン＝１：１，Rf=0.50）で精製した。次いで、シリカゲルカラムクロマトグラフィによる精製によって得られた化合物の再結晶（ヘキサン：ジクロロメタン＝１：１）を行い、先に析出した無色固体の化合物10a及び後に析出した無色固体の化合物10bを得た。これら化合物10a及び10bの構造解析を行った。結果を以下に記載する。

Example 10 After dissolving 1.290 g (3.00 mmol) of (R) -binaphthylselenophosphoric chloride as the selenophosphate chloride at 25 ° C. in 10 mL of toluene, 0.786 phenylethylamine as the amine was dissolved in the toluene. mL (6.10 mmol) was added to prepare a reaction solution. The reaction solution was then refluxed for 2 hours. Subsequently, a residue was obtained in the same manner as in Test Example 1, and then the residue was purified by silica gel column chromatography (hexane: dichloromethane = 1: 1, Rf = 0.50). Then, the compound obtained by purification by silica gel column chromatography was recrystallized (hexane: dichloromethane = 1: 1) to obtain the colorless solid compound 10a deposited earlier and the colorless solid compound 10b deposited later. The structures of these compounds 10a and 10b were analyzed. The results are described below.

(Compound 10a)
<Infrared absorption spectrum (KBr tablet)> 3358, 3061, 2974, 1618, 1588,1507, 1460, 1407, 1371, 1322, 1260, 1220, 1201, 1156, 1114, 1068, 1038, 980,868, 858, 830, 772, 565, 530, 512 cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ 1.50 (d, J = 6.3 Hz, 3H, CH ₃ ), 3.68 (dd, J = 5.1 Hz, 10.0 Hz, 1H, NH), 4.79-4.90 (m, 1H, CH), 6.63-8.02 (m, 17H, Ar)., ¹³ C-NMR (CDCl ₃ ): δ 24.2 (CH ₃ ), 53.1 (CH ), 121.2, 121.6, 122.3, 122.5, 125.7, 125.8, 126.4, 126.5, 126.9, 127.0, 127.2, 127.7, 128.4, 128.6, 128.8, 130.4, 130.9, 131.6, 132.0, 132.4, 144.1, 144.1, 146.4, 146.5, 147.4, 147.6 (Ar)., ³¹ P-NMR (CDCl ₃ ): δ 83.8 ( ¹ J _P-Se = 971.1 Hz). ⁷⁷ Se-NMR (CDCl ₃ ): δ-301.3 ( ¹ J _Se-P = 971.1Hz).
<Mass Spectrometry> MS (EI) m / z 515 (M ⁺ ).
<Elemental analysis> Anal Calcd for C ₂₈ H ₂₂ NO ₂ PSe (515.06): C, 65.38; H, 4.31; N, 2.72 Found: C, 65.37; H, 4.24; N, 2.67.
(Compound 10b)
<Infrared absorption spectrum (KBr tablet)> 3367, 3055, 2983, 1618, 1587, 1502, 1454, 1438, 1378, 1332, 1329, 1259, 1193, 1148, 1110, 1089, 1006, 995,998, 878, 868, 854, 844, 832, 779, 565, 555, 524, 511 cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ 1.54 (d, J = 6.3 Hz, 3H, CH ₃ ), 3.74 (dd, J = 4.9 Hz, 10.2 Hz, 1H, NH), 4.60-4.70 (m, 1H, CH), 6.60-8.00 (m, 17H, Ar)., ¹³ C-NMR (CDCl ₃ ): δ 25.3 (CH ₃ ), 53.1 (CH ), 121.0, 121.6, 122.3, 125.7, 125.8, 125.9, 125.9, 126.5, 126.7, 127.0, 127.2, 127.4, 128.4, 128.6, 128.6, 130.6, 130.9, 131.5, 132.0, 132.4, 143.5, 143.6, 146.5, 146.6, 147.7, 147.8 (Ar)., ³¹ P-NMR (CDCl ₃ ): δ 82.2 ( ¹ J _P-Se = 971.1 Hz). ⁷⁷ Se-NMR (CDCl ₃ ): δ-295.6 ( ¹ J _Se-P = 971.1Hz).
<Mass Spectrometry> MS (EI) m / z 515 (M ⁺ ).
<Elemental analysis> Anal Calcd for C ₂₈ H ₂₂ NO ₂ PSe (515.06): C, 65.38; H, 4.31; N, 2.72 Found: C, 65.37; H, 4.24; N, 2.67.

From the above results, compound 10a had a structure represented by one of the following formulas (31) and (32), and compound 10b had a structure represented by the other. Therefore, these compounds 10a and 10b were identified as (R) -O, O-binaphthyl-N-1-phenylethylselenophosphoric acid amide. The yield of compound 10a was 35% (yield: 0.540 g, 1.05 mmol), the melting point was 294-296 ° C., and the optical rotation [α] _D ²⁰ (c 0.50, CHCl ₃ ) was −322 °. . On the other hand, the yield of compound 10b is 54% (yield: 0.834 g, 1.62 mmol), the melting point is 221 to 223 ° C., and the optical rotation [α] _D ²⁰ (c 0.50, CHCl ₃ ) is −276 °. there were. This selenophosphoric acid amide is a novel compound and was stable in the air.

（実施例１１） 25℃で(R)-ビナフチルセレノリン酸クロリド1.290g（3.00mmol）を10mLのトルエンに溶解させた後、該トルエンに前記アミンとしてのナフチルエチルアミン0.985mL（6.10mmol）を加えて反応溶液を調製した。次いで、反応溶液を2時間還流した。続いて、試験例1と同様にして残渣を得た後、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：ジクロロメタン＝１：１，Rf=0.40）で精製した。次いで、試験例10と同様にして、先に析出した無色固体の化合物11a及び後に析出した無色固体の化合物11bを得た。これら化合物11a及び11bの構造解析を行った。結果を以下に記載する。

Example 11 After dissolving 1.290 g (3.00 mmol) of (R) -binaphthylselenophosphoric chloride in 10 mL of toluene at 25 ° C., 0.985 mL (6.10 mmol) of naphthylethylamine as the amine was added to the toluene. A reaction solution was prepared. The reaction solution was then refluxed for 2 hours. Subsequently, after a residue was obtained in the same manner as in Test Example 1, the residue was purified by silica gel column chromatography (hexane: dichloromethane = 1: 1, Rf = 0.40). Then, in the same manner as in Test Example 10, a colorless solid compound 11a deposited earlier and a colorless solid compound 11b deposited later were obtained. The structures of these compounds 11a and 11b were analyzed. The results are described below.

(Compound 11a)
<Infrared absorption spectrum (KBr tablet)> 3367, 3051, 2970, 1931, 1691,1588, 1508, 1461, 1428, 1371, 1258, 1223, 1173, 1155, 1068, 984, 952, 836, 798,751, 706, 696, 650, 627, 612, 566, 524, 508 cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ1.57 (d, J = 6.3 Hz, 3H, CH ₃ ), 3.87 (dd, J = 7.3 Hz, 9.8 Hz, 1H, NH), 5.43-5.53 (m, 1H, CH), 6.65-8.04 (m, 19H, Ar)., ¹³ C-NMR (CDCl ₃ ): δ 24.7 (CH ₃ ), 49.3 (CH ), 121.0, 121.5, 122.2, 122.4, 122.7, 123.0, 125.3, 125.6, 125.8, 126.4, 126.5, 126.7, 126.9, 127.2, 128.1, 128.3, 128.5, 128.8, 130.2, 130.4, 130.8, 131.5, 132.4, 133.8, 139.8, 139.9, 146.4, 146.5, 147.6, 147.8 (Ar)., ³¹ P-NMR (CDCl ₃ ): δ 83.1 ( ¹ J _P-Se = 974.2 Hz). ⁷⁷ Se-NMR (CDCl ₃ ): δ -302.5 ( ¹ J _Se-P = 974.2Hz).
<Mass Spectrometry> MS (EI) m / z 565 (M ⁺ ).
<Elemental analysis> Anal Calcd for C ₃₂ H ₂₄ NO ₂ PSe (565.07): C, 68.09; H, 4.29; N, 2.48. Found: C, 68.07; H, 4.31; N, 2.48.
(Compound 11b)
<Infrared absorption spectrum (KBr tablet)> 3367, 3055, 2983, 1618, 1587, 1502, 1454, 1438, 1378, 1332, 1329, 1259, 1193, 1148, 1110, 1089, 1006, 995,998, 878, 868, 854, 844, 832, 779, 565, 555, 524, 511 cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ 1.64 (d, J = 6.8 Hz, 3H, CH ₃ ), 4.07 (dd, J = 7.3 Hz, 9.8 Hz, 1H), 5.24-5.34 (m, 1H, CH), 6.67-8.04 (m, 19H, Ar)., ¹³ C-NMR (CDCl ₃ ): δ 24.8 (CH ₃ ), 49.5 (CH), 120.5, 121.6, 121.9, 122.3, 122.8, 125.3, 125.5, 125.6, 125.8, 126.2,126.5, 127.0, 128.1, 128.4, 128.5, 128.6, 130.1, 130.2, 130.9, 131.3, 132.0,132.2, 132.4, 133.8, 139.5, 139.6, 146.5, 146.6, 147.6, 147.7 (Ar)., ³¹ P-NMR (CDCl ₃ ): δ 80.3 ( ¹ J _P-Se = 971.2 Hz). ⁷⁷ Se-NMR (CDCl ₃ ): δ-297.0 ( ¹ J _Se-P = 971.2Hz).
<Mass Spectrometry> MS (EI) m / z 565 (M ⁺ ).
<Elemental analysis> Anal Calcd for C ₃₂ H ₂₄ NO ₂ PSe (565.07): C, 68.09; H, 4.29; N, 2.48. Found: C, 68.07; H, 4.31; N, 2.48.

From the above results, compound 11a had a structure represented by either the following formula (33) or formula (34), and compound 11b had a structure represented by the other. Therefore, these compounds 11a and 11b were identified as (R) -O, O-binaphthyl-N-1-naphthylethylselenophosphoric acid amide. The yield of compound 11a was 35% (yield: 0.594 g, 1.05 mmol), the melting point was 257-259 ° C., and the optical rotation [α] _D ²⁰ (c 0.50, CHCl ₃ ) was −450 °. . On the other hand, the yield of compound 11b is 57% (yield: 0.966 g, 1.71 mmol), the melting point is 270 to 272 ° C., and the optical rotation [α] _D ²⁰ (c 0.50, CHCl ₃ ) is −261 °. there were. This selenophosphoric acid amide is a novel compound and was stable in the air.

（実施例１２） 25℃で(R)-ビナフチルセレノリン酸クロリド1.290g（3.00mmol）を10mLのトルエンに溶解させた後、該トルエンに前記アミンとしての1-メチルプロピルアミン0.616mL（6.10mmol）を加えて反応溶液を調製した。次いで、反応溶液を2時間還流した。続いて、試験例1と同様にして残渣を得た後、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：ジクロロメタン＝１：１，Rf=0.43）で精製し、さらにHPLCで精製して無色固体の化合物12a及ぶ無色固体の化合物12bを得た。これら化合物12a及び12bの構造解析を行った。結果を以下に記載する。

Example 12 1.290 g (3.00 mmol) of (R) -binaphthylselenophosphoric chloride was dissolved in 10 mL of toluene at 25 ° C., and then 0.616 mL (6.10 mmol) of 1-methylpropylamine as the amine was dissolved in the toluene. ) Was added to prepare a reaction solution. The reaction solution was then refluxed for 2 hours. Subsequently, after a residue was obtained in the same manner as in Test Example 1, the residue was purified by silica gel column chromatography (hexane: dichloromethane = 1: 1, Rf = 0.43) and further purified by HPLC to reach a colorless solid compound 12a A colorless solid compound 12b was obtained. The structures of these compounds 12a and 12b were analyzed. The results are described below.

(Compound 12a)
<Infrared absorption spectrum (KBr tablet)> 3253, 3056, 2966, 2930, 2871,1619, 1587, 1507, 1460, 1414, 1359, 1292, 1255, 1223, 1120, 1066, 1019, 980,948, 851, 772, 754, 697, 651, 613, 566, 531, 510 cm ^-1
<Nuclear magnetic resonance spectrum (CDCl _3, TMS internal ^{standard)> 1 H-NMR (CDCl} 3): δ0.85 (t, J = 7.3Hz, 3H, CH 3 in the _{CH 2 CH 3), 1.21 (} d, J = 6.4Hz, 3H, CH ₃ in _{CHCH 3), 1.40-1.48 (m,} 2H, CH 2), 3.23 (m, 1H, NH), 3.38-3.48 (m, 1H, CH), 7.22-7.60 . (m, 8H, Ar) , 7.91-8.02 (m, 4H, Ar), 13 C-NMR (CDCl 3): δ10.3 (CH 3 in CHCH _3), 23.1 (CH ₃ in CHCH ₃₎ , 31.4 (CH ₂ ), 51.5 (CH _{3 in} CHCH ₃ ), 121.1, 121.7, 122.3, 122.5, 125.6, 125.8, 126.5, 126.8, 127.0, 127.2, 128.5, 130.6, 130.9, 131.5, 131.9, 132.5, 146.5 , 146.6, 147.7, 147.8 (Ar)., ³¹ P-NMR (CDCl ₃ ): δ 83.6 ( ¹ J _P-Se = 966.7 Hz), ⁷⁷ Se-NMR (CDCl ₃ ): δ-297.9 ( ¹ J _(Se-P = 966.7Hz).
<Mass spectrometry> MS (EI) m / z 467 (M ⁺ ).
<Elemental _{analysis> Anal Calcd for C 24 H 22} NO 2 PSe (467.06):. C, 61.81; H, 4.75; N, 3.00 Found: C, 61.66; H, 4.75; N, 2.92.
(Compound 12b)
<Infrared absorption spectrum (KBr tablet)> 3253, 3056, 2966, 2930, 2871,1619, 1587, 1507, 1460, 1414, 1359, 1292, 1255, 1223, 1120, 1066, 1019, 980,948, 851, 772, 754, 697, 651, 613, 566, 531, 510 cm ^-1
<Nuclear magnetic resonance spectrum (CDCl _3, TMS internal ^{standard)> 1 H-NMR (CDCl} 3): δ0.93 (t, J = 7.5Hz, 3H, CH 3 in the _{CH 2 CH 3), 1.12 (} d, J = 6.3Hz, 3H, CH ₃ in _{CHCH 3), 1.55-1.61 (m,} 2H, CH 2), 3.23 (m, 1H, NH), 3.40-3.55 (m, 1H, CH), 7.24-7.61 . (m, 8H, Ar) , 7.92-8.03 (m, 4H, Ar), 13 C-NMR (CDCl 3): δ10.3 (CH 3 in CHCH _3), 22.1 (CH ₃ in CHCH ₃₎ , 33.4 (CH ₂ ), 51.7 (CH _{3 in} CHCH ₃ ), 121.1, 121.7, 122.3, 122.5, 125.6, 125.8, 126.5, 126.8, 127.0, 127.3, 128.5, 130.6, 130.9, 131.5, 131.9, 132.4, 146.5 , 146.6, 147.7, 147.8 (Ar)., ³¹ P-NMR (CDCl ₃ ): δ 83.3 ( ¹ J _P-Se = 966.8 Hz), ⁷⁷ Se-NMR (CDCl ₃ ): δ-299.3 ( ¹ J _(Se-P = 966.8Hz).
<Mass spectrometry> MS (EI) m / z 467 (M ⁺ ).
<Elemental _{analysis> Anal Calcd for C 24 H 22} NO 2 PSe (467.06):. C, 61.81; H, 4.75; N, 3.00 Found: C, 61.66; H, 4.75; N, 2.92.

From the above results, compound 12a had a structure represented by either the following formula (35) or formula (36), and compound 12b had a structure represented by the other. Therefore, these compounds 12a and 12b were identified as (R) -O, O-binaphthyl-N-1-methylpropylselenophosphoric acid amide. The yield of compound 12a was 45% (yield: 0.645 g, 1.38 mmol), the melting point was 268-269 ° C., and the optical rotation [α] _D ²⁰ (c 0.50, CHCl ₃ ) was −385 °. . On the other hand, the yield of compound 12b is 49% (yield: 0.687 g, 1.47 mmol), the melting point is 211 to 212 ° C., and the optical rotation [α] _D ²⁰ (c 0.50, CHCl ₃ ) is −366 °. there were. This selenophosphoric acid amide is a novel compound and was stable in the air.

（実施例１３） 25℃で(R)-ビナフチルセレノリン酸クロリド1.290g（3.00mmol）を10mLのトルエンに溶解させた後、該トルエンに前記アミンとしての1,2-ジメチルプロピルアミン0.702mL（6.10mmol）を加えて反応溶液を調製した。次いで、反応溶液を2時間還流した。続いて、試験例12と同様にして無色固体の化合物13a及び無色固体の化合物13bを得た。これら化合物13a及び13bの構造解析を行った。結果を以下に記載する。

Example 13 After dissolving 1.290 g (3.00 mmol) of (R) -binaphthylselenophosphoric chloride in 10 mL of toluene at 25 ° C., 0.702 mL of 1,2-dimethylpropylamine as the amine was added to the toluene. 6.10 mmol) was added to prepare a reaction solution. The reaction solution was then refluxed for 2 hours. Subsequently, in the same manner as in Test Example 12, a colorless solid compound 13a and a colorless solid compound 13b were obtained. Structural analysis of these compounds 13a and 13b was performed. The results are described below.

(Compound 13a)
<Infrared absorption spectrum (KBr tablet)> 3251, 3056, 2959, 1619, 1587, 1507, 1461, 1411, 1369, 1133, 1115, 1070, 981, 940, 832, 771, 750, 696, 651,610, 563, 535, 517cm ^-1
<Nuclear magnetic resonance spectrum (CDCl _3, TMS internal ^{standard)> 1 H-NMR (CDCl} 3): δ0.84 (d, J = 6.8Hz, 3H, CH (CH 3) CH 3 in _2), 0.88 ( d, J = 6.8Hz, 3H, CH (CH 3) CH 3 in _{2), 1.20 (d, J} = 6.3Hz, 3H, CH 3 in _{CHCH 3), 1.68-1.78 (m,} 1H, CH ( CH ₃₎ CH to bind to CH ₃ in _{2), 3.28 (dd, J} = 5.6Hz, 10.0Hz, 1H, NH), 3.45-3.56 (m, 1H, CH of binding to CH ₃ in CHCH _3), 7.18 -7.56 (m, 8H, Ar), 7.87-7.97 (m, 4H, Ar)., ¹³ C-NMR (CDCl ₃ ): δ 17.7 (CH ₃ ), 18.7 (CH in CH (CH ₃ ) _{2 3),} 19.7 (CH (CH ₃₎ CH ₃ in _{2), 34.2 (CH (CH} 3) CH to bind to CH ₃ in _{2), 54.7 (NCH (CH} 3) CH which bind to N in), 121.1, 121.7, 121.9, 122.3, 122.6, 125.6, 126.5, 126.8, 128.4, 128.6, 130.6, 130.8, 131.5, 131.9, 132.4, 132.5, 146.6, 146.6, 147.6, 147.7 (Ar)., ³¹ P-NMR (CDCl ₃ ): δ 84.8 ( ¹ J _P-Se = 966.6Hz). ⁷⁷ Se-NMR (CDCl ₃ ): δ-300.9 ( ¹ J _Se-P = 966.6Hz).
<Mass Spectrometry> MS (EI) m / z 481 (M ⁺ ).
<Elemental _{analysis> Anal Calcd for C 25 H 24} NO 2 PSe (481.07):. C, 62.50; H, 5.04; N, 2.92 Found: C, 62.31; H, 5.09; N, 2.87.
(Compound 13b)
<Infrared absorption spectrum (KBr tablet)> 3258, 3065, 3013, 2968, 1617,1557, 1518, 1464, 1423, 1351, 1134, 1106, 1072, 981, 946, 842, 770, 753, 699,654, 611, 566, 535, 517 cm ^-1
<Nuclear magnetic resonance spectrum (CDCl _3, TMS internal ^{standard)> 1 H-NMR (CDCl} 3): δ0.89 (d, J = 6.8Hz, 3H, CH (CH 3) CH 3 in _2), 0.93 ( d, J = 6.8Hz, 3H, CH (CH 3) CH 3 in _{2), 1.07 (d, J} = 6.3Hz, 3H, CH 3 in _{CHCH 3), 1.65-1.70 (m,} 1H, CH ( CH ₃₎ CH to bind to CH ₃ in _{2), 3.28 (dd, J} = 5.6Hz, 10.0Hz, 1H, NH), 3.37-3.49 (m, 1H, CH of binding to CH ₃ in CHCH _3), 7.17 -7.55 (m, 8H, Ar), 7.85-7.97 (m, 4H, Ar)., ¹³ C-NMR (CDCl ₃ ): δ 17.7 (CH ₃ ), 18.7 (CH in CH (CH ₃ ) _{2 3),} 19.7 (CH (CH ₃₎ CH ₃ in _{2), 34.2 (CH (CH} 3) CH to bind to CH ₃ in _{2), 54.7 (NCH (CH} 3) CH which bind to N in), 121.1 , 121.7, 121.9, 122.3, 122.6, 125.6, 126.5, 126.8, 128.4, 128.6, 130.6, 130.8, 131.5, 131.9, 132.4, 132.5, 146.6, 146.6, 147.6, 147.7 (Ar)., ³¹ P-NMR (CDCl ₃ ): Δ 84.7 ( ¹ J _P-Se = 966.7 Hz). ⁷⁷ Se-NMR (CDCl ₃ ): δ-304.8 ( ¹ J _Se-P = 966.7 Hz).
<Mass Spectrometry> MS (EI) m / z 481 (M ⁺ ).
<Elemental _{analysis> Anal Calcd for C 25 H 24} NO 2 PSe (481.07):. C, 62.50; H, 5.04; N, 2.92 Found: C, 62.31; H, 5.09; N, 2.87.

From the above results, Compound 13a had a structure represented by either the following formula (37) or the following formula (38), and Compound 13b had a structure represented by the other. Therefore, these compounds 13a and 13b were identified as (R) -O, O-binaphthyl-N-1,2-dimethylpropylselenophosphoric acid amide. The yield of compound 13a was 44% (yield: 0.633 g, 1.32 mmol), the melting point was 273 to 274 ° C., and the optical rotation [α] _D ²⁰ (c 0.50, CHCl ₃ ) was −373 °. . On the other hand, the yield of compound 13b is 48% (yield: 0.691 g, 1.44 mmol), the melting point is 212 to 213 ° C., and the optical rotation [α] _D ²⁰ (c 0.50, CHCl ₃ ) is −365 °. there were. This selenophosphoric acid amide is a novel compound and was stable in the air.

（実施例１４） 25℃で(R)-ビナフチルセレノリン酸クロリド1.290g（3.00mmol）を10mLのトルエンに溶解させた後、該トルエンに前記アミンとしての2-メチルピペリジン0.716mL（6.10mmol）を加えて反応溶液を調製した。次いで、反応溶液を2時間還流した。続いて、試験例１と同様にして残渣を得た後、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：ジクロロメタン＝１：１，Rf=0.60）で精製し、さらにHPLCで精製して無色固体の化合物14a及ぶ無色固体の化合物14bを得た。これら化合物14a及び14bの構造解析を行った。結果を以下に記載する。

Example 14 After dissolving 1.290 g (3.00 mmol) of (R) -binaphthylselenophosphoric chloride in 10 mL of toluene at 25 ° C., 0.716 mL (6.10 mmol) of 2-methylpiperidine as the amine was dissolved in the toluene. Was added to prepare a reaction solution. The reaction solution was then refluxed for 2 hours. Subsequently, after a residue was obtained in the same manner as in Test Example 1, the residue was purified by silica gel column chromatography (hexane: dichloromethane = 1: 1, Rf = 0.60) and further purified by HPLC to reach a colorless solid compound 14a. A colorless solid compound 14b was obtained. The structures of these compounds 14a and 14b were analyzed. The results are described below.

(Compound 14a)
<Infrared absorption spectrum (KBr tablet)> 3054, 2935, 2864, 1618, 1589,1507, 1461, 1432, 1389, 1322, 1267, 1225, 1208, 1157, 1133, 1085, 1063, 1014,999, 979, 951, 916, 888, 866, 835, 810, 771, 749, 716, 698, 686, 650, 648, 595,568, 528, 503, 485 cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ 1.63 (d, J = 6.8 Hz, 3H, CH ₃ ), 1.26-1.37 (m, 2H, CH ₂ ), 1.42-1.45 (m, 1H, CH ₂ ), 1.57-1.61 (m, 2H, CH ₂ ), 1.76-1.85 (m, 1H, CH ₂ ), 2.88-2.99 (m, 1H, NCH ₂ ), 3.30-3.37 (m, 1H, NCH ₂ ), 4.26-4.35 (m, 1H, NCH),
7.21-7.62 (m, 8H, Ar), 7.92-8.05 (m, 4H, Ar)., ¹³ C-NMR (CDCl ₃ ): δ 16.2 (CH ₃ ), 18.4 (CH ₂ ), 26.0 (CH ₂ ), 30.8 (NCH), 41.4 (CH ₂ ), 49.8 (NCH ₂ ), 121.2, 121.7, 122.2, 125.5, 125.6, 126.4, 126.6, 127.1, 127.4, 128.4, 128.5, 130.4, 130.7, 131.3, 131.9, 132.5 , 147.1, 147.2, 148.9, 149.1 (Ar)., ³¹ P-NMR (CDCl ₃ ): δ 85.3 ( ¹ J _P-Se = 960.0 Hz). ⁷⁷ Se-NMR (CDCl ₃ ): δ-299.1 ( ⁽¹ J _Se-P = 960.0Hz).
<Mass Spectrometry> MS (EI) m / z 493 (M ⁺ ).
<Elemental analysis> Anal Calcd for C ₂₆ H ₂₄ NO ₂ PSe (493.07): C, 63.24; H, 4.91; N, 2.84. Found: C, 63.42; H, 5.18; N, 2.84.
(Compound 14b)
<Infrared absorption spectrum (KBr tablet)> 3054, 2936, 2864, 1619, 1589, 1507, 1461, 1432, 1375, 1322, 1267, 1225, 1208, 1158, 1135, 1087, 1064, 1014,1000, 979, 951, 916, 889, 867, 854, 698, 686, 650, 619, 596, 568, 529, 502,485, 455 cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ1.33 (d, J = 6.8Hz, 3H, CH ₃ ), 1.39-1.43 (m, 2H, CH ₂ ), 1.48-1.52 (m, 1H, CH ₂ ), 1.56-1.58 (m, 2H, CH ₂ ), 1.63-1.72 (m, 1H, CH ₂ ), 2.71-2.80 (m, 1H, NCH ₂ ), 3.35-3.41 (m, 1H, NCH ₂ ), 4.31-4.40 (m, 1H, NCH), 7.21-7.62 (m, 8H, Ar), 7.92-8.05 (m, 4H, Ar)., ¹³ C-NMR (CDCl ₃ ): δ 16.8 (CH ₃ ), 18.6 (CH ₂ ), 26.3 (CH ₂ ), 30.3 (NCH), 41.6 (CH ₂ ), 49.8 (NCH ₂ ), 121.0, 122.1, 122.2, 125.5, 125.6, 126.4, 126.6, 127.1, 127.3, 128.4, 128.5, 130.6, 130.8, 131.4, 131.9, 132.4, 147.1, 147.2, 148.9, 149.1 (Ar)., ³¹ P-NMR (CDCl ₃ ): δ 86.1 ( ¹ J _P-Se = 963.6 Hz), ⁷⁷ Se-NMR (CDCl ₃ ): δ-303.7 ( ¹ J _Se-P = 963.6 Hz).
<Mass Spectrometry> MS (EI) m / z 493 (M ⁺ ).
<Elemental analysis> Anal Calcd for C ₂₆ H ₂₄ NO ₂ PSe (493.07): C, 63.24; H, 4.91; N, 2.84. Found: C, 63.42; H, 5.18; N, 2.84.

From the above results, compound 14a had a structure represented by either the following formula (39) or formula (40), and compound 14b had a structure represented by the other. Therefore, these compounds 14a and 14b were identified as 1- (4-selenidodinaphthodioxaphosfepinyl) -2-methylpiperidine. The yield of compound 14a was 36% (yield: 0.531 g, 1.08 mmol), the melting point was 214 to 215 ° C., and the optical rotation [α] _D ²⁰ (c 0.50, CHCl ₃ ) was −434 °. . On the other hand, the yield of compound 14b was 58% (yield: 0.856 g, 1.74 mmol), the melting point was 238 to 239 ° C., and the optical rotation [α] _D ²⁰ (c 0.50, CHCl ₃ ) was −376 °. there were. This selenophosphoric acid amide is a novel compound and was stable in the air.

（実施例１５） 0℃で、(R)-ビス(1-メチルベンジル)アミン0.709mL（3.10mmol）を5mLのTHFに溶解させた。次いで、該THFにブチルリチウム1.88mL（1.6M solution in hexane; 3.0mmol）を加えた後、THFを10分間撹拌して(R)-ビス(1-メチルベンジル)アミンのリチウム塩を得た。ここで、(R)-ビス(1-メチルベンジル)アミンのリチウム塩は前記アミンであり、THFに溶解した状態で得られた。このTHF溶液を溶液Gとする。一方、前記セレノリン酸塩化物としてのビナフチルセレノリン酸クロリド1.290g（3.00mmol）を5mLのTHFに溶解させた。このTHF溶液を溶液Hとする。続いて、0℃で溶液Gを溶液Hに加えて反応溶液を調製し、該反応溶液を25℃にまで加熱した後に3時間撹拌した。次に、試験例1と同様にして無色固体の化合物15a（Rf=0.55）及び無色固体の化合物15b（Rf=0.49）を得た。これら化合物15a及び15bの構造解析を行った。結果を以下に記載する。

Example 15 At 0 ° C., 0.709 mL (3.10 mmol) of (R) -bis (1-methylbenzyl) amine was dissolved in 5 mL of THF. Subsequently, 1.88 mL (1.6 M solution in hexane; 3.0 mmol) of butyl lithium was added to the THF, and then the THF was stirred for 10 minutes to obtain a lithium salt of (R) -bis (1-methylbenzyl) amine. Here, the lithium salt of (R) -bis (1-methylbenzyl) amine is the amine and was obtained in a state dissolved in THF. This THF solution is designated as Solution G. Meanwhile, 1.290 g (3.00 mmol) of binaphthyl selenophosphoric chloride as the selenophosphate was dissolved in 5 mL of THF. This THF solution is designated as Solution H. Subsequently, the solution G was added to the solution H at 0 ° C. to prepare a reaction solution. The reaction solution was heated to 25 ° C. and then stirred for 3 hours. Next, colorless solid compound 15a (Rf = 0.55) and colorless solid compound 15b (Rf = 0.49) were obtained in the same manner as in Test Example 1. The structures of these compounds 15a and 15b were analyzed. The results are described below.

(Compound 15a)
<Infrared absorption spectrum (KBr tablet)> 3058, 2928, 1957, 1619, 1589,1500, 1462, 1375, 1321, 1278, 1224, 1201, 1156, 1136, 1069, 792, 748, 717, 696,677, 659, 649, 632, 607, 564, 545, 531, 517cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ 1.40 (d, J = 6.8Hz, 6H, CH ₃ ), 5.25-5.35 (m, 2H, CH) , 7.11-7.49 (m, 18H, Ar), 7.88-8.00 (m, 4H, Ar)., ¹³ C-NMR (CDCl ₃ ): δ 20.4 (CH ₃ ), 55.0 (CH), 121.3, 122.0, 122.2, 122.5, 125.6, 126.4, 126.6, 127.0, 127.1, 127.3, 127.7, 128.0, 128.3, 128.5, 130.4, 130.6, 131.2, 131.9, 132.5, 132.6, 141.1, 141.2, 146.0, 146.1, 148.7, 148.9 (Ar) ., ³¹ P-NMR (CDCl ₃ ): δ 87.2 ( ¹ J _P-Se = 959.1 Hz). ⁷⁷ Se-NMR (CDCl ₃ ): δ-175.1 ( ¹ J _Se-P = 959.1 Hz).
<Mass Spectrometry> MS (EI) m / z 619 (M ⁺ ).
<Elemental analysis> Anal Calcd for C ₃₆ H ₃₀ NO ₂ PSe (619.12): C, 69.90; H, 4.89; N, 2.26. Found: C, 69.84; H, 4.89; N, 2.13.
(Compound 15b)
<Infrared absorption spectrum (KBr tablet)> 3058, 2928, 1957, 1619, 1589, 1506, 1462, 1375, 1321, 1278, 1224, 1201, 1156, 1146, 1069, 792, 748, 717, 696,677, 659, 649, 632, 607, 564, 545, 531, 517cm ^-1
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ 1.65 (d, J = 7.3 Hz, 6H, CH ₃ ), 5.11-5.23 (m, 2H, CH) , 6.75-7.97 (m, 22H, Ar)., ¹³ C-NMR (CDCl ₃ ): δ 19.0 (CH ₃ ), 55.8 (CH), 120.6, 122.2, 125.2, 125.4, 125.7, 126.0, 126.2, 126.8 , 126.9, 127.1, 127.3, 127.6, 127.8, 127.9, 128.4, 128.5, 130.1, 130.5, 131.3, 131.8, 132.4, 141.5, 141.6, 146.0, 146.1, 148.4, 148.6 (Ar)., ³¹ P-NMR (CDCl ₃ ): Δ 87.8 ( ¹ J _P-Se = 957.6 Hz). ⁷⁷ Se-NMR (CDCl ₃ ): δ-206.5 ( ¹ J _Se-P = 957.6 Hz).
<Mass Spectrometry> MS (EI) m / z 619 (M ⁺ ).

From the above results, compound 15a has the structure shown in the following formula (41), and is (R, R, R) -binaphthyl-N, N-bis-1-phenylethylselenophosphoric acid amide. Identified. The yield of this selenophosphoric acid amide is 27% (yield: 0.501 g, 0.81 mmol), the melting point is 206-208 ° C., and the optical rotation [α] _D ²⁰ (c 0.50, CHCl ₃ ) is + 246 °. there were.

一方、化合物15bは下記式（42）に示した構造を有しており、(S,R,R)-ビナフチル-N,N-ビス-1-フェニルエチルセレノリン酸アミドであると同定した。このセレノリン酸アミドの収率は28%（収量：0.520g,0.84 mmol）であり、融点は231〜233℃であり、旋光度[α]_D ²⁰（c 0.50, CHCl₃）は-257°であった。これらセレノリン酸アミドは新規化合物であり、空気中で安定であった。

On the other hand, Compound 15b has a structure represented by the following formula (42), and was identified as (S, R, R) -binaphthyl-N, N-bis-1-phenylethylselenophosphoric acid amide. The yield of this selenophosphoric acid amide is 28% (yield: 0.520 g, 0.84 mmol), the melting point is 231 to 233 ° C., and the optical rotation [α] _D ²⁰ (c 0.50, CHCl ₃ ) is −257 °. there were. These selenophosphoric acid amides are novel compounds and were stable in air.

（実施例１６） 0℃で、三塩化リン3.0mL（30.0mmol）、トリエチルアミン8.4mL（60.0mmol）を50mLのトルエンに溶解させた。このトルエン溶液を溶液Iとする。一方、0℃で、前記ビナフトール誘導体としての(R)-1,1’-ビ-2-ナフトール8.58g（30.0mmol）を10mLのトルエンに溶解させた。このトルエン溶液を溶液Jとする。続いて、0℃で溶液Jを溶液Iに加えた後、3分間撹拌した。次に、溶液I及び溶液Jの混合溶液に粉末状のセレン2.45g（31.0mmol）を加えて反応溶液を調製した後、該反応溶液を6時間還流した。次いで、反応溶液の濃縮を行った後、濃縮された反応溶液から溶媒を留去して残渣を得た。続いて、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：ジクロロメタン＝1：1、Rf=0.70）で精製し、無色固体の化合物16を得た。この化合物16の構造解析を行った。結果を以下に記載する。
＜赤外吸収スペクトル（KBr錠剤）＞ 3006, 1588, 1509, 1460, 1433,1355, 1214, 1190, 1157, 1142, 1067, 969, 946, 868, 840, 806, 769, 749, 705, 652cm^-1
＜核磁気共鳴スペクトル（CDCl₃溶媒TMS内部標準）＞ ^１H-NMR(CDCl₃)：δ7.22-8.32(m,12H, C₂₀H₁₂).、 ¹³C-NMR(CDCl₃)：δ120.4,121.1, 122.4, 122.6, 126.3, 126.9, 127.0, 127.1, 127.2, 128.7, 131.3, 131.4,132.0, 132.2, 132.3, 132.5, 146.5, 146.6, 147.8, 148.0(Ar).、 ³¹P-NMR(CDCl₃)：δ69.0(¹J_P-Se=1060.9Hz).、 ⁷⁷Se-NMR(CDCl₃)：δ-69.2(d,¹J_Se-P=1060.9Hz).
＜質量分析＞ MS (EI) m/z 430 (M⁺).
＜元素分析＞ Anal. Calcd for C₂₀H₁₂ClO₂PSe(426.96)：C,55.90；H,2.81. Found：C,55.65；H,2.78.

Example 16 At 0 ° C., 3.0 mL (30.0 mmol) of phosphorus trichloride and 8.4 mL (60.0 mmol) of triethylamine were dissolved in 50 mL of toluene. This toluene solution is designated as Solution I. On the other hand, at 0 ° C., 8.58 g (30.0 mmol) of (R) -1,1′-bi-2-naphthol as the binaphthol derivative was dissolved in 10 mL of toluene. This toluene solution is designated as Solution J. Subsequently, Solution J was added to Solution I at 0 ° C., followed by stirring for 3 minutes. Next, 2.45 g (31.0 mmol) of powdered selenium was added to the mixed solution of Solution I and Solution J to prepare a reaction solution, and then the reaction solution was refluxed for 6 hours. Next, after the reaction solution was concentrated, the solvent was distilled off from the concentrated reaction solution to obtain a residue. Subsequently, the residue was purified by silica gel column chromatography (hexane: dichloromethane = 1: 1, Rf = 0.70) to obtain Compound 16 as a colorless solid. The structure of Compound 16 was analyzed. The results are described below.
<IR (KBr)> 3006, 1588, 1509, 1460, 1433,1355, 1214, 1190, 1157, 1142, 1067, 969, 946, 868, 840, 806, 769, 749, 705, 652cm - ¹
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ7.22-8.32 (m, 12H, C ₂₀ H ₁₂ )., ¹³ C-NMR (CDCl ₃ ): δ120 .4,121.1, 122.4, 122.6, 126.3, 126.9, 127.0, 127.1, 127.2, 128.7, 131.3, 131.4,132.0, 132.2, 132.3, 132.5, 146.5, 146.6, 147.8, 148.0 (Ar)., ³¹ P-NMR (CDCl ₃ ): Δ69.0 ( ¹ J _P-Se = 1060.9 Hz). ⁷⁷ Se-NMR (CDCl ₃ ): δ-69.2 (d, ¹ J _Se-P = 1060.9 Hz).
<Mass Spectrometry> MS (EI) m / z 430 (M ⁺ ).
<Elemental analysis> Anal. Calcd for C ₂₀ H ₁₂ ClO ₂ PSe (426.96): C, 55.90; H, 2.81. Found: C, 55.65; H, 2.78.

From the above results, Compound 16 had the structure shown in the following formula (43) and was identified as (R) -selenophosphate chloride. The yield of this selenophosphate is 94% (yield: 12.12 g, 28.2 mmol), the melting point is 240-241 ° C., and the optical rotation [α] _D ²⁰ (c 1.00, CHCl ₃ ) is −413 °. Met. This selenophosphate chloride is a novel compound and was stable in air and water.

（実施例１７） 0℃で、ビナフトール誘導体としての(S)-1,1’-ビ-2-ナフトール8.58g（30.0mmol）を10mLのトルエンに溶解させた。このトルエン溶液を溶液Kとする。続いて、0℃で溶液Kを試験例16の溶液Iに加えた後、3分間撹拌した。次に、試験例16と同様にして無色固体の化合物１７（Rf=0.70）を得た。この化合物１７の構造解析を行った。結果を以下に記載する。
＜赤外吸収スペクトル（KBr錠剤）＞ 3006, 1588, 1509, 1460, 1433,1355, 1214, 1190, 1157, 1142, 1067, 969, 946, 868, 840, 806, 769, 749, 705, 652cm^-1
＜核磁気共鳴スペクトル（CDCl₃溶媒TMS内部標準）＞ ^１H-NMR(CDCl₃)：δ7.22-8.32(m,12H, C₂₀H₁₂).、 ¹³C-NMR(CDCl₃)：δ120.4,121.1, 122.4, 122.6, 126.3, 126.9, 127.0, 127.1, 127.2, 128.7, 131.3, 131.4,132.0, 132.2, 132.3, 132.5, 146.5, 146.6, 147.8, 148.0 (Ar).、 ³¹P-NMR(CDCl₃)：δ69.0(¹J_P-Se=1060.7Hz).、 ⁷⁷Se-NMR(CDCl₃)：δ-69.2(d,¹J_Se-P=1061.0Hz).
＜質量分析＞ MS (EI) m/z 430 (M⁺).
＜元素分析＞ Anal. Calcd for C₂₀H₁₂ClO₂PSe(426.96)：C,55.90；H,2.81. Found：C,55.65；H,2.78.

(Example 17) At 0 ° C., 8.58 g (30.0 mmol) of (S) -1,1′-bi-2-naphthol as a binaphthol derivative was dissolved in 10 mL of toluene. This toluene solution is designated as Solution K. Subsequently, Solution K was added to Solution I of Test Example 16 at 0 ° C., and then stirred for 3 minutes. Next, a colorless solid compound 17 (Rf = 0.70) was obtained in the same manner as in Test Example 16. The structure analysis of this compound 17 was conducted. The results are described below.
<IR (KBr)> 3006, 1588, 1509, 1460, 1433,1355, 1214, 1190, 1157, 1142, 1067, 969, 946, 868, 840, 806, 769, 749, 705, 652cm - ¹
<Nuclear magnetic resonance spectrum (CDCl ₃ solvent TMS internal standard)> ¹ H-NMR (CDCl ₃ ): δ7.22-8.32 (m, 12H, C ₂₀ H ₁₂ )., ¹³ C-NMR (CDCl ₃ ): δ120 .4,121.1, 122.4, 122.6, 126.3, 126.9, 127.0, 127.1, 127.2, 128.7, 131.3, 131.4,132.0, 132.2, 132.3, 132.5, 146.5, 146.6, 147.8, 148.0 (Ar)., ³¹ P-NMR (CDCl ₃ ): Δ69.0 ( ¹ J _P-Se = 1060.7 Hz). ⁷⁷ Se-NMR (CDCl ₃ ): δ-69.2 (d, ¹ J _Se-P = 1061.0 Hz).
<Mass Spectrometry> MS (EI) m / z 430 (M ⁺ ).
<Elemental analysis> Anal. Calcd for C ₂₀ H ₁₂ ClO ₂ PSe (426.96): C, 55.90; H, 2.81. Found: C, 55.65; H, 2.78.

From the above results, Compound 17 had the structure shown in the following formula (44) and was identified as (S) -selenophosphate chloride. The yield of this selenophosphate is 90% (yield: 11.60 g, 27.0 mmol), the melting point is 240-241 ° C., and the optical rotation [α] _D ²⁰ (c 1.00, CHCl ₃ ) is + 413 °. Met. This selenophosphate chloride is a novel compound and was stable in air and water.

（実施例１８） 25℃で、(R)-O,O-ビナフチル-N-1-フェニルエチルセレノリン酸アミド0.041g（0.08mmol）と、クロロシクロオクタンジエンロジウムダイマー0.017g（[Rh(COD)Cl]₂、0.04mmol）とを5mlのトルエンに加えてトルエン溶液を調製した後、1.5時間撹拌した。続いて、-10℃で、アセトフェノン0.24g（2.0mmol）と、ジフェニルシラン0.442g（2.4mmol）とをトルエン溶液に加えた後、1時間撹拌した。次に、5mlのメタノールと、パラトルエンスルホン酸・一水和物0.038g（0.2mmol）とをトルエン溶液に加えて反応溶液を調製した後、反応溶液を25℃で5時間撹拌した。次いで、反応溶液の濃縮を行った後、濃縮された反応溶液から溶媒を留去して残渣を得た。続いて、残渣をシリカゲルカラムクロマトグラフィ（酢酸エチル：ヘキサン＝1：2、Rf=0.5）で精製し、(S)-フェネチルアルコール0.126g（1.04mmol、収率：52%、鏡像体過剰率：40%ee）を得た。この結果から、光学活性セレノリン酸アミドは、金属原子と配位結合して金属錯体を形成することによって鏡像異性体を有する化合物の合成反応の触媒として作用し、合成される化合物の立体配置の選択性を容易に高めることが分かる。

Example 18 At 25 ° C., 0.041 g (0.08 mmol) of (R) —O, O-binaphthyl-N-1-phenylethylselenophosphoric acid amide and 0.017 g of chlorocyclooctanediene rhodium dimer ([Rh (COD ) Cl] ₂ , 0.04 mmol) was added to 5 ml of toluene to prepare a toluene solution, which was then stirred for 1.5 hours. Subsequently, at −10 ° C., 0.24 g (2.0 mmol) of acetophenone and 0.442 g (2.4 mmol) of diphenylsilane were added to the toluene solution, and then stirred for 1 hour. Next, 5 ml of methanol and 0.038 g (0.2 mmol) of paratoluenesulfonic acid monohydrate were added to the toluene solution to prepare a reaction solution, and then the reaction solution was stirred at 25 ° C. for 5 hours. Next, after the reaction solution was concentrated, the solvent was distilled off from the concentrated reaction solution to obtain a residue. Subsequently, the residue was purified by silica gel column chromatography (ethyl acetate: hexane = 1: 2, Rf = 0.5), and 0.126 g (1.04 mmol, yield: 52%, enantiomeric excess: 40) of (S) -phenethyl alcohol. % ee). From this result, optically active selenophosphoric acid amide acts as a catalyst for the synthesis reaction of a compound having an enantiomer by coordinating with a metal atom to form a metal complex, and the configuration of the compound to be synthesized is selected. It can be seen that the performance is easily increased.

Example 19 0.026 g (0.06 mmol) (R) -selenophosphate chloride, 2.75 μl (0.03 mmol) racemic-2-butanol, 8.36 μl (0.06 mmol) triethylamine, 0.5 ml in an NMR tube After adding CDCl ₃ to prepare a reaction solution, the reaction solution was refluxed for 1 hour. When the ³¹ P nuclear magnetic resonance spectrum of the reaction solution was measured, a new signal that could not be observed in the CDCl ₃ solution of racemic-2-butanol was observed at 78.08 ppm and 78.21 ppm with an integration value of 1: 1. It was. From this result, it is understood that the chiral compound can be separated from the racemic racemic-2-butanol by the action of (R) -selenophosphoric acid chloride as a chiral discriminating agent.

In addition, this embodiment can also be changed and embodied as follows.
In the production of the selenophosphinic acid amide, a reaction solution may be prepared by adding selenophosphinic acid chloride and an amine lithium salt to the same solvent at a low temperature. In the production of the selenophosphoric acid amide, a solution of binaphthylselenophosphoric chloride and an amine solution may be mixed at a low temperature to prepare a reaction solution. The phosphorus trichloride, triethylamine, binaphthol derivative, and selenium may be added to the same solvent at a low temperature to prepare a reaction solution. Even in the case of such a configuration, the production of each compound is easy.

Claims (2)

A selenophosphate chloride having a structure represented by the following general formula (7) and being an (R) isomer or an (S) isomer.

(In the formula, R ⁸ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or a silyl group.) A method for producing a selenophosphate chloride according to claim 1 , comprising phosphorus trichloride, triethylamine, a binaphthol derivative having a structure represented by the following general formula (8) and being an (R) isomer or an (S) isomer: And a process for producing a selenophosphate chloride, characterized by reacting selenium with each other.

(In the formula, R ⁸ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or a silyl group.)