JP2007031344A5

JP2007031344A5 -

Info

Publication number: JP2007031344A5
Application number: JP2005217154A
Authority: JP
Filing date: 2005-07-27
Publication date: 2009-04-30

Description

即ち、本発明は、水溶液中又は水と有機溶媒との混合溶媒中で下式(化１)

（式中、Ｒ^１は、炭素数が３以上のアルキル基又はアリール基を表し、Ｒ^２は、水素原子又は炭素数１〜４のアルキル基若しくはアルコキシ基を表し、Ｘは、−ＯＨ、−ＳＨ、又は−ＮＨＲ^３（式中、Ｒ^３は水素原子又はアルキル基を表す。）を表す。）で表される配位子又はその対称体とＭ（ＯＳＯ_２Ｒ^４）_３又はＭ（ＯＳＯ_３Ｒ^４）_３（式中、ＭはＳｃ、Ｙ又はランタノイド元素を表し、Ｒ^４は炭素数が６以上の脂肪族炭化水素基、芳香族炭化水素基又はパーフルオロアルキル基を表す。）で表されるルイス酸とを混合させて得られる触媒の存在下で、下式（式２）

（式中、Ｒ^５及びＲ^６は、それぞれ同じであっても異なってもよく、水素原子、又は置換基を有していてもよい脂肪族炭化水素基、芳香族炭化水素基若しくは複素環基を表し、但し、Ｒ^５及びＲ^６の少なくとも一方は水素原子ではない。）で表されるエポキシドと、Ｒ^７Ｒ^８ＮＨ（式中、Ｒ^７及びＲ^８は、それぞれ同じであっても異なってもよく、水素原子、置換基を有していてもよい脂肪族炭化水素基、芳香族炭化水素基又は複素環基を表し、但し、Ｒ^７及びＲ^８の少なくとも一方は水素原子ではない。）で表される１級又は２級アミン化合物とを反応させることから成る光学活性β−アミノアルコール化合物の製法である。 That is, the present invention provides the following formula (chemical formula 1) in an aqueous solution or a mixed solvent of water and an organic solvent.

(In the formula, R ¹ represents an alkyl group having 3 or more carbon atoms or an aryl group, R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group, and X represents —OH, — A ligand represented by SH or —NHR ³ (wherein R ³ represents a hydrogen atom or an alkyl group) or a symmetric product thereof and M (OSO ₂ R ⁴ ) ₃ or M (OSO ₃ R ⁴ ) ₃ (wherein M represents Sc, Y or a lanthanoid element, and R ⁴ represents an aliphatic hydrocarbon group having 6 or more carbon atoms, an aromatic hydrocarbon group or a perfluoroalkyl group). In the presence of a catalyst obtained by mixing with the Lewis acid represented, the following formula (Formula 2)

(In the formula, R ⁵ and R ⁶ may be the same or different and each is a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group which may have a substituent. Wherein at least one of R ⁵ and R ⁶ is not a hydrogen atom) and R ⁷ R ⁸ NH (wherein R ⁷ and R ⁸ are the same or different from each other) And may represent a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group or a heterocyclic group, provided that at least one of R ⁷ and R ⁸ is not a hydrogen atom. And a primary amine compound or a secondary amine compound represented by formula (I).

本発明で用いるエポキシドの構造としては、下式(化２)

で表される一置換及び二置換のエポキシドが用いられる。
Ｒ^５及びＲ^６は、それぞれ同じであっても異なってもよく、水素原子、置換基を有していてもよい脂肪族炭化水素基、芳香族炭化水素基又は複素環基、好ましくはアルキル基、アリール基又はアルキルアリール基を表す。但し、Ｒ^５及びＲ^６の少なくとも一方は水素原子ではない。またＲ^５及びＲ^６は、ハロゲン原子、水酸基、ニトロ基、シアノ基、エステル基、エーテル基、チオエーテル基、アミド基等の置換基を有していてもよい。
このエポキシドは好ましくは二置換のシス体のエポキシド、より好ましくはメソ体（即ち、Ｒ^５とＲ^６とが同一である。）のエポキシドである。 The structure of the epoxide used in the present invention is as follows:

And mono- and di-substituted epoxides represented by
R ⁵ and R ⁶ may be the same or different and each is a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group which may have a substituent, preferably an alkyl group. Represents an aryl group or an alkylaryl group. However, at least one of R ⁵ and R ⁶ is not a hydrogen atom. R ⁵ and R ⁶ may have a substituent such as a halogen atom, a hydroxyl group, a nitro group, a cyano group, an ester group, an ether group, a thioether group, or an amide group.
This epoxide is preferably a disubstituted cis epoxide, more preferably a meso epoxide (ie, R ⁵ and R ⁶ are the same).

エポキシドへの求核剤となるアミンは、下式
Ｒ^７Ｒ^８ＮＨ
で表される一級又は二級アミンが用いられる。
Ｒ^７及びＲ^８は、それぞれ同じであっても異なってもよく、水素原子、置換基を有していてもよい脂肪族炭化水素基、芳香族炭化水素基又は複素環基を表し、但し、Ｒ^７及びＲ^８の少なくとも一方は水素原子ではない。これらのアミンの中でも特に芳香族アミンが好ましい。またＲ^７及びＲ^８は、ハロゲン原子、水酸基、ニトロ基、シアノ基、エステル基、エーテル基、チオエーテル基、アミド基等の置換基を有していてもよい。

Amines that are nucleophiles for epoxides are represented by the formula R ⁷ R ⁸ NH
The primary or secondary amine represented by these is used.
R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group which may have a substituent, provided that At least one of R ⁷ and R ⁸ is not a hydrogen atom. Among these amines, aromatic amines are particularly preferable. R ⁷ and R ⁸ may have a substituent such as a halogen atom, a hydroxyl group, a nitro group, a cyano group, an ester group, an ether group, a thioether group, or an amide group.

Claims

In an aqueous solution or a mixed solvent of water and an organic solvent,

(In the formula, R ⁵ and R ⁶ may be the same or different and each is a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group which may have a substituent. Wherein at least one of R ⁵ and R ⁶ is not a hydrogen atom) and R ⁷ R ⁸ NH (wherein R ⁷ and R ⁸ are the same or different from each other) And may represent a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group or a heterocyclic group, provided that at least one of R ⁷ and R ⁸ is not a hydrogen atom. The production method of an optically active β-amino alcohol compound comprising reacting with a primary or secondary amine compound represented by