JP2005314354A - Optically active sulfinic acid compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new axially asymmetric compound capable of being used as an asymmetric group-introducing assistant compound. <P>SOLUTION: This optically active sulfinic acid compound is expressed by formula (1) [wherein, R<SP>1</SP>is a 1-4C alkoxy or group expressed by formula (A) or the like, R<SP>2</SP>is hydroxy, a halogen, a 1-4C alkoxy or the like; R<SP>3</SP>is H, a halogen atom or the like, R<SP>4</SP>is H or the like; R<SP>5</SP>is the same group with that of the R<SP>4</SP>or hydrogen; and R<SP>12</SP>is hydroxy, a halogen atom, a 1-10C alkoxy or a substitutable amino]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an optically active sulfinic acid compound.

  Since most of the physiologically active substances that control physiological actions in the living body are optically active compounds, it is extremely important to determine their absolute configuration in synthetic studies and structural analysis. In recent years, optically active compounds are also extremely important compounds in the fields of pharmaceuticals, agricultural chemicals, etc., and efficacy, toxicity, etc. are often different depending on the difference in absolute configuration, and it is extremely important to determine the absolute configuration. It was work.

  As a method for determining the absolute configuration of such an optically active compound, for example, a substituent having a known absolute configuration (asymmetric auxiliary group) is introduced into the optically active compound, and subjected to NMR analysis, so that the asymmetric auxiliary group is internally contained. As a standard, there is a method for determining the absolute configuration of an optically active compound. This method is a method using the magnetic anisotropy effect of NMR, which is called the Mosher method, and can determine the absolute configuration with a simpler operation than the method based on the X-ray crystal analysis. (For example, refer nonpatent literature 1.).

  The Moscher method is based on the premise that the compound into which the asymmetric auxiliary group is introduced takes a conformation that more strongly receives the anisotropic effect of the aromatic ring derived from the asymmetric auxiliary group in the NMR measurement solution. Since the asymmetric auxiliary group introducing agent is optically active α-methoxy-α- (trifluoromethyl) phenylacetic acid which is a C-centered optically active compound, the bond axis between the asymmetric carbon atom and the carbonyl group or phenyl group In general, it is not applicable to anything other than optically active secondary alcohols, and there is a need for a compound that can be used as an asymmetric auxiliary group introducing agent that can be applied to other optically active compounds. It was.

  On the other hand, as an asymmetric auxiliary group introducing agent different from optically active α-methoxy-α- (trifluoromethyl) phenylacetic acid, for example, optically active 2′-methoxy-1,1′-binaphthalene-2-carboxylic acid, optical activity An axially asymmetric compound such as 2′-methoxy-1,1′-binaphthalene-2-carbohydroxymoyl chloride has been developed (for example, see Non-Patent Document 2), but its production method is complicated and easier. There has been a demand for a compound that can be used as an asymmetric auxiliary group-introducing agent that can be produced.

Journal of Synthetic Organic Chemistry, 56, 134 (1998) Journal of Synthetic Organic Chemistry, 55, 121 (1997)

（式中、Ｒ¹は炭素数１〜４のアルコキシ基、炭素数１〜４のパーフルオロアルコキシ基、置換されていてもよいアリール基、置換されていてもよいアリールオキシ基、置換されていてもよいアラルキルオキシ基または

で示される基を表わす。
（Ａ）Ｒ¹が炭素数１〜４のアルコキシ基、炭素数１〜４のパーフルオロアルコキシ基、置換されていてもよいアリール基、置換されていてもよいアリールオキシ基または置換されていてもよいアラルキルオキシ基のとき、Ｒ²は水酸基、ハロゲン原子、炭素数１〜４のアルコキシ基または置換されていてもよいアミノ基を表わし、Ｒ³は水素原子、ハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基を表わし、（ａ）Ｒ³が水素原子のときに、Ｒ⁴は水素原子、ハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基を、Ｒ⁵はＲ⁴と同一の基または水素原子を表わし、（ｂ）Ｒ³がハロゲン原子のときに、Ｒ⁴およびＲ⁵は水素原子を表わし、（ｃ）Ｒ³がフェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基のときに、Ｒ⁴は水素原子、ハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基を、Ｒ⁵は水素原子を表わす。（Ｂ）Ｒ¹が

で示される基のとき、Ｒ¹²は、水酸基、ハロゲン原子、炭素数１〜１０のアルコキシ基または置換されていてもよいアミノ基を表わし、（ｄ）Ｒ¹²が水酸基のときに、Ｒ²は炭素数１〜１０のアルコキシ基または置換されていてもよいアミノ基を表わし、（ｅ）Ｒ¹²がハロゲン原子、炭素数１〜１０のアルコキシ基または置換されていてもよいアミノ基のときに、Ｒ²はＲ¹²と同一の基を表わす。Ｒ³は水素原子、ハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基を表わし、Ｒ³が水素原子のときに、Ｒ⁴は水素原子、ハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基を表わし、Ｒ⁵はＲ⁴と同一の基を表わし、Ｒ³がハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基のときに、Ｒ⁴およびＲ⁵は水素原子を表わす。）
で示される光学活性スルフィン酸化合物が、不斉補助基導入剤として使用でき、しかも、従来の軸不斉化合物である２’−メトキシ−１，１’−ビナフタレン−２−カルボン酸等よりも異方性効果がより強く、光学異性体の絶対配置の決定がより容易になることを見出し、本発明に至った。 Under such circumstances, the present inventor has intensively studied to develop a novel axially asymmetric compound that can be used as an asymmetric auxiliary group introducing agent, and can be easily derived from readily available optically active binaphthol. The following formula (1) represented by optically active 2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinic acid bromide and the like

(In the formula, R ¹ is an alkoxy group having 1 to 4 carbon atoms, a perfluoroalkoxy group having 1 to 4 carbon atoms, an aryl group that may be substituted, an aryloxy group that may be substituted, May be an aralkyloxy group or

Represents a group represented by
(A) R ¹ may be an alkoxy group having 1 to 4 carbon atoms, a perfluoroalkoxy group having 1 to 4 carbon atoms, an aryl group that may be substituted, an aryloxy group that may be substituted, or a substituent. When it is a good aralkyloxy group, R ² represents a hydroxyl group, a halogen atom, an alkoxy group having 1 to 4 carbon atoms or an optionally substituted amino group, and R ³ represents a hydrogen atom, a halogen atom, a phenyl group, or 1 carbon atom. Represents an alkyl group of ˜4, a perfluoroalkyl group of 1 to 4 carbon atoms or a trisubstituted silyl group, and (a) when R ³ is a hydrogen atom, R ⁴ is a hydrogen atom, a halogen atom, a phenyl group, a carbon number An alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group, R ⁵ represents the same group as R ⁴ or a hydrogen atom, and (b) when R ³ is a halogen atom , R ⁴ And R ⁵ represents a hydrogen atom, (c) R ³ is a phenyl group, an alkyl group having 1 to 4 carbon atoms, when perfluoroalkyl group or trisubstituted silyl group having 1 to 4 carbon atoms, R ⁴ is hydrogen An atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group, R ⁵ represents a hydrogen atom. (B) R ¹ is

R ¹² represents a hydroxyl group, a halogen atom, an alkoxy group having 1 to 10 carbon atoms or an optionally substituted amino group. (D) When R ¹² is a hydroxyl group, R ² represents Represents an alkoxy group having 1 to 10 carbon atoms or an optionally substituted amino group, and (e) when R ¹² is a halogen atom, an alkoxy group having 1 to 10 carbon atoms or an optionally substituted amino group, R ² represents the same group as R ¹² . R ³ represents a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or a trisubstituted silyl group, and when R ³ is a hydrogen atom, R ⁴ Represents a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group; R ⁵ represents the same group as R ⁴ ; ^{When 3} is a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or a trisubstituted silyl group, R ⁴ and R ⁵ represent a hydrogen atom. )
The optically active sulfinic acid compound represented by the above formula can be used as an asymmetric auxiliary group introducing agent and is different from the conventional axially asymmetric compound 2′-methoxy-1,1′-binaphthalene-2-carboxylic acid and the like. It has been found that the isotropic effect is stronger and the determination of the absolute configuration of the optical isomer is easier, and the present invention has been achieved.

（式中、Ｒ¹は炭素数１〜４のアルコキシ基、炭素数１〜４のパーフルオロアルコキシ基、置換されていてもよいアリール基、置換されていてもよいアリールオキシ基、置換されていてもよいアラルキルオキシ基または

で示される基を表わす。
（Ａ）Ｒ¹が炭素数１〜４のアルコキシ基、炭素数１〜４のパーフルオロアルコキシ基、置換されていてもよいアリール基、置換されていてもよいアリールオキシ基または置換されていてもよいアラルキルオキシ基のとき、Ｒ²は水酸基、ハロゲン原子、炭素数１〜４のアルコキシ基または置換されていてもよいアミノ基を表わし、Ｒ³は水素原子、ハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基を表わし、（ａ）Ｒ³が水素原子のときに、Ｒ⁴は水素原子、ハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基を、Ｒ⁵はＲ⁴と同一の基または水素原子を表わし、（ｂ）Ｒ³がハロゲン原子のときに、Ｒ⁴およびＲ⁵は水素原子を表わし、（ｃ）Ｒ³がフェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基のときに、Ｒ⁴は水素原子、ハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基を、Ｒ⁵は水素原子を表わす。（Ｂ）Ｒ¹が

で示される基のとき、Ｒ¹²は、水酸基、ハロゲン原子、炭素数１〜１０のアルコキシ基または置換されていてもよいアミノ基を表わし、（ｄ）Ｒ¹²が水酸基のときに、Ｒ²は炭素数１〜１０のアルコキシ基または置換されていてもよいアミノ基を表わし、（ｅ）Ｒ¹²がハロゲン原子、炭素数１〜１０のアルコキシ基または置換されていてもよいアミノ基のときに、Ｒ²はＲ¹²と同一の基を表わす。Ｒ³は水素原子、ハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基を表わし、Ｒ³が水素原子のときに、Ｒ⁴は水素原子、ハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基を表わし、Ｒ⁵はＲ⁴と同一の基を表わし、Ｒ³がハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基のときに、Ｒ⁴およびＲ⁵は水素原子を表わす。）
で示される光学活性スルフィン酸化合物；
２．式（１）の式中、Ｒ¹が、炭素数１〜４のアルコキシ基または炭素数１〜４のパーフルオロアルコキシ基である前項１に記載の光学活性スルフィン酸化合物；
３．式（１）の式中、Ｒ³が水素原子で、Ｒ⁴が水素原子またはハロゲン原子で、Ｒ⁵がＲ⁴と同一の基または水素原子である前項２に記載の光学活性スルフィン酸化合物；
４．式（１）の式中、Ｒ³がハロゲン原子で、Ｒ⁴およびＲ⁵が水素原子である前項３に記載の光学活性スルフィン酸化合物；
５．式（１）の式中、Ｒ¹が

で示される基で、Ｒ³、Ｒ⁴およびＲ⁵が水素原子である前項１に記載の光学活性スルフィン酸化合物；
６．式（１）の式中、Ｒ¹²が水酸基であり、Ｒ²が炭素数１〜１０のアルコキシ基または置換されていてもよいアミノ基である前項５に記載の光学活性スルフィン酸化合物；
等を提供するものである。 That is, the present invention
1. Formula (1)

(In the formula, R ¹ is an alkoxy group having 1 to 4 carbon atoms, a perfluoroalkoxy group having 1 to 4 carbon atoms, an aryl group that may be substituted, an aryloxy group that may be substituted, May be an aralkyloxy group or

Represents a group represented by
(A) R ¹ may be an alkoxy group having 1 to 4 carbon atoms, a perfluoroalkoxy group having 1 to 4 carbon atoms, an aryl group that may be substituted, an aryloxy group that may be substituted, or a substituent. When it is a good aralkyloxy group, R ² represents a hydroxyl group, a halogen atom, an alkoxy group having 1 to 4 carbon atoms or an optionally substituted amino group, and R ³ represents a hydrogen atom, a halogen atom, a phenyl group, or 1 carbon atom. Represents an alkyl group of ˜4, a perfluoroalkyl group of 1 to 4 carbon atoms or a trisubstituted silyl group, and (a) when R ³ is a hydrogen atom, R ⁴ is a hydrogen atom, a halogen atom, a phenyl group, a carbon number An alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group, R ⁵ represents the same group as R ⁴ or a hydrogen atom, and (b) when R ³ is a halogen atom , R ⁴ And R ⁵ represents a hydrogen atom, (c) R ³ is a phenyl group, an alkyl group having 1 to 4 carbon atoms, when perfluoroalkyl group or trisubstituted silyl group having 1 to 4 carbon atoms, R ⁴ is hydrogen An atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group, R ⁵ represents a hydrogen atom. (B) R ¹ is

R ¹² represents a hydroxyl group, a halogen atom, an alkoxy group having 1 to 10 carbon atoms or an optionally substituted amino group. (D) When R ¹² is a hydroxyl group, R ² represents Represents an alkoxy group having 1 to 10 carbon atoms or an optionally substituted amino group, and (e) when R ¹² is a halogen atom, an alkoxy group having 1 to 10 carbon atoms or an optionally substituted amino group, R ² represents the same group as R ¹² . R ³ represents a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or a trisubstituted silyl group, and when R ³ is a hydrogen atom, R ⁴ Represents a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group; R ⁵ represents the same group as R ⁴ ; ^{When 3} is a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or a trisubstituted silyl group, R ⁴ and R ⁵ represent a hydrogen atom. )
An optically active sulfinic acid compound represented by:
2. The optically active sulfinic acid compound according to item ¹ , wherein R ¹ is an alkoxy group having 1 to 4 carbon atoms or a perfluoroalkoxy group having 1 to 4 carbon atoms in the formula of formula (1);
3. The optically active sulfinic acid compound according to item 2, wherein R ³ is a hydrogen atom, R ⁴ is a hydrogen atom or a halogen atom, and R ⁵ is the same group or hydrogen atom as R ^{4 in} the formula of formula (1);
4). The optically active sulfinic acid compound according to item ³ , wherein R ³ is a halogen atom and R ⁴ and R ⁵ are hydrogen atoms in the formula of formula (1);
5). In the formula (1), R ¹ is

The optically active sulfinic acid compound according to item 1 above, wherein R ³ , R ⁴ and R ⁵ are hydrogen atoms;
6). In the formula of formula (1), R ¹² is a hydroxyl group, and R ² is an alkoxy group having 1 to 10 carbon atoms or an optionally substituted amino group;
Etc. are provided.

  The novel optically active sulfinic acid compound of the present invention can be easily produced from readily available optically active binaphthol, and has a stronger anisotropic effect than the conventionally known axially asymmetric compounds. Thus, the absolute configuration of the optical isomer can be determined more easily.

で示される光学活性スルフィン酸化合物（以下、光学活性スルフィン酸化合物（１）と略記する。）の式中、Ｒ¹は炭素数１〜４のアルコキシ基、炭素数１〜４のパーフルオロアルコキシ基、置換されていてもよいアリール基、置換されていてもよいアリールオキシ基、置換されていてもよいアラルキルオキシ基または

で示される基を表わす。 Formula (1)

In the formula of the optically active sulfinic acid compound represented by (hereinafter abbreviated as optically active sulfinic acid compound (1)), R ¹ is an alkoxy group having 1 to 4 carbon atoms and a perfluoroalkoxy group having 1 to 4 carbon atoms. An optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted aralkyloxy group, or

Represents a group represented by

  Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group. Examples of the perfluoroalkoxy group having 1 to 4 carbon atoms include a trifluoromethoxy group, a pentafluoroethoxy group, a heptafluoropropoxy group, and a nonafluorobutoxy group. Examples of the optionally substituted aryl group include an unsubstituted aryl group such as a phenyl group and a naphthyl group, and one or two or more hydrogen atoms of the unsubstituted aryl group, for example, a fluorine atom, a chlorine atom, Halogen atoms such as bromine atom and iodine atom, for example, alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, isopropyl group and tert-butyl group, for example, acyl groups having 2 to 5 carbon atoms such as acetyl group, Those substituted with a substituent such as an alkoxy group having 1 to 4 carbon atoms, such as a 2-fluorophenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, a 4-acetylphenyl group, and a 3-methoxyphenyl group. It is done. As the optionally substituted aryloxy group, those composed of the optionally substituted aryl group and an oxygen atom, for example, phenoxy group, 2-fluorophenoxy group, 4-chlorophenoxy group, 4-methyl A phenoxy group, 4-acetylphenoxy group, 3-methoxyphenoxy group, etc. are mentioned. As the aralkyloxy group which may be substituted, those composed of the aryl group which may be substituted and the alkoxy group having 1 to 4 carbon atoms, such as benzyl group, 2-fluorobenzyl group, 4- Examples include chlorobenzyl group, 4-methylbenzyl group, 4-acetylbenzyl group, 3-methoxybenzyl group, phenylethyl group and the like.

First, (A) R ¹ is an alkoxy group having 1 to 4 carbon atoms, a perfluoroalkoxy group having 1 to 4 carbon atoms, an optionally substituted aryl group, an optionally substituted aryloxy group or a substituted group. The optically active sulfinic acid compound which may be an aralkyloxy group may be described. In the above formula (1), R ¹ is an alkoxy group having 1 to 4 carbon atoms, a perfluoroalkoxy group having 1 to 4 carbon atoms, an optionally substituted aryl group, an optionally substituted aryloxy group or a substituted group. R ² represents a hydroxyl group, a halogen atom, an alkoxy group having 1 to 4 carbon atoms or an optionally substituted amino group, and R ³ represents a hydrogen atom, a halogen atom or a phenyl group. Represents an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or a trisubstituted silyl group, and (a) when R ³ is a hydrogen atom, R ⁴ is a hydrogen atom, a halogen atom, phenyl A group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group, R ⁵ represents the same group as R ⁴ or a hydrogen atom, and (b) R ³ represents a halogen atom. Atomic and R ⁴ and R ⁵ represent a hydrogen atom, and (c) when R ³ is a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or a trisubstituted silyl group. , R ⁴ represents a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group, and R ⁵ represents a hydrogen atom.

  Examples of the halogen atom and the alkoxy group having 1 to 4 carbon atoms are the same as those described above. Examples of the optionally substituted amino group include an amino group, for example, one or two hydrogen atoms of the amino group substituted with the alkyl group having 1 to 4 carbon atoms, for example, a methylamino group, dimethylamino Group, ethylamino group, monoalkylamino group such as diethylamino group or dialkylamino group such as hydrazino group such as guanidyl group such as morpholinyl group, pyrrolidinyl group, piperidinyl group, pyrazinyl group, imidazolyl group, etc. And a cyclic amino group having 4 to 5 carbon atoms which may contain.

In the above formula (1), R ³ represents a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or a trisubstituted silyl group. Examples of the halogen atom and the alkyl group having 1 to 4 carbon atoms include the same ones as described above. Examples of the perfluoroalkyl group having 1 to 4 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, and heptafluoro. A propyl group and a nonafluorobutyl group are mentioned. Examples of the trisubstituted silyl group include a trimethylsilyl group, a triethylsilyl group, a phenyldimethylsilyl group, and a diphenylmethylsilyl group.

In the above formula (1), (a) when R ³ is a hydrogen atom, R ⁴ is a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, or a perfluoroalkyl group having 1 to 4 carbon atoms. Or a trisubstituted silyl group, wherein R ⁵ represents the same group or hydrogen atom as R ⁴ , (b) when R ³ is a halogen atom, R ⁴ and R ⁵ represent a hydrogen atom, and (c) R ³ Is a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or a trisubstituted silyl group, R ⁴ is a hydrogen atom, a halogen atom, a phenyl group, or an alkyl group having 1 to 4 carbon atoms. R ⁵ represents a hydrogen atom, an alkyl group, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group. Examples of the halogen atom, the alkyl group having 1 to 4 carbon atoms, the perfluoroalkyl group having 1 to 4 carbon atoms, and the trisubstituted silyl group include the same ones as described above. Among them, in R ³ is a hydrogen atom, with R ⁴ is a hydrogen atom or a halogen atom and R ⁵ are the same group or a hydrogen atom and R ^4, with R ³ is a halogen atom, R ⁴ and R ⁵ are hydrogen Those that are atoms are preferred.

  Examples of such optically active sulfinic acid compounds include optically active 2-methoxy-1,1′-binaphthalene-2′-sulfinic acid and optically active 2-methoxy-6-fluoro-1,1′-binaphthalene-2′-sulfin. Acid, optically active 2-methoxy-6-bromo-1,1'-binaphthalene-2'-sulfinic acid, optically active 2-methoxy-6-chloro-1,1'-binaphthalene-2'-sulfinic acid, optical activity 2-methoxy-6-iodo-1,1′-binaphthalene-2′-sulfinic acid, optically active 2-methoxy-6,6′-difluoro-1,1′-binaphthalene-2′-sulfinic acid, optically active 2 -Methoxy-6,6'-dichloro-1,1'-binaphthalene-2'-sulfinic acid, optically active 2-methoxy-6,6'-dibromo-1,1'-binaphthalene 2'-sulfinic acid, optically active 2-methoxy-6,6'-diiodo-1,1'-binaphthalene-2'-sulfinic acid, optically active 2-methoxy-3,3'-difluoro-1,1'- Binaphthalene-2′-sulfinic acid, optically active 2-methoxy-3,3′-dichloro-1,1′-binaphthalene-2′-sulfinic acid, optically active 2-methoxy-3,3′-dibromo-1,1 '-Binaphthalene-2'-sulfinic acid, optically active 2-methoxy-3,3'-diiodo-1,1'-binaphthalene-2'-sulfinic acid, optically active 2-methoxy-6-phenyl-1,1' -Binaphthalene-2'-sulfinic acid, optically active 2-methoxy-6,6'-diphenyl-1,1'-binaphthalene-2'-sulfinic acid, optically active 2-methoxy-6-methyl-1,1'- Naphthalene-2′-sulfinic acid, optically active 2-methoxy-6-tert-butyl-1,1′-binaphthalene-2′-sulfinic acid, optically active 2-methoxy-6,6′-dimethyl-1,1 ′ -Binaphthalene-2'-sulfinic acid, optically active 2-methoxy-6,6'-di (tert-butyl) -1,1'-binaphthalene-2'-sulfinic acid, optically active 2-methoxy-3,3 ' , 6-Trimethyl-1,1′-binaphthalene-2′-sulfinic acid, optically active 2-methoxy-6-trifluoromethyl-1,1′-binaphthalene-2′-sulfinic acid, optically active 2-methoxy-6 , 6'-bis (trifluoromethyl) -1,1'-binaphthalene-2'-sulfinic acid, optically active 2-methoxy-6-trimethylsilyl-1,1'-binaphthalene-2'- Sulfinic acid, optically active 2-methoxy-6,6′-bis (trimethylsilyl) -1,1′-binaphthalene-2′-sulfinic acid, optically active 2-methoxy-3,3′-dimethyl-6-bromo-1 , 1′-Binaphthalene-2′-sulfinic acid, optically active 2-methoxy-3,3′-di (tert-butyl) -6-bromo-1,1′-binaphthalene-2′-sulfinic acid, optically active 2 -Methoxy-3,3'-dimethyl-6- (trimethylsilyl) -1,1'-binaphthalene-2'-sulfinic acid,

Optically active 2-methoxy-1,1′-binaphthalene-2′-sulfinate methyl, optically active 2-methoxy-6-fluoro-1,1′-binaphthalene-2′-sulfinate methyl, optically active 2-methoxy- 6-chloro-1,1′-binaphthalene-2′-sulfinate methyl, optically active 2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinate methyl, optically active 2-methoxy-6- Iodo-1,1′-binaphthalene-2′-sulfinate methyl, optically active 2-methoxy-6,6′-difluoro-1,1′-binaphthalene-2′-sulfinate methyl, optically active 2-methoxy-6 , 6′-Dichloro-1,1′-binaphthalene-2′-sulfinate methyl ester, optically active 2-methoxy-6,6′-dibromo-1,1′-binaphthalene-2 ′ Methyl sulfinate, optically active 2-methoxy-6,6'-diiodo-1,1'-binaphthalene-2'-methyl sulfinate, optically active 2-methoxy-3,3'-difluoro-1,1'-binaphthalene -2'-methyl sulfinate, optically active 2-methoxy-3,3'-dichloro-1,1'-binaphthalene-2'-methyl sulfinate, optically active 2-methoxy-3,3'-dibromo-1, 1'-Binaphthalene-2'-sulfinate methyl, optically active 2-methoxy-3,3'-diiodo-1,1'-binaphthalene-2'-sulfinate methyl, optically active 2-methoxy-6-phenyl-1 , 1'-binaphthalene-2'-sulfinate methyl, optically active 2-methoxy-6,6'-diphenyl-1,1'-binaphthalene-2'-sulfinate methyl, light Active methyl 2-methoxy-6-methyl-1,1′-binaphthalene-2′-sulfinate, optically active methyl 2-methoxy-6-tert-butyl-1,1′-binaphthalene-2′-sulfinate, optical Active methyl 2-methoxy-6,6′-dimethyl-1,1′-binaphthalene-2′-sulfinate, optically active 2-methoxy-6,6′-di (tert-butyl) -1,1′-binaphthalene -2'-methyl sulfinate, optically active 2-methoxy-3,3 ', 6-trimethyl-1,1'-binaphthalene-2'-methyl sulfinate, optically active 2-methoxy-6-trifluoromethyl-1 , 1′-Binaphthalene-2′-sulfinate, optically active 2-methoxy-6,6′-bis (trifluoromethyl) -1,1′-binaphthalene-2′-sulfine Acid methyl, optically active 2-methoxy-6-trimethylsilyl-1,1′-binaphthalene-2′-sulfinate methyl, optically active 2-methoxy-6,6′-bis (trimethylsilyl) -1,1′-binaphthalene- 2'-methyl sulfinate, optically active 2-methoxy-3,3'-dimethyl-6-bromo-1,1'-binaphthalene-2'-methyl sulfinate, optically active 2-methoxy-3,3'-di (Tert-Butyl) -6-bromo-1,1′-binaphthalene-2′-sulfinate methyl ester, optically active 2-methoxy-3,3′-dimethyl-6- (trimethylsilyl) -1,1′-binaphthalene- Methyl 2′-sulfinate,

Optically active 2-methoxy-1,1′-binaphthalene-2′-sulfinate ethyl, optically active 2-methoxy-6-fluoro-1,1′-binaphthalene-2′-sulfinate, optically active 2-methoxy- 6-chloro-1,1′-binaphthalene-2′-sulfinate ethyl, optically active 2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinate, optically active 2-methoxy-6- Iodo-1,1′-binaphthalene-2′-sulfinate ethyl, optically active 2-methoxy-6,6′-difluoro-1,1′-binaphthalene-2′-sulfinate ethyl, optically active 2-methoxy-6 , 6′-dichloro-1,1′-binaphthalene-2′-sulfinic acid ethyl ester, optically active 2-methoxy-6,6′-dibromo-1,1′-binaphthalene-2 ′ Ethyl sulfinate, optically active 2-methoxy-6,6′-diiodo-1,1′-binaphthalene-2′-ethyl sulfinate, optically active 2-methoxy-3,3′-difluoro-1,1′-binaphthalene -2'-ethyl sulfinate, optically active 2-methoxy-3,3'-dichloro-1,1'-binaphthalene-2'-ethyl sulfinate, optically active 2-methoxy-3,3'-dibromo-1, 1′-Binaphthalene-2′-sulfinate ethyl, optically active 2-methoxy-3,3′-diiodo-1,1′-binaphthalene-2′-sulfinate ethyl, optically active 2-methoxy-6-phenyl-1 , 1′-Binaphthalene-2′-sulfinate ethyl, optically active 2-methoxy-6,6′-diphenyl-1,1′-binaphthalene-2′-sulfinate ethyl, light Active 2-methoxy-6-methyl-1,1′-binaphthalene-2′-sulfinate ethyl, optically active 2-methoxy-6-tert-butyl-1,1′-binaphthalene-2′-sulfinate ethyl, optical Active ethyl 2-methoxy-6,6′-dimethyl-1,1′-binaphthalene-2′-sulfinate, optically active 2-methoxy-6,6′-di (tert-butyl) -1,1′-binaphthalene -2'-ethyl sulfinate, optically active 2-methoxy-3,3 ', 6-trimethyl-1,1'-binaphthalene-2'-ethyl sulfinate, optically active 2-methoxy-6-trifluoromethyl-1 , 1′-Binaphthalene-2′-sulfinate ethyl, optically active 2-methoxy-6,6′-bis (trifluoromethyl) -1,1′-binaphthalene-2′-sulfine Ethyl acetate, optically active 2-methoxy-6-trimethylsilyl-1,1′-binaphthalene-2′-sulfinate, optically active 2-methoxy-6,6′-bis (trimethylsilyl) -1,1′-binaphthalene- 2′-ethyl sulfinate, optically active 2-methoxy-3,3′-dimethyl-6-bromo-1,1′-binaphthalene-2′-ethyl sulfinate, optically active 2-methoxy-3,3′-di (Tert-Butyl) -6-bromo-1,1′-binaphthalene-2′-sulfinate ethyl, optically active 2-methoxy-3,3′-dimethyl-6- (trimethylsilyl) -1,1′-binaphthalene- 2'-ethyl sulfinate,

Optically active 2-methoxy-1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-methoxy-6-fluoro-1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-methoxy- 6-chloro-1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-methoxy-6- Iodo-1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-methoxy-6,6′-difluoro-1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-methoxy-6 , 6'-dichloro-1,1'-binaphthalene-2'-sulfinic acid bromide, optically active 2-methoxy-6,6'-dibromo-1,1'-bina Talen-2'-sulfinic acid bromide, optically active 2-methoxy-6,6'-diiodo-1,1'-binaphthalene-2'-sulfinic acid bromide, optically active 2-methoxy-3,3'-difluoro-1 , 1′-Binaphthalene-2′-sulfinic acid bromide, optically active 2-methoxy-3,3′-dichloro-1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-methoxy-3,3 ′ -Dibromo-1,1'-binaphthalene-2'-sulfinic acid bromide, optically active 2-methoxy-3,3'-diiodo-1,1'-binaphthalene-2'-sulfinic acid bromide, optically active 2-methoxy- 6-phenyl-1,1'-binaphthalene-2'-sulfinic acid bromide, optically active 2-methoxy-6,6'-diphenyl-1,1'-binaphthalene- '-Sulfinic acid bromide, optically active 2-methoxy-6-methyl-1,1'-binaphthalene-2'-sulfinic acid bromide, optically active 2-methoxy-6-tert-butyl-1,1'-binaphthalene-2 '-Sulfinic acid bromide, optically active 2-methoxy-6,6'-dimethyl-1,1'-binaphthalene-2'-sulfinic acid bromide, optically active 2-methoxy-6,6'-di (tert-butyl) -1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-methoxy-3,3 ′, 6-trimethyl-1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-methoxy- 6-trifluoromethyl-1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-methoxy-6,6′-bis (trifluoromethyl) -1,1'-binaphthalene-2'-sulfinic acid bromide, optically active 2-methoxy-6-trimethylsilyl-1,1'-binaphthalene-2'-sulfinic acid bromide, optically active 2-methoxy-6,6'- Bis (trimethylsilyl) -1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-methoxy-3,3′-dimethyl-6-bromo-1,1′-binaphthalene-2′-sulfinic acid bromide, Optically active 2-methoxy-3,3′-di (tert-butyl) -6-bromo-1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-methoxy-3,3′-dimethyl-6 -(Trimethylsilyl) -1,1'-binaphthalene-2'-sulfinic acid bromide,

Optically active 2-methoxy-1,1′-binaphthalene-2′-sulfinic acid chloride, optically active 2-methoxy-6-fluoro-1,1′-binaphthalene-2′-sulfinic acid chloride, optically active 2-methoxy- 6-chloro-1,1′-binaphthalene-2′-sulfinic acid chloride, optically active 2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinic acid chloride, optically active 2-methoxy-6- Iodo-1,1′-binaphthalene-2′-sulfinic acid chloride, optically active 2-methoxy-6,6′-difluoro-1,1′-binaphthalene-2′-sulfinic acid chloride, optically active 2-methoxy-6 , 6′-Dichloro-1,1′-binaphthalene-2′-sulfinic acid chloride, optically active 2-methoxy-6,6′-dibromo-1,1′-bina Talen-2′-sulfinic acid chloride, optically active 2-methoxy-6,6′-diiodo-1,1′-binaphthalene-2′-sulfinic acid chloride, optically active 2-methoxy-3,3′-difluoro-1 , 1′-Binaphthalene-2′-sulfinic acid chloride, optically active 2-methoxy-3,3′-dichloro-1,1′-binaphthalene-2′-sulfinic acid chloride, optically active 2-methoxy-3,3 ′ -Dibromo-1,1'-binaphthalene-2'-sulfinic acid chloride, optically active 2-methoxy-3,3'-diiodo-1,1'-binaphthalene-2'-sulfinic acid chloride, optically active 2-methoxy- 6-phenyl-1,1'-binaphthalene-2'-sulfinic acid chloride, optically active 2-methoxy-6,6'-diphenyl-1,1'-binaphthalene- '-Sulfinic acid chloride, optically active 2-methoxy-6-methyl-1,1'-binaphthalene-2'-sulfinic acid chloride, optically active 2-methoxy-6-tert-butyl-1,1'-binaphthalene-2 '-Sulfinic acid chloride, optically active 2-methoxy-6,6'-dimethyl-1,1'-binaphthalene-2'-sulfinic acid chloride, optically active 2-methoxy-6,6'-di (tert-butyl) -1,1'-binaphthalene-2'-sulfinic acid chloride, optically active 2-methoxy-3,3 ', 6-trimethyl-1,1'-binaphthalene-2'-sulfinic acid chloride, optically active 2-methoxy- 6-trifluoromethyl-1,1′-binaphthalene-2′-sulfinic acid chloride, optically active 2-methoxy-6,6′-bis (trifluoromethyl) -1,1'-binaphthalene-2'-sulfinic acid chloride, optically active 2-methoxy-6-trimethylsilyl-1,1'-binaphthalene-2'-sulfinic acid chloride, optically active 2-methoxy-6,6'- Bis (trimethylsilyl) -1,1′-binaphthalene-2′-sulfinic acid chloride, optically active 2-methoxy-3,3′-dimethyl-6-bromo-1,1′-binaphthalene-2′-sulfinic acid chloride, Optically active 2-methoxy-3,3′-di (tert-butyl) -6-bromo-1,1′-binaphthalene-2′-sulfinic acid chloride, optically active 2-methoxy-3,3′-dimethyl-6 -(Trimethylsilyl) -1,1'-binaphthalene-2'-sulfinic acid chloride,

Optically active 2-methoxy-1,1′-binaphthalene-2′-sulfinamide, optically active 2-methoxy-6-fluoro-1,1′-binaphthalene-2′-sulfinamide, optically active 2-methoxy-6- Chloro-1,1′-binaphthalene-2′-sulfinamide, optically active 2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinamide, optically active 2-methoxy-6-iodo-1, 1′-Binaphthalene-2′-sulfinamide, optically active 2-methoxy-6,6′-difluoro-1,1′-binaphthalene-2′-sulfinamide, optically active 2-methoxy-6,6′-dichloro- 1,1′-Binaphthalene-2′-sulfinamide, optically active 2-methoxy-6,6′-dibromo-1,1′-binaphthalene-2′-sulfinamide Optically active 2-methoxy-6,6′-diiodo-1,1′-binaphthalene-2′-sulfinamide, optically active 2-methoxy-3,3′-difluoro-1,1′-binaphthalene-2 ′ -Sulfinamide, optically active 2-methoxy-3,3'-dichloro-1,1'-binaphthalene-2'-sulfinamide, optically active 2-methoxy-3,3'-dibromo-1,1'-binaphthalene- 2'-sulfinamide, optically active 2-methoxy-3,3'-diiodo-1,1'-binaphthalene-2'-sulfinamide, optically active 2-methoxy-6-phenyl-1,1'-binaphthalene-2 '-Sulfinamide, optically active 2-methoxy-6,6'-diphenyl-1,1'-binaphthalene-2'-sulfinamide, optically active 2-methoxy-6-methyl 1,1′-binaphthalene-2′-sulfinamide, optically active 2-methoxy-6-tert-butyl-1,1′-binaphthalene-2′-sulfinamide, optically active 2-methoxy-6,6′-dimethyl -1,1′-binaphthalene-2′-sulfinamide, optically active 2-methoxy-6,6′-di (tert-butyl) -1,1′-binaphthalene-2′-sulfinamide, optically active 2-methoxy -3,3 ', 6-trimethyl-1,1'-binaphthalene-2'-sulfinamide, optically active 2-methoxy-6-trifluoromethyl-1,1'-binaphthalene-2'-sulfinamide, optically active 2-methoxy-6,6′-bis (trifluoromethyl) -1,1′-binaphthalene-2′-sulfinamide, optically active 2-methoxy-6-trimethyl Rusilyl-1,1′-binaphthalene-2′-sulfinamide, optically active 2-methoxy-6,6′-bis (trimethylsilyl) -1,1′-binaphthalene-2′-sulfinamide, optically active 2-methoxy- 3,3′-dimethyl-6-bromo-1,1′-binaphthalene-2′-sulfinamide, optically active 2-methoxy-3,3′-di (tert-butyl) -6-bromo-1,1 ′ -Binaphthalene-2'-sulfinamide, optically active 2-methoxy-3,3'-dimethyl-6- (trimethylsilyl) -1,1'-binaphthalene-2'-sulfinamide,

Optically active N-isopropyl-2-methoxy-1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-methoxy-6-fluoro-1,1′-binaphthalene-2′-sulfinamide, Optically active N-isopropyl-2-methoxy-6-chloro-1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-methoxy-6-bromo-1,1′-binaphthalene-2 ′ -Sulfinamide, optically active N-isopropyl-2-methoxy-6-iodo-1,1'-binaphthalene-2'-sulfinamide, optically active N-isopropyl-2-methoxy-6,6'-difluoro-1, 1′-Binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-methoxy-6,6′-dichloro-1,1 -Binaphthalene-2'-sulfinamide, optically active N-isopropyl-2-methoxy-6,6'-dibromo-1,1'-binaphthalene-2'-sulfinamide, optically active N-isopropyl-2-methoxy-6 , 6′-Diiodo-1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-methoxy-3,3′-difluoro-1,1′-binaphthalene-2′-sulfinamide, optical Active N-isopropyl-2-methoxy-3,3′-dichloro-1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-methoxy-3,3′-dibromo-1,1 ′ -Binaphthalene-2'-sulfinamide, optically active N-isopropyl-2-methoxy-3,3'-diiodo-1,1'-binaphthalene 2′-sulfinamide, optically active N-isopropyl-2-methoxy-6-phenyl-1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-methoxy-6,6′-diphenyl- 1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-methoxy-6-methyl-1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-methoxy- 6-tert-butyl-1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-methoxy-6,6′-dimethyl-1,1′-binaphthalene-2′-sulfinamide, optical Active N-isopropyl-2-methoxy-6,6'-di (tert-butyl) -1,1'-binaphthalene-2'-sulfi Amide, optically active N-isopropyl-2-methoxy-3,3 ′, 6-trimethyl-1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-methoxy-6-trifluoromethyl- 1,1′-Binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-methoxy-6,6′-bis (trifluoromethyl) -1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-methoxy-6-trimethylsilyl-1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-methoxy-6,6′-bis (trimethylsilyl) -1,1′- Binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-methoxy-3,3′-dimethyl-6-bromo 1,1′-Binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-methoxy-3,3′-di (tert-butyl) -6-bromo-1,1′-binaphthalene-2′-sulfin Amide, optically active N-isopropyl-2-methoxy-3,3′-dimethyl-6- (trimethylsilyl) -1,1′-binaphthalene-2′-sulfinamide,

Optically active 2-methoxy-1,1′-binaphthalene-2′-sulfinyl hydrazide, optically active 2-methoxy-6-fluoro-1,1′-binaphthalene-2′-sulfinyl hydrazide, optically active 2-methoxy-6 Chloro-1,1′-binaphthalene-2′-sulfinyl hydrazide, optically active 2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinyl hydrazide, optically active 2-methoxy-6-iodo-1, 1′-Binaphthalene-2′-sulfinyl hydrazide, optically active 2-methoxy-6,6′-difluoro-1,1′-binaphthalene-2′-sulfinyl hydrazide, optically active 2-methoxy-6,6′-dichloro- 1,1′-binaphthalene-2′-sulfinyl hydrazide, optically active 2-methoxy-6,6′-dibromo- , 1′-Binaphthalene-2′-sulfinyl hydrazide, optically active 2-methoxy-6,6′-diiodo-1,1′-binaphthalene-2′-sulfinylhydrazide, optically active 2-methoxy-3,3′-difluoro -1,1′-binaphthalene-2′-sulfinyl hydrazide, optically active 2-methoxy-3,3′-dichloro-1,1′-binaphthalene-2′-sulfinylhydrazide, optically active 2-methoxy-3,3 ′ -Dibromo-1,1'-binaphthalene-2'-sulfinyl hydrazide, optically active 2-methoxy-3,3'-diiodo-1,1'-binaphthalene-2'-sulfinyl hydrazide, optically active 2-methoxy-6 Phenyl-1,1′-binaphthalene-2′-sulfinyl hydrazide, optically active 2-methoxy-6,6′-dipheni -1,1'-binaphthalene-2'-sulfinyl hydrazide, optically active 2-methoxy-6-methyl-1,1'-binaphthalene-2'-sulfinyl hydrazide, optically active 2-methoxy-6-tert-butyl-1 , 1′-Binaphthalene-2′-sulfinyl hydrazide, optically active 2-methoxy-6,6′-dimethyl-1,1′-binaphthalene-2′-sulfinylhydrazide, optically active 2-methoxy-6,6′-di (Tert-Butyl) -1,1′-binaphthalene-2′-sulfinyl hydrazide, optically active 2-methoxy-3,3 ′, 6-trimethyl-1,1′-binaphthalene-2′-sulfinylhydrazide, optically active 2 -Methoxy-6-trifluoromethyl-1,1'-binaphthalene-2'-sulfinyl hydrazide, optically active 2-meth Xyl-6,6′-bis (trifluoromethyl) -1,1′-binaphthalene-2′-sulfinyl hydrazide, optically active 2-methoxy-6-trimethylsilyl-1,1′-binaphthalene-2′-sulfinyl hydrazide, Optically active 2-methoxy-6,6′-bis (trimethylsilyl) -1,1′-binaphthalene-2′-sulfinylhydrazide, optically active 2-methoxy-3,3′-dimethyl-6-bromo-1,1 ′ -Binaphthalene-2'-sulfinyl hydrazide, optically active 2-methoxy-3,3'-di (tert-butyl) -6-bromo-1,1'-binaphthalene-2'-sulfinylhydrazide, optically active 2-methoxy- 3,3′-dimethyl-6- (trimethylsilyl) -1,1′-binaphthalene-2′-sulfinyl hydrazide,

Optically active 2-methoxy-1,1′-binaphthalene-2′-sulfinylguanide, optically active 2-methoxy-6-fluoro-1,1′-binaphthalene-2′-sulfinylguanide, optically active 2- Methoxy-6-chloro-1,1′-binaphthalene-2′-sulfinylguanide, optically active 2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinylguanide, optically active 2- Methoxy-6-iodo-1,1′-binaphthalene-2′-sulfinylguanide, optically active 2-methoxy-6,6′-difluoro-1,1′-binaphthalene-2′-sulfinylguanide, optical Active 2-methoxy-6,6′-dichloro-1,1′-binaphthalene-2′-sulfinylguanidide, optically active 2-methoxy-6,6′-dibromo- , 1′-Binaphthalene-2′-sulfinylguanide, optically active 2-methoxy-6,6′-diiodo-1,1′-binaphthalene-2′-sulfinylguanide, optically active 2-methoxy-3, 3'-difluoro-1,1'-binaphthalene-2'-sulfinylguanide, optically active 2-methoxy-3,3'-dichloro-1,1'-binaphthalene-2'-sulfinylguanidide, optically active 2-methoxy-3,3′-dibromo-1,1′-binaphthalene-2′-sulfinylguanidide, optically active 2-methoxy-3,3′-diiodo-1,1′-binaphthalene-2′-sulfinyl Guanidide, optically active 2-methoxy-6-phenyl-1,1'-binaphthalene-2'-sulfinylguanidide, optically active 2-methoxy-6,6'-dipheni -1,1′-binaphthalene-2′-sulfinylguanidide, optically active 2-methoxy-6-methyl-1,1′-binaphthalene-2′-sulfinylguanidide, optically active 2-methoxy-6-tert -Butyl-1,1'-binaphthalene-2'-sulfinylguanide, optically active 2-methoxy-6,6'-dimethyl-1,1'-binaphthalene-2'-sulfinylguanidide, optically active 2- Methoxy-6,6′-di (tert-butyl) -1,1′-binaphthalene-2′-sulfinylguanidide, optically active 2-methoxy-3,3 ′, 6-trimethyl-1,1′-binaphthalene -2'-sulfinylguanidide, optically active 2-methoxy-6-trifluoromethyl-1,1'-binaphthalene-2'-sulfinylguanidide, optically active 2-meth Xyl-6,6'-bis (trifluoromethyl) -1,1'-binaphthalene-2'-sulfinylguanide, optically active 2-methoxy-6-trimethylsilyl-1,1'-binaphthalene-2'-sulfinyl Guanide, optically active 2-methoxy-6,6′-bis (trimethylsilyl) -1,1′-binaphthalene-2′-sulfinylguanidide, optically active 2-methoxy-3,3′-dimethyl-6 Bromo-1,1′-binaphthalene-2′-sulfinylguanidide, optically active 2-methoxy-3,3′-di (tert-butyl) -6-bromo-1,1′-binaphthalene-2′-sulfinyl Guanidide, optically active 2-methoxy-3,3′-dimethyl-6- (trimethylsilyl) -1,1′-binaphthalene-2′-sulfinylguanidide,

Optically active 2-trifluoromethoxy-1,1′-binaphthalene-2′-sulfinate methyl, optically active 2-trifluoromethoxy-6-fluoro-1,1′-binaphthalene-2′-sulfinate methyl, optically active 2-trifluoromethoxy-6-chloro-1,1′-binaphthalene-2′-sulfinate methyl, optically active 2-trifluoromethoxy-6-bromo-1,1′-binaphthalene-2′-sulfinate methyl, Optically active 2-trifluoromethoxy-6-iodo-1,1′-binaphthalene-2′-sulfinate methyl, optically active 2-trifluoromethoxy-6,6′-difluoro-1,1′-binaphthalene-2 ′ -Methyl sulfinate, optically active 2-trifluoromethoxy-6,6'-dichloro-1,1'-binaphthalene-2'-sulfur Methyl acetate, optically active 2-trifluoromethoxy-6,6′-dibromo-1,1′-binaphthalene-2′-sulfinate, optically active 2-trifluoromethoxy-6,6′-diiodo-1, 1′-Binaphthalene-2′-sulfinate methyl, optically active 2-trifluoromethoxy-3,3′-difluoro-1,1′-binaphthalene-2′-sulfinate methyl, optically active 2-trifluoromethoxy-3 , 3'-dichloro-1,1'-binaphthalene-2'-sulfinate methyl, optically active 2-trifluoromethoxy-3,3'-dibromo-1,1'-binaphthalene-2'-sulfinate methyl, optical Active methyl 2-trifluoromethoxy-3,3′-diiodo-1,1′-binaphthalene-2′-sulfinate, optically active 2-trifluoromethyl Methyl xyl-6-phenyl-1,1′-binaphthalene-2′-sulfinate, optically active methyl 2-trifluoromethoxy-6,6′-diphenyl-1,1′-binaphthalene-2′-sulfinate, optical Active methyl 2-trifluoromethoxy-6-methyl-1,1′-binaphthalene-2′-sulfinate, optically active 2-trifluoromethoxy-6-tert-butyl-1,1′-binaphthalene-2′-sulfine Acid methyl, optically active 2-trifluoromethoxy-6,6′-dimethyl-1,1′-binaphthalene-2′-sulfinate, optically active 2-trifluoromethoxy-6,6′-di (tert-butyl) ) -1,1′-binaphthalene-2′-sulfinate methyl, optically active 2-trifluoromethoxy-3,3 ′, 6-trimethyl-1,1 '-Binaphthalene-2'-methyl sulfinate, optically active 2-trifluoromethoxy-6-trifluoromethyl-1,1'-binaphthalene-2'-methyl sulfinate, optically active 2-trifluoromethoxy-6,6 '-Bis (trifluoromethyl) -1,1'-binaphthalene-2'-sulfinic acid methyl, optically active 2-trifluoromethoxy-6-trimethylsilyl-1,1'-binaphthalene-2'-sulfinic acid methyl, optical Active 2-trifluoromethoxy-6,6′-bis (trimethylsilyl) -1,1′-binaphthalene-2′-sulfinate methyl ester, optically active 2-trifluoromethoxy-3,3′-dimethyl-6-bromo- 1,1′-Binaphthalene-2′-sulfinate methyl ester, optically active 2-trifluoromethoxy-3,3′-di (t rt-butyl) -6-bromo-1,1′-binaphthalene-2′-sulfinate, optically active 2-trifluoromethoxy-3,3′-dimethyl-6- (trimethylsilyl) -1,1′-binaphthalene -2'-methyl sulfinate,

Optically active 2-trifluoromethoxy-1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-trifluoromethoxy-6-fluoro-1,1′-binaphthalene-2′-sulfinic acid bromide, optical activity 2-trifluoromethoxy-6-chloro-1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-trifluoromethoxy-6-bromo-1,1′-binaphthalene-2′-sulfinic acid bromide, Optically active 2-trifluoromethoxy-6-iodo-1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-trifluoromethoxy-6,6′-difluoro-1,1′-binaphthalene-2 ′ -Sulfinic acid bromide, optically active 2-trifluoromethoxy-6,6'-dichloro-1,1'-binaphthalene- '-Sulfinic acid bromide, optically active 2-trifluoromethoxy-6,6'-dibromo-1,1'-binaphthalene-2'-sulfinic acid bromide, optically active 2-trifluoromethoxy-6,6'-diiodo- 1,1′-Binaphthalene-2′-sulfinic acid bromide, optically active 2-trifluoromethoxy-3,3′-difluoro-1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-trifluoromethoxy -3,3'-dichloro-1,1'-binaphthalene-2'-sulfinic acid bromide, optically active 2-trifluoromethoxy-3,3'-dibromo-1,1'-binaphthalene-2'-sulfinic acid bromide Optically active 2-trifluoromethoxy-3,3′-diiodo-1,1′-binaphthalene-2′-sulfinic acid bromide, Optically active 2-trifluoromethoxy-6-phenyl-1,1'-binaphthalene-2'-sulfinic acid bromide, optically active 2-trifluoromethoxy-6,6'-diphenyl-1,1'-binaphthalene-2 ' -Sulfinic acid bromide, optically active 2-trifluoromethoxy-6-methyl-1,1'-binaphthalene-2'-sulfinic acid bromide, optically active 2-trifluoromethoxy-6-tert-butyl-1,1'- Binaphthalene-2′-sulfinic acid bromide, optically active 2-trifluoromethoxy-6,6′-dimethyl-1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-trifluoromethoxy-6,6 ′ -Di (tert-butyl) -1,1'-binaphthalene-2'-sulfinic acid bromide, optically active 2-trifluorometh Xi-3,3 ′, 6-trimethyl-1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-trifluoromethoxy-6-trifluoromethyl-1,1′-binaphthalene-2′-sulfin Acid bromide, optically active 2-trifluoromethoxy-6,6′-bis (trifluoromethyl) -1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-trifluoromethoxy-6-trimethylsilyl-1 , 1′-Binaphthalene-2′-sulfinic acid bromide, optically active 2-trifluoromethoxy-6,6′-bis (trimethylsilyl) -1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-trimethyl Fluoromethoxy-3,3′-dimethyl-6-bromo-1,1′-binaphthalene-2′-sulfinic acid bromide, Chemically active 2-trifluoromethoxy-3,3′-di (tert-butyl) -6-bromo-1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-trifluoromethoxy-3,3 ′ -Dimethyl-6- (trimethylsilyl) -1,1'-binaphthalene-2'-sulfinic acid bromide,

Optically active 2-methoxy-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-methoxy-6-fluoro-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-methoxy- 6-chloro-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-methoxy-6 Iodo-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-methoxy-6,6′-difluoro-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-methoxy-6 , 6′-Dichloro-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-methoxy-6,6 -Dibromo-1,1'-binaphthalene-2'-sulfinylimidazolide, optically active 2-methoxy-6,6'-diiodo-1,1'-binaphthalene-2'-sulfinylimidazolide, optically active 2-methoxy- 3,3′-difluoro-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-methoxy-3,3′-dichloro-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-methoxy-3,3′-dibromo-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-methoxy-3,3′-diiodo-1,1′-binaphthalene-2′-sulfinylimidazolide Lido, optically active 2-methoxy-6-phenyl-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2- Toxi-6,6′-diphenyl-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-methoxy-6-methyl-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2 -Methoxy-6-tert-butyl-1,1'-binaphthalene-2'-sulfinylimidazolide, optically active 2-methoxy-6,6'-dimethyl-1,1'-binaphthalene-2'-sulfinylimidazolide, Optically active 2-methoxy-6,6′-di (tert-butyl) -1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-methoxy-3,3 ′, 6-trimethyl-1,1 '-Binaphthalene-2'-sulfinylimidazolide, optically active 2-methoxy-6-trifluoromethyl-1,1'-binaphthalene-2'- Sulfinyl imidazolide, optically active 2-methoxy-6,6′-bis (trifluoromethyl) -1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-methoxy-6-trimethylsilyl-1,1 ′ -Binaphthalene-2'-sulfinylimidazolide, optically active 2-methoxy-6,6'-bis (trimethylsilyl) -1,1'-binaphthalene-2'-sulfinylimidazolide, optically active 2-methoxy-3,3 ' -Dimethyl-6-bromo-1,1'-binaphthalene-2'-sulfinylimidazolide, optically active 2-methoxy-3,3'-di (tert-butyl) -6-bromo-1,1'-binaphthalene- 2'-sulfinylimidazolide, optically active 2-methoxy-3,3'-dimethyl-6- (trimethylsilyl) -1,1 ' Binaphthalen-2'-sulfinyl imidazolide, and the like.

で示される基である光学活性スルフィン酸化合物について説明する。Ｒ¹が

で示される基のとき、Ｒ¹²は、水酸基、ハロゲン原子、炭素数１〜１０のアルコキシ基または置換されていてもよいアミノ基を表わし、（ｄ）Ｒ¹²が水酸基のときに、Ｒ²は炭素数１〜１０のアルコキシ基または置換されていてもよいアミノ基を表わし、（ｅ）Ｒ¹²がハロゲン原子、炭素数１〜１０のアルコキシ基または置換されていてもよいアミノ基のときに、Ｒ²はＲ¹²と同一の基を表わす。Ｒ³は水素原子、ハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基を表わし、Ｒ³が水素原子のときに、Ｒ⁴は水素原子、ハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基を表わし、Ｒ⁵はＲ⁴と同一の基を表わし、Ｒ³がハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基のときに、Ｒ⁴およびＲ⁵は水素原子を表わす。 Then, (B) R ¹ is

The optically active sulfinic acid compound which is a group represented by R ¹ is

R ¹² represents a hydroxyl group, a halogen atom, an alkoxy group having 1 to 10 carbon atoms or an optionally substituted amino group. (D) When R ¹² is a hydroxyl group, R ² represents Represents an alkoxy group having 1 to 10 carbon atoms or an optionally substituted amino group, and (e) when R ¹² is a halogen atom, an alkoxy group having 1 to 10 carbon atoms or an optionally substituted amino group, R ² represents the same group as R ¹² . R ³ represents a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or a trisubstituted silyl group, and when R ³ is a hydrogen atom, R ⁴ Represents a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group; R ⁵ represents the same group as R ⁴ ; ^{When 3} is a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or a trisubstituted silyl group, R ⁴ and R ⁵ represent a hydrogen atom.

  Examples of the halogen atom, the optionally substituted amino group, the alkyl group having 1 to 4 carbon atoms, the perfluoroalkyl group having 1 to 4 carbon atoms, and the trisubstituted silyl group include those described above. Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, n-hexyloxy group, isooctyloxy group, menthyloxy Groups and the like.

  Examples of the optically active sulfinic acid compound include optically active 2-sulfino-1,1′-binaphthalene-2′-sulfinic acid methyl, optically active 2-sulfino-6,6′-difluoro-1,1′-binaphthalene— 2′-methyl sulfinate, optically active 2-sulfino-6,6′-dichloro-1,1′-binaphthalene-2′-methyl sulfinate, optically active 2-sulfino-6,6′-dibromo-1,1 '-Binaphthalene-2'-methyl sulfinate, optically active 2-sulfino-6,6'-diiodo-1,1'-binaphthalene-2'-methyl sulfinate, optically active 2-sulfino-3,3'-difluoro -1,1'-binaphthalene-2'-sulfinic acid methyl ester, optically active 2-sulfino-3,3'-dichloro-1,1'-binaphthalene-2 -Methyl sulfinate, optically active 2-sulfino-3,3'-dibromo-1,1'-binaphthalene-2'-methyl sulfinate, optically active 2-sulfino-3,3'-diiodo-1,1'- Binaphthalene-2′-sulfinate methyl, optically active 2-sulfino-6,6′-diphenyl-1,1′-binaphthalene-2′-sulfinate methyl, optically active 2-sulfino-6,6′-dimethyl-1 , 1′-Binaphthalene-2′-sulfinate methyl, optically active 2-sulfino-6,6′-di (tert-butyl) -1,1′-binaphthalene-2′-sulfinate methyl, optically active 2-sulfino -6,6'-bis (trifluoromethyl) -1,1'-binaphthalene-2'-sulfinate methyl, optically active 2-sulfino-6,6'-bis (tri Chirushiriru) -1,1'-binaphthalene-2'-sulfinic acid methyl, optically active 2-sulfino-3,3'-dimethyl-1,1'-binaphthalene-2'-sulfinic acid methyl,

Optically active 2-sulfino-1,1′-binaphthalene-2′-sulfinate ethyl, optically active 2-sulfino-6,6′-difluoro-1,1′-binaphthalene-2′-sulfinate ethyl, optically active 2 -Ethyl sulfino-6,6'-dichloro-1,1'-binaphthalene-2'-sulfinate, optically active ethyl 2-sulfino-6,6'-dibromo-1,1'-binaphthalene-2'-sulfinate Optically active 2-sulfino-6,6′-diiodo-1,1′-binaphthalene-2′-ethyl sulfinate, optically active 2-sulfino-3,3′-difluoro-1,1′-binaphthalene-2 ′ -Ethyl sulfinate, optically active 2-sulfino-3,3'-dichloro-1,1'-binaphthalene-2'-ethyl sulfinate, optically active 2-sulfino- , 3′-dibromo-1,1′-binaphthalene-2′-sulfinate ethyl, optically active 2-sulfino-3,3′-diiodo-1,1′-binaphthalene-2′-sulfinate ethyl, optically active 2 -Sulfino-6,6'-diphenyl-1,1'-binaphthalene-2'-sulfinate ethyl, optically active 2-sulfino-6,6'-dimethyl-1,1'-binaphthalene-2'-sulfinate ethyl , Optically active 2-sulfino-6,6′-di (tert-butyl) -1,1′-binaphthalene-2′-sulfinate ethyl, optically active 2-sulfino-6,6′-bis (trifluoromethyl) -1,1′-Binaphthalene-2′-sulfinate ethyl, optically active 2-sulfino-6,6′-bis (trimethylsilyl) -1,1′-binaphthalene-2′-sulfate Ethyl fins acid, optically active 2-sulfino-3,3'-dimethyl-1,1'-binaphthalene-2'-ethyl sulfinic acid,

Optically active 2-sulfino-1,1′-binaphthalene-2′-sulfinate isopropyl, optically active 2-sulfino-6,6′-difluoro-1,1′-binaphthalene-2′-sulfinate isopropyl, optically active 2 -Sulfino-6,6'-dichloro-1,1'-binaphthalene-2'-sulfinate isopropyl, optically active 2-sulfino-6,6'-dibromo-1,1'-binaphthalene-2'-sulfinate isopropyl Optically active 2-sulfino-6,6′-diiodo-1,1′-binaphthalene-2′-isopropyl sulfinate, optically active 2-sulfino-3,3′-difluoro-1,1′-binaphthalene-2 ′ -Isopropyl sulfinate, optically active 2-sulfino-3,3'-dichloro-1,1'-binaphthalene-2'-sulfi Isopropyl acid, optically active 2-sulfino-3,3'-dibromo-1,1'-binaphthalene-2'-sulfinic acid isopropyl, optically active 2-sulfino-3,3'-diiodo-1,1'-binaphthalene- Isopropyl 2'-sulfinate, optically active 2-sulfino-6,6'-diphenyl-1,1'-binaphthalene-2'-isopropyl sulfinate, optically active 2-sulfino-6,6'-dimethyl-1,1 '-Binaphthalene-2'-isopropyl sulfinate, optically active 2-sulfino-6,6'-di (tert-butyl) -1,1'-binaphthalene-2'-isopropyl sulfinate, optically active 2-sulfino-6 , 6'-bis (trifluoromethyl) -1,1'-binaphthalene-2'-sulfinic acid isopropyl ester, optically active 2-sulfone Fino-6,6′-bis (trimethylsilyl) -1,1′-binaphthalene-2′-sulfinic acid isopropyl, optically active 2-sulfino-3,3′-dimethyl-1,1′-binaphthalene-2′-sulfin Isopropyl acid,

Optically active 1,1'-binaphthalene-2,2'-disulfinate dimethyl, optically active 6,6'-difluoro-1,1'-binaphthalene-2,2'-disulfinate, optically active 6,6'- Dichloro-1,1'-binaphthalene-2,2'-disulfinate dimethyl, optically active 6,6'-dibromo-1,1'-binaphthalene-2,2'-disulfinate dimethyl, optically active 6,6'- Diiodo-1,1'-binaphthalene-2,2'-disulfinate dimethyl, optically active 3,3'-difluoro-1,1'-binaphthalene-2,2'-disulfinate dimethyl, optically active 3,3'- Dimethyl-1,1′-binaphthalene-2,2′-disulfinate, dimethyl 3,3′-dibromo-1,1′-binaphthalene-2,2′-disulfinate , Optically active 3,3′-diiodo-1,1′-binaphthalene-2,2′-disulfinic acid dimethyl, optically active 6,6′-diphenyl-1,1′-binaphthalene-2,2′-disulfinic acid Dimethyl, optically active 6,6′-dimethyl-1,1′-binaphthalene-2,2′-disulfinate dimethyl, optically active 6,6′-di (tert-butyl) -1,1′-binaphthalene-2, Dimethyl 2'-disulfinate, optically active 6,6'-bis (trifluoromethyl) -1,1'-binaphthalene-2,2'-disulfinate dimethyl, optically active 6,6'-bis (trimethylsilyl) -1 , 1′-binaphthalene-2,2′-disulfinate dimethyl, optically active 3,3′-dimethyl-1,1′-binaphthalene-2,2′-dimethyl sulfinate,

Optically active 2-sulfino-1,1′-binaphthalene-2′-sulfinamide, optically active 2-sulfino-6,6′-difluoro-1,1′-binaphthalene-2′-sulfinamide, optically active 2-sulfino -6,6'-dichloro-1,1'-binaphthalene-2'-sulfinamide, optically active 2-sulfino-6,6'-dibromo-1,1'-binaphthalene-2'-sulfinamide, optically active 2 -Sulfino-6,6'-diiodo-1,1'-binaphthalene-2'-sulfinamide, optically active 2-sulfino-3,3'-difluoro-1,1'-binaphthalene-2'-sulfinamide, optical Active 2-sulfino-3,3′-dichloro-1,1′-binaphthalene-2′-sulfinamide, optically active 2-sulfino-3,3′-dibu Mo-1,1′-binaphthalene-2′-sulfinamide, optically active 2-sulfino-3,3′-diiodo-1,1′-binaphthalene-2′-sulfinamide, optically active 2-sulfino-6,6 '-Diphenyl-1,1'-binaphthalene-2'-sulfinamide, optically active 2-sulfino-6,6'-dimethyl-1,1'-binaphthalene-2'-sulfinamide, optically active 2-sulfino-6 , 6′-di (tert-butyl) -1,1′-binaphthalene-2′-sulfinamide, optically active 2-sulfino-6,6′-bis (trifluoromethyl) -1,1′-binaphthalene-2 '-Sulfinamide, optically active 2-sulfino-6,6'-bis (trimethylsilyl) -1,1'-binaphthalene-2'-sulfinamide, optically active 2 Sulfino-3,3'-dimethyl-1,1'-binaphthalene-2'-sulfinamide,

Optically active N-isopropyl-2-sulfino-1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-sulfino-6,6′-difluoro-1,1′-binaphthalene-2′- Sulfinamide, optically active N-isopropyl-2-sulfino-6,6′-dichloro-1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-sulfino-6,6′-dibromo- 1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-sulfino-6,6′-diiodo-1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2 -Sulfino-3,3'-difluoro-1,1'-binaphthalene-2'-sulfinamide, optically active N-isopropylene 2-sulfino-3,3′-dichloro-1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-sulfino-3,3′-dibromo-1,1′-binaphthalene-2 '-Sulfinamide, optically active N-isopropyl-2-sulfino-3,3'-diiodo-1,1'-binaphthalene-2'-sulfinamide, optically active N-isopropyl-2-sulfino-6,6'- Diphenyl-1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-sulfino-6,6′-dimethyl-1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl -2-sulfino-6,6'-di (tert-butyl) -1,1'-binaphthalene-2'-sulfinamide, optically active N- Sopropyl-2-sulfino-6,6′-bis (trifluoromethyl) -1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-sulfino-6,6′-bis (trimethylsilyl) -1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-sulfino-3,3′-dimethyl-1,1′-binaphthalene-2′-sulfinamide,

Optically active 2-sulfino-1,1′-binaphthalene-2′-sulfinyl hydrazide, optically active 2-sulfino-6,6′-difluoro-1,1′-binaphthalene-2′-sulfinylhydrazide, optically active 2-sulfino -6,6'-dichloro-1,1'-binaphthalene-2'-sulfinyl hydrazide, optically active 2-sulfino-6,6'-dibromo-1,1'-binaphthalene-2'-sulfinyl hydrazide, optically active 2 -Sulfino-6,6'-diiodo-1,1'-binaphthalene-2'-sulfinyl hydrazide, optically active 2-sulfino-3,3'-difluoro-1,1'-binaphthalene-2'-sulfinyl hydrazide, optical Active 2-sulfino-3,3′-dichloro-1,1′-binaphthalene-2′-sulfinylhydrazide Optically active 2-sulfino-3,3′-dibromo-1,1′-binaphthalene-2′-sulfinyl hydrazide, optically active 2-sulfino-3,3′-diiodo-1,1′-binaphthalene-2′- Sulfinyl hydrazide, optically active 2-sulfino-6,6′-diphenyl-1,1′-binaphthalene-2′-sulfinylhydrazide, optically active 2-sulfino-6,6′-dimethyl-1,1′-binaphthalene-2 '-Sulfinylhydrazide, optically active 2-sulfino-6,6'-di (tert-butyl) -1,1'-binaphthalene-2'-sulfinylhydrazide, optically active 2-sulfino-6,6'-bis (tri Fluoromethyl) -1,1′-binaphthalene-2′-sulfinyl hydrazide, optically active 2-sulfino-6,6′-bis ( Trimethylsilyl) -1,1'-binaphthalene-2'-sulfinyl hydrazide, optically active 2-sulfino-3,3'-dimethyl-1,1'-binaphthalene-2'-sulfinyl hydrazide,

Optically active 2-sulfino-1,1′-binaphthalene-2′-sulfinylguanide, optically active 2-sulfino-6,6′-difluoro-1,1′-binaphthalene-2′-sulfinylguanide, optical Active 2-sulfino-6,6′-dichloro-1,1′-binaphthalene-2′-sulfinylguanidide, optically active 2-sulfino-6,6′-dibromo-1,1′-binaphthalene-2′- Sulfinylguanidide, optically active 2-sulfino-6,6′-diiodo-1,1′-binaphthalene-2′-sulfinylguanidide, optically active 2-sulfino-3,3′-difluoro-1,1 ′ -Binaphthalene-2'-sulfinylguanidide, optically active 2-sulfino-3,3'-dichloro-1,1'-binaphthalene-2'-sulfinylguanidi , Optically active 2-sulfino-3,3′-dibromo-1,1′-binaphthalene-2′-sulfinylguanidide, optically active 2-sulfino-3,3′-diiodo-1,1′-binaphthalene-2 '-Sulfinylguanidide, optically active 2-sulfino-6,6'-diphenyl-1,1'-binaphthalene-2'-sulfinylguanidide, optically active 2-sulfino-6,6'-dimethyl-1, 1′-Binaphthalene-2′-sulfinylguanide, optically active 2-sulfino-6,6′-di (tert-butyl) -1,1′-binaphthalene-2′-sulfinylguanidide, optically active 2- Sulfino-6,6′-bis (trifluoromethyl) -1,1′-binaphthalene-2′-sulfinylguanidide, optically active 2-sulfino-6,6′-bis ( Trimethylsilyl) -1,1'-binaphthalene-2'-sulfinyl Heidelberg Ani disilazide, optically active 2-sulfino-3,3'-dimethyl-1,1'-binaphthalene-2'-sulfinyl Heidelberg Ani disilazide,

Optically active 2-sulfino-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-sulfino-6,6′-difluoro-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2 -Sulfino-6,6'-dichloro-1,1'-binaphthalene-2'-sulfinyl imidazolide, optically active 2-sulfino-6,6'-dibromo-1,1'-binaphthalene-2'-sulfinyl imidazolide , Optically active 2-sulfino-6,6′-diiodo-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-sulfino-3,3′-difluoro-1,1′-binaphthalene-2 ′ -Sulfinyl imidazolide, optically active 2-sulfino-3,3'-dichloro-1,1'-binaphthalene-2'-sulfi Louis imidazolide, optically active 2-sulfino-3,3′-dibromo-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-sulfino-3,3′-diiodo-1,1′-binaphthalene-2 '-Sulfinylimidazolide, optically active 2-sulfino-6,6'-diphenyl-1,1'-binaphthalene-2'-sulfinylimidazolide, optically active 2-sulfino-6,6'-dimethyl-1,1' -Binaphthalene-2'-sulfinylimidazolide, optically active 2-sulfino-6,6'-di (tert-butyl) -1,1'-binaphthalene-2'-sulfinylimidazolide, optically active 2-sulfino-6 6′-bis (trifluoromethyl) -1,1′-binaphthalene-2′-sulfinyl imidazolide, optically active 2-s Fino-6,6′-bis (trimethylsilyl) -1,1′-binaphthalene-2′-sulfinyl imidazolide, optically active 2-sulfino-3,3′-dimethyl-1,1′-binaphthalene-2′-sulfinyl Imidazolide,

Optically active 1,1′-binaphthalene-2,2′-disulfinic acid dichloride, optically active 6,6′-difluoro-1,1′-binaphthalene-2,2′-disulfinic acid dichloride, optically active 6,6′- Dichloro-1,1′-binaphthalene-2,2′-disulfinic acid dichloride, optically active 6,6′-dibromo-1,1′-binaphthalene-2,2′-disulfinic acid dichloride, optically active 6,6′- Diiodo-1,1′-binaphthalene-2,2′-disulfinic acid dichloride, optically active 3,3′-difluoro-1,1′-binaphthalene-2,2′-disulfinic acid dichloride, optically active 3,3′- Dichloro-1,1′-binaphthalene-2,2′-disulfinic acid dichloride, optically active 3,3′-dibromo-1,1′-binaphthalene-2,2′-dis Finic acid dichloride, optically active 3,3′-diiodo-1,1′-binaphthalene-2,2′-disulfinic acid dichloride, optically active 6,6′-diphenyl-1,1′-binaphthalene-2,2′- Disulfinic acid dichloride, optically active 6,6'-dimethyl-1,1'-binaphthalene-2,2'-disulfinic acid dichloride, optically active 6,6'-di (tert-butyl) -1,1'-binaphthalene- 2,2′-disulfinic acid dichloride, optically active 6,6′-bis (trifluoromethyl) -1,1′-binaphthalene-2,2′-disulfinic acid dichloride, optically active 6,6′-bis (trimethylsilyl) -1,1'-binaphthalene-2,2'-disulfinic acid dichloride, optically active 3,3'-dimethyl-1,1'-binaphthalene-2,2'-dis Fin acid dichloride, and the like.

  The optically active sulfinic acid compound (1) of the present invention is an axially asymmetric compound, and there are two optical isomers, an (R) isomer and an (S) isomer. Such an optically active sulfinic acid compound (1) includes only an optically active alcohol whose absolute configuration is unknown because the terminal of the substituent at the 2 ′ position is a hydroxyl group, a halogen atom, an optionally substituted amino group, or the like. In addition, it can be used as an agent for introducing an asymmetric auxiliary group into other optically active compounds such as carboxylic acid, and by analyzing the compound introduced with the asymmetric auxiliary group by NMR analysis, the aromatic ring possessed by the asymmetric auxiliary group is different. By utilizing the isotropic effect, the absolute configuration of the optically active compound whose absolute configuration is unknown can be determined. Moreover, the absolute configuration of the optically active compound whose absolute configuration is unknown can also be determined by measuring the NOE spectrum or NOESY spectrum of the compound into which the asymmetric auxiliary group has been introduced, and performing conformational analysis.

  When determining the absolute configuration of the optically active compound used as an agent for introducing an asymmetric auxiliary group into an optically active compound such as an optically active alcohol or optically active carboxylic acid whose absolute configuration is unknown, for example, according to a known Mosher method Just do it. In addition, a method for introducing a chiral auxiliary group using the optically active sulfinic acid compound of the present invention, measuring the NOE spectrum or NOESY spectrum of the compound into which the chiral auxiliary group is introduced, and performing a conformational analysis is a known NOE spectrum. Or NOESY spectrum measurement method and conformation analysis method thereof.

（式中、Ａは炭素数１〜４のアルコキシ基、炭素数１〜４のパーフルオロアルコキシ基、置換されていてもよいアリール基、置換されていてもよいアリールオキシ基または置換されていてもよいアラルキルオキシ基を表わし、Ｒ²は水酸基、ハロゲン原子、炭素数１〜４のアルコキシ基または置換されていてもよいアミノ基を表わし、Ｒ³は水素原子、ハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基を表わし、（ａ）Ｒ³が水素原子のときに、Ｒ⁴は水素原子、ハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基を、Ｒ⁵はＲ⁴と同一の基または水素原子を表わし、（ｂ）Ｒ³がハロゲン原子のときに、Ｒ⁴およびＲ⁵は水素原子を表わし、（ｃ）Ｒ³がフェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基のときに、Ｒ⁴は水素原子、ハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基を、Ｒ⁵は水素原子を表わす。）
で示される光学活性スルフィン酸化合物（以下、光学活性スルフィン酸化合物（２）と略記する。）の製造方法について説明する。 Hereinafter, the method for producing the optically active sulfinic acid compound (1) of the present invention will be described. First, in the optically active sulfinic acid compound (1), (A) R ¹ is an alkoxy group having 1 to 4 carbon atoms, a perfluoroalkoxy group having 1 to 4 carbon atoms, an aryl group that may be substituted, The following formula (2) which is an aryloxy group which may be substituted or an aralkyloxy group which may be substituted

(In the formula, A represents an alkoxy group having 1 to 4 carbon atoms, a perfluoroalkoxy group having 1 to 4 carbon atoms, an optionally substituted aryl group, an optionally substituted aryloxy group, or an optionally substituted group. R ² represents a good aralkyloxy group, R ² represents a hydroxyl group, a halogen atom, an alkoxy group having 1 to 4 carbon atoms or an optionally substituted amino group, and R ³ represents a hydrogen atom, a halogen atom, a phenyl group, or 1 carbon atom. Represents an alkyl group of ˜4, a perfluoroalkyl group of 1 to 4 carbon atoms or a trisubstituted silyl group, and (a) when R ³ is a hydrogen atom, R ⁴ is a hydrogen atom, a halogen atom, a phenyl group, a carbon number An alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group, R ⁵ represents the same group as R ⁴ or a hydrogen atom, and (b) when R ³ is a halogen atom , ⁴ and R ⁵ represents a hydrogen atom, (c) R ³ is a phenyl group, an alkyl group having 1 to 4 carbon atoms, when perfluoroalkyl group or trisubstituted silyl group having 1 to 4 carbon atoms, R ⁴ is A hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group, and R ⁵ represents a hydrogen atom.)
A method for producing the optically active sulfinic acid compound (hereinafter abbreviated as optically active sulfinic acid compound (2)) will be described.

（式中、Ａは上記と同一の意味を表わし、Ｘ¹は臭素原子または塩素原子を表わし、Ｒ⁶は炭素数１〜４の直鎖状アルコキシ基を表わす。）
で示される光学活性スルフィン酸エステル（以下、光学活性スルフィン酸エステル（３）と略記する。）は、下記式（４）

（式中、Ａは上記と同一の意味を表わし、Ｒ⁷は炭素数１〜４のアルキル基を表わす。）
で示される光学活性カーバメート化合物（以下、光学活性カーバメート化合物（４）と略記する。）と式（５）

（式中、Ｘ¹は上記と同一の意味を表わす。）
で示される化合物（以下、化合物（５）と略記する。）と炭素数１〜４の一級アルコールとを反応させることにより製造することができる。 Among the optically active sulfinic acid compounds (2), R ² is a linear alkoxy group having 1 to 4 carbon atoms, R ³ and R ⁵ are hydrogen atoms, and R ⁴ is a bromine atom or a chlorine atom. (3)

(In the formula, A represents the same meaning as described above, X ¹ represents a bromine atom or a chlorine atom, and R ⁶ represents a linear alkoxy group having 1 to 4 carbon atoms.)
The optically active sulfinic acid ester represented by (hereinafter abbreviated as optically active sulfinic acid ester (3)) is represented by the following formula (4).

(In the formula, A represents the same meaning as described above, and R ⁷ represents an alkyl group having 1 to 4 carbon atoms.)
And an optically active carbamate compound (hereinafter abbreviated as optically active carbamate compound (4)) and formula (5)

(In the formula, X ¹ represents the same meaning as described above.)
It can manufacture by making the compound (henceforth abbreviating as a compound (5)) shown by these, and C1-C4 primary alcohol react.

  Examples of the optically active carbamate compound (4) include optically active 2-methoxy-1,1′-binaphthalene-2′-thiol N, N-dimethylcarbamate, optically active 2-trifluoromethoxy-1,1′-binaphthalene— 2′-thiol N, N-dimethylcarbamate, optically active 2-pentafluoroethoxy-1,1′-binaphthalene-2′-thiol N, N-dimethylcarbamate, optically active 2-heptafluoropropoxy-1,1′- Binaphthalene-2′-thiol N, N-dimethylcarbamate, optically active 2-phenoxy-1,1′-binaphthalene-2′-thiol N, N-dimethylcarbamate, optically active 2-methoxy-1,1′-binaphthalene- 2'-thiol N, N-diethyl carbamate and the like can be mentioned.

  Examples of the compound (5) include N-bromosuccinimide or N-chlorosuccinimide.

  Examples of the primary alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, and n-butanol, and the amount used thereof is usually 1 mol times or more based on the optically active carbamate compound (4). The upper limit is not particularly limited, and a large excess may be used also as a solvent.

  The usage-amount of a compound (5) is 1-5 mol times normally with respect to an optically active carbamate compound (4), Preferably it is 2.5-4 mol times.

  The reaction of the optically active carbamate compound (4), the compound (5) and the primary alcohol having 1 to 4 carbon atoms is usually carried out by mixing the three in a solvent. As the solvent, as described above, a primary alcohol having 1 to 4 carbon atoms, for example, an ether solvent such as tetrahydrofuran, an aromatic hydrocarbon solvent such as toluene, a halogenated hydrocarbon solvent such as chloroform, such as ethyl acetate, etc. These may be used alone or as a mixed solvent, such as an ester solvent, and the amount used is not particularly limited.

  The reaction temperature is usually in the range of −50 to 100 ° C.

  After completion of the reaction, for example, the optically active sulfinic acid ester (3) can be taken out by concentrating the reaction solution. In addition, after the reaction solution is directly or after being concentrated, extraction is performed by adding water and, if necessary, an organic solvent insoluble in water, and the resulting organic layer is concentrated to obtain an optically active sulfinate (3). Can also be taken out. The extracted optically active sulfinic acid ester (3) may be further purified by ordinary purification means such as recrystallization and column chromatography.

In the optically active sulfinic acid compound (2), R ² is a linear alkoxy group having 1 to 4 carbon atoms, R ³ and R ⁵ are hydrogen atoms, R ⁴ is a hydrogen atom, a phenyl group, and a carbon number. The optically active sulfinic acid compound which is an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group is obtained by reducing the optically active sulfinic acid ester (3) obtained above, for example, by reducing phenyl , Alkylation, perfluoroalkylation or silylation. Such reduction, phenylation, alkylation, perfluoroalkylation or silylation can be achieved by reducing, phenylating, alkylating, perfluoroalkylating or silylating aromatic halides, aromatic compounds, phenyl substituted aromatic compounds, What is necessary is just to carry out according to the well-known method of obtaining an alkyl substituted aromatic compound, a perfluoroalkyl substituted aromatic compound, or a silyl substituted aromatic compound. In addition, by subjecting the optically active sulfinic acid ester (3) to a halogen substitution reaction, the 6-position bromine atom or chlorine atom can be substituted with another halogen atom. In addition, the optically active sulfinic acid ester (3) is hydrolyzed, converted into an acid halogen compound, and then esterified, whereby R ² has a carbon number other than a linear alkoxy group having 1 to 4 carbon atoms. An optically active sulfinic acid compound having 1 to 4 alkoxy groups can be produced.

（式中、Ｒ⁷は上記と同一の意味を表わし、Ｘ²はハロゲン原子を表わす。）
で示される化合物（以下、化合物（６）と略記する。）とを、塩基の存在下に反応させて、式（７）

（式中、Ｒ⁷は上記と同一の意味を表わす。）
で示される光学活性化合物（以下、光学活性化合物（７）と略記する。）を得、該光学活性化合物（７）の水酸基を、Ｏ−アルキル化、Ｏ−パーフルオロアルキル化、Ｏ−アリール化、Ｏ−アラルキル化またはアリール化して、式（８）

（式中、ＡおよびＲ⁷は上記と同一の意味を表わす。）
で示される光学活性化合物（以下、光学活性化合物（８）と略記する。）を得、該光学活性化合物（８）を熱転位反応せしめることにより製造することができる（下記スキーム１参照。）。

The optically active carbamate compound (4) can be prepared according to, for example, the method described in Synlett, 1054 (1996) and optically active 1,1′-binaphthalene-2,2′-diol and the formula (6).

(In the formula, R ⁷ represents the same meaning as described above, and X ² represents a halogen atom.)
(Hereinafter abbreviated as compound (6)) is reacted in the presence of a base to give a compound of formula (7)

(Wherein R ⁷ represents the same meaning as described above.)
And the hydroxyl group of the optically active compound (7) is O-alkylated, O-perfluoroalkylated, O-arylated. , O-aralkylation or arylation to give a compound of formula (8)

(In the formula, A and R ⁷ have the same meaning as described above.)
Can be produced by thermal rearrangement reaction of the optically active compound (8) (see Scheme 1 below).

  In the formula of compound (6), examples of the halogen atom include the same ones as described above. Examples of the compound (6) include N, N-dimethylthiocarbamoyl chloride, N, N-dimethylthiocarbamoyl bromide, N, N-diethylthiocarbamoyl chloride and the like, and usually commercially available products are used.

  The amount of compound (6) to be used is generally 1 to 2 mol times based on the optically active 1,1'-binaphthalene-2,2'-diol. Examples of the base include alkali metal hydrides such as sodium hydride, and the amount used is usually 1 to 2 mol times the optically active 1,1′-binaphthalene-2,2′-diol. is there.

  The reaction between the compound (6) and the optically active 1,1′-binaphthalene-2,2′-diol is usually carried out by mixing the two in a solvent, and the solvent is a solvent inert to the reaction. For example, an amide solvent such as N, N-dimethylformamide may be used. The amount of solvent used is not particularly limited. The reaction temperature is usually 0 to 100 ° C.

  After completion of the reaction, for example, the reaction solution and water are mixed, an organic solvent insoluble in water is added for extraction treatment, and the resulting organic layer is concentrated to extract the optically active compound (7). You may convert into an optically active compound (8) as it is, without taking out an optically active compound (7).

  Examples of the optically active compound (7) include optically active 2-hydroxy-1,1′-binaphthalene-2′-ol N, N-dimethylthiocarbamate, optically active 2-hydroxy-1,1′-binaphthalene-2 ′. -All N, N-diethylthiocarbamate and the like.

  As a method for O-alkylation, O-perfluoroalkylation, O-arylation, O-aralkylation or arylation of the hydroxyl group of the optically active compound (7), an ordinary O-alkylation reaction of a hydroxyl group, O— A perfluoroalkylation reaction, an O-arylation reaction, an O-aralkylation reaction or an arylation reaction may be mentioned. After completion of the O-alkylation reaction, O-perfluoroalkylation reaction, O-arylation reaction, O-aralkylation reaction or arylation reaction, for example, the reaction solution is mixed with water or an aqueous alkali solution, and is insoluble in water. The optically active compound (8) can be taken out by subjecting to extraction treatment and concentrating the resulting organic layer.

  Examples of the optically active compound (8) thus obtained include optically active 2-methoxy-1,1′-binaphthalen-2′-ol N, N-dimethylthiocarbamate, optically active 2-trifluoromethoxy-1,1 ′. -Binaphthalen-2'-ol N, N-dimethylthiocarbamate, optically active 2-pentafluoroethoxy-1,1'-binaphthalen-2'-ol N, N-dimethylthiocarbamate, optically active 2-heptafluoropropoxy- 1,1′-Binaphthalen-2′-ol N, N-dimethylthiocarbamate, optically active 2-phenoxy-1,1′-binaphthalene-2′-ol N, N-dimethylthiocarbamate, optically active 2-methoxy- 1,1'-binaphthalene-2'-ol N, N-diethylthiocarbamate .

  The thermal rearrangement reaction of the optically active compound (8) is carried out by heating the optically active compound (8) as it is or in the presence of a solvent, if necessary, usually at 240 to 300 ° C. After completion of the reaction, the optically active carbamate compound (4) may be used for the reaction with the compound (5) as it is without taking out, or the reaction solution may be subjected to, for example, crystallization treatment to give the optically active carbamate compound (4). ) May be taken out and used for the reaction with the compound (5).

（式中、Ａは上記と同一の意味を表わし、Ｒ⁸は水素原子、ハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基を表わす。）
で示される光学活性スルフィン酸化合物（以下、光学活性スルフィン酸化合物（９）と略記する。）の製造方法について説明する。 Subsequently, in the optically active sulfinic acid compound (2), R ² is a hydroxyl group, R ³ and R ⁵ are hydrogen atoms, R ⁴ is a hydrogen atom, a halogen atom, a phenyl group, or an alkyl group having 1 to 4 carbon atoms. A perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group (9)

(In the formula, A represents the same meaning as described above, and R ⁸ represents a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or a trisubstituted silyl group. Represents.)
A method for producing the optically active sulfinic acid compound (hereinafter abbreviated as optically active sulfinic acid compound (9)) will be described.

  The optically active sulfinic acid compound (9) can be produced by subjecting the optically active sulfinic acid compound (3) obtained above to an alkali treatment and then an acidification treatment. The alkali treatment is usually carried out by mixing an optically active sulfinic acid ester (3) and an alkali such as sodium hydroxide in an organic solvent. The amount of alkali used is usually 1 mole or more with respect to the optically active sulfinic acid ester (3), and there is no particular upper limit, but if it is too much, the amount of acid used in the subsequent acidification treatment is large. Therefore, practically, it is 2 mol times or less. The treatment temperature of the alkali treatment is usually 0 to 100 ° C.

  The acidification treatment performed after the alkali treatment is usually carried out by mixing the alkali treatment liquid and a mineral acid such as hydrochloric acid and acidifying the mixture. The amount used in the acidification treatment using a mineral acid varies depending on the amount of alkali used in the alkali treatment, and the amount that the acidification treatment solution exhibits acidity is used. Alternatively, the alkali treatment liquid may be subjected to an acidification treatment as it is or after concentration treatment, if necessary after removing insoluble components, and then treating with an acidic column filled with silica gel or the like. The treatment temperature of the acidification treatment is usually 0 to 100 ° C.

  After the acidification treatment, the optically active sulfinic acid compound (9) can be taken out by performing a usual removal operation such as an extraction treatment.

（式中、ＡおよびＲ⁸は上記と同一の意味を表わし、Ｘ³はハロゲン原子を表わす。）
で示される光学活性スルフィン酸ハロゲン化物（以下、光学活性スルフィン酸ハロゲン化物（１０）と略記する。）の製造方法について説明する。 Subsequently, in the optically active sulfinic acid compound (2), R ² is a halogen atom, R ³ and R ⁵ are hydrogen atoms, R ⁴ is a hydrogen atom, a halogen atom, a phenyl group, an alkyl having 1 to 4 carbon atoms. Group, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group (10)

(In the formula, A and R ⁸ represent the same meaning as described above, and X ³ represents a halogen atom.)
A method for producing an optically active sulfinic acid halide represented by (hereinafter abbreviated as optically active sulfinic acid halide (10)) will be described.

  The optically active sulfinic acid halide (10) can be produced by reacting the optically active sulfinic acid compound (9) with a halogenating agent such as thionyl chloride or thionyl bromide and halogenating the compound. The reaction between the optically active sulfinic acid compound (9) and the halogenating agent may be carried out according to a known method for obtaining a carboxylic acid halide by reacting a carboxylic acid with a halogenating agent.

（式中、ＡおよびＲ⁸は上記と同一の意味を表わし、Ｒ⁹は置換されていてもよいアミノ基を表わす。）
で示される光学活性スルフィン酸アミド化合物（以下、光学活性スルフィン酸アミド化合物（１１）と略記する。）の製造方法について説明する。 Subsequently, in the optically active sulfinic acid compound (2), R ² is an optionally substituted amino group, R ³ and R ⁵ are hydrogen atoms, R ⁴ is a hydrogen atom, a halogen atom, a phenyl group, carbon Formula (11) which is an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or a trisubstituted silyl group

(In the formula, A and R ⁸ represent the same meaning as described above, and R ⁹ represents an optionally substituted amino group.)
A method for producing the optically active sulfinic acid amide compound (hereinafter abbreviated as optically active sulfinic acid amide compound (11)) will be described.

  The optically active sulfinic acid amide compound (11) includes the optically active sulfinic acid halide (10) and ammonia, methylamine, ethylamine, isopropylamine, dimethylamine, diethylamine, hydrazine, guanidine, pyrrolidine, piperidine, imidazole and the like. It can be produced by reacting with an amine compound.

  The reaction between the optically active sulfinic acid halide (10) and the amine compound may be performed according to a known method for obtaining a carboxylic acid amide by reacting a carboxylic acid halide with an amine compound. When an amine compound having a plurality of amino groups that react in the molecule, such as guanidine, is used as the amine compound, an amine compound protected with a protecting group such as guanylurea sulfate may be used.

（式中、Ａ、Ｒ²およびＲ⁸は上記と同一の意味を表わす。）
で示される光学活性スルフィン酸化合物（以下、光学活性スルフィン酸化合物（１２）と略記する。）の製造方法について説明する。 Subsequently, in the optically active sulfinic acid compound (2), R ² represents a hydroxyl group, a halogen atom, an alkoxy group having 1 to 4 carbon atoms or an optionally substituted amino group, R ³ is a hydrogen atom, R Wherein ⁴ is a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group, and R ⁵ is the same group as R ⁴ (12)

(In the formula, A, R ² and R ⁸ have the same meaning as described above.)
A method for producing an optically active sulfinic acid compound (hereinafter abbreviated as optically active sulfinic acid compound (12)) will be described.

（式中、Ａ、Ｒ⁷およびＲ⁸は上記と同一の意味を表わす。）
で示される光学活性カーバメート化合物（以下、光学活性カーバメート化合物（１３）と略記する。）を用いる以外は前記と同様に実施することにより製造することができる。 The optically active sulfinic acid compound (12) is a compound represented by the following formula (13) instead of the optically active carbamate compound (4) in the method for producing the optically active sulfinic acid compound (3).

(In the formula, A, R ⁷ and R ⁸ represent the same meaning as described above.)
It can manufacture by implementing similarly to the above except using the optically active carbamate compound shown below (it abbreviates as optically active carbamate compound (13) hereafter).

  Examples of the optically active carbamate compound (13) include optically active 2-methoxy-6,6′-dibromo-1,1′-binaphthalene-2′-thiol N, N-dimethylcarbamate, optically active 2-trifluoromethoxy- 6,6′-dibromo-1,1′-binaphthalene-2′-thiol N, N-dimethylcarbamate, optically active 2-methoxy-6,6′-dimethyl-1,1′-binaphthalene-2′-thiol N , N-dimethylcarbamate, optically active 2-methoxy-6,6′-diphenyl-1,1′-binaphthalene-2′-thiol N, N-dimethylcarbamate, optically active 2-methoxy-6,6′-bis ( Trimethylsilyl) -1,1′-binaphthalene-2′-thiol N, N-dimethylcarbamate, optically active 2-methoxy-6,6 ′ -Dibromo-1,1'-binaphthalene-2'-thiol N, N-diethyl carbamate and the like.

（式中、Ｒ⁸は上記と同一の意味を表わす。）
で示される光学活性ビナフタレン化合物を用い、前記スキーム１と同様に実施することにより製造することができる。かかる式（１４）で示される光学活性ビナフタレン化合物は、例えば市販されている光学活性６，６’−ジブロモ−１，１’−ビナフタレン−２，２’−ジオールから容易に得ることができる。 Such optically active carbamate compound (13) is replaced with optically active 1,1′-binaphthalene-2,2′-diol in Scheme 1 in the following formula (14).

(Wherein R ⁸ represents the same meaning as described above.)
It can manufacture by implementing similarly to the said scheme 1 using the optically active binaphthalene compound shown by these. Such an optically active binaphthalene compound represented by the formula (14) can be easily obtained from, for example, commercially available optically active 6,6′-dibromo-1,1′-binaphthalene-2,2′-diol.

（式中、ＡおよびＲ²は上記と同一の意味を表わし、Ｒ¹⁰はハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基もしくは三置換シリル基を表わす。Ｒ¹⁰がハロゲン原子のとき、Ｒ¹¹は水素原子を表わし、Ｒ¹⁰がフェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基もしくは三置換シリル基のとき、Ｒ¹¹は水素原子、ハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基もしくは三置換シリル基を表わす。）
で示される光学活性スルフィン酸化合物（以下、光学活性スルフィン酸化合物（１５）と略記する。）の製造方法について説明する。 Subsequently, in the optically active sulfinic acid compound (2), R ² represents a hydroxyl group, a halogen atom, an alkoxy group having 1 to 4 carbon atoms or an optionally substituted amino group, R ³ is a halogen atom, R ⁴ and R ⁵ are hydrogen atoms, or R ³ is a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group, and R ⁴ is a hydrogen atom, A halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group, wherein R ⁵ is a hydrogen atom (15)

(In the formula, A and R ² represent the same meaning as described above, and R ¹⁰ represents a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or a trisubstituted silyl group. When R ¹⁰ is a halogen atom, R ¹¹ represents a hydrogen atom, and R ¹⁰ is a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or a trisubstituted silyl group. R ¹¹ represents a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or a trisubstituted silyl group.)
A method for producing an optically active sulfinic acid compound represented by the following (hereinafter abbreviated as optically active sulfinic acid compound (15)) will be described.

（式中、Ａ、Ｒ⁷およびＲ¹⁰は上記と同一の意味を表わす。）
で示される光学活性カーバメート化合物（以下、光学活性カーバメート化合物（１６）と略記する。）を用いる以外は前記と同様に実施することにより製造することができる。 In the method for producing the optically active sulfinic acid compound (3), the optically active sulfinic acid compound (15) is replaced by the following formula (16) instead of the optically active carbamate compound (4).

(In the formula, A, R ⁷ and R ¹⁰ have the same meaning as described above.)
It can manufacture by implementing similarly to the above except using the optically active carbamate compound shown below (it abbreviates as optically active carbamate compound (16) hereafter).

  Examples of the optically active carbamate compound (16) include optically active 2-methoxy-3,3′-dibromo-1,1′-binaphthalene-2′-thiol N, N-dimethylcarbamate, optically active 2-methoxy-3, 3′-dimethyl-1,1′-binaphthalene-2′-thiol N, N-dimethylcarbamate, optically active 2-methoxy-3,3′-diphenyl-1,1′-binaphthalene-2′-thiol N, N -Dimethyl carbamate, optically active 2-methoxy-3,3'-bis (trimethylsilyl) -1,1'-binaphthalene-2'-thiol N, N-dimethyl carbamate and the like.

（式中、Ｒ¹⁰は上記と同一の意味を表わす。）
で示される光学活性ビナフタレン化合物を用い、前記スキーム１と同様に実施することにより製造することができる。かかる式（１７）で示される光学活性ビナフタレン化合物は、例えば市販されている光学活性３，３’−ジブロモ−１，１’−ビナフタレン−２，２’−ジオールから容易に得ることができる。 Such an optically active carbamate compound (16) is represented by the following formula (17) in place of the optically active 1,1′-binaphthalene-2,2′-diol in Scheme 1.

(In the formula, R ¹⁰ represents the same meaning as described above.)
It can manufacture by implementing similarly to the said scheme 1 using the optically active binaphthalene compound shown by these. The optically active binaphthalene compound represented by the formula (17) can be easily obtained from, for example, commercially available optically active 3,3′-dibromo-1,1′-binaphthalene-2,2′-diol.

で示される基である下記式（１８）

（式中、Ｒ¹²は、水酸基、ハロゲン原子、炭素数１〜１０のアルコキシ基または置換されていてもよいアミノ基を表わし、（ｄ）Ｒ¹²が水酸基のときに、Ｒ¹³は炭素数１〜１０のアルコキシ基または置換されていてもよいアミノ基を表わし、（ｅ）Ｒ¹²がハロゲン原子、炭素数１〜１０のアルコキシ基または置換されていてもよいアミノ基のときに、Ｒ¹³はＲ¹²と同一の基を表わす。Ｒ¹⁴は水素原子、ハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基を表わし、Ｒ¹⁴が水素原子のときに、Ｒ¹⁵は水素原子、ハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基を表わし、Ｒ¹⁴がハロゲン原子、フェニル基、炭素数１〜４のアルキル基、炭素数１〜４のパーフルオロアルキル基または三置換シリル基のときに、Ｒ¹⁵は水素原子を表わす。）
で示される光学活性ジスルフィン酸化合物（以下、光学活性ジスルフィン酸化合物（１８）と略記する。）の製造方法について説明する。 Subsequently, in the optically active sulfinic acid compound (1) of the present invention, (B) R ¹ is

The following formula (18) which is a group represented by

(In the formula, R ¹² represents a hydroxyl group, a halogen atom, an alkoxy group having 1 to 10 carbon atoms or an optionally substituted amino group. (D) When R ¹² is a hydroxyl group, R ¹³ represents 1 carbon atom. Represents an alkoxy group having 10 to 10 or an amino group which may be substituted, and (e) when R ¹² is a halogen atom, an alkoxy group having 1 to 10 carbon atoms or an amino group which may be substituted, R ¹³ is .R ¹⁴ representing the same group as R ¹² represents a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group or a trisubstituted silyl group having 1 to 4 carbon atoms, R ¹⁴ Is a hydrogen atom, R ¹⁵ represents a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group, and R ¹⁴ represents a halogen atom Atom, phenyl group Alkyl group having 1 to 4 carbon atoms, when perfluoroalkyl group or trisubstituted silyl group having 1 to 4 carbon atoms, R ¹⁵ represents a hydrogen atom.)
A method for producing the optically active disulfinic acid compound (hereinafter abbreviated as optically active disulfinic acid compound (18)) will be described.

（式中、Ｒ⁶、Ｒ¹⁴およびＲ¹⁵は上記と同一の意味を表わす。）
で示される光学活性ジスルフィン酸ジエステル（以下、光学活性ジスルフィン酸ジエステル（１９）と略記する。）は、下記式（２０）

（式中、Ｒ⁷、Ｒ¹⁴およびＲ¹⁵は上記と同一の意味を表わす。）
で示される光学活性ビスカーバメート化合物（以下、光学活性ビスカーバメート化合物（２０）と略記する。）と前記化合物（５）と炭素数１〜４の一級アルコールとを反応させることにより製造できる。 Of the optically active disulfinic acid compound (18), R ¹² and R ¹³ are linear alkoxy groups having 1 to 4 carbon atoms.

(Wherein R ⁶ , R ¹⁴ and R ¹⁵ represent the same meaning as described above.)
An optically active disulfinic acid diester represented by formula (hereinafter abbreviated as optically active disulfinic acid diester (19)) is represented by the following formula (20).

(Wherein R ⁷ , R ¹⁴ and R ¹⁵ represent the same meaning as described above.)
It can manufacture by making the said compound (5) and a C1-C4 primary alcohol react with the optically active biscarbamate compound shown below (it abbreviates as optically active biscarbamate compound (20) hereafter).

  Examples of the optically active biscarbamate compound (20) include optically active 1,1′-binaphthalene-2,2′-dithiol bis (N, N-dimethylcarbamate) and optically active 1,1′-binaphthalene-2,2 ′. -Dithiol bis (N, N-diethyl carbamate) etc. are mentioned.

  The usage-amount of a compound (5) is 1-20 mol times normally with respect to an optically active biscarbamate compound (20), Preferably it is 10-15 mol times. The amount of the primary alcohol having 1 to 4 carbon atoms is usually 2 moles or more with respect to the optically active biscarbamate compound (20), and the upper limit is not particularly limited. Also good.

  The reaction of the optically active biscarbamate compound (20), the compound (5) and the primary alcohol having 1 to 4 carbon atoms is usually carried out by mixing the three in a solvent. As the solvent, as described above, a primary alcohol having 1 to 4 carbon atoms, for example, an ether solvent such as tetrahydrofuran, an aromatic hydrocarbon solvent such as toluene, a halogenated hydrocarbon solvent such as chloroform, such as ethyl acetate, etc. These may be used alone or as a mixed solvent, such as an ester solvent, and the amount used is not particularly limited.

  The reaction temperature is usually in the range of −50 to 100 ° C.

  After completion of the reaction, the optically active disulfinic acid diester (19) can be taken out, for example, by concentrating the reaction solution. In addition, after the reaction solution is directly or concentrated, extraction is performed by adding water and, if necessary, an organic solvent insoluble in water, and the resulting organic layer is concentrated to obtain an optically active disulfinic acid diester (19). Can also be taken out.

（式中、Ｒ¹⁴およびＲ¹⁵は上記と同一の意味を表わし、Ｘ⁴はハロゲン原子を表わす。）
で示される光学活性ジスルフィン酸ジハロゲン化物（以下、光学活性ジスルフィン酸ジハロゲン化物（２１）と略記する。）は、前記で得られた光学活性ジスルフィン酸ジエステル（１９）をアルカリ処理し、次いで酸性化処理して得られる下記式（２２）

（式中、Ｒ¹⁴およびＲ¹⁵は上記と同一の意味を表わす。）
で示される光学活性ジスルフィン酸化合物（以下、光学活性ジスルフィン酸化合物（２２）と略記する。）とハロゲン化剤とを反応させることにより製造することができる。 Of the optically active disulfinic acid compound (18), R ¹² and R ¹³ are halogen atoms, and the following formula (21)

(Wherein R ¹⁴ and R ¹⁵ represent the same meaning as described above, and X ⁴ represents a halogen atom.)
The optically active disulfinic acid dihalide represented by (hereinafter abbreviated as optically active disulfinic acid dihalide (21)) is obtained by subjecting the optically active disulfinic acid diester (19) obtained above to alkali treatment and then acidification treatment. The following formula (22)

(Wherein R ¹⁴ and R ¹⁵ represent the same meaning as described above.)
Can be produced by reacting an optically active disulfinic acid compound (hereinafter abbreviated as optically active disulfinic acid compound (22)) with a halogenating agent.

  The optically active disulfinic acid diester (19) is alkali-treated and then acidified. The optically active sulfinic acid ester (3) is alkali-treated and then acidified to give the optically active sulfinic acid compound (9). The method similar to the method of manufacturing is mentioned. The reaction between the optically active disulfinic acid compound (22) and the halogenating agent may be carried out according to a method for producing a dicarboxylic acid dihalide by reacting a dicarboxylic acid and a halogenating agent.

（式中、Ｒ¹⁴およびＲ¹⁵は上記と同一の意味を表わし、Ｒ１６は炭素数１〜１０のアルコキシ基を表わす。）
で示される光学活性ジスルフィン酸ジエステル（以下、光学活性ジスルフィン酸ジエステル（２３）と略記する。）は、前記光学活性ジスルフィン酸ジハロゲン化物（２１）と炭素数１〜１０のアルコールを、塩基の存在下に反応させることにより製造することができる。炭素数１〜１０のアルコールとしては、例えばメタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、ｔｅｒｔ−ブタノール、ｎ−ヘキサノール、メントール等が挙げられる。光学活性ジスルフィン酸ジハロゲン化物（２１）と炭素数１〜１０のアルコールとの反応は、カルボン酸ハロゲン化物とアルコールとを反応させてカルボン酸エステルを製造する公知の方法に準じて行えばよい。 Of the optically active disulfinic acid compound (18), R ¹² and R ¹³ are the following C1-10 alkoxy groups (23)

(Wherein R ¹⁴ and R ¹⁵ represent the same meaning as described above, and R ¹⁶ represents an alkoxy group having 1 to 10 carbon atoms.)
In the presence of a base, the optically active disulfinic acid diester (hereinafter abbreviated as optically active disulfinic acid diester (23)) is prepared by combining the optically active disulfinic acid dihalide (21) with an alcohol having 1 to 10 carbon atoms. It can manufacture by making it react. Examples of the alcohol having 1 to 10 carbon atoms include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, n-hexanol, and menthol. The reaction between the optically active disulfinic acid dihalide (21) and the alcohol having 1 to 10 carbon atoms may be carried out in accordance with a known method for producing a carboxylic acid ester by reacting a carboxylic acid halide with an alcohol.

（式中、Ｒ⁹、Ｒ¹⁴およびＲ¹⁵は上記と同一の意味を表わす。）
で示される光学活性ジスルフィン酸ジアミド化合物（以下、光学活性ジスルフィン酸ジアミド化合物（２４）と略記する。）は、前記光学活性ジスルフィン酸ジハロゲン化物（２１）と、前記アミノ化合物とを反応させることにより製造でき、光学活性ジスルフィン酸ジハロゲン化物（２１）とアミノ化合物との反応は、上記した光学活性スルフィン酸ハロゲン化物（１０）とアミノ化合物との反応と同様に実施すればよい。 Of the optically active disulfinic acid compound (18), R ¹² and R ¹³ are an optionally substituted amino group represented by the following formula (24)

(In the formula, R ⁹ , R ¹⁴ and R ¹⁵ represent the same meaning as described above.)
The optically active disulfinic acid diamide compound (hereinafter abbreviated as optically active disulfinic acid diamide compound (24)) is produced by reacting the optically active disulfinic acid dihalide (21) with the amino compound. The reaction between the optically active disulfinic acid dihalide (21) and the amino compound may be carried out in the same manner as the reaction between the above optically active sulfinic acid halide (10) and the amino compound.

（式中、Ｒ¹⁴およびＲ¹⁵は上記と同一の意味を表わし、Ｒ¹⁷は、炭素数１〜１０のアルコキシ基または置換されていてもよいアミノ基を表わす。）
で示される光学活性ジスルフィン酸化合物（以下、光学活性ジスルフィン酸化合物（２５）と略記する。）は、前記光学活性ジスルフィン酸化合物（２２）と、前記炭素数１〜１０のアルコールまたは前記アミノ化合物とを、縮合剤および塩基の存在下に反応させることにより、光学活性スルフィン酸無水物を経由し、しかも該光学活性スルフィン酸無水物を取り出すことなく、製造することができる（下記スキーム参照。）。

Of the optically active disulfinic acid compound (18), R ¹² is a hydroxyl group, and R ¹³ is an alkoxy group having 1 to 10 carbon atoms or an optionally substituted amino group (25)

(Wherein R ¹⁴ and R ¹⁵ represent the same meaning as described above, and R ¹⁷ represents an alkoxy group having 1 to 10 carbon atoms or an optionally substituted amino group.)
The optically active disulfinic acid compound represented by (hereinafter abbreviated as optically active disulfinic acid compound (25)) is composed of the optically active disulfinic acid compound (22) and the alcohol having 1 to 10 carbon atoms or the amino compound. Can be produced via the optically active sulfinic anhydride through the reaction in the presence of a condensing agent and a base (see the following scheme).

  Examples of the condensing agent include N, N′-dicyclohexylcarbodiimide, N, N′-diisopropylcarbodiimide, and the use amount thereof is usually 1 to 5 mol times based on the optically active disulfinic acid compound (22). is there. Examples of the base include organic bases such as triethylamine, N-methylimidazole, and pyridine, and inorganic bases such as sodium hydroxide. Organic bases are preferable, and N-methylimidazole is particularly preferable. The usage-amount of this base is 1-20 mol times normally with respect to an optically active disulfinic acid compound (22), Preferably it is 5-15 mol times. The usage-amount of a C1-C10 alcohol or an amino compound is 1 mol times or more normally with respect to an optically active disulfinic acid compound (22), and there is no upper limit in particular.

  The reaction temperature is usually 0 to 100 ° C. The reaction may be carried out without solvent or in a solvent inert to the reaction. Examples of the solvent inert to the reaction include acetonitrile.

  After the completion of the reaction, for example, the reaction solution is washed with an acid aqueous solution, and if necessary, an organic solvent insoluble in water is added and extracted, and the resulting organic layer is concentrated to obtain an optically active disulfinic acid. Compound (25) can be removed.

（式中、Ｒ¹⁴およびＲ¹⁵は上記と同一の意味を表わす。）
で示される光学活性ビナフタレン化合物を用い、前記と同様に実施することにより製造することができる。 The optically active biscarbamate compound (20) is replaced with optically active 1,1′-binaphthalene-2,2′-diol in the above scheme 1 by the following formula (26).

(Wherein R ¹⁴ and R ¹⁵ represent the same meaning as described above.)
It can manufacture by implementing similarly to the above using the optically active binaphthalene compound shown by these.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

Example 1
(S) -2-Methoxy-1,1′-binaphthalene-2′-thiol After dissolving 4 g of N, N-dimethylcarbamate in 100 mL of ethanol, 9.2 g of N-bromosuccinimide was added at an internal temperature of 0 ° C. . The temperature was raised to room temperature and reacted for 1 hour. After completion of the reaction, the mixture was concentrated, and chloroform was added to the resulting concentrated residue, washed twice with saturated brine, and the resulting chloroform layer was dried. Thereafter, concentration treatment was performed to obtain ethyl (S) -2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinate.
¹ H-NMR (270 MHz, CDCl ₃ , δ / ppm)
1.23 (t, 3H), 2.88 (s, 3H), 4.10 (q, 2H), 6.73-8.23 (m, 11H)

Example 2
The ethyl (S) -2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinate obtained in Example 1 was dissolved in a mixed solution of 50 mL of chloroform and 50 mL of methanol, and water was added at room temperature. After adding 3 g of sodium oxide and reacting for 2 hours, concentration treatment was performed, and the concentrated residue was subjected to column chromatography (silica gel, chloroform / methanol = 4/1 → 2/1), and (S) -2-methoxy-6. 1.05 g of -bromo-1,1'-binaphthalene-2'-sulfinic acid was obtained.
ESI (-)-MS m / s 427 [MH ^<+ > calcd. forC ₂₁ H ₁₆ BrO ₃ S 426.9925]

Example 3
0.1 g of (S) -2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinic acid obtained in Example 2 and 1 mL of thionyl chloride were mixed at room temperature and reacted ( S) -2-Methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinic acid chloride was obtained.

Example 4
(S) -2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinic acid chloride obtained in Example 3 and isopropylamine were mixed and reacted to give (S) —N-isopropyl. 2-Methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinamide (as a mixture of two isomers) was obtained.
¹ H-NMR of isomer 1 (400 MHz, CDCl ₃ , δ / ppm)
0.34 (d, 3H), 0.71 (d, 3H), 2.97 (sept, 1H), 3.82 (s, 3H), 6.77-8.26 (m, 11H)
¹ H-NMR of isomer 2 (400 MHz, CDCl ₃ , δ / ppm)
0.87 (d, 3H), 0.97 (d, 3H), 3.22 (sept, 1H), 3.79 (s, 3H), 6.92-8.26 (m, 11H)
Isomer 1: Isomer 2 = 3: 2 (NMR integrated value ratio)

Reference example 1
(S) -6-Bromo-2-methoxy-1,1′-binaphthalene-2′-sulfinic acid chloride and (R) -6-bromo-2-methoxy obtained in the same manner as in Example 3 -1,1′-Binaphthalene-2′-sulfinic acid chloride and optically active menthol whose absolute configuration is unknown were each reacted in N-methylimidazole to obtain a compound into which an asymmetric auxiliary group was introduced (Scheme 2). reference.).

The obtained two compounds were each subjected to NMR measurement, and the difference in chemical shift value of each proton (see the following formula (27)) was calculated. The calculation results are shown in Table 1. In Table 1, (S) origin is the proton chemical shift value of the compound obtained using (S) -2-methoxy-1,1′-binaphthalene-2′-sulfinic acid, and (R) origin is , (R) -2-methoxy-1,1′-binaphthalene-2′-sulfinic acid, the chemical shift value of the proton of the compound obtained and Δδ represents (S) -2-methoxy-1 , 1'-Binaphthalene-2'-sulfinic acid, obtained using (R) -2-methoxy-1,1'-binaphthalene-2'-sulfinic acid It means the difference in the chemical shift value of protons of the compounds.

Based on the results shown in Table 1 above and the following empirical rule (I) obtained from the stable conformation analysis of optically active menthol with known absolute configuration, the absolute configuration of menthol whose absolute configuration is unknown is 1R, 2S, 5R- Decided to body.

Reference example 2
The compound obtained by reacting optically active 2-methoxy-6-bromo-1,1'-binaphthalene-2-sulfinic acid with thionyl chloride and then reacting with isopropyl alcohol was subjected to NMR measurement. Due to the sexual effect, non-equivalent peaks derived from the two methyl groups constituting the isopropyl group were detected, and the optically active 2-methoxy-6-bromo-1,1′-binaphthalene-2-sulfinic acid was converted into the optically active alcohol. It was found that it can be used as an agent for introducing an asymmetric auxiliary group into the.
Chemical shift values of two methyl groups constituting the isopropyl group δ = 1.00 ppm and 0.25 ppm, difference in chemical shift value Δδ = 0.75 ppm.

  According to JP-A-3-220159, two methyl groups constituting an isopropyl group of a compound obtained by reacting optically active 2-methoxy-1,1′-binaphthalene-2-carboxylic acid with isopropyl alcohol. The chemical shift values of non-equivalent peaks derived from are δ = 0.49 ppm and 0.72 ppm, and the difference between the chemical shift values is Δδ = 0.23 ppm. -6-Bromo-1,1'-binaphthalene-2-sulfinic acid has the above-mentioned non-equivalent peak compared to the case of using the known 2-methoxy-1,1'-binaphthalene-2-carboxylic acid. It was found that the difference in chemical shift value was large and the anisotropic effect was larger.

Reference example 3
(S) -2-Methoxy-6-bromo-1,1′-binaphthalene-2-sulfinic acid was reacted with menthol of unknown absolute configuration, and the obtained compound was subjected to two-dimensional NMR analysis (NOESY and COSY). As a result, the NOESY phase between each proton of the isopropyl group of menthol and the hydrogen atom of the ring to which the bromine atom of (S) -2-methoxy-6-bromo-1,1′-binaphthalene-2-sulfinic acid was bonded was observed. Therefore, the spatial position of the isopropyl group of the binaphthalene ring and menthol can be grasped, and the absolute configuration of the menthol is determined as 1R, 2S, 5R-form from the result of relative conformational analysis from the isopropyl group. did.

Reference example 4
(R) -2-Methoxy-6-bromo-1,1′-binaphthalene-2-sulfinic acid and menthol whose absolute configuration is unknown are reacted, and the obtained compound is subjected to two-dimensional NMR analysis (NOESY and COSY). As a result, the 5-position methyl proton and the 2-position axial proton of the cyclohexane ring of menthol were bonded to the bromine atom of (R) -2-methoxy-6-bromo-1,1′-binaphthalene-2-sulfinic acid. The NOESY phase between the hydrogen atom and the hydrogen atom of the ring was observed, so that the spatial position of the 5-position methyl proton and the 2-position axial proton of the binaphthalene ring and the cyclohexane ring of menthol can be grasped. From the results of the relative conformational analysis from the methyl proton and the axial proton at position 2, the absolute configuration of the menthol 1R, 2S, was determined to 5R- body.

Example 5
After dissolving 10 g of (S) -1,1′-binaphthalene-2,2′-dithiol bis (N, N-dimethylcarbamate) in 100 mL of methanol, 23 g of N-bromosuccinimide was added at an internal temperature of 0 ° C. The temperature was raised to room temperature and reacted for 1 hour. Thereafter, 10 g of sodium carbonate and 100 mL of water were added to quench the reaction. Chloroform was added for extraction, and the resulting chloroform layer was washed twice with saturated brine and then dried. Thereafter, concentration treatment was performed to obtain 5.5 g of dimethyl (S) -1,1′-binaphthalene-2,2′-disulfinate (a mixture of three isomers).
¹ H-NMR of isomer 1 (270 MHz, CDCl ₃ , δ / ppm)
3.12 (s, 3H), 3.51 (s, 3H), 7.07-8.25 (m, 12H)
¹ H-NMR of isomer 2 (270 MHz, CDCl ₃ , δ / ppm)
2.96 (s, 6H), 7.07-8.25 (m, 12H)
¹ H-NMR of isomer 3 (270 MHz, CDCl ₃ , δ / ppm)
3.55 (s, 6H), 7.07-8.25 (m, 12H)
Isomer 1: Isomer 2: Isomer 3 = 2.4: 1: 0.6 (NMR integrated value ratio)

Reference Example 5
2 g of dimethyl (S) -1,1′-binaphthalene-2,2′-disulfinate obtained in Example 5 was dissolved in a mixed solution of 50 mL of chloroform and 50 mL of methanol, and 3 g of sodium hydroxide was added at room temperature. It was. After stirring and reacting at room temperature for 2 hours, 50 mL of water was added to carry out a liquid separation treatment. The obtained aqueous layer was washed with chloroform, and then concentrated hydrochloric acid was added to the aqueous layer for acidification. The acidified aqueous layer was extracted with chloroform, and the resulting organic layer was dried and concentrated. The resulting concentrated residue was washed with hexane, and (S) -1,1′-binaphthalene-2, 1.5 g of 2′-disulfinic acid was obtained.

Example 6
(S) -1,1′-binaphthalene-2,2′-disulfinic acid 45 mg, isopropanol 7 mg and N-methylimidazole 100 mg obtained in the same manner as in Reference Example 5 were dissolved in 0.5 mL of acetonitrile, N, N′-dicyclohexylcarbodiimide (31 mg) was added, and the mixture was stirred and reacted at room temperature for 1 hour. Thereafter, the reaction solution was purified by thin layer chromatography (silica gel, chloroform / methanol = 10/1 → ethyl acetate / methanol = 5/1), and (S) -1,1′-binaphthalene-2-sulfino-2 ′. -20 mg of isopropyl sulfinate were obtained.
¹ H-NMR (270 MHz, CDCl ₃ , δ / ppm)
0.17 (d, J = 5.9 Hz, 3H), 0.76 (d, J = 5.9 Hz, 3H), 3.43 (m, 1H), 6.86-8.01 (m, 12H) )

Example 7
(S) -1,1′-binaphthalene-2,2′-disulfinic acid 45 mg, (−)-menthol 15 mg and N-methylimidazole 100 mg obtained in the same manner as in Reference Example 5 were mixed with 0.5 mL of acetonitrile. And 31 mg of N, N′-dicyclohexylcarbodiimide was added, and the mixture was stirred and reacted at room temperature for 1 hour. Thereafter, the reaction solution was purified by thin layer chromatography (silica gel, chloroform / methanol = 10/1 → ethyl acetate / methanol = 5/1), and (S) -1,1′-binaphthalene-2-sulfino-2 ′. -35 mg of menthyl sulfinate was obtained.
¹ H-NMR (270 MHz, CDCl ₃ , δ / ppm)
-0.11 (d, J = 6.6 Hz, 3H), 0.39 (d, J = 6.6 Hz, 3H), 0.68 (m, 2H), 0.78 (d, J = 5. 6 Hz, 3H), 0.91 (m, 1H), 0.94 (m, 3H), 1.45 (m, 2H), 1.88 (m, 1H), 3.54 (m, 1H), 6.94-8.28 (m, 12H)

Example 8
The same procedure as in Example 7 was conducted except that (+)-menthol was used instead of (−)-menthol in Example 7, and (S) -1,1′-binaphthalene-2-sulfino-2 was used. 30 mg of menthyl sulfinate was obtained.
¹ H-NMR (270 MHz, CDCl ₃ , δ / ppm)
−0.36 (m, 1H), 0.43 (m, 1H), 0.44 (d, J = 6.3 Hz, 3H), 0.45 (m, 1H), 0.65 (d, J = 6.9 Hz, 3H), 0.75 (m, 1H), 0.82 (d, J = 6.9 Hz, 3H), 0.82 (m, 1H), 0.92 (m, 1H), 1.33 (m, 1H), 1.43 (m, 1H), 2.12 (sept, J = 6.3 Hz, 1H), 3.44 (m, 1H), 6.93-8.18 ( m, 12H)

Example 9
The same procedure as in Example 7 was performed except that 7 mg of (+)-2-butanol was used in place of (−)-menthol in Example 7, and (S) -1,1′-binaphthalene-2- 24 mg of sulfino-2′-sulfinic acid (2-butyl) was obtained.
¹ H-NMR (270 MHz, CDCl ₃ , δ / ppm)
0.06 (d, J = 6.3 Hz, 3H), 0.66 (t, J = 7.2 Hz, 3H), 1.26 (m, 2H), 3.69 (m, 1H), 7. 04-8.27 (m, 12H)

Example 10
The same procedure as in Example 7 was performed except that 7 mg of (-)-2-butanol was used instead of (-)-menthol in Example 7, and (S) -1,1'-binaphthalene-2- 28 mg of sulfino-2′-sulfinic acid (2-butyl) was obtained.
¹ H-NMR (270 MHz, CDCl ₃ , δ / ppm)
0.31 (d, J = 7.4 Hz, 3H), 0.70 (m, 2H), 0.99 (t, J = 6.2 Hz, 3H), 3.63 (m, 1H), 7. 05-8.27 (m, 12H)

Example 11
The same procedure as in Example 7 was performed except that 12 mg of (-)-1-phenylethanol was used in place of (-)-menthol, and (S) -1,1'-binaphthalene-2 was used. 30 mg of sulfino-2′-sulfinic acid (1-phenylethyl) was obtained.
¹ H-NMR (270 MHz, acetone-d ₆ , δ / ppm)
0.54 (d, J = 6.6 Hz, 3H), 4.56 (q, J = 6.3 Hz, 1H), 6.89-8.11 (m, 17H)

Example 12
The same procedure as in Example 7 was performed except that 12 mg of (+)-1-phenylethanol was used in place of (−)-menthol, and (S) -1,1′-binaphthalene-2 was used. -29 mg of sulfino-2'-sulfinic acid (1-phenylethyl) was obtained.
¹ H-NMR (270 MHz, acetone-d ₆ , δ / ppm)
1.15 (d, J = 6.3 Hz, 3H), 4.65 (q, J = 6.3 Hz, 1H), 6.58 (d, J = 7.2 Hz, 2H), 6.85-8 .15 (m, 15H)

Claims (6)

Formula (1)

(In the formula, R ¹ is an alkoxy group having 1 to 4 carbon atoms, a perfluoroalkoxy group having 1 to 4 carbon atoms, an aryl group that may be substituted, an aryloxy group that may be substituted, May be an aralkyloxy group or

Represents a group represented by
(A) R ¹ may be an alkoxy group having 1 to 4 carbon atoms, a perfluoroalkoxy group having 1 to 4 carbon atoms, an aryl group that may be substituted, an aryloxy group that may be substituted, or a substituent. When it is a good aralkyloxy group, R ² represents a hydroxyl group, a halogen atom, an alkoxy group having 1 to 4 carbon atoms or an optionally substituted amino group, and R ³ represents a hydrogen atom, a halogen atom, a phenyl group, or 1 carbon atom. Represents an alkyl group of ˜4, a perfluoroalkyl group of 1 to 4 carbon atoms or a trisubstituted silyl group, and (a) when R ³ is a hydrogen atom, R ⁴ is a hydrogen atom, a halogen atom, a phenyl group, a carbon number An alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group, R ⁵ represents the same group as R ⁴ or a hydrogen atom, and (b) when R ³ is a halogen atom , R ⁴ And R ⁵ represents a hydrogen atom, (c) R ³ is a phenyl group, an alkyl group having 1 to 4 carbon atoms, when perfluoroalkyl group or trisubstituted silyl group having 1 to 4 carbon atoms, R ⁴ is hydrogen An atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group, R ⁵ represents a hydrogen atom. (B) R ¹ is

R ¹² represents a hydroxyl group, a halogen atom, an alkoxy group having 1 to 10 carbon atoms or an optionally substituted amino group. (D) When R ¹² is a hydroxyl group, R ² represents Represents an alkoxy group having 1 to 10 carbon atoms or an optionally substituted amino group, and (e) when R ¹² is a halogen atom, an alkoxy group having 1 to 10 carbon atoms or an optionally substituted amino group, R ² represents the same group as R ¹² . R ³ represents a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or a trisubstituted silyl group, and when R ³ is a hydrogen atom, R ⁴ Represents a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group; R ⁵ represents the same group as R ⁴ ; ^{When 3} is a halogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or a trisubstituted silyl group, R ⁴ and R ⁵ represent a hydrogen atom. )
An optically active sulfinic acid compound represented by: 2. The optically active sulfinic acid compound according to claim 1, wherein R ^{1 in} the formula (1) is an alkoxy group having 1 to 4 carbon atoms or a perfluoroalkoxy group having 1 to 4 carbon atoms. The optically active sulfinic acid compound according to claim 2, wherein in the formula (1), R ³ is a hydrogen atom, R ⁴ is a hydrogen atom or a halogen atom, and R ⁵ is the same group or hydrogen atom as R ⁴ . . The optically active sulfinic acid compound according to claim 3, wherein, in the formula of formula (1), R ³ is a halogen atom, and R ⁴ and R ⁵ are hydrogen atoms. In the formula (1), R ¹ is

The optically active sulfinic acid compound according to claim 1, wherein R ³ , R ⁴ and R ⁵ are a hydrogen atom. The optically active sulfinic acid compound according to claim 5, wherein in the formula of formula (1), R ¹² is a hydroxyl group, and R ² is an alkoxy group having 1 to 10 carbon atoms or an optionally substituted amino group.