JP2005134365A - Chiral shift reagent for nmr consisting of optical active binaphthyl compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound using as a NMR shift reagent which is manufactured easily, without using a complicated manufacturing method. <P>SOLUTION: The chiral shift reagent for NMR consists of optically active binaphthyl compound expressed by Formula (1), (in Formula, each of R<SP>1</SP>, R<SP>3</SP>, R<SP>4</SP>and R<SP>5</SP>express a proton, containing substituent or a non-proton containing substituent with the same or different substituent. R<SP>2</SP>denotes a substituent or a detaching group which has reactivity with respect to a sample compound, n denotes 1 or 2). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an NMR chiral shift reagent comprising an optically active binaphthyl 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 have become very important also in the fields of pharmaceuticals, agricultural chemicals, etc., and efficacy, toxicity, etc. are often different depending on the difference in absolute configuration, and determining the absolute configuration is extremely important. It was work.

  As a method for determining the absolute configuration of such an optically active compound, for example, a compound in which an optically active compound and a chiral shift reagent for NMR are reacted and a substituent having a known absolute configuration (asymmetric auxiliary group) is introduced is obtained. There is a method of determining the absolute configuration of the optically active compound by NMR analysis and using the asymmetric auxiliary group as an internal standard. 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 X-ray crystal analysis. (For example, refer nonpatent literature 1.).

  In the Moscher method, a compound in which an asymmetric auxiliary group is introduced using a chiral shift reagent for NMR can adopt a conformation in which the anisotropic effect of the aromatic ring derived from the asymmetric auxiliary group is more strongly received in the NMR measurement solution. As a premise, since the chiral chiral shift reagent for introducing the chiral auxiliary group is optically active α-methoxy-α- (trifluoromethyl) phenylacetic acid which is a C-centered optically active compound, NMR that can be applied to other optically active compounds because it is affected by the rotation of the bond axis between the carbon atom and the carbonyl group or phenyl group. There has been a need for compounds that can be used as chiral shift reagents.

  On the other hand, as a chiral shift reagent for NMR different from optically active α-methoxy-α- (trifluoromethyl) phenylacetic acid, for example, optically active 2′-methoxy-1,1′-binaphthalene-2-carboxylic acid, optically active 2 ′ An axially asymmetric compound such as -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. A compound that can be produced and can be used as a chiral shift reagent for NMR has been desired.

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

（式中、Ｒ¹、Ｒ³、Ｒ⁴およびＲ⁵は、各々、同一または異なって、プロトン含有置換基または非プロトン含有置換基を表わし、Ｒ²は、分析する化合物との反応性を有する置換基または脱離基を表わし、ｎは、１または２を表わす。）
で示される光学活性ビナフチル化合物からなるＮＭＲ用キラルシフト試薬が、不斉補助基を導入する試薬として使用でき、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 these circumstances, the present inventors have intensively studied to develop a novel axially asymmetric compound that can be used as a chiral shift reagent for NMR. As a result, an optical that can be easily derived from readily available optically active binaphthol. The following formula (1) represented by active 2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinic acid, optically active 1,1′-binaphthalene-2,2′-disulfinic acid and the like

(Wherein R ¹ , R ³ , R ⁴ and R ⁵ are the same or different and each represents a proton-containing substituent or a non-proton-containing substituent, and R ² has reactivity with the compound to be analyzed) And represents a substituent or a leaving group, and n represents 1 or 2.)
The chiral shift reagent for NMR which consists of the optically active binaphthyl compound shown by these can be used as a reagent which introduce | transduces an asymmetric auxiliary group, and also 2'-methoxy-1, 1'- binaphthalene-2 which is a conventional axially asymmetric compound -It has been found that the anisotropic effect is stronger than that of carboxylic acid and the like, and determination of the absolute configuration of the optical isomer becomes easier, and the present invention has been achieved.

（式中、Ｒ¹、Ｒ³、Ｒ⁴およびＲ⁵は、各々、同一または異なって、プロトン含有置換基または非プロトン含有置換基を表わし、Ｒ²は、分析する化合物との反応性を有する置換基または脱離基を表わし、ｎは、１または２を表わす。）
で示される光学活性ビナフチル化合物からなるＮＭＲ用キラルシフト試薬（以下、本発明試薬と記すこともある。）；
２．式（１）で示される光学活性ビナフチル化合物のうち、Ｒ²が、水酸基、ハロゲン原子、無置換もしくは置換アミノ基、アルキル基およびヘテロアリール基のいずれかの置換基または脱離基である光学活性ビナフチル化合物からなる前項１記載のＮＭＲ用キラルシフト試薬；
３．式（１）で示される光学活性ビナフチル化合物のうち、Ｒ²が、水酸基、ハロゲン原子または無置換もしくは置換アミノ基である光学活性ビナフチル化合物からなる前項２記載のＮＭＲ用キラルシフト試薬；
４．式（１）で示される光学活性ビナフチル化合物のうち、Ｒ⁴が水素原子またはハロゲン原子である光学活性ビナフチル化合物からなる前項１、２または３記載のＮＭＲ用キラルシフト試薬；
５．式（１）で示される光学活性ビナフチル化合物のうち、Ｒ⁴が臭素原子である光学活性ビナフチル化合物からなる前項４記載のＮＭＲ用キラルシフト試薬；
６．式（１）で示される光学活性ビナフチル化合物のうち、Ｒ¹はメトキシ基または炭素数１〜４のパーフルオロアルコキシ基を表わし、Ｒ²は水酸基、ハロゲン原子、無置換もしくは置換アミノ基を表わし、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、ｎは１または２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光学活性ビナフチル化合物からなる前項１記載のＮＭＲ用キラルシフト試薬；
７．式（１）で示される光学活性ビナフチル化合物のうち、ｎが１を表わし、Ｒ¹が、

で示される基を表わし、Ｒ²およびＲ¹⁴が同一の水酸基、ハロゲン原子または無置換もしくは置換アミノ基を表わすか、または、Ｒ²が無置換もしくは置換アミノ基で、Ｒ¹⁴が水酸基を表わし、Ｒ³およびＲ⁴のうちのいずれか一方が、水素原子を、他方が、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がＲ⁴と同一の基を表わす光学活性ビナフチル化合物からなる前項１記載のＮＭＲ用キラルシフト試薬；
８．式（１）で示される光学活性ビナフチル化合物のうち、ｎが２を表わし、Ｒ¹が、

で示される基を表わし、Ｒ²が水酸基または無置換もしくは置換アミノ基を表わし、Ｒ¹⁵が水酸基を表わし、Ｒ³およびＲ⁴のうちのいずれか一方が水素原子を、他方が水素原子、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がＲ⁴と同一の基を表わす光学活性ビナフチル化合物からなる前項１記載のＮＭＲ用キラルシフト試薬；
等を提供するものである。 That is, the present invention
1. Formula (1)

(Wherein R ¹ , R ³ , R ⁴ and R ⁵ are the same or different and each represents a proton-containing substituent or a non-proton-containing substituent, and R ² has reactivity with the compound to be analyzed) And represents a substituent or a leaving group, and n represents 1 or 2.)
A chiral shift reagent for NMR comprising the optically active binaphthyl compound represented by the formula (hereinafter also referred to as the reagent of the present invention);
2. Of the optically active binaphthyl compounds represented by the formula (1), R ² is an optical activity in which any one of a hydroxyl group, a halogen atom, an unsubstituted or substituted amino group, an alkyl group and a heteroaryl group, or a leaving group. The chiral shift reagent for NMR according to item 1, comprising a binaphthyl compound;
3. The chiral shift reagent for NMR according to item 2 above, wherein among the optically active binaphthyl compounds represented by formula (1), R ² is an optically active binaphthyl compound in which R ² is a hydroxyl group, a halogen atom, or an unsubstituted or substituted amino group;
4). ^{4. The} chiral shift reagent for NMR according to the above 1, 2 or 3, comprising an optically active binaphthyl compound wherein R ⁴ is a hydrogen atom or a halogen atom among the optically active binaphthyl compounds represented by formula (1);
5). The chiral shift reagent for NMR according to item 4, wherein the optically active binaphthyl compound represented by formula (1) is an optically active binaphthyl compound in which R ⁴ is a bromine atom;
6). Of the optically active binaphthyl compounds represented by the formula (1), R ¹ represents a methoxy group or a C 1-4 perfluoroalkoxy group, R ² represents a hydroxyl group, a halogen atom, an unsubstituted or substituted amino group, 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, n represents 1 or 2, and (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, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group, and R ⁵ is R ⁴ represents the same group or hydrogen atom, (b) when R ³ is a halogen atom, R ⁴ and R ⁵ represent a hydrogen atom, and (c) R ³ represents a phenyl group, an alkyl group having 1 to 4 carbon atoms. 1 to 4 carbon atoms When R ⁴ is a fluoroalkyl group 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; 2. The NMR chiral shift reagent according to item 1 above, which comprises an optically active binaphthyl compound in which R ⁵ represents a hydrogen atom;
7). Of the optically active binaphthyl compounds represented by formula (1), n represents 1 and R ¹ represents

R ² and R ¹⁴ represent the same hydroxyl group, a halogen atom or an unsubstituted or substituted amino group, or R ² represents an unsubstituted or substituted amino group, and R ¹⁴ represents a hydroxyl group, One of R ³ and R ⁴ is a hydrogen atom, and the other 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 three 2. The NMR chiral shift reagent according to item 1 above, comprising an optically active binaphthyl compound which represents a substituted silyl group and R ⁵ represents the same group as R ⁴ ;
8). Of the optically active binaphthyl compounds represented by the formula (1), n represents 2 and R ¹ represents

R ² represents a hydroxyl group or an unsubstituted or substituted amino group, R ¹⁵ represents a hydroxyl group, one of R ³ and R ⁴ represents a hydrogen atom, the other represents a hydrogen atom, halogen The preceding item comprising an optically active binaphthyl compound which represents an 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 the same group as R ⁴ The chiral shift reagent for NMR according to 1,
Etc. are provided.

  The chiral shift reagent for NMR of the present invention can be easily produced from readily available optically active binaphthol, and has a stronger anisotropic effect than a conventionally known axially asymmetric compound, The absolute configuration of the optical isomer can be determined more easily.

で示される光学活性ビナフチル化合物（以下、本光学活性ビナフチル化合物と記すこともある。）の式中、ｎは１または２を表わす。Ｒ¹はプロトン含有置換基または非プロトン含有置換基を表わし、好ましくは、メトキシ基、炭素数１〜４のパーフルオロアルコキシ基、下記

で示される基または下記

で示される基を表わす。ここで、炭素数１〜４のパーフルオロアルコキシ基としては、例えばトリフルオロメトキシ基、ペンタフルオロエトキシ基、ヘプタフルオロプロポキシ基およびノナフルオロブトキシ基等を挙げることができる。 Formula (1) which is an active ingredient of the reagent of the present invention

In the formula of the optically active binaphthyl compound represented by (hereinafter, also referred to as the present optically active binaphthyl compound), n represents 1 or 2. R ¹ represents a proton-containing substituent or a non-proton-containing substituent, preferably a methoxy group, a C 1-4 perfluoroalkoxy group,

Or a group represented by

Represents a group represented by Here, 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.

In the above formula (1), R ² represents a substituent or a leaving group having reactivity with the compound to be analyzed, and preferably a hydroxyl group, a halogen atom, an unsubstituted or substituted amino group, an alkyl group and a heteroaryl group (for example, , An imidazole group), a hydroxyl group, a chlorine atom, a bromine atom, an unsubstituted or substituted amino group. Here, examples of the substituted amino group include one or two alkyl groups having 1 to 4 carbon atoms such as a methylamino group, an ethylamino group, an isopropylamino group, a hydrazino group, and a guanidino group, an amino group, and an aminoimino group. An amino group substituted with a substituent, for example, a cyclic amino group such as a pyrrolidino group and a piperidino group can be exemplified.

で示される基のとき、好ましくはＲ²およびＲ¹⁴が同一の水酸基、ハロゲン原子または無置換もしくは置換アミノ基を表わすか、または、Ｒ²が無置換もしくは置換アミノ基で、Ｒ¹⁴が水酸基を表わす。また、Ｒ¹で示される基が、下記

で示される基のとき、好ましくはＲ²が水酸基または無置換もしくは置換アミノ基を表わす。 The group represented by R ¹ is

When the groups represented in, preferably hydroxyl groups R ² and R ¹⁴ are the same, or a halogen atom or an unsubstituted or substituted amino group, or by R ² is an unsubstituted or substituted amino group, R ¹⁴ is a hydroxyl group Represent. In addition, the group represented by R ¹ is

In the group represented by the formula (1), R ² preferably represents a hydroxyl group or an unsubstituted or substituted amino group.

In the above formula (1), R ³ represents a proton-containing substituent or a non-proton-containing substituent, preferably a hydrogen atom, a chlorine atom, a bromine atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, or 1 to 1 carbon atoms. 4 represents a perfluoroalkyl group or a trisubstituted silyl group. Here, examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an isopropyl group, and an n-butyl group. Examples of the perfluoroalkyl group having 1 to 4 carbon atoms include, for example, Examples thereof include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a nonafluorobutyl group. Examples of the trisubstituted silyl group include a trimethylsilyl group, a triethylsilyl group, a phenylmethylsilyl group, and a diphenylmethylsilyl group.

In the above formula (1), R ⁴ and R ⁵ are the same or different and each represents a proton-containing substituent or a non-proton-containing substituent, and examples thereof include the same as R ³ described above.

で示される基を表わし、Ｒ²およびＲ¹⁴が同一の水酸基、ハロゲン原子または無置換もしくは置換アミノ基を表わすか、または、Ｒ²が無置換もしくは置換アミノ基で、Ｒ¹⁴が水酸基を表わし、Ｒ³およびＲ⁴のうちのいずれか一方が、水素原子を、他方が、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がＲ⁴と同一の基を表わす。
（Ｃ）ｎが２を表わし、Ｒ¹が、

で示される基を表わし、Ｒ²が水酸基または無置換もしくは置換アミノ基を表わし、Ｒ³およびＲ⁴のうちのいずれか一方が水素原子を、他方が水素原子、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がＲ⁴と同一の基を表わす。 Examples of suitable combinations of such substituents include the following combinations.
(A) R ¹ represents a methoxy group or a C 1-4 perfluoroalkoxy group, R ² represents a hydroxyl group, a halogen atom, an unsubstituted or 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, n represents 1 or 2, and (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, 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. (B) When R ³ is a halogen atom, R ⁴ and R ⁵ represent a hydrogen atom. (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 is a hydrogen atom, a halogen atom, a phenyl group, or a carbon number 1-4 alkyl group, a perfluoroalkyl group or a trisubstituted silyl group having 1 to 4 carbon atoms, R ⁵ represents a hydrogen atom.
(B) n represents 1 and R ¹ is

R ² and R ¹⁴ represent the same hydroxyl group, a halogen atom or an unsubstituted or substituted amino group, or R ² represents an unsubstituted or substituted amino group, and R ¹⁴ represents a hydroxyl group, One of R ³ and R ⁴ is a hydrogen atom, and the other 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 three Represents a substituted silyl group, and R ⁵ represents the same group as R ⁴ .
(C) n represents 2 and R ¹ is

R ² represents a hydroxyl group or an unsubstituted or substituted amino group, one of R ³ and R ⁴ represents a hydrogen atom, the other represents a hydrogen atom, a halogen atom, a phenyl group, or a carbon number. It represents a 1-4 alkyl group, a C 1-4 perfluoroalkyl group or a trisubstituted silyl group, and R ⁵ represents the same group as R ⁴ .

  Examples of the optically active binaphthyl compound 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-6,6′-difluoro-1,1′-binaphthalene-2′-sulfinic acid, optically active 2-methoxy-3,3′-difluoro-1,1′-binaphthalene-2 ′ -Sulfinic acid, optically active 2-methoxy-6-chloro-1,1'-binaphthalene-2'-sulfinic acid, optically active 2-methoxy-6,6'-dichloro-1,1'-binaphthalene-2'- Sulfinic acid, optically active 2-methoxy-3,3′-dichloro-1,1′-binaphthalene-2′-sulfinic acid, optically active 2-methoxy-6-bromo-1,1′-bi Phthalene-2′-sulfinic acid, optically active 2-methoxy-6,6′-dibromo-1,1′-binaphthalene-2′-sulfinic acid, optically active 2-methoxy-3,3′-dibromo-1,1 '-Binaphthalene-2'-sulfinic acid, optically active 2-methoxy-6-iodo-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'-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′-binaphthalene-2′-sulfinic acid, optically active 2-methoxy-6-tert-butyl-1,1′-binaphthalene-2′-sulfinic acid, optical activity 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-to Methylsilyl-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′-sulfonic acid, optically active 2-methoxy-6-fluoro-1,1′-binaphthalene-2′-sulfonic acid, optically active 2-methoxy-6, 6'-difluoro-1,1'-binaphthalene-2'-sulfonic acid, optically active 2-methoxy-3,3'-difluoro-1,1'-binaphthalene-2'-sulfonic acid, optically active 2-methoxy- 6-chloro-1,1′-binaphthalene-2′-sulfonic acid, optically active 2-methoxy-6,6′-dichloro-1,1′-binaphthalene-2′-sulfonic acid, optically active 2-methoxy-3 , 3′-dichloro-1,1′-binaphthalene-2′-sulfonic acid, optically active 2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfonic acid, optically active 2-methoxy-6, 6'- Bromo-1,1′-binaphthalene-2′-sulfonic acid, optically active 2-methoxy-3,3′-dibromo-1,1′-binaphthalene-2′-sulfonic acid, optically active 2-methoxy-6-iodo -1,1'-binaphthalene-2'-sulfonic acid, optically active 2-methoxy-6,6'-diiodo-1,1'-binaphthalene-2'-sulfonic acid, optically active 2-methoxy-3,3 ' -Diiodo-1,1'-binaphthalene-2'-sulfonic acid, optically active 2-methoxy-6-phenyl-1,1'-binaphthalene-2'-sulfonic acid, optically active 2-methoxy-6,6'- Diphenyl-1,1′-binaphthalene-2′-sulfonic acid,

Optically active 2-methoxy-6-methyl-1,1′-binaphthalene-2′-sulfonic acid, optically active 2-methoxy-6-tert-butyl-1,1′-binaphthalene-2′-sulfonic acid, optical activity 2-methoxy-6,6′-dimethyl-1,1′-binaphthalene-2′-sulfonic acid, optically active 2-methoxy-6,6′-di (tert-butyl) -1,1′-binaphthalene-2 '-Sulfonic acid, optically active 2-methoxy-3,3', 6-trimethyl-1,1'-binaphthalene-2'-sulfonic acid, optically active 2-methoxy-6-trifluoromethyl-1,1'- Binaphthalene-2′-sulfonic acid, optically active 2-methoxy-6,6′-bis (trifluoromethyl) -1,1′-binaphthalene-2′-sulfonic acid, optically active 2-methoxy-6-trimethylsilyl 1,1′-binaphthalene-2′-sulfonic acid, optically active 2-methoxy-6,6′-bis (trimethylsilyl) -1,1′-binaphthalene-2′-sulfonic acid, optically active 2-methoxy-3, 3′-Dimethyl-6-bromo-1,1′-binaphthalene-2′-sulfonic acid, optically active 2-methoxy-3,3′-di (tert-butyl) -6-bromo-1,1′-binaphthalene -2'-sulfonic acid, optically active 2-methoxy-3,3'-dimethyl-6- (trimethylsilyl) -1,1'-binaphthalene-2'-sulfonic acid,

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- 6,6′-difluoro-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-6-chloro-1,1′-binaphthalene-2′-sulfinic acid chloride, optically active 2-methoxy-6,6′-dichloro-1,1′-binaphthalene-2′-sulfinic acid chloride, optical Active 2-methoxy-3,3′-dichloro-1,1′-binaphthalene-2′-sulfinic acid chloride, optically active 2-methoxy-6-bromo-1, '-Binaphthalene-2'-sulfinic acid chloride, optically active 2-methoxy-6,6'-dibromo-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-6-iodo-1,1′-binaphthalene-2′-sulfinic acid chloride, optically active 2-methoxy-6,6′- Diiodo-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-6,6′-dimethyl-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′-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- '-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′-sulfonic acid chloride, optically active 2-methoxy-6-fluoro-1,1′-binaphthalene-2′-sulfonic acid chloride, optically active 2-methoxy- 6,6′-Difluoro-1,1′-binaphthalene-2′-sulfonic acid chloride, optically active 2-methoxy-3,3′-difluoro-1,1′-binaphthalene-2′-sulfonic acid chloride, optically active 2-methoxy-6-chloro-1,1'-binaphthalene-2'-sulfonic acid chloride, optically active 2-methoxy-6,6'-dichloro-1,1'-binaphthalene-2'-sulfonic acid chloride, optical Active 2-methoxy-3,3′-dichloro-1,1′-binaphthalene-2′-sulfonic acid chloride, optically active 2-methoxy-6-bromo-1,1′-binaphtha -2'-sulfonic acid chloride, optically active 2-methoxy-6,6'-dibromo-1,1'-binaphthalene-2'-sulfonic acid chloride, optically active 2-methoxy-3,3'-dibromo-1 , 1′-Binaphthalene-2′-sulfonic acid chloride, optically active 2-methoxy-6-iodo-1,1′-binaphthalene-2′-sulfonic acid chloride, optically active 2-methoxy-6,6′-diiodo- 1,1′-Binaphthalene-2′-sulfonic acid chloride, optically active 2-methoxy-3,3′-diiodo-1,1′-binaphthalene-2′-sulfonic acid chloride, optically active 2-methoxy-6-phenyl -1,1'-binaphthalene-2'-sulfonic acid chloride, optically active 2-methoxy-6,6'-diphenyl-1,1'-binaphthalene-2'-sulfonic acid chloride,

Optically active 2-methoxy-6-methyl-1,1′-binaphthalene-2′-sulfonic acid chloride, optically active 2-methoxy-6,6′-dimethyl-1,1′-binaphthalene-2′-sulfonic acid chloride Optically active 2-methoxy-6-tert-butyl-1,1′-binaphthalene-2′-sulfonic acid chloride, optically active 2-methoxy-6,6′-di (tert-butyl) -1,1′- Binaphthalene-2′-sulfonic acid chloride, optically active 2-methoxy-3,3 ′, 6-trimethyl-1,1′-binaphthalene-2′-sulfonic acid chloride, optically active 2-methoxy-6-trifluoromethyl- 1,1′-Binaphthalene-2′-sulfonic acid chloride, optically active 2-methoxy-6,6′-bis (trifluoromethyl) -1,1′-binaphthalene-2′-sulfo Acid chloride, optically active 2-methoxy-6-trimethylsilyl-1,1'-binaphthalene-2'-sulfonic acid chloride, optically active 2-methoxy-6,6'-bis (trimethylsilyl) -1,1'-binaphthalene- 2'-sulfonic acid chloride, optically active 2-methoxy-3,3'-dimethyl-6-bromo-1,1'-binaphthalene-2'-sulfonic acid chloride, optically active 2-methoxy-3,3'-di (Tert-Butyl) -6-bromo-1,1′-binaphthalene-2′-sulfonic acid chloride, optically active 2-methoxy-3,3′-dimethyl-6- (trimethylsilyl) -1,1′-binaphthalene- 2'-sulfonic acid chloride,

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- 6,6′-difluoro-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-6-chloro-1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-methoxy-6,6′-dichloro-1,1′-binaphthalene-2′-sulfinic acid bromide, optical Active 2-methoxy-3,3′-dichloro-1,1′-binaphthalene-2′-sulfinic acid bromide, optically active 2-methoxy-6-bromo-1, '-Binaphthalene-2'-sulfinic acid bromide, optically active 2-methoxy-6,6'-dibromo-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-6-iodo-1,1'-binaphthalene-2'-sulfinic acid bromide, optically active 2-methoxy-6,6'- Diiodo-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-6,6′-dimethyl-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'-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- '-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′-sulfonic acid bromide, optically active 2-methoxy-6-fluoro-1,1′-binaphthalene-2′-sulfonic acid bromide, optically active 2-methoxy- 6,6′-difluoro-1,1′-binaphthalene-2′-sulfonic acid bromide, optically active 2-methoxy-3,3′-difluoro-1,1′-binaphthalene-2′-sulfonic acid bromide, optically active 2-methoxy-6-chloro-1,1′-binaphthalene-2′-sulfonic acid bromide, optically active 2-methoxy-6,6′-dichloro-1,1′-binaphthalene-2′-sulfonic acid bromide, optical Active 2-methoxy-3,3′-dichloro-1,1′-binaphthalene-2′-sulfonic acid bromide, optically active 2-methoxy-6-bromo-1,1′-binaphtha -2'-sulfonic acid bromide, optically active 2-methoxy-6,6'-dibromo-1,1'-binaphthalene-2'-sulfonic acid bromide, optically active 2-methoxy-3,3'-dibromo-1 , 1′-Binaphthalene-2′-sulfonic acid bromide, optically active 2-methoxy-6-iodo-1,1′-binaphthalene-2′-sulfonic acid bromide, optically active 2-methoxy-6,6′-diiodo- 1,1′-Binaphthalene-2′-sulfonic acid bromide, optically active 2-methoxy-3,3′-diiodo-1,1′-binaphthalene-2′-sulfonic acid bromide, optically active 2-methoxy-6-phenyl -1,1′-binaphthalene-2′-sulfonic acid bromide, optically active 2-methoxy-6,6′-diphenyl-1,1′-binaphthalene-2′-sulfonic acid bromide,

Optically active 2-methoxy-6-methyl-1,1′-binaphthalene-2′-sulfonic acid bromide, optically active 2-methoxy-6,6′-dimethyl-1,1′-binaphthalene-2′-sulfonic acid bromide Optically active 2-methoxy-6-tert-butyl-1,1′-binaphthalene-2′-sulfonic acid bromide, optically active 2-methoxy-6,6′-di (tert-butyl) -1,1′- Binaphthalene-2′-sulfonic acid bromide, optically active 2-methoxy-3,3 ′, 6-trimethyl-1,1′-binaphthalene-2′-sulfonic acid bromide, optically active 2-methoxy-6-trifluoromethyl- 1,1′-Binaphthalene-2′-sulfonic acid bromide, optically active 2-methoxy-6,6′-bis (trifluoromethyl) -1,1′-binaphthalene-2′-sulfo Acid bromide, optically active 2-methoxy-6-trimethylsilyl-1,1'-binaphthalene-2'-sulfonic acid bromide, optically active 2-methoxy-6,6'-bis (trimethylsilyl) -1,1'-binaphthalene- 2′-sulfonic acid bromide, optically active 2-methoxy-3,3′-dimethyl-6-bromo-1,1′-binaphthalene-2′-sulfonic acid bromide, optically active 2-methoxy-3,3′-di (Tert-Butyl) -6-bromo-1,1′-binaphthalene-2′-sulfonic acid bromide, optically active 2-methoxy-3,3′-dimethyl-6- (trimethylsilyl) -1,1′-binaphthalene- 2'-sulfonic acid bromide,

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, 6′-difluoro-1,1′-binaphthalene-2′-sulfinamide, optically active 2-methoxy-3,3′-difluoro-1,1′-binaphthalene-2′-sulfinamide, optically active 2-methoxy- 6-chloro-1,1′-binaphthalene-2′-sulfinamide, optically active 2-methoxy-6,6′-dichloro-1,1′-binaphthalene-2′-sulfinamide, optically active 2-methoxy-3 , 3'-dichloro-1,1'-binaphthalene-2'-sulfinamide, optically active 2-methoxy-6-bromo-1,1'-binaphthalene-2'-s Finamide, optically active 2-methoxy-6,6′-dibromo-1,1′-binaphthalene-2′-sulfinamide, optically active 2-methoxy-3,3′-dibromo-1,1′-binaphthalene-2 ′ -Sulfinamide, optically active 2-methoxy-6-iodo-1,1'-binaphthalene-2'-sulfinamide, optically active 2-methoxy-6,6'-diiodo-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′-sulfin Amide, 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-6,6′-dimethyl-1,1′-binaphthalene-2′-sulfinamide, optical Active 2-methoxy-6-tert-butyl-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-trimethylsilyl-1,1'-binaphthalene-2'-sulfinamide, optically active 2-methoxy-6,6'-bis (trimethylsilyl) -1,1'-binaphthalene-2'-sulfin Amide, 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 2-methoxy-1,1′-binaphthalene-2′-sulfonamide, optically active 2-methoxy-6-fluoro-1,1′-binaphthalene-2′-sulfonamide, optically active 2-methoxy-6, 6′-difluoro-1,1′-binaphthalene-2′-sulfonamide, optically active 2-methoxy-3,3′-difluoro-1,1′-binaphthalene-2′-sulfonamide, optically active 2-methoxy- 6-chloro-1,1′-binaphthalene-2′-sulfonamide, optically active 2-methoxy-6,6′-dichloro-1,1′-binaphthalene-2′-sulfonamide, optically active 2-methoxy-3 , 3′-dichloro-1,1′-binaphthalene-2′-sulfonamide, optically active 2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfonamide, Optically active 2-methoxy-6,6′-dibromo-1,1′-binaphthalene-2′-sulfonamide, optically active 2-methoxy-3,3′-dibromo-1,1′-binaphthalene-2′-sulfone Amide, optically active 2-methoxy-6-iodo-1,1′-binaphthalene-2′-sulfonamide, optically active 2-methoxy-6,6′-diiodo-1,1′-binaphthalene-2′-sulfonamide Optically active 2-methoxy-3,3′-diiodo-1,1′-binaphthalene-2′-sulfonamide, optically active 2-methoxy-6-phenyl-1,1′-binaphthalene-2′-sulfonamide, Optically active 2-methoxy-6,6′-diphenyl-1,1′-binaphthalene-2′-sulfonamide,

Optically active 2-methoxy-6-methyl-1,1′-binaphthalene-2′-sulfonamide, optically active 2-methoxy-6,6′-dimethyl-1,1′-binaphthalene-2′-sulfonamide, optical Active 2-methoxy-6-tert-butyl-1,1′-binaphthalene-2′-sulfonamide, optically active 2-methoxy-6,6′-di (tert-butyl) -1,1′-binaphthalene-2 '-Sulfonamide, optically active 2-methoxy-3,3', 6-trimethyl-1,1'-binaphthalene-2'-sulfonamide, optically active 2-methoxy-6-trifluoromethyl-1,1'- Binaphthalene-2′-sulfonamide, optically active 2-methoxy-6,6′-bis (trifluoromethyl) -1,1′-binaphthalene-2′-sulfonamide, optically active 2-methyl Xyl-6-trimethylsilyl-1,1′-binaphthalene-2′-sulfonamide, optically active 2-methoxy-6,6′-bis (trimethylsilyl) -1,1′-binaphthalene-2′-sulfonamide, optically active 2-methoxy-3,3′-dimethyl-6-bromo-1,1′-binaphthalene-2′-sulfonamide, optically active 2-methoxy-3,3′-di (tert-butyl) -6-bromo- 1,1′-binaphthalene-2′-sulfonamide, optically active 2-methoxy-3,3′-dimethyl-6- (trimethylsilyl) -1,1′-binaphthalene-2′-sulfonamide,

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-6,6′-difluoro-1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-methoxy-3,3′-difluoro-1,1 '-Binaphthalene-2'-sulfinamide, optically active N-isopropyl-2-methoxy-6-chloro-1,1'-binaphthalene-2'-sulfinamide, optically active N-isopropyl-2-methoxy-6,6 '-Dichloro-1,1'-binaphthalene-2'-sulfinamide, optically active N-isopropyl-2-methoxy-3,3' Dichloro-1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2- Methoxy-6,6′-dibromo-1,1′-binaphthalene-2′-sulfinamide, optically active N-isopropyl-2-methoxy-3,3′-dibromo-1,1′-binaphthalene-2′-sulfine Amide, optically active N-isopropyl-2-methoxy-6-iodo-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'-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-6,6'-dimethyl-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 ' -Di (tert-butyl) -1,1'-binaphthalene-2'-sulfinamide, 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'-sulfinamide, optically active N-isopropyl-2-methoxy-3,3'-di Chill-6- (trimethylsilyl) -1,1'-binaphthalene-2'-sulfinamide,

Optically active N-isopropyl-2-methoxy-1,1′-binaphthalene-2′-sulfonamide, optically active N-isopropyl-2-methoxy-6-fluoro-1,1′-binaphthalene-2′-sulfonamide, Optically active N-isopropyl-2-methoxy-6,6′-difluoro-1,1′-binaphthalene-2′-sulfonamide, optically active N-isopropyl-2-methoxy-3,3′-difluoro-1,1 '-Binaphthalene-2'-sulfonamide, optically active N-isopropyl-2-methoxy-6-chloro-1,1'-binaphthalene-2'-sulfonamide, optically active N-isopropyl-2-methoxy-6,6 '-Dichloro-1,1'-binaphthalene-2'-sulfonamide, optically active N-isopropyl-2-methoxy-3,3'-dichloro- , 1′-Binaphthalene-2′-sulfonamide, optically active N-isopropyl-2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfonamide, optically active N-isopropyl-2-methoxy-6 , 6′-dibromo-1,1′-binaphthalene-2′-sulfonamide, optically active N-isopropyl-2-methoxy-3,3′-dibromo-1,1′-binaphthalene-2′-sulfonamide, optical Active N-isopropyl-2-methoxy-6-iodo-1,1'-binaphthalene-2'-sulfonamide, optically active N-isopropyl-2-methoxy-6,6'-diiodo-1,1'-binaphthalene- 2′-sulfonamide, optically active N-isopropyl-2-methoxy-3,3′-diiodo-1,1′-binaphthalene-2′-sulfonamide, Optically active N-isopropyl-2-methoxy-6-phenyl-1,1'-binaphthalene-2'-sulfonamide, optically active N-isopropyl-2-methoxy-6,6'-diphenyl-1,1'-binaphthalene -2'-sulfonamide,

Optically active N-isopropyl-2-methoxy-6-methyl-1,1'-binaphthalene-2'-sulfonamide, optically active N-isopropyl-2-methoxy-6,6'-dimethyl-1,1'-binaphthalene -2'-sulfonamide, optically active N-isopropyl-2-methoxy-6-tert-butyl-1,1'-binaphthalene-2'-sulfonamide, optically active N-isopropyl-2-methoxy-6,6 ' -Di (tert-butyl) -1,1'-binaphthalene-2'-sulfonamide, optically active N-isopropyl-2-methoxy-3,3 ', 6-trimethyl-1,1'-binaphthalene-2'- Sulfonamide, optically active N-isopropyl-2-methoxy-6-trifluoromethyl-1,1′-binaphthalene-2′-sulfonamide, optically active N— Sopropyl-2-methoxy-6,6′-bis (trifluoromethyl) -1,1′-binaphthalene-2′-sulfonamide, optically active N-isopropyl-2-methoxy-6-trimethylsilyl-1,1′- Binaphthalene-2′-sulfonamide, optically active N-isopropyl-2-methoxy-6,6′-bis (trimethylsilyl) -1,1′-binaphthalene-2′-sulfonamide, optically active N-isopropyl-2-methoxy -3,3'-dimethyl-6-bromo-1,1'-binaphthalene-2'-sulfonamide, optically active N-isopropyl-2-methoxy-3,3'-di (tert-butyl) -6-bromo -1,1'-binaphthalene-2'-sulfonamide, optically active N-isopropyl-2-methoxy-3,3'-dimethyl-6- (trimethy Silyl) -1,1' binaphthalene-2'-sulfonamide,

Optically active 2-methoxy-1,1′-binaphthalene-2′-sulfinyl hydrazide, optically active 2-methoxy-6-chloro-1,1′-binaphthalene-2′-sulfinyl hydrazide, optically active 2-methoxy-6 6'-dichloro-1,1'-binaphthalene-2'-sulfinyl hydrazide, optically active 2-methoxy-3,3'-dichloro-1,1'-binaphthalene-2'-sulfinyl hydrazide, optically active 2-methoxy- 6-Fluoro-1,1′-binaphthalene-2′-sulfinyl hydrazide, optically active 2-methoxy-6,6′-difluoro-1,1′-binaphthalene-2′-sulfinyl hydrazide, optically active 2-methoxy-3 , 3′-Difluoro-1,1′-binaphthalene-2′-sulfinyl hydrazide, optically active 2-methoxy-6 Bromo-1,1′-binaphthalene-2′-sulfinyl hydrazide, optically active 2-methoxy-6,6′-dibromo-1,1′-binaphthalene-2′-sulfinylhydrazide, optically active 2-methoxy-3,3 '-Dibromo-1,1'-binaphthalene-2'-sulfinyl hydrazide, optically active 2-methoxy-6-iodo-1,1'-binaphthalene-2'-sulfinyl hydrazide, optically active 2-methoxy-6,6' -Diiodo-1,1'-binaphthalene-2'-sulfinylhydrazide, optically active 2-methoxy-3,3'-diiodo-1,1'-binaphthalene-2'-sulfinylhydrazide, 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-6,6′-dimethyl-1,1′-binaphthalene-2′-sulfinylhydrazide, optical Active 2-methoxy-6-tert-butyl-1,1′-binaphthalene-2′-sulfinylhydrazide, optically active 2-methoxy-6,6′-di (tert-butyl) -1,1′-binaphthalene-2 '-Sulfinylhydrazide, 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-methoxy-6,6′-bis (trifluoromethyl) -1,1′-bi Phthalene-2′-sulfinylhydrazide, optically active 2-methoxy-6-trimethylsilyl-1,1′-binaphthalene-2′-sulfinylhydrazide, optically active 2-methoxy-6,6′-bis (trimethylsilyl) -1,1 '-Binaphthalene-2'-sulfinyl hydrazide, optically active 2-methoxy-3,3'-dimethyl-6-bromo-1,1'-binaphthalene-2'-sulfinylhydrazide, 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′-sulfonyl hydrazide, optically active 2-methoxy-6-fluoro-1,1′-binaphthalene-2′-sulfonylhydrazide, optically active 2-methoxy-6, 6′-difluoro-1,1′-binaphthalene-2′-sulfonyl hydrazide, optically active 2-methoxy-3,3′-difluoro-1,1′-binaphthalene-2′-sulfonyl hydrazide, optically active 2-methoxy- 6-chloro-1,1′-binaphthalene-2′-sulfonyl hydrazide, optically active 2-methoxy-6,6′-dichloro-1,1′-binaphthalene-2′-sulfonylhydrazide, optically active 2-methoxy-3 , 3′-dichloro-1,1′-binaphthalene-2′-sulfonyl hydrazide, optically active 2-methoxy-6-bromo-1, '-Binaphthalene-2'-sulfonylhydrazide, optically active 2-methoxy-6,6'-dibromo-1,1'-binaphthalene-2'-sulfonylhydrazide, optically active 2-methoxy-3,3'-dibromo-1 , 1′-Binaphthalene-2′-sulfonylhydrazide, optically active 2-methoxy-6-iodo-1,1′-binaphthalene-2′-sulfonylhydrazide, optically active 2-methoxy-6,6′-diiodo-1, 1'-Binaphthalene-2'-sulfonylhydrazide, optically active 2-methoxy-3,3'-diiodo-1,1'-binaphthalene-2'-sulfonylhydrazide, optically active 2-methoxy-6-phenyl-1,1 '-Binaphthalene-2'-sulfonylhydrazide, optically active 2-methoxy-6,6'-diphenyl-1,1'-binaphthalene- '- sulfonyl hydrazide,

Optically active 2-methoxy-6-methyl-1,1′-binaphthalene-2′-sulfonyl hydrazide, optically active 2-methoxy-6,6′-dimethyl-1,1′-binaphthalene-2′-sulfonylhydrazide, optical Active 2-methoxy-6-tert-butyl-1,1′-binaphthalene-2′-sulfonylhydrazide, optically active 2-methoxy-6,6′-di (tert-butyl) -1,1′-binaphthalene-2 '-Sulfonylhydrazide, optically active 2-methoxy-3,3', 6-trimethyl-1,1'-binaphthalene-2'-sulfonylhydrazide, optically active 2-methoxy-6-trifluoromethyl-1,1'- Binaphthalene-2′-sulfonylhydrazide, optically active 2-methoxy-6,6′-bis (trifluoromethyl) -1,1′-binaphthalene— '-Sulfonylhydrazide, optically active 2-methoxy-6-trimethylsilyl-1,1'-binaphthalene-2'-sulfonylhydrazide, optically active 2-methoxy-6,6'-bis (trimethylsilyl) -1,1'-binaphthalene -2'-sulfonylhydrazide, optically active 2-methoxy-3,3'-dimethyl-6-bromo-1,1'-binaphthalene-2'-sulfonylhydrazide, optically active 2-methoxy-3,3'-di ( tert-butyl) -6-bromo-1,1'-binaphthalene-2'-sulfonylhydrazide, optically active 2-methoxy-3,3'-dimethyl-6- (trimethylsilyl) -1,1'-binaphthalene-2 ' -Sulfonyl hydrazide,

Optically active 2-methoxy-1,1′-binaphthalene-2′-sulfinylguanide, optically active 2-methoxy-6-chloro-1,1′-binaphthalene-2′-sulfinylguanide, optically active 2- Methoxy-6,6′-dichloro-1,1′-binaphthalene-2′-sulfinylguanidide, optically active 2-methoxy-3,3′-dichloro-1,1′-binaphthalene-2′-sulfinylguanide Zido, optically active 2-methoxy-6-fluoro-1,1'-binaphthalene-2'-sulfinylguanidide, optically active 2-methoxy-6,6'-difluoro-1,1'-binaphthalene-2'- Sulfinyl guanidide, optically active 2-methoxy-3,3′-difluoro-1,1′-binaphthalene-2′-sulfinyl guanidide, optically active 2-methoxy-6 Bromo-1,1′-binaphthalene-2′-sulfinylguanide, optically active 2-methoxy-6,6′-dibromo-1,1′-binaphthalene-2′-sulfinylguanide, optically active 2-methoxy -3,3'-dibromo-1,1'-binaphthalene-2'-sulfinylguanide, optically active 2-methoxy-6-iodo-1,1'-binaphthalene-2'-sulfinylguanidide, optically active 2-methoxy-6,6′-diiodo-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'-sulfinyl Heidelberg Ani disilazide,

Optically active 2-methoxy-6-methyl-1,1′-binaphthalene-2′-sulfinylguanidide, optically active 2-methoxy-6,6′-dimethyl-1,1′-binaphthalene-2′-sulfinyl Anidide, optically active 2-methoxy-6-tert-butyl-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-methoxy-6,6'-bis (trifluoromethyl) -1,1'-bi Phthalene-2′-sulfinylguanidide, optically active 2-methoxy-6-trimethylsilyl-1,1′-binaphthalene-2′-sulfinylguanidide, optically active 2-methoxy-6,6′-bis (trimethylsilyl) -1,1′-Binaphthalene-2′-sulfinylguanide, 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′-sulfinylguanidide, optically active 2-methoxy-3,3′-dimethyl-6 (Trimethylsilyl) -1,1′-binaphthalene-2′-sulfinylguanidide,

Optically active 2-methoxy-1,1′-binaphthalene-2′-sulfonylguanide, optically active 2-methoxy-6-chloro-1,1′-binaphthalene-2′-sulfonylguanidide, optically active 2- Methoxy-6,6′-dichloro-1,1′-binaphthalene-2′-sulfonylguanidide, optically active 2-methoxy-3,3′-dichloro-1,1′-binaphthalene-2′-sulfonylguanide Zido, optically active 2-methoxy-6-fluoro-1,1'-binaphthalene-2'-sulfonylguanidide, optically active 2-methoxy-6,6'-difluoro-1,1'-binaphthalene-2'- Sulfonyl guanidide, optically active 2-methoxy-3,3′-difluoro-1,1′-binaphthalene-2′-sulfonyl guanidide, optically active 2-methoxy-6-bromo-1, '-Binaphthalene-2'-sulfonylguanidide, optically active 2-methoxy-6,6'-dibromo-1,1'-binaphthalene-2'-sulfonylguanidide, optically active 2-methoxy-3,3' -Dibromo-1,1'-binaphthalene-2'-sulfonylguanidide, optically active 2-methoxy-6-iodo-1,1'-binaphthalene-2'-sulfonylguanidide, optically active 2-methoxy-6 , 6'-diiodo-1,1'-binaphthalene-2'-sulfonylguanide, optically active 2-methoxy-3,3'-diiodo-1,1'-binaphthalene-2'-sulfonylguanide, optical Active 2-methoxy-6-phenyl-1,1′-binaphthalene-2′-sulfonylguanidide, optically active 2-methoxy-6,6′-diphenyl-1,1′-binaphthalene- '- sulfonyl guanylyl disilazide,

Optically active 2-methoxy-6-methyl-1,1′-binaphthalene-2′-sulfonylguanide, optically active 2-methoxy-6,6′-dimethyl-1,1′-binaphthalene-2′-sulfonylguanide Anidide, optically active 2-methoxy-6-tert-butyl-1,1′-binaphthalene-2′-sulfonylguanidide, optically active 2-methoxy-6,6′-di (tert-butyl) -1, 1′-Binaphthalene-2′-sulfonylguanide, optically active 2-methoxy-3,3 ′, 6-trimethyl-1,1′-binaphthalene-2′-sulfonylguanidide, optically active 2-methoxy-6 -Trifluoromethyl-1,1'-binaphthalene-2'-sulfonylguanidide, optically active 2-methoxy-6,6'-bis (trifluoromethyl) -1,1'-binaphthalene- '-Sulfonylguanidide, optically active 2-methoxy-6-trimethylsilyl-1,1'-binaphthalene-2'-sulfonylguanidide, optically active 2-methoxy-6,6'-bis (trimethylsilyl) -1, 1′-Binaphthalene-2′-sulfonyl guanidide, optically active 2-methoxy-3,3′-dimethyl-6-bromo-1,1′-binaphthalene-2′-sulfonylguanidide, optically active 2-methoxy -3,3'-di (tert-butyl) -6-bromo-1,1'-binaphthalene-2'-sulfonylguanidide, optically active 2-methoxy-3,3'-dimethyl-6- (trimethylsilyl) -1,1'-binaphthalene-2'-sulfonylguanidide,

Optically active 2-methoxy-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-methoxy-6-chloro-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-methoxy- 6,6′-dichloro-1,1′-binaphthalene-2′-sulfinyl imidazolide, optically active 2-methoxy-3,3′-dichloro-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-methoxy-6-fluoro-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-methoxy-6,6′-difluoro-1,1′-binaphthalene-2′-sulfinylimidazolide, optical Active 2-methoxy-3,3′-difluoro-1,1′-binaphthalene-2′-sulfinyl imidazolide, optical activity 2 Methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-methoxy-6,6′-dibromo-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2 -Methoxy-3,3'-dibromo-1,1'-binaphthalene-2'-sulfinylimidazolide, optically active 2-methoxy-6-iodo-1,1'-binaphthalene-2'-sulfinylimidazolide, optically active 2-methoxy-6,6′-diiodo-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- Butoxy-6,6'-diphenyl-1,1'-binaphthalene-2'-sulfinyl imidazolide,

Optically active 2-methoxy-6-methyl-1,1′-binaphthalene-2′-sulfinylimidazolide, optically active 2-methoxy-6,6′-dimethyl-1,1′-binaphthalene-2′-sulfinylimidazolide , Optically active 2-methoxy-6-tert-butyl-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′-sulfinylimidazolide, optically active 2-methoxy-6,6′-bis (trifluoromethyl)- , 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′-binaphthalene-2′-sulfinylimidazolide,

Optically active 2-methoxy-1,1′-binaphthalene-2′-sulfonylimidazolide, optically active 2-methoxy-6-chloro-1,1′-binaphthalene-2′-sulfonylimidazolide, optically active 2-methoxy- 6,6′-Dichloro-1,1′-binaphthalene-2′-sulfonylimidazolide, optically active 2-methoxy-3,3′-dichloro-1,1′-binaphthalene-2′-sulfonylimidazolide, optically active 2-methoxy-6-fluoro-1,1′-binaphthalene-2′-sulfonyl imidazolide, optically active 2-methoxy-6,6′-difluoro-1,1′-binaphthalene-2′-sulfonyl imidazolide, optical Active 2-methoxy-3,3′-difluoro-1,1′-binaphthalene-2′-sulfonylimidazolide, optically active 2-methoxy-6 Bromo-1,1′-binaphthalene-2′-sulfonylimidazolide, optically active 2-methoxy-6,6′-dibromo-1,1′-binaphthalene-2′-sulfonylimidazolide, optically active 2-methoxy-3 , 3′-Dibromo-1,1′-binaphthalene-2′-sulfonylimidazolide, optically active 2-methoxy-6-iodo-1,1′-binaphthalene-2′-sulfonylimidazolide, optically active 2-methoxy- 6,6′-Diiodo-1,1′-binaphthalene-2′-sulfonylimidazolide, optically active 2-methoxy-3,3′-diiodo-1,1′-binaphthalene-2′-sulfonylimidazolide, optically active 2-methoxy-6-phenyl-1,1'-binaphthalene-2'-sulfonylimidazolide, optically active 2-methoxy-6,6'-diphenyl 1,1'-binaphthalene-2'-sulfonyl imidazolide,

Optically active 2-methoxy-6-methyl-1,1'-binaphthalene-2'-sulfonylimidazolide, optically active 2-methoxy-6,6'-dimethyl-1,1'-binaphthalene-2'-sulfonylimidazolide , Optically active 2-methoxy-6-tert-butyl-1,1′-binaphthalene-2′-sulfonylimidazolide, optically active 2-methoxy-6,6′-di (tert-butyl) -1,1′- Binaphthalene-2′-sulfonylimidazolide, optically active 2-methoxy-3,3 ′, 6-trimethyl-1,1′-binaphthalene-2′-sulfonylimidazolide, optically active 2-methoxy-6-trifluoromethyl- 1,1′-Binaphthalene-2′-sulfonylimidazolide, optically active 2-methoxy-6,6′-bis (trifluoromethyl) -1,1′-bi Phthalene-2′-sulfonylimidazolide, optically active 2-methoxy-6-trimethylsilyl-1,1′-binaphthalene-2′-sulfonylimidazolide, optically active 2-methoxy-6,6′-bis (trimethylsilyl) -1 , 1′-Binaphthalene-2′-sulfonylimidazolide, optically active 2-methoxy-3,3′-dimethyl-6-bromo-1,1′-binaphthalene-2′-sulfonylimidazolide, optically active 2-methoxy- 3,3′-di (tert-butyl) -6-bromo-1,1′-binaphthalene-2′-sulfonylimidazolide, optically active 2-methoxy-3,3′-dimethyl-6- (trimethylsilyl) -1 , 1′-binaphthalene-2′-sulfonylimidazolide,

Optically active 1,1′-binaphthalene-2,2′-disulfinic acid, optically active 6,6′-dibromo-1,1′-binaphthalene-2,2′-disulfinic acid, optically active 3,3′-dibromo- 1,1′-binaphthalene-2,2′-disulfinic acid, optically active 6,6′-dimethyl-1,1′-binaphthalene-2,2′-disulfinic acid, optically active 3,3′-dimethyl-1, 1′-Binaphthalene-2,2′-disulfinic acid, 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′-dibu Mo-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, optically active 2-sulfino-3,3'-dichloro-1,1'-binaphthalene-2'-sulfinamide, optically active 2-sulfino-3 , 3′-Dibromo-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'-bi Phthalene-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, optical 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′-sulfinylhydrazide, 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,

Optically active 1,1′-binaphthalene-2,2′-disulfonic acid, optically active 6,6′-dibromo-1,1′-binaphthalene-2,2′-disulfonic acid, optically active 3,3′-dibromo- 1,1′-binaphthalene-2,2′-disulfonic acid, optically active 6,6′-dimethyl-1,1′-binaphthalene-2,2′-disulfonic acid, optically active 3,3′-dimethyl-1, 1′-Binaphthalene-2,2′-disulfonic acid, optically active 2-sulfo-1,1′-binaphthalene-2′-sulfonamide, optically active 2-sulfo-6,6′-dibromo-1,1′- Binaphthalene-2′-sulfonamide, optically active 2-sulfo-3,3′-dibromo-1,1′-binaphthalene-2′-sulfonamide, optically active 2-sulfo-6,6′-diphenyl-1,1 '-Binaphthalene-2 -Sulfonamide, optically active 2-sulfo-6,6'-dimethyl-1,1'-binaphthalene-2'-sulfonamide, optically active 2-sulfo-6,6'-di (tert-butyl) -1, 1′-Binaphthalene-2′-sulfonamide, optically active 2-sulfo-6,6′-bis (trifluoromethyl) -1,1′-binaphthalene-2′-sulfonamide, optically active 2-sulfo-6 6′-bis (trimethylsilyl) -1,1′-binaphthalene-2′-sulfonamide, optically active 2-sulfo-3,3′-dimethyl-1,1′-binaphthalene-2′-sulfonamide, optically active 2 -Sulfo-3,3'-di (tert-butyl) -1,1'-binaphthalene-2'-sulfonamide,

Optically active N-isopropyl-2-sulfo-1,1′-binaphthalene-2′-sulfonamide, optically active N-isopropyl-2-sulfo-6,6′-dibromo-1,1′-binaphthalene-2′- Sulfonamide, optically active N-isopropyl-2-sulfo-3,3′-dibromo-1,1′-binaphthalene-2′-sulfonamide, optically active N-isopropyl-2-sulfo-6,6′-diphenyl- 1,1′-Binaphthalene-2′-sulfonamide, optically active N-isopropyl-2-sulfo-6,6′-dimethyl-1,1′-binaphthalene-2′-sulfonamide, optically active N-isopropyl-2 -Sulfo-6,6'-di (tert-butyl) -1,1'-binaphthalene-2'-sulfonamide, optically active N-isopropyl-2-sulfo-6,6 ' Bis (trifluoromethyl) -1,1′-binaphthalene-2′-sulfonamide, optically active N-isopropyl-2-sulfo-6,6′-bis (trimethylsilyl) -1,1′-binaphthalene-2′- Sulfonamide, optically active N-isopropyl-2-sulfo-3,3′-dimethyl-1,1′-binaphthalene-2′-sulfonamide, optically active N-isopropyl-2-sulfo-3,3′-di ( tert-butyl) -1,1'-binaphthalene-2'-sulfonamide,

Optically active 2-sulfo-1,1′-binaphthalene-2′-sulfonyl hydrazide, optically active 2-sulfo-6,6′-dibromo-1,1′-binaphthalene-2′-sulfonylhydrazide, optically active 2-sulfo -3,3'-dibromo-1,1'-binaphthalene-2'-sulfonylhydrazide, optically active 2-sulfo-6,6'-diphenyl-1,1'-binaphthalene-2'-sulfonylhydrazide, optically active 2 -Sulfo-6,6'-dimethyl-1,1'-binaphthalene-2'-sulfonylhydrazide, optically active 2-sulfo-6,6'-di (tert-butyl) -1,1'-binaphthalene-2 ' -Sulfonyl hydrazide, optically active 2-sulfo-6,6'-bis (trifluoromethyl) -1,1'-binaphthalene-2'-sulfonylhydrazide, optically active -Sulfo-6,6'-bis (trimethylsilyl) -1,1'-binaphthalene-2'-sulfonylhydrazide, optically active 2-sulfo-3,3'-dimethyl-1,1'-binaphthalene-2'-sulfonyl Hydrazide, optically active 2-sulfo-3,3′-di (tert-butyl) -1,1′-binaphthalene-2′-sulfonylhydrazide,

Optically active 2-sulfo-1,1′-binaphthalene-2′-sulfonylguanidide, optically active 2-sulfo-6,6′-dibromo-1,1′-binaphthalene-2′-sulfonylguanide, optical Active 2-sulfo-3,3′-dibromo-1,1′-binaphthalene-2′-sulfonylguanidide, optically active 2-sulfo-6,6′-diphenyl-1,1′-binaphthalene-2′- Sulfonylguanidide, optically active 2-sulfo-6,6′-dimethyl-1,1′-binaphthalene-2′-sulfonylguanidide, optically active 2-sulfo-6,6′-di (tert-butyl) -1,1′-binaphthalene-2′-sulfonylguanide, optically active 2-sulfo-6,6′-bis (trifluoromethyl) -1,1′-binaphthalene-2′-sulfonylguanide, optical Activity -Sulfo-6,6'-bis (trimethylsilyl) -1,1'-binaphthalene-2'-sulfonylguanidide, optically active 2-sulfo-3,3'-dimethyl-1,1'-binaphthalene-2 ' -Sulfonyl guanidide, optically active 2-sulfo-3,3'-di (tert-butyl) -1,1'-binaphthalene-2'-sulfonyl guanide, etc. can be mentioned.

This optically active binaphthyl compound is an axially asymmetric compound, and there are two optical isomers, an (R) isomer and an (S) isomer. Such an optically active binaphthyl compound has a substituent having reactivity with a compound to be analyzed, such as an unsubstituted amino group, a substituted amino group, or an alkyl group, at the terminal end of the substituent at the 2 ′ position (ie, R ² ), For example, since it is a leaving group having reactivity with the compound to be analyzed such as a hydroxyl group, a halogen atom, a substituted amino group, a heteroaryl group, etc., not only an optically active alcohol whose absolute configuration is unknown, but also other carboxylic acids, etc. It can be used as a chiral shift reagent for NMR, which introduces an asymmetric auxiliary group into an optically active compound, and the aromatic compound possessed by the asymmetric auxiliary group is analyzed by NMR analysis of the compound introduced with the asymmetric auxiliary group using such a chiral shift reagent for NMR. By utilizing the anisotropic effect of the ring, the absolute configuration of the optically active compound whose absolute configuration is unknown can be determined. In addition, 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.

  As a method for determining the absolute configuration of an optically active compound having an unknown absolute configuration using the NMR chiral shift reagent of the present invention, for example, a known Moscher method may be used. In addition, using the chiral shift reagent for NMR of the present invention, an asymmetric auxiliary group is introduced into an optically active compound whose absolute configuration is unknown, and the NOE spectrum and NOESY spectrum of the compound into which the asymmetric auxiliary group is introduced are measured. A method for performing the conformation analysis may be performed in accordance with a known NOE spectrum or NOESY spectrum measurement method, a conformation analysis method thereof, and the like.

  As a method for producing the present optically active binaphthyl compound, for example, a known synthesis method or the like from a known compound may be used. A typical method for producing a compound will be described below.

（式中、Ｘはハロゲン原子を表わし、Ｙはメトキシ基または炭素数１〜４のパーフルオロアルコキシ基を表わす。）
で示される光学活性ビナフチル化合物（以下、光学活性ビナフチル化合物（２）と記すこともある。）は、下記式（３）

（式中、Ｒ⁶は炭素数１〜４のアルキル基を表わし、Ｙ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（３）と記すこともある。）とＮ−ハロスクシンイミドと炭素数１〜４の一級アルコールとを反応させて、式（４）

（式中、Ｒ⁷は炭素数１〜４の直鎖状アルコキシ基を表わし、ＸおよびＹ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（４）と記すこともある。）を得、前記光学活性化合物（４）をアルカリ処理し、次いで酸性化処理することにより製造することができる（スキーム１参照。）。

First, among the optically active binaphthyl compounds, n is 1, R ¹ is a methoxy group or a C 1-4 perfluoroalkoxy group, R ² is a hydroxyl group, R ³ and R ⁵ are hydrogen atoms, R ^{The following} formula (2), wherein ⁴ is a halogen atom

(In the formula, X represents a halogen atom, and Y represents a methoxy group or a perfluoroalkoxy group having 1 to 4 carbon atoms.)
An optically active binaphthyl compound represented by the formula (hereinafter sometimes referred to as an optically active binaphthyl compound (2)) is represented by the following formula (3):

(Wherein R ⁶ represents an alkyl group having 1 to 4 carbon atoms, and Y represents the same meaning as described above.)
Is reacted with an optically active carbamate compound (hereinafter also referred to as an optically active carbamate compound (3)), N-halosuccinimide, and a primary alcohol having 1 to 4 carbon atoms.

(In the formula, R ⁷ represents a linear alkoxy group having 1 to 4 carbon atoms, and X and Y have the same meaning as described above.)
Can be produced by subjecting the optically active compound (4) to an alkali treatment and then an acidification treatment (hereinafter referred to as an optically active compound (4)). (See Scheme 1).

  Examples of the optically active carbamate compound (3) 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-nonafluorobutoxy-1,1′-binaphthalene-2′-thiol N, N-dimethylcarbamate, optically active 2-methoxy-1,1′- Binaphthalene-2'-thiol N, N-diethyl carbamate That.

  Examples of the primary alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, and n-butanol. The amount used is usually 1 mole or more with respect to the optically active carbamate compound (3). The upper limit is not particularly limited, and a large excess amount may be used also as a solvent.

  Examples of N-halosuccinimide include N-bromosuccinimide and N-chlorosuccinimide. The amount of use is usually 1 to 5 mol times, preferably 2 to 4 mol times based on the optically active carbamate compound (3).

  The reaction of the optically active carbamate compound (3), N-halosuccinimide and a primary alcohol having 1 to 4 carbon atoms is usually carried out by mixing the three in a solvent. As described above, a primary alcohol having 1 to 4 carbon atoms may be used as the solvent. For example, an ether solvent such as tetrahydrofuran, an aromatic hydrocarbon solvent such as toluene, and a halogenated hydrocarbon solvent such as chloroform. A solvent such as an ester solvent such as ethyl acetate may be used alone or in combination. The amount of such solvent 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 compound (4) can be taken out by concentrating the reaction solution. Further, 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 the optically active compound (4). It can also be taken out. The taken out optically active compound (4) may be further purified by ordinary purification means such as recrystallization and column chromatography. Examples of the organic solvent insoluble in water include aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chloroform, dichloromethane and chlorobenzene, and ester solvents such as ethyl acetate.

  Examples of the optically active compound (4) include optically active 2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinate methyl, optically active 2-methoxy-6-bromo-1,1′-. Binaphthalene-2'-ethyl sulfinate, optically active 2-methoxy-6-chloro-1,1'-binaphthalene-2'-sulfinic acid methyl, optically active 2-methoxy-6-chloro-1,1'-binaphthalene- 2'-ethyl sulfinate, 2-trifluoromethoxy-6-bromo-1,1'-binaphthalene-2'-sulfinate methyl, optically active 2-trifluoromethoxy-6-bromo-1,1'-binaphthalene- 2′-ethyl sulfinate, 2-pentafluoroethoxy-6-bromo-1,1′-binaphthalene-2′-sulfinate methyl, optically active 2-pe Tafluoroethoxy-6-bromo-1,1′-binaphthalene-2′-sulfinate ethyl, 2-heptafluoropropoxy-6-bromo-1,1′-binaphthalene-2′-sulfinate methyl, optically active 2- Heptafluoropropoxy-6-bromo-1,1′-binaphthalene-2′-sulfinate ethyl, 2-nonafluorobutoxy-6-bromo-1,1′-binaphthalene-2′-sulfinate methyl, optical activity 2- Nonafluorobutoxy-6-bromo-1,1'-binaphthalene-2'-ethyl sulfinate and the like can be mentioned.

  The optically active binaphthyl compound (2) can be obtained by subjecting the optically active compound (4) thus obtained to an alkali treatment and then an acidification treatment. The alkali treatment is usually carried out by mixing the optically active compound (4) and an alkali such as sodium hydroxide in an organic solvent. The amount of alkali used is usually 1 mol times or more with respect to the optically active compound (4), and there is no particular upper limit. 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, for example, removing the solvent of the alkali treatment solution, adding chloroform or the like to remove insoluble alkali by filtration, and treating the concentrate of the filtrate with an acid column packed with silica gel or the like. Is implemented. Moreover, you may implement by mixing the said alkali treatment liquid and mineral acids, such as hydrochloric acid, and acidifying. The amount of acid used varies depending on the amount of alkali used in the alkali treatment, and the amount that the acidification treatment solution exhibits acidity is used. The treatment temperature of the acidification treatment is usually 0 to 100 ° C. When a mineral acid such as hydrochloric acid is mixed and acidified, the optically active binaphthyl compound (2) can be extracted by a normal extraction operation such as extraction.

（式中、ＸおよびＹは上記と同一の意味を表わし、Ｘ’はハロゲン原子を表わす。）
で示される光学活性ビナフチル化合物（以下、光学活性ビナフチル化合物（５）と記すこともある。）は、前記光学活性ビナフチル化合物（２）と、例えば塩化チオニル等のハロゲン化剤とを反応させることにより得ることができる（下記スキーム２参照。）。かかるハロゲン化は、カルボン酸とハロゲン化剤を反応させてカルボン酸ハロゲン化物を得る公知の方法に準じて行えばよい。

Among the present optically active binaphthyl compounds, n is 1, R ¹ is a methoxy group or a C 1-4 perfluoroalkoxy group, R ² is a halogen atom, R ³ and R ⁵ are hydrogen atoms, R ⁴ In which is a halogen atom (5)

(Wherein X and Y represent the same meaning as described above, and X ′ represents a halogen atom.)
The optically active binaphthyl compound represented by the formula (hereinafter sometimes referred to as optically active binaphthyl compound (5)) is obtained by reacting the optically active binaphthyl compound (2) with a halogenating agent such as thionyl chloride. Can be obtained (see Scheme 2 below). Such halogenation may be performed according to a known method for obtaining a carboxylic acid halide by reacting a carboxylic acid with a halogenating agent.

（式中、ＸおよびＹは上記と同一の意味を表わし、Ｒ⁸は無置換もしくは置換アミノ基を表わす。）
で示される光学活性ビナフチル化合物（以下、光学活性ビナフチル化合物（６）と記すこともある。）を得ることができる（下記スキーム３参照。）。

By reacting the optically active binaphthyl compound (5) with ammonia or an amine compound such as isopropylamine, hydrazine, guanidine, imidazole, etc., among the optically active binaphthyl compounds, n is 1 and R ¹ is a methyl group or A perfluoroalkoxy group having 1 to 4 carbon atoms, wherein R ² is an unsubstituted or substituted amino group, R ³ and R ⁵ are hydrogen atoms, and R ⁴ is a halogen atom;

(Wherein X and Y represent the same meaning as described above, and R ⁸ represents an unsubstituted or substituted amino group.)
(Hereinafter also referred to as an optically active binaphthyl compound (6)) (see Scheme 3 below).

  The reaction between the optically active binaphthyl compound (5) 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. For example, when an amine compound having a plurality of reaction points such as guanidine is used, an amine compound protected with a protecting group such as guanylurea sulfate may be used.

  Furthermore, the optically active binaphthyl compound (2) can be converted into an optically active binaphthyl compound in which the halogen atom at the 6-position is replaced with a hydrogen atom, for example, by reacting with butyllithium.

Further, the optically active binaphthyl compound (2), the optically active binaphthyl compound (5) or the optically active binaphthyl compound (6) is subjected to 6-position by, for example, reduction, phenylation, alkylation, perfluoroalkylation or silylation. Can be converted into an optically active binaphthyl compound in place of a hydrogen 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. Such reduction, phenylation, alkylation, perfluoroalkylation or silylation can be achieved by reducing, phenylating, alkylating, perfluoroalkylating or silylating aromatic halides to form phenyl-substituted aromatic compounds, alkyl-substituted aromatics. A known method for obtaining a compound, a perfluoroalkyl-substituted aromatic compound or a silyl-substituted aromatic compound may be used. Alternatively, the optically active binaphthyl compound (5) and an alcohol having 1 to 40 carbon atoms are reacted in the presence of a base such as methylimidazole, or the optically active binaphthyl compound (6) is reacted in the presence of an acid catalyst such as trifluoroacetic acid. By carrying out the amide-ester exchange reaction, an optically active sulfinic acid compound other than a linear alkoxy group having ² to 4 carbon atoms can be produced.

（式中、Ｒ⁶は上記と同一の意味を表わし、Ｘ’’はハロゲン原子を表わす。）
で示される化合物（以下、化合物（７）と記すこともある。）とを、塩基の存在下に反応させて、式（８）

（式中、Ｒ⁶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）と記すこともある。）を得、該光学活性化合物（８）と、例えばメチル化剤等の試剤とを、塩基の存在下に反応させて、式（９）

（式中、ＹおよびＲ⁶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（９）と記すこともある。）を得、該光学活性化合物（９）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４参照。）。

In addition, the said optically active carbamate compound (3) is optically active 1,1'- binaphthalene-2,2'-diol and Formula (7) according to the method described in Synlett, 1054 (1996), for example.

(Wherein R ⁶ represents the same meaning as described above, and X ″ represents a halogen atom.)
And a compound represented by formula (8) (hereinafter also referred to as compound (7)) in the presence of a base,

(Wherein R ⁶ represents the same meaning as described above.)
And the optically active compound (8) and a reagent such as a methylating agent are reacted in the presence of a base. Let equation (9)

(In the formula, Y and R ⁶ have the same meaning as described above.)
Can be produced by subjecting the optically active compound (9) to a thermal rearrangement reaction (see Scheme 4 below). ).

  In the formula of the compound (7), X ″ represents a halogen atom, and examples thereof include a chlorine atom, a bromine atom and an iodine atom. Examples of the compound (7) include N, N-dimethylthiocarbamoyl chloride, N, N-dimethylthiocarbamoyl bromide, N, N-diethylthiocarbamoyl chloride and the like can be mentioned, and commercially available products are usually used.

  The amount of compound (7) 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. The amount used is usually 1 to 2 mol times the optically active 1,1'-binaphthalene-2,2'-diol.

  The reaction between the compound (7) 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 an inert solvent. For example, amide solvents such as N, N-dimethylformamide can 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 an aqueous alkali solution are mixed, an organic solvent insoluble in water is added thereto, extraction treatment is performed, and the resulting organic layer is concentrated to extract the optically active compound (8). Can do. Moreover, you may synthesize | combine optically active compound (9) within the same system, without isolating after completion | finish of reaction.

  Examples of the optically active compound (8) 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 can be mentioned.

The reagent such as a methylating agent that reacts with the optically active compound (8) can be appropriately selected according to the substituent R ^1. For example, when R ¹ is a methoxy group, the methylating agent is, for example, R ^1. Is a perfluoroalkoxy group having 1 to 4 carbon atoms, a perfluoroalkylating agent is used. Examples of the methylating agent include methyl halides such as methyl iodide, methyl bromide, and methyl chloride. The usage-amount is 1 to 2 mol times normally with respect to an optically active compound (8).

  Examples of the base include alkali metal hydrides such as sodium hydride. The usage-amount is 1-2 mole times normally with respect to an optically active compound (8).

  The reaction between the optically active compound (8) and the methylating agent is usually carried out by mixing the two in a solvent, and the solvent may be any solvent inert to the reaction. For example, N, N -Amide type solvents such as dimethylformamide. 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 an aqueous alkaline solution are mixed, an organic solvent insoluble in water is added thereto, extraction treatment is performed, and the resulting organic layer is concentrated to extract the optically active compound (9). Can do.

  Examples of the optically active compound (9) include optically active 2-methoxy-1,1′-binaphthalene-2′-ol N, N-dimethylthiocarbamate, optically active 2-trifluoromethoxy-1,1′-binaphthalene- 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-nonafluorobutoxy-1,1'-binaphthalen-2'-ol N, N-dimethylthiocarbamate, optically active 2-methoxy-1 , 1'-Binaphthalen-2'-ol N, N-diethylthiocarbamate That.

  The thermal rearrangement reaction of the optically active compound (9) is usually carried out by heating the optically active compound (9) as it is or in the presence of a solvent, if necessary, to 240 to 300 ° C. After completion of the reaction, it may be used for the reaction with the N-halosuccinimide as it is, or the reaction solution is recrystallized, for example, to take out the obtained optically active carbamate compound (3), and with the N-halosuccinimide. It may be used for the reaction.

（式中、Ｙは上記と同一の意味を表わし、Ｒ⁹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ビナフチル化合物（以下、光学活性ビナフチル化合物（１０）と記すこともある。）の製造方法について説明する。 Subsequently, in the present optically active binaphthyl compound, n is 1, R ¹ is a methoxy group or a C 1-4 perfluoroalkoxy group, R ² is a hydroxyl group, R ³ is a hydrogen atom, 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 the same group as R ⁴ (10 )

Wherein Y represents the same meaning as described above, and R ⁹ 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 an optically active binaphthyl compound represented by the formula (hereinafter sometimes referred to as optically active binaphthyl compound (10)) will be described.

（式中、Ｙ、Ｒ⁶およびＲ⁹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（１１）と記すこともある。）を用い、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 binaphthyl compound (2), the optically active binaphthyl compound (10) is replaced by the following formula (11) instead of the optically active carbamate compound (3).

(In the formula, Y, R ⁶ and R ⁹ represent the same meaning as described above.)
It can manufacture by carrying out similarly using the optically active carbamate compound shown by (Hereinafter, it may be described as an optically active carbamate compound (11).).

  Examples of the optically active carbamate compound (11) 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′-dichloro-1,1′-binaphthalene-2′-thiol N , N-dimethylcarbamate, optically active 2-trifluoromethoxy-6,6′-dichloro-1,1′-binaphthalene-2′-thiol N, N-dimethylcarbamate, optically active 2-methoxy-6,6′- Difluoro-1,1′-binaphthalene-2′-thiol N, N-dimethylcarbamate, optically active 2-trifluoromethoxy- 6,6′-difluoro-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 Carbamates can be mentioned.

The obtained optically active binaphthyl compound (10) is halogenated and aminated, for example, in the same manner as in Scheme 2 and Scheme 3, so that n is 1 and R ¹ is a methoxy group or a carbon number of 1 to 4 A perfluoroalkoxy group, R ² is a halogen atom, or an unsubstituted or substituted amino group, 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, perfluoroalkyl group or a trisubstituted silyl group having 1 to 4 carbon atoms, can be R ⁵ is obtained an optically active binaphthyl compound of the same group as R ^4.

（式中、Ｒ⁹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４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（１２）で示される光学活性ビナフタレン化合物は、例えば市販の光学活性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。 The optically active carbamate compound (11) is replaced with the following formula (12) in the scheme 4 instead of the optically active 1,1′-binaphthalene-2,2′-diol.

(Wherein R ⁹ represents the same meaning as described above.)
It can manufacture by implementing similarly to the said scheme 4 using the optically active binaphthalene compound shown by these. The optically active binaphthalene compound represented by the formula (12) can be easily obtained from, for example, a commercially available optically active 6,6′-dibromo-1,1′-binaphthalene-2,2′-diol.

In the optically active binaphthyl compound (1), n is 1, R ¹ is a methoxy group or a C 1-4 perfluoroalkoxy group, R ² is a hydroxyl group, R ³ is a halogen atom, R ^In the optically active binaphthyl compound in which ⁴ and R ⁵ are hydrogen atoms, the hydrogen atoms at the 3rd and 3 ′ positions of the optically active carbamate compound (3) are replaced with halogen atoms instead of the optically active carbamate compound (3). It can manufacture by implementing similarly to the above using the compound which was prepared.

（式中、ＸおよびＹは上記と同一の意味を表わし、Ｒ¹⁰は水素原子、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ビナフチル化合物（以下、光学活性ビナフチル化合物（１３）と記すこともある。）の製造方法について説明する。 Subsequently, among the optically active binaphthyl compounds, n is 1, R ¹ is a methoxy group or a perfluoroalkoxy group having 1 to 4 carbon atoms, R ² is a hydroxyl group, R ³ is a hydrogen atom, a phenyl group, The following formula (13): 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 ⁴ is a halogen atom and R ⁵ is a hydrogen atom

(In the formula, X and Y represent the same meaning as described above, and R ¹⁰ represents a hydrogen 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 an optically active binaphthyl compound represented by the formula (hereinafter sometimes referred to as an optically active binaphthyl compound (13)) will be described.

（式中、Ｙ、Ｒ⁶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（１４）と記すこともある。）を用い、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 binaphthyl compound (2), the optically active binaphthyl compound (13) is replaced by the following formula (14) instead of the optically active carbamate compound (3).

(In the formula, Y, R ⁶ and R ¹⁰ have the same meaning as described above.)
It can manufacture by carrying out similarly using the optically active carbamate compound shown below (it may be described hereafter as an optically active carbamate compound (14)).

  Examples of the optically active carbamate compound (14) include 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-dimethylcarbamate, optically active 2-methoxy-3,3′-bis (trimethylsilyl) -1,1′-binaphthalene-2′-thiol N, N-dimethylcarbamate, optically active 2-trifluoromethoxy-3,3′-dimethyl-1,1′-binaphthalene-2′-thiol N, N-dimethylcarbamate, optically active 2-trifluoromethoxy-3, 3′-diphenyl-1,1′-binaphthalene-2′-thiol N, N-dimethylcarbamate, optically active 2-tri And fluoromethoxy-3,3'-bis (trimethylsilyl) -1,1'-binaphthalene-2'-thiol N, N-dimethylcarbamate.

The optically active binaphthyl compound (13) is halogenated and aminated, for example, in the same manner as in Scheme 2 and Scheme 3, so that R ⁶ of the optically active binaphthyl compound represented by the formula (13) is a halogen atom, or An optically active binaphthyl compound substituted with an unsubstituted or substituted amino group can be obtained.

  Further, by reacting the optically active binaphthyl compound (13) with, for example, butyllithium, an optically active binaphthyl compound in which the halogen atom at the 6-position is replaced with a hydrogen atom can be obtained. For example, alkylation, phenylation, perfluoro Optically active binaphthyl compound in which the halogen atom at the 6-position is replaced by an alkyl group having 1 to 4 carbon atoms, a phenyl group, a perfluoroalkyl group having 1 to 4 carbon atoms, or a trisubstituted silyl group by alkylation or silylation Is obtained.

（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４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（１５）で示される光学活性ビナフタレン化合物は、例えば市販の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製造することができる。 The optically active carbamate compound (14) is replaced with the following formula (15) in the scheme 4 instead of the optically active 1,1′-binaphthalene-2,2′-diol.

(In the formula, R ¹⁰ represents the same meaning as described above.)
It can manufacture by implementing similarly to the said scheme 4 using the optically active binaphthalene compound shown by these. The optically active binaphthalene compound represented by the formula (15) can be easily produced from, for example, commercially available 3,3′-dibromo-1,1′-binaphthalene-2,2′-diol.

The optically active binaphthyl compound (2), the optically active binaphthyl compound (10), or the optically active binaphthyl compound (13) is oxidized with an oxidizing agent such as m-chloroperbenzoic acid, for example. In 1), an optically active binaphthyl compound in which n is 2, R ¹ is a methoxy group or a perfluoroalkoxy group having 1 to 4 carbon atoms, and R ² is a hydroxyl group can be obtained. Such oxidation treatment may be performed according to a known method of oxidizing a sulfinic acid compound to convert it into a sulfonic acid compound.

The obtained optically active binaphthyl compound in which n is 2, R ¹ is a methoxy group or a perfluoroalkoxy group having 1 to 4 carbon atoms, and R ² is a hydroxyl group is subjected to halogenation, amination, etc. as described above. To obtain an optically active binaphthyl compound in which R ² is a halogen atom, an unsubstituted or substituted amino group, R ¹ is a methoxy group or a perfluoroalkoxy group having 1 to 4 carbon atoms, and n is 2. it can.

（式中、ＸおよびＹは上記と同一の意味を表わし、Ｒ¹¹は、水素原子、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）Ｒ¹¹が水素原子のときにＲ¹²はハロゲン原子を、Ｒ¹³は水素原子を表わすか、またはＲ¹²は水素原子、臭素原子、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若しくは三置換シリル基を表わし、Ｒ¹³はＲ¹²と同一の基を表わす。（ｂ）Ｒ¹¹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Ｒ¹²はハロゲン原子を、Ｒ¹³は水素原子を表わす。）
で示される光学活性スルホン酸ハロゲン化物（以下、光学活性スルホン酸ハロゲン化物（１６）と記すこともある。）を得、該光学活性スルホン酸ハロゲン化物（１６）を、アルカリ処理および酸性化処理、さらにエステル化、アミノ化等することにより、ｎが２である光学活性ビナフチル化合物を得ることもできる。 In addition, by reacting the optically active carbamate compound (3), the optically active carbamate compound (10) or the optically active carbamate compound (13) with N-halosuccinimide in the presence of a tertiary alcohol, the following formula ( 16)

(Wherein, X and Y represent the same meaning as described above, and R ¹¹ represents a hydrogen 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) When R ¹¹ is a hydrogen atom, R ¹² represents a halogen atom, R ¹³ represents a hydrogen atom, or R ¹² represents a hydrogen atom, a bromine atom, a phenyl group, or an alkyl having 1 to 4 carbon atoms. A group, a C 1-4 perfluoroalkyl group or a trisubstituted silyl group, R ¹³ represents the same group as R ^12. (b) R ¹¹ is a phenyl group, a C 1-4 alkyl group, (In the case of a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group, R ¹² represents a halogen atom, and R ¹³ represents a hydrogen atom.)
An optically active sulfonic acid halide represented by the following (hereinafter sometimes referred to as optically active sulfonic acid halide (16)), and the optically active sulfonic acid halide (16) is subjected to alkali treatment and acidification treatment, Furthermore, an optically active binaphthyl compound in which n is 2 can also be obtained by esterification, amination or the like.

  Examples of the tertiary alcohol include tert-butanol. The amount used is usually 1 mole or more based on the optically active carbamate compound (3), optically active carbamate compound (10) or optically active carbamate compound (13), and the upper limit is not particularly limited.

  Examples of the N-halosuccinimide include the same as those described above, and the amount used thereof is based on the optically active carbamate compound (3), the optically active carbamate compound (10) or the optically active carbamate compound (13). Usually, it is 1-5 mol times, Preferably it is 2-4 mol times.

  The reaction of optically active carbamate compound (3), optically active carbamate compound (10) or optically active carbamate compound (13) with N-halosuccinimide is usually carried out in a solvent in the presence of optically active carbamate compound (3), optically active carbamate compound ( 10) or an optically active carbamate compound (13), N-halosuccinimide and a tertiary alcohol are mixed. Examples of the solvent include ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene, halogenated hydrocarbon solvents such as chloroform, and ester solvents such as ethyl acetate alone or mixed solvents. The amount used is not particularly limited. A tertiary alcohol may also be used as a solvent.

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

  After completion of the reaction, the optically active sulfonic acid halide (16) can be taken out by, for example, concentrating the reaction solution. Further, the reaction solution is directly or after being concentrated, and then extracted by adding water and, if necessary, an organic solvent insoluble in water. The resulting organic layer is concentrated, whereby an optically active sulfonic acid halide ( 16) can also be taken out. The taken out optically active sulfonic acid halide (16) may be further purified by ordinary purification means such as recrystallization and column chromatography.

  The obtained optically active sulfonic acid halide (16) can be converted to sulfonic acid amide or the like by reacting with the amino compound or the like, for example.

で示される基を表わし、Ｒ²およびＲ¹⁴が同一の水酸基、ハロゲン原子または無置換もしくは置換アミノ基を表わすか、または、Ｒ²が無置換もしくは置換アミノ基で、Ｒ¹⁴が水酸基を表わし、Ｒ³およびＲ⁴のうちのいずれか一方が、水素原子を、他方が、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がＲ⁴と同一の基を表わす下記式（１７）

（式中、Ｒ¹⁴およびＲ¹⁵が同一の水酸基、ハロゲン原子または無置換もしくは置換アミノ基を表わすか、または、Ｒ¹⁴が水酸基で、Ｒ¹⁵が無置換もしくは置換アミノ基を表わし、Ｒ¹⁶およびＲ¹⁷のうちのいずれか一方が、水素原子を、他方が、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ビナフチル化合物（以下、光学活性ビナフチル化合物（１７）と記すこともある。）の製造方法について説明する。 Subsequently, in the present optically active binaphthyl compound, n represents ¹ , R ¹ is

R ² and R ¹⁴ represent the same hydroxyl group, a halogen atom or an unsubstituted or substituted amino group, or R ² represents an unsubstituted or substituted amino group, and R ¹⁴ represents a hydroxyl group, One of R ³ and R ⁴ is a hydrogen atom, and the other 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 three A substituted silyl group, wherein R ⁵ represents the same group as R ⁴

(Wherein R ¹⁴ and R ¹⁵ represent the same hydroxyl group, halogen atom or unsubstituted or substituted amino group, or R ¹⁴ represents a hydroxyl group, R ¹⁵ represents an unsubstituted or substituted amino group, R ¹⁶ and One of R ¹⁷ is a hydrogen atom, and the other 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. Represents.)
A method for producing an optically active binaphthyl compound represented by the formula (hereinafter sometimes referred to as an optically active binaphthyl compound (17)) will be described.

（式中、Ｒ¹⁶およびＲ¹⁷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チル化合物（以下、光学活性ビナフチル化合物（１８）と記すこともある。）は、下記式（１９）

（式中、Ｒ⁶、Ｒ¹⁶およびＲ¹⁷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（１９）と記すこともある。）とＮ−ハロスクシンイミドと炭素数１〜４の一級アルコールとを反応させて得られる下記式（２０）

（式中、Ｒ⁷、Ｒ¹⁶およびＲ¹⁷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をアルカリ処理し、次いで酸性化処理することにより製造できる。 Of the optically active binaphthyl compound (17), the following formula (18), wherein R ¹⁴ and R ¹⁵ are hydroxyl groups:

(Wherein R ¹⁶ and R ¹⁷ represent the same meaning as described above.)
An optically active binaphthyl compound represented by formula (hereinafter also referred to as an optically active binaphthyl compound (18)) is represented by the following formula (19).

(Wherein R ⁶ , R ¹⁶ and R ¹⁷ represent the same meaning as described above.)
The following formula (1) obtained by reacting an optically active biscarbamate compound (hereinafter also referred to as optically active biscarbamate compound (19)), N-halosuccinimide, and a primary alcohol having 1 to 4 carbon atoms ( 20)

(Wherein R ⁷ , R ¹⁶ and R ¹⁷ represent the same meaning as described above.)
It can manufacture by carrying out the alkali treatment of the optically active compound shown by and then acidifying.

  Examples of the optically active biscarbamate compound (19) include optically active 1,1′-binaphthalene-2,2′-dithiol bis (N, N-dimethylcarbamate), optically active 1,1′-binaphthalene-2,2 ′. -Dithiol bis (N, N-diethyl carbamate), optically active 1,1'-binaphthyl-6,6'-dimethyl-2,2'-dithiol bis (N, N-dimethylcarbamate), optically active 1,1 ' -Binaphthyl-3,3'-dimethyl-2,2'-dithiol bis (N, N-dimethylcarbamate) and the like.

  As N-halosuccinimide, the same thing as mentioned above is mentioned, The usage-amount is 1-20 mol times normally with respect to an optically active biscarbamate compound (19), Preferably it is 10-15 mol times. is there. The use amount of the primary alcohol having 1 to 4 carbon atoms is usually 2 mole times or more with respect to the optically active biscarbamate compound (19), and the upper limit is not particularly limited. Also good.

  The reaction of the optically active biscarbamate compound (19), N-halosuccinimide and a 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 compound (20) can be taken out 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, whereby the optically active compound (20) is taken out. You can also.

  The method of treating the optically active compound (2) with an alkali and then treating with an acid is the same as the method for obtaining the optically active binaphthyl compound (2) by treating the optically active compound (4) with an alkali and then treating with an acid. A method is mentioned.

（式中、Ｘ’、Ｒ¹⁶およびＲ¹⁷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チル化合物（以下、光学活性ビナフチル化合物（２１）と記すこともある。）は、前記光学活性ビナフチル化合物（１８）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。光学活性ビナフチル化合物（１８）とハロゲン化剤との反応は、ジカルボン酸とハロゲン化剤とを反応させてジカルボン酸ジハロゲン化物を製造する方法に準じて行えばよい。 Of the optically active binaphthyl compound (17), R ¹⁴ and R ¹⁵ are the same halogen atom, and the following formula (21)

(In the formula, X ′, R ¹⁶ and R ¹⁷ represent the same meaning as described above.)
Can be produced by reacting the optically active binaphthyl compound (18) with a halogenating agent. The optically active binaphthyl compound (hereinafter also referred to as an optically active binaphthyl compound (21)) is represented by the following formula. The reaction between the optically active binaphthyl compound (18) and the halogenating agent may be carried out according to a method for producing a dicarboxylic acid dihalide by reacting a dicarboxylic acid with a halogenating agent.

（式中、Ｒ⁸、Ｒ¹⁶およびＲ¹⁷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チル化合物は、前記光学活性ビナフチル化合物（２１）と前記アミン化合物とを反応させることにより製造することができる。光学活性ビナフチル化合物（２１）とアミン化合物との反応は、カルボン酸ハロゲン化物とアミン化合物とを反応させて、カルボン酸アミドを得る公知の方法に準じて行えばよい。 Of the optically active binaphthyl compound (17), R ¹⁴ and R ¹⁵ are the same unsubstituted or substituted amino group (22)

(Wherein R ⁸ , R ¹⁶ and R ¹⁷ represent the same meaning as described above.)
The optically active binaphthyl compound shown by can be manufactured by making the said optically active binaphthyl compound (21) and the said amine compound react. The reaction between the optically active binaphthyl compound (21) and the amine compound may be carried out according to a known method for obtaining a carboxylic acid amide by reacting a carboxylic acid halide with an amine compound.

Of the optically active binaphthyl compound (17), an optically active binaphthyl compound in which R ¹⁴ is a hydroxyl group and R ¹⁵ is an unsubstituted or substituted amino group is obtained by combining the optically active binaphthyl compound (18) and the amino compound with a condensing agent. And can be produced by reacting in the presence of a base. Examples of the condensing agent include dicyclohexyl carbodiimide and isopropyl carbodiimide, and the amount used is usually 1 to 5 times the mol of the optically active binaphthyl compound (18). 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 binaphthyl compound (18), Preferably it is 5-15 mol times. The usage-amount of an amino compound is 1 mol times or more normally with respect to an optically active binaphthyl compound (18), and there is no upper limit in particular.

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

After completion of the reaction, for example, the reaction solution is washed with an aqueous acid solution, and if necessary, an extraction process is performed by adding an insoluble organic solvent to water, and the resulting organic layer is concentrated to give R ^{14 a} hydroxyl group. Thus, an optically active binaphthyl compound in which R ¹⁵ is an unsubstituted or substituted amino group can be taken out.

で示される基を表わし、Ｒ²が水酸基または無置換もしくは置換アミノ基を表わし、Ｒ³およびＲ⁴のうちのいずれか一方が水素原子を、他方が水素原子、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がＲ⁴と同一の基を表わす下記式（２３）

（式中、Ｒ¹⁶およびＲ¹⁷は上記と同一の意味を表わし、Ｒ¹⁸は水酸基または無置換もしくは置換アミノ基を表わす。）
で示される光学活性ビナフチル化合物（以下、光学活性ビナフチル化合物（２３）と記すこともある。）の製造方法について説明する。 Subsequently, in the present optically active binaphthyl compound, n represents 2 and R ¹ is

R ² represents a hydroxyl group or an unsubstituted or substituted amino group, one of R ³ and R ⁴ represents a hydrogen atom, the other represents a hydrogen atom, a halogen atom, a phenyl group, or a carbon number. The following formula (23), which represents 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 represents the same group as R ⁴

(Wherein R ¹⁶ and R ¹⁷ represent the same meaning as described above, and R ¹⁸ represents a hydroxyl group or an unsubstituted or substituted amino group.)
A method for producing an optically active binaphthyl compound represented by the formula (hereinafter also referred to as optically active binaphthyl compound (23)) will be described.

（式中、Ｒ¹⁶およびＲ¹⁷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チル化合物（以下、光学活性ビナフチル化合物（２４）と記すこともある。）は、光学活性ビスカーバメート化合物（１９）とＮ−ブロモスクシンイミドとを、第三級アルコールの存在下に反応させて得られる式（２５）

（式中、Ｒ¹⁶およびＲ¹⁷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を加水分解処理することにより製造することができる。 Of the optically active binaphthyl compound (23), R ¹⁸ is a hydroxyl group.

(Wherein R ¹⁶ and R ¹⁷ represent the same meaning as described above.)
An optically active binaphthyl compound represented by the following (hereinafter sometimes referred to as an optically active binaphthyl compound (24)) is obtained by combining an optically active biscarbamate compound (19) and N-bromosuccinimide in the presence of a tertiary alcohol. Formula (25) obtained by reaction

(Wherein R ¹⁶ and R ¹⁷ represent the same meaning as described above.)
It can manufacture by hydrolyzing the optically active compound shown by these.

  What is marketed normally is used for N-bromosuccinimide, and the usage-amount is 2-10 mol times or more with respect to an optically active biscarbamate compound (19) normally. Examples of the tertiary alcohol include the same ones as described above, and the amount used is usually 1 mol times or more with respect to the optically active biscarbamate compound (19), and the upper limit is not particularly limited. For example, a large excess amount may be used also as a solvent.

  The reaction between the optically active biscarbamate compound (19) and N-bromosuccinimide is usually carried out by mixing the optically active biscarbamate compound (19), N-bromosuccinimide and a tertiary alcohol as they are or in a solvent. The Examples of the solvent include ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene, halogenated hydrocarbon solvents such as chloroform, nitrile solvents such as acetonitrile, and ester solvents such as ethyl acetate. Or a single or mixed solvent. The amount of such solvent used is not particularly limited.

  The reaction temperature is usually −50 to 100 ° C.

After completion of the reaction, the optically active compound represented by the formula (25) can be taken out by, for example, concentrating the reaction solution. The hydrolysis treatment of the optically active compound represented by the formula (25) is usually carried out by bringing the optically active compound represented by the formula (25) into contact with water or alkaline water. After the hydrolysis treatment, for example, an organic solvent insoluble in water is added for extraction treatment, and the resulting organic layer is concentrated to extract the optically active binaphthyl compound in which R ¹⁸ is a hydroxyl group.

（式中、Ｒ⁸、Ｒ¹⁶およびＲ¹⁷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チル化合物は、前記光学活性ビナフチル化合物（２４）と脱水剤とを反応させた後、前記アミノ化合物と反応させることにより製造することができる。 Of the optically active binaphthyl compound (23), R ¹⁸ is an unsubstituted or substituted amino group (26)

(Wherein R ⁸ , R ¹⁶ and R ¹⁷ represent the same meaning as described above.)
The optically active binaphthyl compound shown by can be manufactured by making the said optically active binaphthyl compound (24) and a dehydrating agent react, and making it react with the said amino compound.

  Examples of the dehydrating agent include thionyl chloride. The usage-amount of a dehydrating agent is 1-10 mole times normally with respect to an optically active binaphthyl compound (24).

  The reaction temperature of the reaction between the optically active binaphthyl compound (24) and the dehydrating agent is usually 30 to 100 ° C. After completion of the reaction, if necessary, the remaining dehydrating agent is removed by concentration treatment or the like, and then the reaction with the amino compound is performed. The usage-amount of an amino compound is 1 mol times or more normally with respect to an optically active binaphthyl compound (24), The upper limit in particular is not restrict | limited. The reaction temperature of the reaction with such an amino compound is usually 0 to 100 ° C. The reaction may be carried out without a solvent or in the presence of a solvent inert to the reaction.

  After completion of the reaction, the optically active binaphthyl compound (26) can be taken out by mixing the reaction solution, water and, if necessary, an organic solvent insoluble in water, subjecting to extraction, and concentrating the resulting organic layer. .

（式中、Ｒ¹⁶およびＲ¹⁷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チル化合物（以下、光学活性ビナフチル化合物（２７）と略記する。）と前記化合物（７）とを、塩基の存在下に反応させて、式（２８）

（式中、Ｒ⁶、Ｒ¹⁶およびＲ¹⁷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（２８）と略記する。）を得、光学活性化合物（２８）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。 The optically active biscarbamate compound (19) has the formula (27)

(Wherein R ¹⁶ and R ¹⁷ represent the same meaning as described above.)
And an optically active binaphthyl compound (hereinafter abbreviated as optically active binaphthyl compound (27)) and the compound (7) in the presence of a base to give a compound of formula (28)

(Wherein R ⁶ , R ¹⁶ and R ¹⁷ represent the same meaning as described above.)
Can be produced by thermal rearrangement reaction of the optically active compound (28).

  The usage-amount of a compound (7) is 2-5 mol times normally with respect to an optically active binaphthyl compound (27). Examples of the base include alkali metal hydrides such as sodium hydride, and the amount used is usually 2 to 5 mol times based on the optically active binaphthyl compound.

  The reaction of the compound (7) and the optically active binaphthyl compound (27) is usually carried out by mixing the two in a solvent. The solvent may be any solvent inert to the reaction, for example, N, Examples include amide solvents such as N-dimethylformamide. 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 optically active compound (28) can be taken out by mixing the reaction solution and water, adding an organic solvent insoluble in water, performing an extraction treatment, and concentrating the resulting organic layer. You may convert into an optically active compound (28) as it is, without taking out an optically active compound (28).

  Examples of the optically active compound (28) include optically active 1,1′-binaphthalene-2,2′-diol bis (N, N-dimethylthiocarbamate), optically active 1,1′-binaphthalene-2,2′-. Examples thereof include diol bis (N, N-diethylthiocarbamate) and optically active 1,1′-binaphthalene-6,6′-dimethyl-2,2′-diol bis (N, N-dimethylthiocarbamate).

The heat transfer reaction of the optically active compound (28) is usually carried out by heating the optically active compound (28) to 240 to 300 ° C. as it is or in the presence of a solvent as necessary. After completion of the reaction, it may be used for the reaction with N-bromosuccinimide as it is, or the reaction solution is subjected to, for example, a distillation treatment, and the resulting optically active biscarbamate compound (19) is taken out and reacted with N-bromosuccinimide. You may use for.

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

Reference Example 1 (Production Example of the Optically Active Binaphthyl Compound: Part 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)

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

Reference Example 2 (Production Example of the Optically Active Binaphthyl Compound: Part 2)
0.1 g of (S) -2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinic acid obtained in Reference Example 1 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.

Reference Example 3 (Production Example of the Optically Active Binaphthyl Compound: Part 3)
(S) -2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinic acid chloride obtained in Reference Example 2 and isopropylamine were mixed and reacted, and (S) —N-isopropyl. 2-Methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinamide was obtained.

Example 1 (Utilization of the present optically active binaphthyl compound as a chiral shift reagent for NMR: Part 1)
(S) -2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfinic acid chloride and (R) -2-methoxy-6-bromo-1 obtained in the same manner as in Reference Example 2 above. , 1′-Binaphthalene-2′-sulfinic acid chloride and optically active menthol whose absolute configuration is unknown are each reacted in N-methylimidazole to obtain a compound introduced with an asymmetric auxiliary group (see Scheme 7). ).

The obtained two compounds were each subjected to NMR measurement, and the difference in chemical shift value of each proton (see formula (29)) 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 with the body.

Example 2 ((Utilization of the present optically active binaphthyl compound as a chiral shift reagent for NMR: Part 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 as compared with 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.

Example 3 (Utilization of the present optically active binaphthyl compound as a chiral shift reagent for NMR: Part 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.

Example 4 (Utilization of the present optically active binaphthyl compound as a chiral shift reagent for NMR: Part 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.

Reference Example 4 (Production Example of the Optically Active Binaphthyl Compound: Part 4)
(S) -2-Methoxy-1,1′-binaphthalene-2′-thiol 2.5 g of N, N-dimethylcarbamate was dissolved in a mixed solution of 50 mL of tert-butanol and 50 mL of acetonitrile and then N-bromosuccinimide. 7 g 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 (S) -2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfonic acid bromide.
FD-MS m / s 504 [M ⁺ calcd. forC ₂₁ H ₁₄ Br ₂ O ₃ S 503.9030]

Reference Example 5 (Production Example of the Optically Active Binaphthyl Compound: Part 5)
(S) -2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfonic acid bromide obtained in Reference Example 4 was dissolved in 40 mL of acetonitrile, and 10 mL of concentrated aqueous ammonia was added at room temperature. The reaction was held at the same temperature for 1 hour. After completion of the reaction, 30 mL of water was added, and acidified by adding concentrated hydrochloric acid while cooling in an ice bath, followed by extraction with chloroform. The obtained organic layer was concentrated, and the resulting concentrated residue was purified by column chromatography (silica gel, hexane / acetone = 2/1) to obtain (S) -2-methoxy-6-bromo-1,1 ′. -0.74 g of binaphthalene-2'-sulfonamide was obtained.
FD-MS m / s 441 [M ⁺ calcd. forC ₂₁ H ₁₆ BrNO ₃ S 441.0034]

Reference Example 6 (Production Example of the Optically Active Binaphthyl Compound: Part 6)
(S) -2-Methoxy-1,1′-binaphthalene-2′-thiol 1 g of N, N-dimethylcarbamate was dissolved in a mixed solution of 20 mL of tert-butanol and 20 mL of acetonitrile, and then 2.3 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 (S) -2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfonic acid bromide. The obtained (S) -2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfonic acid bromide was dissolved in 15 mL of acetonitrile, and 0.19 g of hydrazine was added at room temperature for 1 hour. Then, 10 mL of water was added, and acidified by adding hydrochloric acid under ice cooling. Ethyl acetate was added and extracted, and the resulting organic layer was concentrated and then purified by column chromatography (silica gel, hexane / ethyl acetate = 1/1), and (S) -2-methoxy-6-bromo-1 , 1′-Binaphthalene-2′-sulfonylhydrazide 0.35 g was obtained. Yield: 30%.
¹ H-NMR (270 MHz, CDCl ₃ , δ / ppm)
3.61 (s, 3H), 6.64-8.21 (m, 11H)

Reference Example 7 (Production Example of the Optically Active Binaphthyl Compound: Part 7)
(S) -2-Methoxy-6-bromo-1,1′-binaphthalene-2′-sulfonic acid bromide prepared in the same manner as in Reference Example 4 was dissolved in 5 mL of acetonitrile, and 1 g of guanylurea sulfate and hydroxylated were dissolved. 10 mL of an aqueous sodium solution (containing 1 g of sodium hydroxide) was added. After stirring and reacting for 10 hours, the mixture was extracted with chloroform, and the resulting organic layer was dried and then concentrated. To the concentrated residue, 5 mL of methanol, 5 mL of water and 1 g of sodium hydroxide were added and refluxed for 5 hours. Thereafter, 10 mL of water was added and the mixture was extracted with chloroform. The resulting organic layer was concentrated and then purified by column chromatography (silica gel, ethyl acetate), and (S) -2-methoxy-6-bromo-1,1. 0.44 g of '-binaphthalene-2'-sulfonyl guanidide was obtained. Yield: 35%.
R _f 0.48 (Merck Kieselgel 60F ₂₅₄ plates, ethyl acetate)

Example 5 (Utilization of the present optically active binaphthyl compound as a chiral shift reagent for NMR: Part 5)
(S) -2-methoxy-6-bromo-1,1′-binaphthalene-2′-sulfonamide and (R) -2-methoxy-6-bromo-1, which were obtained in the same manner as in Reference Example 5, 1'-Binaphthalene-2'-sulfonamide is reacted with optically active 3,3-dimethyl-2- (2-methyl-1-propenyl) -1-carboxylic acid chloride, whose absolute configuration is unknown, respectively, to provide asymmetric assistance A compound into which a group was introduced was obtained (see Scheme 8).

Each of the obtained two compounds was subjected to NMR measurement, and the difference in chemical shift value of each proton (see formula (30)) was calculated. The calculation results are shown in Table 2. In Table 2, (S) origin refers to the chemical shift value of protons of compounds obtained using (S) -2-methoxy-1,1′-binaphthalene-2′-sulfonamide, , (R) -2-methoxy-1,1′-binaphthalene-2′-sulfonamide represents a chemical shift value of protons of a compound, and Δδ represents (S) -2-methoxy-1 , 1'-Binaphthalene-2'-sulfonamide compound obtained by using proton chemical shift value and (R) -2-methoxy-1,1'-binaphthalene-2'-sulfonamide It means the difference in the chemical shift value of protons of the compounds.

Results shown in Table 2 above and the following rule of thumb (II) obtained from stable conformational analysis of optically active 3,3-dimethyl-2- (2-methyl-1-propenyl) -1-carboxylic acid with known absolute configuration The absolute configuration at the 1-position of the optically active 3,3-dimethyl-2- (2-methyl-1-propenyl) -1-carboxylic acid chloride whose absolute configuration is unknown was determined as R. Furthermore, the absolute configuration at the 3rd position was determined as R from the result of the relative configuration analysis.

Example 6 (Utilization of the present optically active binaphthyl compound as a chiral shift reagent for NMR: Part 6)
NMR measurement of a compound obtained by reacting optically active 2-methoxy-6-bromo-1,1′-binaphthalene-2-sulfonic acid bromide with isopropylamine revealed that the isopropyl group The non-equivalent peak derived from the two methyl groups constituting is detected, and optically active 2-methoxy-6-bromo-1,1′-binaphthalene-2-sulfonic acid bromide is asymmetrically aided to the optically active amine It was found that it can be used as a group introduction reagent.
Chemical shift values of two methyl groups δ = 1.01 ppm and 0.98 ppm
Difference in chemical shift value Δδ = 0.03ppm

Example 7 (Utilization of the present optically active binaphthyl compound as a chiral shift reagent for NMR: Part 7)
When a compound obtained by reacting optically active 2-methoxy-6-bromo-1,1′-binaphthalene-2-sulfonic acid bromide with isopropyl alcohol in the presence of N-methylimidazole was subjected to NMR measurement, a naphthalene ring was obtained. As a result of the anisotropic 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-sulfonic acid bromide was obtained. It has been found that it can be used as a reagent for introducing an asymmetric auxiliary group into an optically active alcohol.
Chemical shift values of two methyl groups constituting the isopropyl group δ = 1.11 ppm and 0.85 ppm, difference in chemical shift value Δδ = 0.26 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. The -6-bromo-1,1'-binaphthalene-2-sulfonic acid bromide has the above non-equivalent peak as compared with the case where the known 2-methoxy-1,1'-binaphthalene-2-carboxylic acid is used. It was found that the difference in the chemical shift value was large and the anisotropy effect was greater.

Example 8 (Utilization of the present optically active binaphthyl compound as a chiral shift reagent for NMR: Part 8)
NMR measurement of a compound obtained by reacting optically active 2-methoxy-6-bromo-1,1′-binaphthalene-2-sulfonylhydrazide with acetone revealed that an isopropyl group was formed by the anisotropic effect of the naphthalene ring. Non-equivalent peaks derived from two methyl groups were detected, and optically active 2-methoxy-6-bromo-1,1′-binaphthalene-2-sulfonylhydrazide was used as an agent for introducing an asymmetric auxiliary group into an optically active ketone. It was found that it could be used.
Chemical shift values of two methyl groups δ = 1.00 ppm and 1.76 ppm
Difference in chemical shift value Δδ = 0.76ppm

Reference Example 8 (Production Example of the Optically Active Binaphthyl Compound: Part 8)
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. After completion of the reaction, 50 mL of a saturated aqueous solution of sodium carbonate was added, extracted twice with 50 mL of chloroform, and the resulting chloroform layer was mixed and dried. Thereafter, the mixture was concentrated and purified by column chromatography (silica gel, hexane / ethyl acetate = 2/1) to obtain 5.5 g of dimethyl (S) -1,1′-binaphthalene-2,2′-disulfinate. 2 g of the obtained methyl (S) -1,1′-binaphthalene-2,2′-disulfinate was dissolved in a mixed solution of 50 mL of chloroform and 50 mL of methanol. At room temperature, 3 g of sodium hydroxide was added, and the mixture was stirred and reacted at room temperature for 2 hours. Thereafter, 50 mL of water was added, and chloroform was added for washing treatment. The obtained aqueous layer was acidified with concentrated hydrochloric acid, extracted with chloroform, and the obtained organic layer was dried. The dried organic layer was concentrated, and the concentrated residue was washed with hexane to obtain 1.5 g of (S) -1,1′-binaphthalene-2,2′-disulfinic acid.
¹ H-NMR (270 MHz, acetone-d ₆ , δ / ppm)
7.10 (d, J = 8.6 Hz, 2H,), 7.42 (ddd, J = 1.2, 6.8, 6.8 Hz, 2H), 7.65 (ddd, J = 1.2 , 6.9, 6.9 Hz, 2H), 8.14 (d, J = 8.2 Hz, 2H), 8.24 (d, J = 8.7 Hz, 2H), 8.36 (d, J = (8.6Hz, 2H)

Reference Example 9 (Production Example of the Optically Active Binaphthyl Compound: Part 9)
After 5 g of (S) -1,1′-binaphthalene-2,2′-dithiol bis (N, N-dimethylcarbamate) was dissolved in 100 mL of methanol, 15 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, 50 mL of a saturated aqueous solution of sodium carbonate was added, extracted twice with 50 mL of chloroform, and the resulting chloroform layer was mixed and dried. Thereafter, concentration treatment was performed to obtain crude (S) -1,1′-binaphthalene-2,2′-disulfinate dimethyl. The resulting crude methyl (S) -1,1′-binaphthalene-2,2′-disulfinate is dissolved in a mixed solution of 50 mL of chloroform and 50 mL of methanol, 5 g of sodium hydroxide is added at room temperature, and the mixture is stirred for 2 hours. Reacted. Thereafter, the mixture was concentrated, 100 mL of a methanol / chloroform (1/1) mixture was added to the concentrated residue, and the insoluble matter was filtered off. The insoluble matter was washed with 100 mL of a methanol / chloroform (1/1) mixture, and the washing was combined with the previously obtained filtrate. The combined filtrate was concentrated, 100 mL of chloroform was added to the concentrated residue, and the solid content was collected by filtration. The solid content collected by filtration was washed with chloroform, acidified with 1N hydrochloric acid, extracted with chloroform, and the resulting organic layer was dried. The dried organic layer was concentrated, and the concentrated residue was washed with hexane to obtain 0.8 g of (S) -1,1′-binaphthalene-2,2′-disulfinic acid.

Reference Example 10 (Production Example of the Optically Active Binaphthyl Compound: Part 10)
1 g of dimethyl (S) -1,1′-binaphthalene-2,2′-disulfinate obtained in the same manner as in Reference Example 8 was dissolved in chloroform, 2 g of m-chloroperbenzoic acid was added, and the internal temperature The mixture was stirred and reacted at 40 ° C. for 2 hours. Saturated aqueous sodium hydrogen carbonate solution is added to quench, extract with chloroform, and the resulting organic layer is dried and concentrated to give crude (S) -1,1′-binaphthalene-2,2′-dimethyl sulfonate. Got. Crude (S) -1,1′-binaphthalene-2,2′-disulfonic acid dimethyl was dissolved in methanol, 0.5 g of sodium hydride was added, and the mixture was stirred and reacted at room temperature for 1 hour. The concentrated residue was purified by silica gel chromatography (chloroform → chloroform / methanol = 3/1) to obtain 0.2 g of (S) -1,1′-binaphthalene-2,2′-disulfonic acid.
¹ H-NMR (270 MHz, CD ₃ OD, δ / ppm)
7.10 (d, J = 8.6 Hz, 2H,), 7.22 (ddd, J = 1.3, 6.8, 6.7 Hz, 2H), 7.42 (ddd, J = 1.3 6.8, 6.9 Hz, 2H), 7.90 (d, J = 8.3 Hz, 2H), 8.08 (d, J = 8.8 Hz, 2H), 8.15 (d, J = (8.4Hz, 2H)

Example 9 (Utilization of the present optically active binaphthyl compound as a chiral shift reagent for NMR: Part 9)
(S) -1,1′-binaphthalene-2,2′-disulfinic acid, (−)-menthol, N-methylimidazole and dicyclohexylcarbodiimide obtained in the same manner as in Reference Example 8 were mixed and reacted. A compound in which an asymmetric auxiliary group was introduced into (-)-menthol was obtained. Similarly, a compound in which an asymmetric auxiliary group was introduced into (+)-menthol was obtained (see Scheme 9).

The two obtained compounds were each subjected to NMR measurement, and the difference in chemical shift value of each proton (see formula (31)) was calculated. The calculation results are shown in Table 3. In Table 3, (-) origin is the proton chemical shift value of the compound obtained using (-)-menthol, and (+) origin is the proton of the compound obtained using (+)-menthol. Δδ is the difference between the chemical shift value of the proton of the compound obtained using (−)-menthol and the chemical shift value of the proton of the compound obtained using (+)-menthol. Means.

  Menthol of unknown absolute configuration is reacted with (S) -1,1′-binaphthalene-2,2′-disulfinic acid to obtain a compound into which an asymmetric auxiliary group has been introduced, the compound is subjected to NMR measurement, and the result is shown above. By comparing with Table 3, the absolute configuration of menthol whose absolute configuration was unknown could be determined.

Example 10 (Use of the present optically active binaphthyl compound as a chiral shift reagent for NMR: Part 10)
NMR measurement of a compound obtained by reacting optically active 1,1′-binaphthalene-2,2′-disulfinic acid with isopropyl alcohol revealed that the two methyl groups constituting the isopropyl group by the anisotropic effect of the naphthalene ring. A non-equivalent peak derived from the group was detected, and it was found that optically active 1,1′-binaphthalene-2,2′-disulfinic acid can be used as a reagent for introducing an asymmetric auxiliary group into optically active alcohol. It was.
Chemical shift values of two methyl groups constituting the isopropyl group δ = 0.17 ppm and 0.76 ppm, difference in chemical shift values Δδ = 0.59 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 in chemical shift value is Δδ = 0.23 ppm, so that optically active 1,1′-binaphthalene -2,2'-disulfinic acid has a larger difference in chemical shift value of the non-equivalent peak than when known 2-methoxy-1,1'-binaphthalene-2-carboxylic acid is used, It was found that the anisotropic effect was greater.

Example 11 (Utilization of the present optically active binaphthyl compound as a chiral shift reagent for NMR: 11)
(S) -1,1′-binaphthalene-2,2′-disulfinic acid 45 mg, (+)-2-butanol 7 mg and N-methylimidazole 100 mg obtained in the same manner as in Reference Example 8 were mixed with 0.5 mL of acetonitrile. And 31 mg of N, N′-dicyclohexylcarbodiimide was added. After stirring and reacting at room temperature for 1 hour, the reaction solution was purified by thin layer chromatography (silica gel, chloroform / methanol = 10/1 → ethyl acetate / methanol = 5/1), and (S) -1,1 ′. -24 mg of binaphthalene-2-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)

(-)-2-Butanol was used in the same manner as described above to obtain 28 mg of (S) -1,1′-binaphthalene-2-sulfino-2′-sulfinic acid (2-butyl).
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)

  An optically active 2-butanol of unknown absolute configuration was reacted with (S) -1,1'-binaphthalene-2,2'-disulfinic acid to obtain a compound into which an asymmetric auxiliary group was introduced. The absolute configuration of optically active 2-butanol of unknown absolute configuration could be determined by NMR measurement of the compound and comparing the result with the above.

Example 12 (Utilization of the present optically active binaphthyl compound as a chiral shift reagent for NMR: No. 12)
45 mg of (S) -1,1′-binaphthalene-2,2′-disulfinic acid, 12 mg of (−)-1-phenylethanol and 100 mg of N-methylimidazole obtained in the same manner as in Reference Example 8 were added to acetonitrile. After dissolving in 5 mL, 31 mg of N, N′-dicyclohexylcarbodiimide was added. After stirring and reacting at room temperature for 1 hour, 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'-sulfinic acid (1-phenylethyl) 30 mg 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)

(S) -1,1′-Binaphthalene-2-sulfino-2′-sulfinic acid (1-phenylethyl) 30 mg was obtained in the same manner as described above using (+)-1-phenylethanol.
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)

  Optically active 1-phenylethanol of unknown absolute configuration was reacted with (S) -1,1'-binaphthalene-2,2'-disulfinic acid to obtain a compound into which an asymmetric auxiliary group was introduced. The absolute configuration of optically active 1-phenylethanol of unknown absolute configuration could be determined by NMR measurement of the compound and comparing the result with the above.

Example 13 (Utilization of the present optically active binaphthyl compound as a chiral shift reagent for NMR: Part 13)
(S) -1,1′-Binaphthalene-2,2′-disulfonic acid (10 mg) and thionyl chloride (5 mL) were mixed and reacted under reflux conditions for 3 hours. Thereafter, the remaining thionyl chloride was concentrated and removed, and 1 mL of acetonitrile and 5 mg of 1-phenylethylamine were added to the concentrated residue, and reacted at room temperature for 1 hour. The reaction solution is quenched by adding water, extracted with chloroform, the resulting organic layer is concentrated, purified by preparative thin layer chromatography (chloroform / methanol = 10/1), and (S) -N. 5 mg of a diastereomeric mixture of-(1-phenylethyl) -1,1'-binaphthalene-2-sulfo-2'-sulfonamide was obtained. NMR measurement of the mixture revealed that a non-equivalent peak (Δδ = 0.16 ppm) derived from the α-position proton of the phenyl group of the amide portion of the diastereomer was detected due to the anisotropic effect of the naphthalene ring, It was found that optically active 1,1′-binaphthalene-2,2′-disulfonic acid can be used as a reagent for introducing an asymmetric auxiliary group into an optically active amine.
The chemical shift values of non-equivalent peaks derived from the α-position proton of the phenyl group of the amide portion of the diastereomer were δ = 4.27 ppm and 4.11 ppm.

Example 14 (Use of optically active binaphthyl compound as chiral shift reagent for NMR: Part 14)
(S) -1,1′-Binaphthalene-2,2′-disulfonic acid (10 mg) and thionyl chloride (5 mL) were mixed and reacted under reflux conditions for 3 hours. Thereafter, the remaining thionyl chloride was concentrated and removed, and 1 mL of acetonitrile and 5 mg of isopropylamine were added to the concentrated residue, followed by reaction at room temperature for 1 hour. The reaction solution is quenched by adding water, extracted with chloroform, the resulting organic layer is concentrated, purified by preparative thin layer chromatography (chloroform / methanol = 10/1), and (S) -N. 5 mg of a diastereomeric mixture of -isopropyl-1,1'-binaphthalene-2-sulfo-2'-sulfonamide was obtained. NMR measurement of the mixture revealed that a non-equivalent peak (Δδ = 0.08 ppm) derived from the two methyl group protons of the isopropyl group in the amide portion of the diastereomer was detected due to the anisotropic effect of the naphthalene ring. Thus, it was found that optically active 1,1′-binaphthalene-2,2′-disulfonic acid can be used as a reagent for introducing an asymmetric auxiliary group into an optically active amine.
The chemical shift values of non-equivalent peaks derived from the two methyl group protons of the isopropyl group of the amide portion of the diastereomer were δ = 0.77 ppm and 0.85 ppm.

Claims (8)

Formula (1)

(Wherein R ¹ , R ³ , R ⁴ and R ⁵ are the same or different and each represents a proton-containing substituent or a non-proton-containing substituent, and R ² has reactivity with the compound to be analyzed) And represents a substituent or a leaving group, and n represents 1 or 2.)
A chiral shift reagent for NMR comprising an optically active binaphthyl compound represented by the formula: Of the optically active binaphthyl compounds represented by the formula (1), R ² is an optical activity in which any one of a hydroxyl group, a halogen atom, an unsubstituted or substituted amino group, an alkyl group and a heteroaryl group, or a leaving group. The chiral shift reagent for NMR according to claim 1, comprising a binaphthyl compound. Of optically active binaphthyl compound represented by the formula (1), R ² is a hydroxyl group, a halogen atom or an unsubstituted or NMR for chiral shift reagent according to claim 2, wherein comprising the optically active binaphthyl compound substituted amino group. ^{4. The} chiral shift reagent for NMR according to claim 1, 2, or 3, wherein the optically active binaphthyl compound represented by the formula (1) comprises an optically active binaphthyl compound in which R4 is a hydrogen atom or a halogen atom. Of optically active binaphthyl compound represented by the formula (1), NMR for chiral shift reagent of claim 4, wherein R ⁴ consists of an optically active binaphthyl compound is bromine atom. In the optically active binaphthyl compound represented by the formula (1), R ¹ represents a methoxy group or a C 1-4 perfluoroalkoxy group, R ² represents a hydroxyl group, a halogen atom or an unsubstituted or substituted amino group, 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, n represents 1 or 2, and (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, a perfluoroalkyl group having 1 to 4 carbon atoms or a trisubstituted silyl group, and R ⁵ is R ⁴ represents the same group or hydrogen atom, (b) when R ³ is a halogen atom, R ⁴ and R ⁵ represent a hydrogen atom, and (c) R ³ represents a phenyl group, an alkyl group having 1 to 4 carbon atoms. , C1-4 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. The NMR chiral shift reagent according to claim 1, wherein R ⁵ is an optically active binaphthyl compound representing a hydrogen atom. Of the optically active binaphthyl compounds represented by formula (1), n represents 1 and R ¹ represents

R ² and R ¹⁴ represent the same hydroxyl group, a halogen atom or an unsubstituted or substituted amino group, or R ² represents an unsubstituted or substituted amino group, and R ¹⁴ represents a hydroxyl group, One of R ³ and R ⁴ is a hydrogen atom, and the other 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 three The chiral shift reagent for NMR according to claim 1, comprising an optically active binaphthyl compound which represents a substituted silyl group and R ⁵ represents the same group as R ⁴ . Of the optically active binaphthyl compounds represented by the formula (1), n represents 2 and R ¹ represents

R ² represents a hydroxyl group or an unsubstituted or substituted amino group, one of R ³ and R ⁴ represents a hydrogen atom, the other represents a hydrogen atom, a halogen atom, a phenyl group, or a carbon number. The chiral shift for NMR according to claim 1, comprising an optically active binaphthyl compound which 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 R ⁵ represents the same group as R ^4. reagent.