JPH11322635A - Production of molecular compound composed of optically active compound and optical resolution agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for efficiently converting an unnecessary enantiomer of an optically active compound into a desired enantiomer of the optically active compound. SOLUTION: The molecular compound composed of an optically active compound and an optical resolution agent is produced by reacting a molecular compound composed of an optically active compound and an optical resolution agent with an enantiomer of the optically active compound constituting the molecular compound in the presence of the optically active compound constituting the molecular compound to obtain a molecular compound wherein the optically active compound constituting the molecular compound is substituted with its enantiomer. The reaction is carried out in the presence of the diastereomer of the molecular compound composed of the optically active compound and the optical resolution agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a molecular compound comprising a novel optically active compound and an optical resolving agent.

[0002]

2. Description of the Related Art In general, as a method of optically resolving a racemate of an optically active compound, a salt or a complex is formed by the action of an optically active optical resolving agent, and two salts having a relation of diastereomers formed. There is known a method for separating phenols based on differences in physical properties such as melting point and solubility.

For example, a method in which an optically active difunctional resolving agent is allowed to act on a polyfunctional compound such as diol, dihydroxybiaryl, or hydroxyoxime to effect optical resolution, or a method in which an optically active diamino compound is allowed to act on optically active binaphthols. (Japanese Patent Laid-Open No. 7-173081, Japanese Patent No. 258)
No. 0404) are known, and an optically active resolving agent is allowed to act on an optically active compound to be resolved to form a complex,
There is known a method of separating crystals and a mother liquor from each other based on a difference in crystallinity and solubility of two formed diastereomeric complexes.

[0004]

The molecular compound comprising an optically active compound represented by a complex comprising an optically active binaphthol and an optically active diamino compound, and a molecular compound comprising an optical resolving agent,
The processing method differs depending on whether or not the optically active compound constituting the molecular compound is a mirror image to be obtained. When the enantiomer is to be obtained, the molecular compound is decomposed by an acid treatment or the like to obtain an optically active compound.

[0005] However, in the case of an unnecessary mirror image, it is necessary to convert the mirror image to a desired mirror image. For example, in the case of a complex comprising the above optically active binaphthols and an optically active diamino compound, the enantiomer containing an unnecessary enantiomer is heated, and the complex containing the enantiomer to be obtained and the complex containing the unnecessary enantiomer are obtained. An inefficient method of repeating racemization to a 1: 1 mixture, separating these, further racemizing a complex containing an unnecessary enantiomer, and separating the mixture was employed (Japanese Patent No. 2580404).

An object of the present invention is to solve the above-mentioned problems, and efficiently converts a molecular compound containing an unnecessary enantiomer of an optically active compound into a molecular compound containing an enantiomer of the desired enantiomer. That is.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that an optically active compound (an optically active compound to be resolved, which is simply referred to as an optically active compound in this specification unless otherwise specified). Optical resolving agent (optically active compound used for resolving the above optically active compound, referred to simply as an optical resolving agent unless otherwise specified in the present specification,
The optically active compound constituting the molecular compound in the presence of the optically active compound constituting the molecular compound in the presence of the optically active compound constituting the molecular compound. It has been found that a molecular compound in which the optically active compound constituting the above is replaced by its enantiomer is produced, and the present invention has been completed.

That is, according to the method for producing a molecular compound comprising an optically active compound and an optical resolving agent of the present invention, a molecular compound comprising an unnecessary optically active compound and an optically resolving agent coexists with an optically active compound constituting the molecular compound. Below, the enantiomer of the optically active compound constituting the molecular compound is allowed to act (that is, a racemate or a partially split optically active compound may be acted on), and the unnecessary optically active compound constituting the molecular compound is eliminated. And producing a molecular compound substituted with the intended enantiomer.

In the method of the present invention, an unnecessary optically active compound used as a starting material and a molecular compound comprising an optical resolution agent are dissolved in two diastereomers formed from the optically active compound and the optical resolution agent. The optical resolving agent is appropriately set so as to obtain a high molecular compound.

In the method of the present invention, a diastereomer of a molecular compound comprising the unnecessary optically active compound and an optical resolving agent (a molecular compound comprising an intended enantiomer and an optical resolving agent) can also be allowed to coexist. . That is, a diastereomer mixture of a molecular compound composed of an optically active compound and an optical resolving agent may be used as a starting material.

The molecular compound in the present invention is a compound formed by directly bonding an optically active compound and an optical resolving agent at a certain ratio, and having a loose bond between molecules (for example, Edited by Tokyo Chemical Doujin Co., Ltd., edited by Michinori Oki et al., Dictionary of Chemistry, 1989, see “Molecular Compounds”). Specifically, it includes an electron donor acceptor complex, an association by hydrogen bonding, a Van der Waals molecule, an inclusion compound, and the like, and is excluded when a salt is formed by ionic bonding.

Accordingly, the present invention is directed to the difference in the physical properties of the molecular compound formed by the combination of the optically active compound and the optical resolving agent through the weak interaction such as hydrogen bonding and van der Waals force as described above. Optical splitting is generally applied.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION As molecular compounds to which the method of the present invention can be applied, compounds comprising an optically active polyfunctional compound and an optically active bifunctional resolving agent described in JP-A-7-173081, and patents No. 2580404, a compound comprising an optically active binaphthol and an optically active diamine compound, and 2,2′-dihydroxy-1,1′-binaphthyl described in Chem. Commun., 1087 (1997). Compound consisting of 1-hydroxymethyl-3-methylbutyl (trimethyl) ammonium, Tetrahedron; Asymmetry, 6, 2
Compound consisting of 2,2′-dihydroxy-1,1′-binaphthyl and N-benzylcinchonidium chloride described in 123 (1995), 10,10 ′ described in Chem. Lett., 1371 (1988) -
Examples thereof include dihydroxy-9,9'-biphenanthryl and 2,3-dimethoxy-N, N, N ', N'-tetramethylsuccinamide.

[0014] Further, published by the Society of Publishing and Publishing, edited by The Chemical Society of Japan, quarterly chemistry review No. 6 separation of optical isomers, 1989,
The present invention can also be effectively applied to the clathrate compounds described on p. That is, an optically active acyclic host molecule (corresponding to an optical resolving agent) recognizes a slight difference in the shape of an optically active guest molecule (corresponding to an optically active compound), and forms a more stable crystal lattice. To form a complex (inclusion compound or host-guest complex; equivalent to a molecular compound)
Optical resolution of guest molecules is possible. For example, the following equation (1)
The optically active acyclic host molecules represented by (9) to (9) are effective as the optical resolving agent of the present invention.

[0015]

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The optically active 1,6-di (o-chlorophenyl) -1,6-diphenylhexa-2,4-diyne-1,6-diol of the formula (1) is a ketone, epoxyketone, lactone, ether,
Incorporates a wide variety of organic compounds such as alcohols, halogen compounds, carboxamides, amines, and sulfoxides to form crystalline complexes with high asymmetric discrimination ability. Equation (2)
The optically active hosts (1) to (4) have a structure in which two hydroxyl groups form a hydrogen bond with a guest compound, and include sulfoxide, sulfoximine, selenoxide, phosphine oxide, phosphate, amine-N-oxide, propionic acid and butyrate, The optically active amide host of formulas (5) and (6) is effective for resolving cyclopentenone derivatives and amines, and the optically active diol host of formula (7) is useful for resolving compounds having C ₂ symmetry. Is effective in resolving ketones, lactones, epoxides, amino alcohols and amines of formula (8) brucine and formula (9)
It is effective for optical resolution of alcohols such as propargyl alcohol, secondary alcohol and dianohydrin.

Hereinafter, the optically active compound is an optically active binaphthol, the optically resolving agent is an optically active diamino compound, and the molecular compound comprising the optically active compound and the optically resolving agent is an optically active binaphthol / optically active diamino compound complex. The present invention will be described in detail by taking a case as an example.

The binaphthols constituting the complex comprising the optically active binaphthols and the optically active diamino compound used as raw materials in the method for producing the optically active binaphthols / diamine complex are represented by the following general formulas (I) to (III). Binaphthols represented can be mentioned.

[0019]

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In the formulas (I) to (III), R ^{1 to} R ⁸ may be the same or different and each represents —H, Me,
t-Bu, -C≡H, -C≡CSiMe ₃ , -SiM
_{e 3, -SiPh 3, Ph,} -OH, -F, -Cl, -
Represents Br, -I, -OMe or -COOMe (in the present specification, Me represents a methyl group, Bu represents a butyl group, and Ph represents a phenyl group).

More specifically, 2,2'-dihydroxy-1,1'-binaphthyl, 3,3'-dibromo-2,
2'-dihydroxy-1,1'-binaphthyl, 3,3 '
-Dimethyl-2,2'-dihydroxy-1,1'-binaphthyl, 3,3'-diphenyl-2,2'-dihydroxy-1,1'-binaphthyl, 2,2 ', 3,3'-tetrahydroxy -1,1'-binaphthyl, 3,3'-dimethoxy-2,2'-dihydroxy-1,1'-binaphthyl, 3,3'-bismethoxycarbonyl-2,2'-dihydroxy-1,1'- Binaphthyl, 4,4'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl,
4,4'-dimethyl-2,2'-dihydroxy-1,
1'-binaphthyl, 4,4'-diphenyl-2,2'-
Dihydroxy-1,1′-binaphthyl, 2,2 ′, 4
4'-tetrahydroxy-1,1'-binaphthyl, 4,
4'-dimethoxy-2,2'-dihydroxy-1,1 '
-Binaphthyl, 4,4'-bismethoxycarbonyl-
2,2'-dihydroxy-1,1'-binaphthyl,

6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,6'-dimethyl-
2,2'-dihydroxy-1,1'-binaphthyl, 6,
6'-diphenyl-2,2'-dihydroxy-1,1 '
-Binaphthyl, 2,2 ', 6,6'-tetrahydroxy-1,1'-binaphthyl, 6,6'-dimethoxy-2,
2'-dihydroxy-1,1'-binaphthyl, 6,6 '
-Bismethoxycarbonyl-2,2'-dihydroxy-
1,1'-binaphthyl, 7,7'-dibromo-2,2 '
-Dihydroxy-1,1'-binaphthyl, 6,6'-dimethyl-2,2'-dihydroxy-1,1'-binaphthyl, 7,7'-diphenyl-2,2'-dihydroxy-
1,1'-binaphthyl, 2,2 ', 7,7'-tetrahydroxy-1,1'-binaphthyl, 7,7'-dimethoxy-2,2'-dihydroxy-1,1'-binaphthyl,
7,7'-bismethoxycarbonyl-2,2'-dihydroxy-1,1'-binaphthyl,

8,8'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 8,8'-dimethyl-
2,2'-dihydroxy-1,1'-binaphthyl, 8,
8'-diphenyl-2,2'-dihydroxy-1,1 '
-Binaphthyl, 2,2 ', 8,8'-tetrahydroxy-1,1'-binaphthyl, 8,8'-dimethoxy-2,
2'-dihydroxy-1,1'-binaphthyl, 8,8 '
-Bismethoxycarbonyl-2,2'-dihydroxy-
1,1'-binaphthyl, 10,10'-dihydroxy-
9,9'-biphenanthryl, 6,6'-dimethyl-
2,2'-dihydroxy-1,1'-biphenyl, 5,
5'-dichloro-4,4 ', 6,6'-tetramethyl-
2,2'-dihydroxy-1,1'-biphenyl, 3,
3 ', 5,5'-tetrachloro-4,4', 6,6'-
(R) -form and (S) -form such as tetramethyl-2,2'-dihydroxy-1,1'-biphenyl.

As the optically active diamino compound constituting the complex comprising the optically active binaphthols and the optically active diamino compound used as a raw material in the method for producing the optically active binaphthols / diamine complex, the following general formulas (A) to (A)
And a diamino compound represented by (E).

[0025]

Embedded image

In the formulas (A) to (E), R ^{11 to} R ¹⁸ may be the same or different and each represents —H, Me,
t-Bu, -C≡H, -C≡CSiMe ₃ , -SiM
_{e 3, -SiPh 3, -CF 3} , Ph, -OH, -F,
Represents -Cl, -Br, -I, -OMe or -COOMe. R 'and R "may be the same or different and each represents -H, Me or Ph.

More specifically, (R) -2,2'-diamino-1,1'-binaphthyl, (R) -6,6'-dimethyl-2,2'-diamino-1,1'- Biphenyl,
(R, R) -1,2-diphenyl-1,2-ethanediamine, (R) -1,2-diaminopropane, (R, R)
-2,3-diaminobutane, (R, R) -1,2-cyclopentanediamine, (R, R) -1,2-cyclohexanediamine, (R, R) -1,2-cycloheptanediamine, ( (R, R) -1,2-cyclooctanediamine, (R, R) -1,2-cyclononanediamine,
(R, R) -1,2-cyclodecanediamine, (R,
R) -1,2-cycloundecanediamine, (R, R)
-1,2-cyclododecanediamine, (S) -2,2 '
-Diamino-1,1'-binaphthyl, (S) -6,6 '
-Dimethyl-2,2'-diamino-1,1'-biphenyl, (S, S) -1,2-diphenyl-1,2-ethanediamine, (S) -1,2-diaminopropane, (S,
S) -2,3-diaminobutane, (S, S) -1,2-
Cyclopentanediamine, (S, S) -1,2-cyclohexanediamine, (S, S) -1,2-cycloheptanediamine, (S, S) -1,2-cyclooctanediamine, (S, S) -1,2-cyclononanediamine,
(S, S) -1,2-cyclodecanediamine, (S,
S) -1,2-cycloundecanediamine, (S, S)
-1,2-cyclododecanediamine and the like, and their N, N'-dimethyl and N, N, N ', N'-tetramethyl forms.

In the present invention, the complex used as a raw material in the method for producing an optically active binaphthol / diamine complex is one of two diastereomers formed from an optically active binaphthol and an optically active diamino compound. (R) -2,2'-dihydroxy-1,1'-binaphthyl. (S, S) -1,2-cyclohexanediamine complex, (S) -2,2'-dihydroxy- 1,1'-binaphthyl. (R, R) -1,2-cyclohexanediamine complex, (R) -2,2'-dihydroxy-1,1'-binaphthyl. (S, S) -1,2-diphenyl -1,2-ethanediamine complex, (S) -2,
2'-dihydroxy-1,1'-binaphthyl. (R,
R) -1,2-diphenyl-1,2-ethanediamine complex, (R) -6,6′-dibromo-2,2′-dihydroxy-1,1′-binaphthyl. (S, S) -1, 2-diphenyl-1,2-ethanediamine complex, (S) -6,
6'-dibromo-2,2'-dihydroxy-1,1'-
Binaphthyl (R, R) -1,2-diphenyl-1,2
-Ethanediamine complex and the like.

In the present invention, the complex obtained as a product of the method for producing an optically active binaphthol / diamine complex is one of two types of diastereomers formed from an optically active binaphthol and an optically active diamino compound. (S) -2,2'-dihydroxy-1,1'-binaphthyl. (S, S) -1,2-cyclohexanediamine complex, (R) -2,2'-dihydroxy -1,1'-binaphthyl. (R, R) -1,2-cyclohexanediamine complex, (S) -2,2'-dihydroxy-1,1'-binaphthyl. (S, S) -1,2- Diphenyl-1,2-ethanediamine complex, (R) -2,
2'-dihydroxy-1,1'-binaphthyl. (R,
R) -1,2-diphenyl-1,2-ethanediamine complex, (S) -6,6′-dibromo-2,2′-dihydroxy-1,1′-binaphthyl. (S, S) -1, 2-diphenyl-1,2-ethanediamine complex, (R) -6,
6'-dibromo-2,2'-dihydroxy-1,1'-
Binaphthyl (R, R) -1,2-diphenyl-1,2
-Ethanediamine complex and the like.

The solvent used in the method for producing the optically active binaphthols / diamine complex is a solvent which does not react with the complex comprising the optically active binaphthols and the optically active diamino compound and the binaphthols and which dissolves the complex and the binaphthols. Okay, benzene, toluene, o-
Aromatic hydrocarbons such as xylene, m-xylene, p-xylene, chlorobenzene and bromobenzene, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and 2-methyl-2
Alcohols such as propanol, diethyl ether,
Examples thereof include ethers such as tetrahydrofuran and dioxane, amides such as dimethylformamide and dimethylacetamide, dimethylsulfoxide, acetonitrile, and a mixed solvent of two or more of these.

The complex used as a raw material comprising an optically active binaphthol and an optically active diamino compound and the complex obtained as a product include benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, bromobenzene and the like. It may contain a crystallization solvent of aromatic hydrocarbons.

The amount of the racemic binaphthols used for the complex used as a raw material comprising the optically active binaphthols and the optically active diamino compound is preferably 1.4 to 2.6 times by mole, more preferably. Is 1.6 to 2.4 times mol.

For a complex used as a raw material comprising an optically active binaphthol and an optically active diamino compound,
When the diastereomer of the complex is used, the amount used is preferably 0.7 to 1.3 times, and more preferably 0.8 to 1.2 times the mol of the complex.

The complex used as a raw material comprising the optically active binaphthols and the optically active diamino compound can be obtained by mixing the optically active binaphthols and the optically active diamino compound. Separation of two kinds of diastereomeric complexes formed by the action of 1.0-fold mole of optically active diamino compound, or action of 0.5-fold mole of optically active diamino compound on racemic binaphthols The complex and the optically active binaphthols formed by the reaction are separated, and can be easily obtained by allowing an optically active diamino compound to act on the optically active binaphthols (JP-A-7-173801, Bulletin of Chemical Co., Ltd.). Society of Japan (Bull. Che
m. Soc. Jpn. ), 66 , 2002 (199
3)).

When a diastereomer of a complex used as a raw material comprising an optically active binaphthol and an optically active diamino compound is allowed to coexist, a 1.0-fold molar amount of the optically active diamino compound is allowed to act on a racemic binaphthol. It can be easily obtained by forming two kinds of diastereomeric complexes or by racemizing one of the complexes by heating (JP-A-7-17).
No. 3081, Patent No. 2580404).

With respect to the complex used as a raw material comprising an optically active binaphthol and an optically active diamino compound,
The temperature at which the racemic binaphthols act may be any temperature at which the complex consisting of the optically active binaphthols and the optically active diamino compound and the racemic binaphthols are dissolved, and is usually 40 ° C. to 120 ° C., preferably 60 ° C to 100 ° C. When the complex comprising the optically active binaphthols and the optically active diamino compound and the racemic binaphthols are dissolved, the heating is stopped and 0
Cool to 40 ° C to 40 ° C, preferably to 20 ° C to 30 ° C.

The complex comprising an optically active binaphthol obtained by the present invention and an optically active diamino compound can be easily converted into an optically active binaphthol by treating with a mineral acid such as hydrochloric acid according to the method of JP-A-7-173081. Can be converted to

A specific method of the present invention using the above optically active binaphthols and an optically active diamine compound is as follows. In a solvent such as toluene, (R)
-2,2'-dihydroxy-1,1'-binaphthyl.
In the presence or absence of (R, R) -1,2-cyclohexanediamine / toluene (1: 1: 1) complex,
The (S) -2,2'-dihydroxy-1,1'-binaphthyl. (R, R) -1,2-cyclohexanediamine (1: 1) complex was (±) -2,2'-dihydroxy- 1,1'-Binaphthyl is added, and after heating and dissolving, it is cooled to room temperature. Crystals of the precipitated (R) -2,2'-dihydroxy-1,1'-binaphthyl. (R, R) -1,2-cyclohexanediamine.toluene (1: 1: 1) complex and (S) -2 , 2'-Dihydroxy-1,1'-binaphthyl was separated from the mother liquor by filtration, and (R)-
2,2'-dihydroxy-1,1'-binaphthyl.
Crystals of the (R, R) -1,2-cyclohexanediamine / toluene (1: 1: 1) complex can be obtained.

[0039]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

Production Example 1 100 g (349 mmol) of (±) -2,2'-dihydroxy-1,1'-binaphthyl, (R, R) -1,2-
20.0 g of cyclohexanediamine (175 mmo
l), a mixture of 450 g of toluene and 50 g of methanol were dissolved by heating. After allowing to cool to room temperature, the precipitated (R) -2,2'-dihydroxy-1,1'-binaphthyl. (R, R) -1,2-cyclohexanediamine.toluene (1: 1: 1) complex64. 0g (130mmo
l) was filtered off and (S) -2,2'-dihydroxy-1,
After concentrating the mother liquor containing 1'-binaphthyl and distilling off the methanol-toluene azeotrope, 16.8 g (147 mmol) of (R, R) -1,2-cyclohexanediamine was added, and the mixture was refluxed for 15 hours. ) -2,2'-Dihydroxy-1,1'-binaphthyl. (R, R) -1,2-cyclohexanediamine.toluene (1: 1: 1) complex (9
6 mmol) and (S) -2,2'-dihydroxy-
1,1′-binaphthyl. (R, R) -1,2-cyclohexanediamine (1: 1) complex (96 mmol)
522.8 g of a toluene solution containing one mixture as a main component (including 2,2'-dihydroxy-1,1'-binaphthyl (27 mmol) in addition) was obtained.

Production Example 2 100 g (349 mmol) of (±) -2,2'-dihydroxy-1,1'-binaphthyl, (S, S) -1,2-
40.0 g of cyclohexanediamine (350 mmo
l) and a mixture of 450 g of toluene were dissolved by heating. After allowing to cool to room temperature, the precipitated (S) -2,2'-dihydroxy-1,1'-binaphthyl. (S, S) -1,2
-83.5 g (169 mmol) of cyclohexanediamine-toluene (1: 1: 1) complex was collected by filtration and (R)-
2,2'-dihydroxy-1,1'-binaphthyl.
The mother liquor containing (S, S) -1,2-cyclohexanediamine was refluxed for 15 hours, and (S) -2,2′-dihydroxy-1,1′-binaphthyl. (S, S) -1,2-cyclohexane Diamine-toluene (1: 1: 1) complex (9
0 mmol) and (R) -2,2'-dihydroxy-
1,1′-binaphthyl. (S, S) -1,2-cyclohexanediamine (1: 1) complex (90 mmol)
506.5 g of a toluene solution of one mixture was obtained.

Production Example 3 100 g (349 mmol) of (±) -2,2'-dihydroxy-1,1'-binaphthyl, (R, R) -1,2-
40.0 g (350 mmol) of cyclohexanediamine
And a mixture of 450 g of toluene were heated and dissolved. After cooling to room temperature, the precipitated (R) -2,2'-dihydroxy-1,1'-binaphthyl. (R, R) -1,2-cyclohexanediamine.toluene (1: 1: 1) complex 8
3.5 g (169 mmol) was collected by filtration, and (S) -2,
2'-dihydroxy-1,1'-binaphthyl. (R,
506 g of a toluene solution of R) -1,2-cyclohexanediamine (1: 1) complex (180 mmol) was obtained.

Production Example 4 100 g (349 mmol) of (±) -2,2'-dihydroxy-1,1'-binaphthyl, (R, R) -1,2-
20.0 g of cyclohexanediamine (175 mmo
l), a mixture of 450 g of toluene and 50 g of methanol were dissolved by heating. After allowing to cool to room temperature, the precipitated (R) -2,2'-dihydroxy-1,1'-binaphthyl. (R, R) -1,2-cyclohexanediamine.toluene (1: 1: 1) complex64. 0g (130mmo
l) was filtered off and (S) -2,2'-dihydroxy-1,
After concentrating the mother liquor containing 1'-binaphthyl and distilling off the methanol-toluene azeotrope, 16.8 g (147 mmol) of (R, R) -1,2-cyclohexanediamine was added, and (S) -2, The main component is 2'-dihydroxy-1,1'-binaphthyl. (R, R) -1,2-cyclohexanediamine (1: 1) complex (175 mmol) (otherwise, (R) -2,2'- Dihydroxy-1,1'-binaphthyl. (R, R) -1,2-cyclohexanediamine.toluene (1: 1: 1) complex (17.5 mmol)
And (R) -2,2'-dihydroxy-1,1'-binaphthyl (27 mmol) in toluene solution 52
2.8 g were obtained.

Example 1 (R) -2,2'-dihydroxy-1, obtained in Production Example 1
1'-binaphthyl. (R, R) -1,2-cyclohexanediamine.toluene (1: 1: 1) complex (96 mmol
1) and (S) -2,2'-dihydroxy-1,1 '
-Binaphthyl · (R, R) -1,2-cyclohexanediamine (1: 1) complex (96 mmol) as a main component (other than 2,2′-dihydroxy-1,
To 525.9 g of a toluene solution containing 1'-binaphthyl (27 mmol) was added (±) -2,2'-dihydroxy-
37.2 g (130 mmol) of 1,1'-binaphthyl and 50 g of methanol were added and dissolved by heating to 75 ° C., and then allowed to cool to room temperature, and the mixture was filtered, and (R)-
2,2'-dihydroxy-1,1'-binaphthyl.
62.0 g (126 mmol) of an (R, R) -1,2-cyclohexanediamine / toluene (1: 1: 1) complex was obtained.

Example 2 (S) -2,2'-dihydroxy-1, obtained in Production Example 2
1'-binaphthyl. (S, S) -1,2-cyclohexanediamine.toluene (1: 1: 1) complex (90 mmol
1) and (R) -2,2'-dihydroxy-1,1 '
-Binaphthyl. (S, S) -1,2-cyclohexanediamine (1: 1) complex (90 mmol) in 506.5 g of a toluene solution of a 1: 1 mixture was added to (±) -2,2′-dihydroxy-1, 5 'g of 1'-binaphthyl (180
mmol) and heated to 110 ° C. to dissolve, then allowed to cool to room temperature, and the mixture was filtered to obtain (S) -2,
2'-dihydroxy-1,1'-binaphthyl (S,
86.2 g (175 mmol) of S) -1,2-cyclohexanediamine / toluene (1: 1: 1) complex was obtained.

Example 3 (S) -2,2'-dihydroxy-1, obtained in Production Example 3
To 506 g of a toluene solution of 1'-binaphthyl. (R, R) -1,2-cyclohexanediamine (1: 1) complex (180 mmol) was added (±) -2,2'-dihydroxy-
103 g (360 mmol) of 1,1'-binaphthyl and 50 g of methanol were added and dissolved by heating to 75 ° C., and then allowed to cool to room temperature. The mixture was filtered, and (R) -2,
2'-dihydroxy-1,1'-binaphthyl. (R,
66.6 g (135 mmol) of R) -1,2-cyclohexanediamine / toluene (1: 1: 1) complex were obtained.

Example 4 (S) -2,2'-dihydroxy-1, obtained in Production Example 4
1'-binaphthyl. (R, R) -1,2-cyclohexanediamine (1: 1) complex (175 mmol) as a main component (in addition to (R) -2,2'-dihydroxy-1,
1'-binaphthyl. (R, R) -1,2-cyclohexanediamine.toluene (1: 1: 1) complex (17.5 m
mol) and (R) -2,2'-dihydroxy-1,
To 522.8 g of a toluene solution containing 1'-binaphthyl (27 mmol) was added (±) -2,2'-dihydroxy-
After 100 g (350 mmol) of 1,1'-binaphthyl and 50 g of methanol were added and dissolved by heating to 75 ° C., the mixture was allowed to cool to room temperature, and the mixture was filtered to obtain (R) -2,
2'-dihydroxy-1,1'-binaphthyl. (R,
64.0 g (130 mmol) of R) -1,2-cyclohexanediamine / toluene (1: 1: 1) complex were obtained.

[0048]

According to the method of the present invention for producing a molecular compound comprising an optically active compound and an optical resolving agent, a racemic optically active compound is allowed to act on a molecular compound comprising an unnecessary optically active compound and an optical resolving agent. It is possible to generate a molecular compound in which the optically active compound constituting the molecular compound is substituted by the enantiomer of the optically active compound to be obtained.

Claims (3)

[Claims] An enantiomer of an optically active compound constituting a molecular compound is allowed to act on a molecular compound comprising an optically active compound and an optical resolving agent in the presence of an optically active compound constituting the molecular compound. A method for producing a molecular compound comprising an optically active compound and an optical resolving agent, wherein the optically active compound constituting the compound is substituted by its enantiomer. 2. The method for producing a molecular compound according to claim 1, wherein a diastereomer of a molecular compound comprising an optically active compound and an optical resolving agent coexists. 3. The optically active compound is an optically active binaphthol, the optically resolving agent is an optically active diamino compound, and the molecular compound comprising the optically active compound and the optically resolving agent is an optically active binaphthol / optically active diamino compound complex. A method for producing the molecular compound according to claim 1.