JP2002080415A - Method for producing optically active 2,2'-binaphthol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an optically active 2,2'-binaphthol derivative useful as a medicament and an agrochemical, an intermediate therefor, and an asymmetric ligand thereof. SOLUTION: This method for producing the optically active 2,2'-binaphthol derivative expressed by the formula (3) (W1 and W2 are each H, a 2-6C alkynyl, a 1-6C alkoxy, a halogen or the like) or its enantiomer comprises treating a 2-naphthol derivative expressed by the formula (1) with an oxygen-containing gas in the presence of an optically active ruthenium complex expressed by the formula (2) (R1, R2, R3 and R4 are each H, a 1-8C alkyl, a phenyl or a 4-8C ring which is formed by any two groups selected from R1, R2, R3 and R4; R is H, phenyl or the like; X1 and X2 are each a halogen, NO or the like; and Y is H or the like) and the light.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an optically active 2,2'-binaphthol derivative from a 2-naphthol derivative using an optically active ruthenium complex.

[0002]

2. Description of the Related Art Optically active 2,2'-binaphthol derivatives are important intermediates of various fine chemical compounds including agriculture and pharmaceuticals, and compounds useful as asymmetric ligands in organic synthesis. is there.

Optically active 2,2-naphthol derivatives
As a method for producing the 2′-binaphthol derivative, for example,
1) Tetrahedron Lett., 1983, 24, 3261 and JP-A-4-14-1
Production method using an optically active amine-copper complex described in 8043 and the like as a catalyst, 2) J. Org. Chem., 1993, 58, 4534 and
Production method using an optically active diamine-copper complex as a catalyst described in J. Org. Chem., 1999, 64, 2264, etc. 3) J. Che
m. Soc., Chem. Commun., 1993, 909, etc., a production method using oxidative coupling using an optically active transition metal complex catalyst such as a production method using an optically active bipyridyl-ruthenium complex as a catalyst is known. ing.

[0004]

However, the above-mentioned production methods do not always give good results for the production of all optically active 2,2'-binaphthol derivatives. It is the current situation.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies on a method for producing an optically active 2,2'-binaphthol derivative, and as a result, completed the present invention.

That is, the present invention provides the following formula (1)

[0007]

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Wherein W ¹ and W ² are each independently a hydrogen atom, a linear, branched or cyclic C ₁ -C ₆ alkyl group, a linear, branched or cyclic C ₂ -C ₆ alkenyl Group, linear, branched or cyclic C ₂ -C ₆ alkynyl group ニ ル The alkyl group, alkenyl group and alkynyl group are a halogen atom, a substituted silyl group or a phenyl group (the phenyl group is a halogen atom, C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group, cyano group or nitro group.). ｝, C ₁ -C ₆
An alkoxy group, a phenyl group (the phenyl group may be optionally substituted with a halogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, a cyano group or a nitro group), C _1- C ₅ alkylcarbonyl group means a C ₁ -C ₅ alkoxycarbonyl group or a halogen atom. And the 2-naphthol derivative represented by the formula (2)

[0009]

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Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a linear, branched or cyclic C ₁
A C ₈ alkyl group (the alkyl group may be optionally substituted with a halogen atom) or a phenyl group (the phenyl group is a halogen atom, a C ₁ -C ₄ alkyl group, a C _1-
It may be optionally substituted with a C ₄ alkoxy group, a cyano group or a nitro group. ), R ¹ , R ² , R ³ and R ⁴
Any two may form a ring of C ₄ -C ₈ together.

R is a hydrogen atom, a linear, branched or cyclic C ₁ -C ₈ alkyl group (the alkyl group may be optionally substituted with a halogen atom), a phenyl group (the phenyl group is Halogen atom, C ₁ -C ₄ alkyl group, C _1-
It may be optionally substituted with a C ₄ alkoxy group, a cyano group or a nitro group. ), C ₁ ~C ₄ alkoxy group, C ₁ ~
C ₅ alkyl group, C ₁ -C ₅ alkylcarbonyloxy group, C ₁ -C ₅ alkoxycarbonyl group, or refers to a substituted silyl group, X ¹ and X ² are each independently, C
_{A 1 to} C ₅ alkylcarbonyloxy group (the alkylcarbonyloxy group may be optionally substituted with a halogen atom), an arylcarbonyloxy group (the arylcarbonyloxy group is optionally substituted with a halogen atom) A C ₁ -C ₄ alkylsulfonyloxy group (the alkylsulfonyloxy group may be optionally substituted with a halogen atom), an arylsulfonyloxy group (the arylsulfonyloxy group is a halogen atom). Atom, a halogen atom, a hydroxyl group, PF ₆ , ClO ₄ , BF ₄ , NO ₃ , 1 / 2C
O ₃ , ＳＯSO ₄ , ３PO ₄ or NO, Y
Represents a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl group,
₁ -C ₄ alkoxy group means a nitro group or a cyano group,
The binaphthyl group may be racemic or optically active. Wherein the compound is treated with an oxygen-containing gas in the presence of an optically active ruthenium complex represented by the formula

[0012]

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Wherein W ¹ and W ² are the same as above. And a method for producing an optically active 2,2'-binaphthol derivative or an enantiomer thereof.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

First, R ¹ , R ² , R ³ , R ⁴ , R, X ¹ ,
The terms in each of the substituents X ² , Y, W ¹ and W ² will be described.

In this specification, "n" represents normal,
"I" is iso, "s" is secondary, "t" is tertiary, "c" is cyclo, "o" is ortho,
"M" means meta and "p" means para.

Examples of the linear, branched or cyclic C ₁ -C ₆ alkyl group include a methyl group, an ethyl group, an n-propyl group,
i-propyl group, c-propyl group, n-butyl group, i-
Butyl, s-butyl, t-butyl, c-butyl, n-pentyl, c-pentyl, n-hexyl and c-hexyl.

The linear, branched or cyclic C ₂ -C ₆ alkenyl group includes vinyl, allyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 2-methyl-2-
Propenyl group, 1-ethyl-2-vinyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1,2-dimethyl-1-propenyl group,
1,2-dimethyl-2-propenyl group, 1-ethyl-1
-Propenyl group, 1-ethyl-2-propenyl group, 1-
A methyl-1-butenyl group, a 1-methyl-2-butenyl group, a 2-methyl-1-butenyl group, a 1-i-propylvinyl group, a 2,4-pentadienyl group, a 1-hexenyl group, a 2-hexenyl group, Examples include a 3-hexenyl group, a 4-hexenyl group, a 5-hexenyl group, a 2,4-hexadienyl group, a 1-methyl-1-pentenyl group, a 1-c-pentenyl group, and a 1-c-hexenyl group.

The linear, branched or cyclic C ₂ -C ₆ alkynyl group includes ethynyl, 1-propynyl, 2-
Propynyl group, 1-butynyl group, 2-butynyl group, 3-
Butynyl group, 1-pentynyl group, 2-pentynyl group, 3
-Pentynyl group, 4-pentynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group and the like, preferably ethynyl group, 1-propynyl group, 1- Butynyl group, 1-pentynyl group, 4-pentynyl group, 1-hexynyl group, 5
-Hexynyl group and the like.

Examples of the linear, branched or cyclic C ₁ -C ₈ alkyl group include a methyl group, an ethyl group, an n-propyl group,
i-propyl group, c-propyl group, n-butyl group, i-
Butyl, s-butyl, t-butyl, c-butyl, n-pentyl, c-pentyl, n-hexyl, c-hexyl, n-heptyl, c-heptyl, n- Examples include an octyl group and a c-octyl group.

The C ₁ -C ₄ alkyl group includes a linear, branched and cyclic alkyl group, and includes a methyl group, an ethyl group,
n-propyl group, i-propyl group, c-propyl group, n
-Butyl group, i-butyl group, s-butyl group, t-butyl group, c-butyl group and the like.

The C ₁ -C ₄ alkoxy groups include straight-chain, branched and cyclic alkoxy groups, and include methoxy, ethoxy, n-propoxy, i-propoxy, c-propoxy and n-alkoxy groups. Butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, c-butoxy group and the like. As the C ₁ -C ₆ alkoxy group, in addition to the above, n
-Pentyloxy group, c-pentyloxy group, n-hexyloxy group, c-hexyloxy group and the like.

The C ₁ -C ₅ alkylcarbonyl group includes
Straight-chain, branched and cyclic alkylcarbonyl groups,
Methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, i-propylcarbonyl group, c-propylcarbonyl group, n-butylcarbonyl group, i-butylcarbonyl group, s-butylcarbonyl group, t-butylcarbonyl group, a c-butylcarbonyl group, an n-pentylcarbonyl group, a c-pentylcarbonyl group, and the like.

The C ₁ -C ₅ alkylcarbonyloxy group includes linear, branched and cyclic alkylcarbonyloxy groups, and includes methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, i-propyl Carbonyloxy group, c-propylcarbonyloxy group, n-butylcarbonyloxy group, i-butylcarbonyloxy group, s-butylcarbonyloxy group, t
-Butylcarbonyloxy group, c-butylcarbonyloxy group, n-pentylcarbonyloxy group, c-pentylcarbonyloxy group and the like.

The arylcarbonyloxy group includes a benzenecarbonyloxy group, an o-methylphenylcarbonyloxy group, an m-methylphenylcarbonyloxy group, a p-methylphenylcarbonyloxy group, an α-naphthalenecarbonyloxy group and a β-naphthalenecarbonyl group. Oxy groups and the like.

The C ₁ -C ₅ alkoxycarbonyl groups include straight-chain, branched and cyclic alkoxycarbonyl groups, methoxycarbonyl group, ethoxycarbonyl group,
n-propoxycarbonyl group, i-propoxycarbonyl group, c-propoxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, s-butoxycarbonyl group, t-butoxycarbonyl group, c-butoxycarbonyl group, n- A pentyloxycarbonyl group and c
-Pentyloxycarbonyl group and the like.

The C ₁ -C ₄ alkylsulfonyloxy group includes linear, branched and cyclic alkylsulfonyloxy groups, and includes methylsulfonyloxy group, ethylsulfonyloxy group, n-propylsulfonyloxy group, i-
Propylsulfonyloxy group, c-propylsulfonyloxy group, n-butylsulfonyloxy group, i-butylsulfonyloxy group, s-butylsulfonyloxy group,
Examples include a t-butylsulfonyloxy group and a c-butylsulfonyloxy group.

The arylsulfonyloxy group includes benzenesulfonyloxy, o-methylphenylsulfonyloxy, m-methylphenylsulfonyloxy, p-methylphenylsulfonyloxy, α-naphthalenesulfonyloxy and β-naphthalenesulfonyl Oxy groups and the like.

The halogen atom includes fluorine, chlorine, bromine and iodine.

Examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, tri-i-propylsilyl group, tri-n-butylsilyl group, tri-i-butylsilyl group and dimethylethylsilyl. Groups, dimethyl-n-propylsilyl group, dimethyl-n-butylsilyl group, dimethyl-i-butylsilyl group, dimethyl-t-butylsilyl group, and the like.

As the C ₄ -C ₈ ring, a c-butane ring, c
A pentane ring, a c-hexane ring, a c-heptane ring and c
-An octane ring and the like.

Preferred are R ¹ , R ² , R ³ , R ⁴ , R,
X ¹ , X ² , Y, W ¹ and W ² will be described.

Preferred R ¹ , R ² , R ³ and R ⁴ include
Each independently includes a hydrogen atom, a methyl group, a phenyl group, and the like. In addition, any ^{two of} R ¹ , R ² , R ^3, and R ⁴ together form a c-hexane ring. Things.

Preferred combinations of R ¹ , R ² , R ³ and R ⁴ are shown below. 1. R ¹ and R ³ are hydrogen atoms, and R ² and R ⁴ are methyl groups. 2. R ¹ and R ³ are methyl groups, and R ² and R ⁴ are hydrogen atoms. 3. R ¹ and R ³ are hydrogen atoms, and R ² and R ⁴ are phenyl groups. 4. R ¹ and R ³ are phenyl groups, and R ² and R ⁴ are hydrogen atoms. 5. R ¹ and R ³ are hydrogen atoms, and R ² and R ⁴ together form a c-hexane ring. 6. R ² and R ⁴ are hydrogen atoms, and R ¹ and R ³ together form a c-hexane ring.

Preferred R includes a phenyl group.

Preferred X ¹ and X ² each independently include a halogen atom and NO, and more preferably a chlorine atom and NO.

Preferred combinations of X ¹ and X ² are shown below. 1. X ¹ is a halogen atom, and X ² is NO. 2. X ¹ is a chlorine atom, and X ² is NO.

Preferred examples of Y include a hydrogen atom.

Preferred examples of W ¹ include a hydrogen atom, a bromine atom, a methoxy group and a 2-phenylethynyl group.

Preferred examples of W ² include a hydrogen atom, an acetyl group, a methoxycarbonyl group and a bromine atom, and more preferably a hydrogen atom.

Next, a method for producing the optically active ruthenium complex represented by the formula (2) will be described.

Formula 1 shows a method for producing a salicylaldehyde compound (7) as a raw material of an imine compound (9) as a ligand of an optically active ruthenium complex. [Tetrahe
It can be produced by referring to the method described in Dron 50 (41), 11827 (1994). ]. Equation 1

[0043]

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Wherein Y and R are as defined above,
f ₂ NPh is N-phenyltrifluoromethanesulfonimide, RMgBr is a Grignard reagent, NiCl
₂ (dppe) is [1,2-bis (diphenylphosphino) ethane] nickel (II) chloride, MOMCl is chloromethyl methyl ether, (i-Pr) ₂ NEt is diisopropylethylamine, and t-BuLi is tertiary L-butyllithium, DMF means N, N-dimethylformamide, TMSBr means trimethylsilyl bromide. That is, the binaphthol derivative (4) is reacted with N-phenyltrifluoromethanesulfonimide in the presence of (a) collidine to convert one hydroxyl group to triflate,
(B) R is introduced with a Grignard reagent using [1,2-bis (diphenylphosphino) ethane] nickel (II) chloride as a catalyst to give (5), and then (c) under basic conditions,
Methoxymethylation with chloromethyl methyl ether,
After (6), (d) lithiation with t-butyllithium, (e) formylation with dimethylformamide,
(F) A salicylaldehyde compound (7) is synthesized through demethoxymethylation with trimethylsilyl bromide.

When an optically active binaphthol derivative is used, an optically active salicylaldehyde compound can be synthesized by the same method.

Formula 2 shows a method for producing the imine compound (9) which is a ligand of the optically active ruthenium complex. Equation 2

[0047]

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Wherein Y, R, R ¹ , R ² , R ³ and R ⁴ are as defined above. The imine compound (9) can be produced by subjecting the salicylaldehyde compound (7) and the diamine compound (8) to dehydration condensation.

As the diamine compound (8), commercially available products can be generally used.

The amount of the diamine compound (8) to be used relative to the salicylaldehyde compound (7) is 0.2 to 2 molar equivalents, preferably about 0.5 equivalent.

The reaction temperature is not particularly limited.
The temperature can be from 0 ° C. to the boiling point of the solvent used, but preferably from 0 ° C. to 50 ° C.

Examples of the solvent include alcohol solvents such as ethanol and methanol; nitrile solvents such as acetonitrile and propionitrile; halogen solvents such as dichloromethane and chloroform; aromatic hydrocarbon solvents such as benzene and toluene; tetrahydrofuran; Examples thereof include ether solvents such as diethyl ether, hydrocarbon solvents such as hexane and heptane, and amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

Preferred solvents are ethanol, methanol, acetonitrile, dichloromethane, toluene, N,
N-dimethylformamide and the like can be mentioned.

In the reaction, a dehydrating agent may coexist in order to remove generated water.

As the dehydrating agent, anhydrous magnesium sulfate,
Examples include boric anhydride, molecular sieves, and the like.

The amount of the dehydrating agent used may be at least equimolar to the generated water.

The generated water may be removed by azeotropic dehydration with the above solvent.

The produced imine compound does not necessarily need to be taken out of the reaction system, and can be continuously used for producing an optically active ruthenium complex.

When an optically active salicylaldehyde compound is used, an imine compound having a binaphthyl group that is optically active can be synthesized in the same manner.

Formula 3 shows the method for producing the optically active ruthenium complex (2).

Equation 3

[0062]

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[Wherein, Y, R, R ¹ , R ² , R ³ , R ⁴ , X
¹ and X ² are the same as described above, and X ³ and X ⁴ are each independently a C ₁ -C ₅ alkylcarbonyloxy group (the alkylcarbonyloxy group may be optionally substituted with a halogen atom. ), an arylcarbonyloxy group (the arylcarbonyl group may be optionally substituted with halogen atoms.), C ₁ -C ₄ alkylsulfonyloxy group (the alkyl sulfonyloxy group is optionally halogen atom An arylsulfonyloxy group (optionally substituted).
It may be optionally substituted with a halogen atom. ), A halogen atom, a hydroxyl group, PF ₆ , ClO ₄ , BF ₄ , NO ₃ , 1
/ 2CO _3, it means a 1 / 2SO ₄ or 1 / 3PO _4. The optically active ruthenium complex (2) can be produced by reacting the imine compound (9) with sodium hydride, deprotonating, and then reacting the ruthenium compound (10).

The amount of sodium hydride used is 1.8 to 3.0 equivalents, preferably 2.
0 to 2.4 equivalents are good.

The temperature at which sodium hydride is added is -30
It is in the range of -60C, preferably in the range of 0-40C.

When sodium hydride is added, hydrogen gas is generated, but it is necessary that the generation of hydrogen gas has been completed before the next reaction.

The time when hydrogen gas is completely completed varies depending on the temperature to be added. For example, when the temperature is 25 ° C., it is sufficient to carry out the reaction for 10 minutes to 3 hours, preferably 30 minutes to 1 hour.

As the solvent, those used in the following reaction with the ruthenium compound can be used.

The amount of the ruthenium compound (10) used is 0.5 to 10 molar equivalents relative to the imine compound.
Preferably 0.8 mol to 2 mol equivalent is good.

The reaction temperature is not particularly limited.
The temperature can be from 0 ° C. to the boiling point of the solvent used, but it is preferably in the range of 80 ° C. to 130 ° C.

The reaction time varies depending on the reaction temperature. For example, when the reaction temperature is 110 ° C., the reaction time is 30 to 100 hours, preferably 40 to 60 hours.

Examples of the solvent include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

Preferred examples of the solvent include N, N-dimethylformamide.

When an imine compound whose binaphthyl group is optically active is used, an optically active ruthenium complex whose binaphthyl group is optically active can be synthesized by the same method.

Next, the optical activity 2, represented by the formula (3),
A method for producing the 2′-binaphthol derivative will be described.

The 2-naphthol derivative of the formula (1) as a substrate includes 2-naphthol, 6-bromo-2-naphthol, 6-methoxy-2-naphthol, 6- (2-phenylethynyl) -2-naphthol , 3-acetyl-2-
Naphthol, 3-methoxycarbonyl-2-naphthol, 3-bromo-2-naphthol, 3-methoxycarbonyl 6-bromo-2-naphthol and the like can be mentioned.

The oxygen-containing gas is not particularly limited as long as it is a gas which does not participate in the reaction containing oxygen. Specific examples include air, oxygen, and any mixed gas of oxygen and nitrogen.

The amount of oxygen used (oxygen content in the oxygen-containing gas) is usually from equimolar (1 molar equivalent) to a large excess with respect to the alcohol derivative of the formula (1) as a substrate. it can.

The reaction may be usually carried out under normal pressure.
If necessary, the reaction may be performed under pressure.

Preferred specific examples of the optically active ruthenium complex of the formula (2) include the following compounds (11) and (1)
2) and (13) and their enantiomers.

[0081]

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The amount of the optically active ruthenium complex used is 0.01 to 5 with respect to the alcohol derivative of the formula (1).
A range of 0 mol%, preferably 0.1 to 10 mol% is sufficient.

The light used is not only sunlight but also
Examples thereof include a halogen lamp, a tungsten lamp, an incandescent lamp, a fluorescent lamp, a high-pressure mercury lamp and a low-pressure mercury lamp, and preferably include a halogen lamp and a fluorescent lamp.

The reaction temperature is usually -50 ° C to 100 ° C.
C., preferably -25.degree. C. to 50.degree.

The reaction time depends on the alcohol derivative used,
Although it depends on the type of optically active ruthenium complex and light, it is usually 0.1 to 1000 hours.

The reaction solvent is not particularly limited as long as it does not participate in the reaction. For example, nitrile solvents such as acetonitrile, propionitrile, and butyronitrile;
Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, xylene,
Mesitylene, chlorobenzene, fluorobenzene, o-
Aromatic hydrocarbon solvents such as dichlorobenzene, aliphatic hydrocarbon solvents such as n-hexane, cyclohexane, n-octane and n-decane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; dichloromethane; Halogenated hydrocarbon solvents such as dichloroethane and carbon tetrachloride; ether solvents such as tetrahydrofuran, diethyl ether, t-butyl methyl ether and dimethoxyethane; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, -Alcoholic solvents such as butanol, isobutanol and cyclohexanol; and the like, and preferred solvents include benzene, toluene and chlorobenzene.

Further, these reaction solvents can be used alone or in combination.

After completion of the reaction, the desired product is extracted with an appropriate solvent, the solvent is concentrated under reduced pressure, and the mixture is concentrated to an optically active 2,2'- by silica gel column chromatography, recrystallization or distillation.
A binaphthol derivative can be obtained.

The optical purity of the target substance can be measured by an optically active chromatography column or optical rotation.

[0090]

The present invention will be described in more detail with reference to the following examples.
The present invention is not limited to these.

Reference Example 1 [Synthesis of Optically Active Imine Compound (14)]

[0092]

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An optically active salicylaldehyde compound (Y
Is a hydrogen atom, and R is a phenyl group (R) -form of the salicylaldehyde compound (7)) 1.97 g (5.25)
mmol) and 300 mg (2.63 mmol) of (1R, 2R)-(-)-1,2-diaminocyclohexane in 60 m of ethanol.
and stirred at room temperature for 4 hours. The resulting yellow-white precipitate was collected by filtration, washed with a small amount of ethanol, and dried under reduced pressure to obtain 2.09 g of the objective optically active imine compound (14).
(Yield 96.0%) was obtained as a yellow-white solid.

Reference Example 2 [Synthesis of Optically Active Ruthenium Complex (11)]

[0095]

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159 mg of Ru (NO) Cl ₃ .nH ₂ O
(0.544 mmol as trihydrate) was dissolved in 1.8 ml of N, N-dimethylformamide and heated at 110 ° C. for 4 hours. After evaporating the solvent under reduced pressure, N, N-dimethylformamide (3.6 ml) was added to the residue to prepare a Ru (NO) Cl ₃ solution. Sodium hydride 19.2 mg (0.8
00 mmol) in 3.6 ml of N, N-dimethylformamide
, And after stirring, the optically active imine compound (14) 300
mg (0.363 mmol) was added. Hydrogen is generated,
The mixture turned to a clear orange solution. After stirring for 30 minutes,
The obtained orange solution was added to the previously prepared solution of Ru (NO) Cl ₃ and stirred at 110 ° C. for 48 hours. The reaction mixture was returned to room temperature, and the solvent was distilled off under reduced pressure while gently warming. The residue was dissolved in dichloromethane and washed with water (3 times) and saturated saline (1 time). The organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was recrystallized twice from dichloromethane-acetonitrile to obtain 163 mg (45%) of the target optically active ruthenium complex (11) as red-brown crystals.

IR (KBr): 3049, 2930, 2860, 1851, 182
0, 1662, 1614, 1579, 1319, 754cm ^-1 Elemental analysis Found H, 4.73%; C 72.16%; N, 4.25% Calculated H, 4.53%; C 72.03%; N, 4.20%

Reference Examples 1 and 2 except that (1R, 2R)-(+)-1,2-diphenylethylenediamine was used instead of (1R, 2R)-(-)-1,2-diaminocyclohexane. By performing the same operation as in 2, optically active ruthenium complex (13)
Got.

[0099] Further, except that (1R, 2R) -1,2-dimethylethylenediamine was used instead of (1R, 2R)-(-)-1,2-diaminocyclohexane, By performing the same operation, an optically active ruthenium complex (12) was obtained.

Example 1 [Optically active 6,6'-dibromo-
Synthesis of 2,2′-dihydroxynaphthalene (R form)]

6-bromo-2-naphthol (223 m
g, 1.0 mmol) and an optically active ruthenium complex (1
1) (50 mg, 5 μmol) of toluene (10 mL)
The solution was charged into a Pyrex glass reaction vessel, and further stirred at 25 ° C. for 24 hours in air under irradiation with a halogen lamp (150 W). The reaction solution is directly subjected to silica gel column chromatography (hexane / ethyl acetate = 10/1 to 4
/ 1 to 2/1) to give (R) -6,6'-dibromo-
181 mg of 2,2'-dihydroxynaphthalene (yield 8
2%). The optical purity of the obtained product was determined by HPLC.
(DAICEL CHIRALCELAS, hexane:
When analyzed by isopropanol = 9: 1), 68
% Ee.

Examples 2 to 11 [Various optically active 2,2'-
Synthesis of Binaphthol Derivatives]

Examples 2 to 11 were carried out in the same manner as in Example 1 except that the substrate, the optically active ruthenium complex and the solvent were changed as shown in the following table. The results are shown in Table 1. still,
The amount of the complex used was shown as mol% based on the substrate. Table 1

[0104]

TABLE 1 Example Substrate Ruthenium Complex Solvent Yield Optical Purity Absolute No. W ¹ W ² Complex Usage (%) (% ee) Allocation ─────────────────────────────── ───── 2 HH (11) 2 mol% C ₆ D ₆ 65 57 R 3 HH (11) 2 mol% Toluene 72 65 R 4 HH (11) 2 mol% Chloropentacene 82 56 R 5 HH (11) 2 mol% Dichloromethane 95 56 R 6 HH (11) 2 mol% diethyl ether 43 61 R 7 HH (13) 2 mol% C ₆ D ₆ 56 57 R 8 HH (12) 2 mol% C ₆ D ₆ 40 56 R 9 Br H (11) 5 mol% Toluene 77 69 R 10 PhC≡CH (11) 5 mol% Toluene 93 68 R 11 OMe H (11) 2 mol% Toluene 73 33 R ───────────────

The optical purity in Example 10 was determined by HPLC
(DAICEL CHIRALCEL AS, hexane: isopropanol = 4: 1). The optical purity in Example 11 was determined by HPLC (DAICEL C
HIRALCEL OD-H, hexane: isopropanol = 4: 1).

[0106]

According to the method of the present invention, a 2-naphthol derivative is treated with an oxygen-containing gas in the presence of an optically active ruthenium complex and light to produce a medical / pesticide or an intermediate thereof, Optically active 2, useful as a ligand
2′-binaphthol derivatives can be produced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 39/14 C07C 39/14 // C07M 7:00 C07M 7:00

Claims (3)

[Claims] (1) Formula (1) Wherein W ¹ and W ² are each independently a hydrogen atom,
Straight-chain, branched or cyclic C ₁ -C ₆ alkyl group, straight-chain,
A branched or cyclic C ₂ -C ₆ alkenyl group, a linear, branched or cyclic C ₂ -C ₆ alkynyl group ニ ル the alkyl group,
Alkenyl and alkynyl groups, halogen atom, substituted silyl group or a phenyl group (said phenyl group is optionally substituted by halogen atom, C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group, a cyano group or a nitro group May be substituted.). ｝, A C ₁ -C ₆ alkoxy group, a phenyl group (this phenyl group may be optionally substituted with a halogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, a cyano group or a nitro group) good.), refers to C ₁ -C ₅ alkylcarbonyl group, C ₁ -C ₅ alkoxycarbonyl group or a halogen atom. And a 2-naphthol derivative represented by the formula (2): Wherein R ¹ , R ² , R ³ and R ⁴ are each independently
A hydrogen atom, a linear, branched or cyclic C ₁ -C ₈ alkyl group (the alkyl group may be optionally substituted with a halogen atom) or a phenyl group (the phenyl group is a halogen atom, C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group, cyano group or nitro group), and any ^{two of} R ¹ , R ² , R ³ and R ⁴ it may form a ring of C ₄ -C ₈ together. R represents a hydrogen atom, a linear, branched or cyclic C ₁ -C ₈ alkyl group (the alkyl group may be optionally substituted with a halogen atom), a phenyl group (the phenyl group is a halogen atom, A C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, a cyano group or a nitro group, which may be optionally substituted), a C ₁ -C ₄ alkoxy group, a C ₁ -C ₅ alkylcarbonyl group, C ₁ -C ₅ alkylcarbonyloxy group, C ₁
Means -C ₅ alkoxycarbonyl group, or a substituted silyl group, X ¹ and X ² are independently, C ₁ -C ₅ alkylcarbonyloxy group (the alkylcarbonyloxy group is optionally substituted with halogen atom An arylcarbonyloxy group (the arylcarbonyloxy group may be optionally substituted with a halogen atom),
C ₁ -C ₄ alkylsulfonyloxy group (the alkyl sulfonyloxy group may be optionally substituted with halogen atoms.), Arylsulfonyloxy group (the aryl sulfonyloxy group is optionally substituted by halogen atom ), A halogen atom, a hydroxyl group, PF ₆ ,
ClO ₄ , BF ₄ , NO ₃ , ＣＯCO ₃ , ＳＯSO ₄ ,
Means 1 / 3PO ₄ or NO, Y is a hydrogen atom, a halogen atom, C ₁ -C ₄ alkyl group,
It means a C ₁ -C ₄ alkoxy group, a nitro group or a cyano group, and the binaphthyl group may be racemic or optically active. Wherein the compound is treated with an oxygen-containing gas in the presence of an optically active ruthenium complex represented by the formula: Wherein W ¹ and W ² are the same as above. ] The method for producing an optically active 2,2'-binaphthol derivative represented by the formula 2. In the formula (2), R ¹ , R ³ and Y are hydrogen atoms, R ² and R ⁴ together form a cyclohexane ring, R is a phenyl group, and X ¹ is chlorine. Atom,
The method according to claim 1, wherein an optically active ruthenium complex in which X ² is NO or an enantiomer thereof is used. 3. The method according to claim 2, wherein an optically active ruthenium complex in which the binaphthyl group of the formula (2) is an optically active substance is used.