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Title:
BINAPHTHOL ALDEHYDE DERIVATIVES AND METHOD FOR PREPARING THE SAME
Document Type and Number:
WIPO Patent Application WO/2010/055966
Kind Code:
A1
Abstract:
The present invention relates to a binaphthol aldehyde derivative represented by Chemical Formula 1 and a method of preparing the same. The binaphthol aldehyde derivative represented by Chemical Formula 1 enables various kinds of substituent groups to be very efficiently introduced into the hydrogen position of a 2' hydroxy group of 2,2'-binaphthol-3-aldehyde. The method is advantageous in that the binaphthol aldehyde derivative represented by Chemical Formula 1 can be prepared in a safe manner at low cost.

Inventors:
KIM, Kwan-Mook (61-307 Banpo Apt, 773 Banpo-dong,Seocho-gu, Seoul 137-040, KR)
AHN, Yoon-Su (1-106 Gyeongnam Apt, 1028-1 Bangbae 3-dongSeocho-gu, Seoul 137-752, KR)
PARK, Hyun-Jung (203 Jeongmyeong Apt, 38-30 Sinsa-dongEunpyeong-gu, Seoul 122-080, KR)
Application Number:
KR2008/007282
Publication Date:
May 20, 2010
Filing Date:
December 10, 2008
Export Citation:
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Assignee:
AMINO LUX, INC. (#1006, Hyundai Goldentel 3 114,Gwangjang-dong, Gwangjin-gu, Seoul 143-802, KR)
KIM, Kwan-Mook (61-307 Banpo Apt, 773 Banpo-dong,Seocho-gu, Seoul 137-040, KR)
AHN, Yoon-Su (1-106 Gyeongnam Apt, 1028-1 Bangbae 3-dongSeocho-gu, Seoul 137-752, KR)
PARK, Hyun-Jung (203 Jeongmyeong Apt, 38-30 Sinsa-dongEunpyeong-gu, Seoul 122-080, KR)
International Classes:
C07C39/23; C07C47/192
Foreign References:
KR100870227B1
Other References:
HYNGJUNG PARK ET AL.: 'Stereoconversion of amino acids and peptides in uryl-pendant binol Schiff Bases' CHEMISTRY-A EUROPEAN JOURNAL vol. 14, no. 32, 24 September 2008, ISSN 0947-6539 pages 9935 - 9942
LIJUN TANG ET AL.: 'Reactive Extraction of Enantiomers of 1,2-Amino Alcohols via Stereoselective Thermodynamic and Kinetic Processes' JOURNAL OF ORGANIC CHEMISTRY vol. 73, no. 15, 04 July 2008, ISSN 0022-3263 pages 5996 - 5999
RAJU NANDHAKUMAR ET AL.: 'Effects of ring substituents on enantioselective recognition of amino alcohols and acids in uryl-based binol receptors' TETRAHEDRON vol. 64, no. 33, 11 June 2008, ISSN 0040-4020 pages 7704 - 7708
LIJUN TANG ET AL.: 'Chirality conversion and enantioselective extraction of amino acids by imidazolium-based binol-aldehyde' TETRAHEDRON LETTERS vol. 49, 23 September 2008, ISSN 0040-4039 pages 6914 - 6916
LILI JIN ET AL.: 'Chiral catalysts for the asymmetric cycloaddition of carbon dioxide with epoxides' TETRAHEDRON: ASYMMETRY vol. 19, no. 16, 29 August 2008, ISSN 0957-4166 pages 1947 - 1953
Attorney, Agent or Firm:
HANYANG PATENT FIRM (9F Keungil Tower, 677-25 Yeoksam-dongGangnam-gu, Seoul 135-914, KR)
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Claims:
Claims

[1] A compound represented by Chemical Formula 1 below:

[Chemical Formula 1]

wherein X is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more substituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, wherein Y is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more substituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, wherein n and m are each independently an integer of 0 - 5, and wherein Rl is selected from the group consisting of an alkyl group of C1-C5, an arylalkyl group of C6-C10, and an alkoxy alkyl group of C2-C10. [2] The compound represented by Chemical Formula 1 above according to claim 1, wherein X is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a cyano group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more substituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, wherein Y is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a cyano group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more substituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, wherein n and m are each independently an integer of 0 - 5, and wherein Rl is selected from the group consisting of an alkyl group of C1-C5 and an arylalkyl group of C6-C10. [3] The compound represented by Chemical Formula 1 above according to claim 2, wherein n and m are each 0, and Rl is a methyl group or an ethyl group. [4] A method of preparing the compound represented by Chemical Formula 1 above, comprising the step of: reacting a compound represented by Chemical Formula 2 below with

(here, Rl is selected from the group consisting of an alkyl group of C1-C5, an arylalkyl group of C6-C10, and an alkoxy alkyl group of C2-C10) in the presence of a base: [Chemical Formula 2]

wherein X is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more substituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, wherein Y is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more substituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, and wherein n and m are each independently an integer of 0 - 5.

[5] The method of preparing the compound represented by Chemical Formula 1 above according to claim 4, wherein the compound represented by Chemical Formula 2 above is prepared by the steps of: reducing a compound represented by Chemical Formula 4 below to obtain a compound represented by Chemical Formula 3 below; and oxidizing the obtained compound represented by Chemical Formula 3: [Chemical Formula 3]

[Chemical Formula 4]

wherein X is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more substituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, wherein Y is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more substituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, wherein n and m are each independently an integer of 0 - 5, and wherein R2 is selected from the group consisting of hydrogen, an alkyl group of C1-C5, a tosyl group, CH3SO2- and CH3CO-.

[6] The method of preparing the compound represented by Chemical Formula 1 above according to claim 5, wherein n and m are each 0, and R2 is a methyl group.

[7] The method of preparing the compound represented by Chemical Formula 1 above according to claim 5, further comprising the step of: hydrolyzing the compound represented by Chemical Formula 4 above to obtain 2,2'-dihydroxy-3-binaphtholic acid and then resolving the obtained 2,2'-dihydroxy-3-binaphtholic acid using cinchonidine to form an optically-pure compound represented by Chemical Formula 4 above, before the step of reducing the compound represented by Chemical Formula 4 above.

[8] The method of preparing the compound represented by Chemical Formula 1 above according to claim 5, wherein the compound represented by Chemical Formula 4 above is prepared by reacting a compound represented by Chemical Formula 5 below with a compound represented by Chemical Formula 6 below using CUCI(OH)-TMEDA: [Chemical Formula 5]

[Chemical Formula 6] wherein X is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more substituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, wherein Y is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more substituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, wherein n and m are each independently an integer of 0 - 5, and wherein R2 is selected from the group consisting of hydrogen, an alkyl group of C1-C5, a tosyl group, CH3SO2- and CH3CO-, on the proviso that X and Y does not exist at carbon number eigh of naphthalene back bone of the above Chemical Formula 5 and Chemical Formula 6.

Description:
Description

BINAPHTHOL ALDEHYDE DERIVATIVES AND METHOD

FOR PREPARING THE SAME

Technical Field

[1] The present invention relates to a binaphthol aldehyde derivative which is a novel compound that is usefully used to selectively introduce various kinds of substituent groups into the hydrogen position of a 2' hydroxy group of 2,2'-binaphthol-3-aldehyde, and a method of preparing the same. Background Art

[2] Compounds in which a hydrogen of a 2' hydroxy group of

2,2'-binaphthol-3-aldehyde is substituted have been used for various purposes. Among the compounds, a compound represented by Chemical Formula 8 below, which is usefully used to separate amino alcohols or amino acids into their respective optical isomers by recognizing their chirality through an imine bond or to convert L-amino acid into D-amino acid, was developed by the present inventors ((a)Park, H.; Kim, K. M.; Lee, A.; Ham, S.; Nam, W.; Chin, J. J. Am. Chem. Soc. 2007, 129, 1518-1519; (b) Kim, K. M.; Park, H.; Kim, H.; Chin, J.; Nam, W. Org. Lett. 2005, 7, 3525-3527.), and was then registered (Korean Patent Registration No. 10-0661280).

[3] [Chemical Formula 8]

[4]

f O

I I f R 3

OR 2 ( I

I [ I

[5] However, according to conventional technologies, when a hydrogen of a 2' hydroxy group of 2,2'-binaphthol-3-aldehyde is substituted, a unwanted side product in which hydrogen of a 2 hydroxy group is substituted is also obtained. Therefore, technologies for preventing side products from being produced by increasing the selectivity of the 2' hydroxy group are required.

[6] Meanwhile, a binaphthol aldehyde derivative, which is a novel compound of the present invention, is represented by Chemical Formula 1 below. A binaphthol aldehyde compound represented by Chemical Formula 2 below can be used to prepare this novel compound.

[7] [Chemical Formula 1] [8]

[9] [Chemical Formula 2]

[10]

[11] According to conventional technologies, the binaphthol aldehyde compound represented by Chemical Formula 2 above is prepared by introducing a formyl group (-CHO) into a starting material of optically-pure binaphthol. In this case, the process of introducing a formyl group (-CHO) into the optically-pure binaphthol is generally performed using n-butyl lithium and dimethylformamide (DMF) after protecting a hydroxy group (-OH) using methoxy methyl (MOM). However, this method is problematic in that it is difficult to be used in general processes because it is very sensitive to water. Therefore, a method of preparing the binaphthol aldehyde compound represented by Chemical Formula 2 above in a safe manner is required.

[12] Further, since binaphthol (represented by Chemical Formula 2) used as a starting material is relatively expensive, a method of preparing the binaphthol aldehyde compound using a cheap starting material is also required. Disclosure of Invention Technical Problem

[13] Accordingly, the present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a binaphthol aldehyde derivative represented by Chemical Formula 1, which is a novel compound that is usefully used to introduce various kinds of substituent groups into the hydrogen position of a 2' hydroxy group of 2,2'-binaphthol-3-aldehyde.

[14] Another object of the present invention is to provide a method of preparing the binaphthol aldehyde derivative represented by Chemical Formula 1 in a safe manner at low cost without using a dangerous material such as n-butyl lithium or the like. Technical Solution [15] An aspect of the present invention provides a compound represented by Chemical

Formula 1 below: [16] [Chemical Formula 1]

[18] wherein X is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more sub- stituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, wherein Y is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more substituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, wherein n and m are each independently an integer of 0 - 5, and wherein Rl is selected from the group consisting of an alkyl group of C1-C5, an arylalkyl group of C6-C10, and an alkoxy alkyl group of C2-C10.

[19] Another aspect of the present invention provides a method of preparing the compound represented by Chemical Formula 1 above, comprising the step of: reacting a compound represented by Chemical Formula 2 below with

(here, Rl is selected from the group consisting of an alkyl group of C1-C5, an arylalkyl group of C6-C10, and an alkoxy alkyl group of C2-C10) in the presence of a base:

[20] [Chemical Formula 2]

[21] H

[22] wherein X is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more sub- stituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, wherein Y is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more substituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, and wherein n and m are each independently an integer of 0 - 5.

Advantageous Effects

[23] When a binaphthol aldehyde derivative represented by Chemical Formula 1, which is a novel compound of the present invention, is used, various kinds of substituent groups can be very efficiently introduced into the hydrogen position of a 2' hydroxy group of 2,2'-binaphthol-3-aldehyde.

[24] Further, the present invention provides a method of preparing the binaphthol aldehyde derivative represented by Chemical Formula 1 above in a safe manner at low cost. Therefore, this method can be very effective when it is used in a large-scale production line. Best Mode for Carrying out the Invention

[25] The present invention provides a compound represented by Chemical Formula 1 below:

[26] [Chemical Formula 1]

[28] wherein X is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more substituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, wherein Y is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more substituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, wherein n and m are each independently an integer of 0 - 5, and wherein Rl is selected from the group consisting of an alkyl group of C1-C5, an arylalkyl group of C6-C10, and an alkoxy alkyl group of C2-C10.

[29] In the compound represented by Chemical Formula 1 above, perferably, X may be each independently selected from the group consisting of hydrogen; a halogen; an amino group; a cyano group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more substituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO; Y may be each independently selected from the group consisting of hydrogen; a halogen; an amino group; a cyano group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more substituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO; n and m may be each independently an integer of 0 - 5; and Rl may be selected from the group consisting of an alkyl group of C1-C5 and an arylalkyl group of C6-C10.

[30] In the compound represented by Chemical Formula 1 above, more preferably, n and m may be each 0, and Rl may be a methyl group or an ethyl group.

[31] The compound represented by Chemical Formula 1 above can be usefully used as an intermediate in the preparation of a compound in which the hydrogen of a 2' hydroxy group of 2,2'-binaphthol-3-aldehyde is substituted.

[32] Further, the present invention provides a method of preparing the compound represented by Chemical Formula 1 above, comprising the step of: reacting a compound represented by Chemical Formula 2 below with

(here, Rl is selected from the group consisting of an alkyl group of C1-C5, an arylalkyl group of C6-C10, and an alkoxy alkyl group of C2-C10) in the presence of a base:

[33] [Chemical Formula 2]

[34]

[35] wherein X is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more sub- stituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, wherein Y is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more substituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, and wherein n and m are each independently an integer of 0 - 5.

[36] The method of preparing the compound represented by Chemical Formula 1 above is represented by the following Reaction Formula 1.

[37] [Reaction Formula 1]

[39] In the reaction, N,N-dimethylformamide (DMF), tetrahydrofuran (THF), CH 2 Cl 2 or the like, preferably DMF, may be used as a solvent. An organic or inorganic base, such as Et 3 N, NaH, NaOH or the like, preferably Et 3 N or NaH, may be used as a base used in the reaction. The reaction may be performed at a temperature of -40 - 3O 0 C, preferably, room temperature.

[40] In the reaction, is chiefly introduced into the hydrogen position of a 2 hydroxy group of the compound represented by Chemical Formula 2, and a side reaction product in which is introduced into the hydrogen positions of both 2 hydroxy group and 2' hydroxy group of the compound represented by Chemical Formula 2 is partially produced. However, this side reaction product can be reused by making the compound represented by Chemical Formula 2 again by the hydrolysis of the side reaction product. The compound represented by Chemical Formula 1 can be obtained at a purity of 98% or more and in a yield of 90% or more by recrystallization.

[41] The compound represented by Chemical Formula 2 above may be prepared by the steps of: reducing a compound represented by Chemical Formula 4 below to obtain a compound represented by Chemical Formula 3 below; and oxidizing the obtained compound represented by Chemical Formula 3:

[42] [Chemical Formula 3]

[43]

[44] [Chemical Formula 4]

[45]

[46] wherein X is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more sub- stituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, wherein Y is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more substituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, wherein n and m are each inde- pendently an integer of 0 ~ 5, and wherein R2 is selected from the group consisting of hydrogen, an alkyl group of C1-C5, a tosyl group, CH 3 SO 2 - and CH 3 CO-.

[47] The method of preparing the compound represented by Chemical Formula 2 above is represented by the following Reaction Formula 2.

[48] [Reaction Formula 2]

4 3 2

[50] Here, reaction a is a reaction in which a reductant (for example: LiAlH 4 or NaBH 4 ) is dissolved in a solvent (for example: THF) and then the compound represented by Chemical Formula 4 is added to the solution. In this reaction a, the reductant and solvent may be used without limitation as long as they are commonly-used in the related field. The reaction a may be performed for 3 ~ 7 hours.

[51] Reaction b is a reaction in which the compound represented by Chemical Formula 3 and an oxidant (for example: pyridinium chlorochromate (PCC) or DMSO/Ac 2 O) are dissolved in a solvent (for example: methylene chloride) and then reacted for 1 - 6 hours. The reaction b may be performed at room temperature. In this reaction b, the oxidant and solvent may be used without limitation as long as they are commonly-used in the related field.

[52] The reactions a and b are advantageous in that they are economical because they are quantitatively performed, and in that they are very safe because dangerous compounds, such as n-butyl lithium and the like, are not used. Therefore, the compound represented by Chemical Formula 1, which is a target compound of the present invention, can be prepared safely and economically.

[53] The compound represented by Chemical Formula 4 may be prepared by reacting a compound represented by Chemical Formula 5 below with a compound represented by Chemical Formula 6 below using CuCl(OH)-TMEDA(Tetramethylethylenediamine):

[54] [Chemical Formula 5]

[56] [Chemical Formula 6] [57] [58] wherein X is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more sub- stituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, wherein Y is each independently selected from the group consisting of hydrogen; a halogen; an amino group; a nitro group; a cyano group; a formyl group; a carboxyl group; an alkyl group of Cl-ClO unsubstituted or substituted with one or more substituent groups selected from among a halogen, a hydroxy group, an amino group, a cyano group, a nitro group and an aryl group of C6-C10; an alkylcarbonyl group of Cl-ClO; an aryl group of C6-C10; and an alkoxy group of Cl-ClO, wherein n and m are each independently an integer of 0 - 5, and wherein R2 is selected from the group consisting of hydrogen, an alkyl group of C1-C5, a tosyl group, CH 3 SO 2 - and CH 3 CO-, on the proviso that X and Y does not exist at carbon number eigh of naphthalene back bone of the above Chemical Formula 5 and Chemical Formula 6.

[59] The method of preparing the compound represented by Chemical Formula 4 above is represented by the following Reaction Formula 3.

[60] [Reaction Formula 3]

[62] This reaction may be performed using the very cheap compounds represented by

Chemical Formulae 5 and 6 by a commonly -known method (Hovorka, M.; Sci gel, R.; gunterova, J.; Tichy, M.; Zavada, J. Tetrahedron 1992, 48, 9503-9516). Briefly explaining, the reaction is characterized in that the compound represented by Chemical Formula 5 is dissolved in THF and then the compound represented by Chemical Formula 6 is added thereto to form a mixed solution, and then CUCI(OH)-TMEDA is added to this mixed solution and then reacted in the presence of oxygen (refer to the following Example 1). Since the compounds represented by Chemical Formulae 5 and 6 are cheap compared to expensive binaphthol used in conventional technologies and can be purchased in large amounts, the compound represented by Chemical Formula 1, which is a target compound of the present invention, can be prepared economically. [63] Since the compound represented by Chemical Formula 4 is obtained as a racemic mixture when it is synthesized by the above reaction, it is required to obtain an optically-pure compound represented by Chemical Formula 4.

[64] Therefore, the method of preparing the compound represented by Chemical Formula 1 may further include the step of: hydrolyzing the compound represented by Chemical Formula 4 above to obtain 2,2'-dihydroxy-3-binaphtholic acid and then resolving the obtained 2,2'-dihydroxy-3-binaphtholic acid using cinchonidine to form an optically- pure compound represented by Chemical Formula 4, before the step of reducing the compound represented by Chemical Formula 4.

[65] The method of preparing the optically-pure compound represented by Chemical Formula 4 is represented by the following Reaction Formula 4.

[66] [Reaction Formula 4]

esterification

(S) - 2

[68] That is, the compound represented by Chemical Formula 4 is hydrolyzed into a 2,2'-dihydroxy-3-binaphtholic acid derivative, and then the

2,2'-dihydroxy-3-binaphtholic acid derivative is resolved. The technology for resolving the 2,2'-dihydroxy-3-binaphtholic acid derivative is commonly known by Hovorka, M et al. (Hovorka, M.; Stibor, I; Holakovsky, R.; Smiskova, L; Struzka, V.r. Czech Rep. (2001), CZ 287879 B6 20010314 Patent written in Czech. Application: CZ 96-64 19960109). Since the resolved (S)-2,2'-dihydroxy-3-binaphtholic acid derivative is easily converted into R2 ester by esterification, an (S) type optically -pure compound represented by Chemical Formula 4 can be obtained. A (R) type optically-pure compound represented by Chemical Formula 4 can also be obtained.

[69] The compound represented by Chemical Formula 1, which is a target compound, can be prepared by performing the reactions represented by Reaction Formulae 1 and 2 using the obtained optically -pure compound represented by Chemical Formula 4.

[70] The compound represented by Chemical Formula 1 according to the present invention is used as an intermediate for preparing a compound represented by Chemical Formula 8 below, which is usefully used to separate amino alcohols or amino acids into their respective isomers by recognizing their chirality through an imine bond or to convert L-amino acid into D-amino acid.

[71] [Chemical Formula 8] [72]

o

- K 3

OR 2 O

I I

[73] One example for preparing the compound represented by Chemical Formula 8 above is represented by the following Reaction Formula 5.

[74] [Reaction Formula 5]

(a) NaH, (3-phenyluryl)benyl bromide, DMSO, (b) HCLTHFZH 2 O

[76] As represented by the above Reaction Formula 5, when the compound represented by Chemical Formula 1 according to the present invention is reacted with (3-phenyluryl)benzyl bromide in the presence of a base and then the reaction product is hydrolyzed, the compound represented by Chemical Formula 8 can be synthesized in a yield of 90% or more. Mode for the Invention

[77] Hereinafter, the present invention will be described in more detail with reference to the following Examples. However, the following Examples are set forth to illustrate the present invention, and the present invention is not limited thereto and can be variously modified.

[78] [79] Example 1: Preparation of a compound (2,2'-dihydroxy-l,l'-binaphthyl-3-carboxylic acid methyl ester) represented by Chemical Formula 4

[80] The compound represented by Chemical Formula 4 was synthesized by the synthesis method disclosed in the paper (Hovorka, M.; Sci gel, R.; gunterova, J.; Tichy, M.; Zavada, J. Tetrahedron 1992, 48, 9503-9516). That is, 3-hydroxy-2-naphthalate methyl ester (2.0 g, 9.89 mmol) was dissolved in THF (20 ml), and then 2-naphthol (1.42 g, 9.89 mmol) was added thereto to form a mixed solution. Subsequently, CUCI(OH)-TMEDA (1.15 g, 4.94 mmol) was added to this mixed solution at room temperature and then stirred for 3 days in the presence of oxygen. After the reaction, THF was removed from the reacted solution, and then the reacted solution was extracted using chloroform (10 ml) and a 1 N hydrochloric acid solution (2 x 5 ml), and the extracted reacted solution was dried to evaporate an organic layer therefrom, thus obtaining a solid compound. Subsequently, the solid compound was recrystallized using CHCl 3 /n-hexane to prepare 2,2'-dihydroxy-l,l'-binaphthyl-3-carboxylic acid methyl ester (3.1 g, a yield of 90%).

[81] m.p. 167 0 C; 1 H NMR(CDCB, 250 MHz): δlO.8O(s, IH), 8.74(s, IH), 7.8-8.0(m,

3H), 7.0-7.5(m, 8H), 4.06(s, 3H).

[82]

[83] Example 2: Preparation of a compound

(2,2'-dihydroxy-3-hydroxymethyl-l,l'-binaphthalene) represented by Chemical Formula 3

[84] Lithium aluminum hydride (LiAlH 4 , 0.51 g, 13.3 mmol) was dissolved in THF (30 ml), and then the 2,2'-dihydroxy-l,l'-binaphthyl-3-carboxylic acid methyl ester (3.07 g, 8.89 mmol) prepared in Example 1 was added thereto in an ice bath to form a mixed solution. Subsequently, the mixed solution was stirred for 5 hours at room temperature, filtered to remove precipitates therefrom, and then evaporated to prepare 2,2'-dihydroxy-3-hydroxymethyl-l,l'-binaphthalene (2.53 g, a yield of 90%).

[85] m.p. 194 0 C; 1 H NMR(DMSOd 6 , 250 MHz): δ7.8-8.0(m, 4H), 6.7-7.4(m, 7H),

4.74(s, 2H).

[86]

[87] Example 3: Preparation of a compound

(2,2'-dihydroxy-l,l'-binaphthyl-3-carboxaldehyde) represented by Chemical Formula 2

[88] The 2,2'-dihydroxy-3-hydroxymethyl- 1 , 1 '-binaphthalene (2.53 g, 7.98 mmol) prepared in Example 2 and pyridinium chlorochromate (PCC, 3.44 g, 15.9 mmol) were mixed with methylene chloride (50 mL) to form a mixed solution, and then the mixed solution was stirred for 3 hours at room temperature to react them. After the reaction, the reacted solution was filtered to remove precipitates therefrom and then dried using a rotary evaporator to prepare solid 2,2'-dihydroxy-l,l'-binaphthyl-3-carboxaldehyde (2.14 g, a yield of 85%).

[89] 1 H NMR(CDCl 3 , 250 MHz): δlθ.24(s, IH), 8.38(s, IH), 7.8-8.1(m, 3H), 7.0-7.6(m,

7H), 4.95(s, IH).

[90]

[91] Example 4: Preparation of a compound

(2-methoxymethoxy-2'-hydroxy- 1 , 1 '-binaphthyl-3-carboxaldehyde) represented by Chemical Formula 1

[92] The 2,2'-dihydroxy-l,l'-binaphthyl-3-carboxaldehyde (3.9 g, 12.4 mmol) prepared in

Example 3 was dissolved in DMF (40 ml), and then NaH (0.45 g, 11 mmol) was added thereto while stirring to form a mixed solution. Subsequently, methoxymethyl chloride (MOMCl, 1.08 ml, 12.4 mmol) dissolved in DMF (40 ml) was added to the mixed solution, and then they were reacted for 15 hours. After the reaction, the reacted solution was extracted using water and ethyl acetate (EA), and the extracted reacted solution was dried to evaporate an organic layer therefrom, thus obtaining a product. Subsequently, the product was column-chromatographed using EA/Hexane (1/5) as an eluent to prepare 2-methoxymethoxy-2'-hydroxy-l,l'-binaphthyl-3-carboxaldehyde (2.9 g, a yield of 65%).

[93] m.p. 164 0 C; [α] D = -108.2(c = 0.42 in EtOH); 1 H NMR(CDCl 3 , 250 MHz): δlθ.59(s,

IH), 8.62(s, IH), 8.09(d, IH), 7.99-7.88(m, 2H), 7.54-7.27(m, 6H), 7.07(d, IH), 5.08(s, IH), 4.74(dd, 2H), 3.03 ppm(s, 3H); 13 C NMR(CDCl 3 , 62.5 MHz): 6154.4, 151.0, 136.6, 133.3, 132.7, 130.0, 130.7, 130.3, 129.7, 128.2, 128.5, 127.3, 126.1, 125.4, 124.3, 124.7, 123.4, 118.5, 114.2, 100.8, 57.3 ppm. HRMS(EI) calcd for C 23 H 18 O 4 : 358.1205; found: 358.1198