KR100217863B1 - Alpha cyclodextrin derivative which is useful for separation of isomer - Google Patents

Alpha cyclodextrin derivative which is useful for separation of isomer Download PDF

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KR100217863B1
KR100217863B1 KR1019950056715A KR19950056715A KR100217863B1 KR 100217863 B1 KR100217863 B1 KR 100217863B1 KR 1019950056715 A KR1019950056715 A KR 1019950056715A KR 19950056715 A KR19950056715 A KR 19950056715A KR 100217863 B1 KR100217863 B1 KR 100217863B1
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KR970042583A (en
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김병억
우순형
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이구택
포항종합제철주식회사
신현준
재단법인포항산업과학연구원
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/38—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36
    • B01D15/3833—Chiral chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/29—Chiral phases

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Abstract

본 발명은-시클로 덱스트린 유도체에 관한 것이며, 보다 상세하게는 광학 이성질체 분리에 유용한-시클로 덱스트린 유도체 및 그 이용에 관한 것으로,The present invention -Cyclodextrin derivatives, and more particularly useful for optical isomer separation To a cyclodextrin derivative and its use,

6번 위치의 탄소에 실란기가 도입된 하기 식(Ⅰ)을 갖는 새로운-CD 유도체가 제공되며 이는 종래 CGC 컬럼에 고정상으로 사용되는 물질과 혼합하여 라세미 광학활성 물질의 분리에 고정상으로 사용된다.A new compound having the following formula (I) in which a silane group is introduced into carbon at position 6 A -CD derivative is provided, which is mixed with materials conventionally used in the CGC column as a stationary phase and used as a stationary phase for the separation of racemic optically active materials.

Description

광학 이성질체 분리에 유용한 알파 시클로텍스트린 유도체Alpha cyclotextrin derivatives useful for optical isomer separation

제1도는 본 발명에 의한-CD 유도체를 이용하여 고리형 알코올 광학 이성질체를 분리한 기체 크로마토그램.1 is according to the present invention Gas chromatogram of cyclic alcohol optical isomers separated using a -CD derivative.

제2도는 본 발명에 의한-CD 유도체를 이용하여 이차 알코올 이성질체를 분리한 기체 크로마토그램.2 is according to the present invention Gas chromatogram of secondary alcohol isomers separated using a -CD derivative.

제3도는 본 발명에 의한-CD 유도체를 이용하여 니트로기 및 페닐기가 포함된 알코올 및 디올 광학 이성질체를 분리한 크로마토그램.3 is according to the present invention -Chromatogram separating alcohol and diol optical isomers containing nitro group and phenyl group using CD derivative.

제4도는 본 발명에 의한-CD 유도체를 이용하여 할로겐화 알칸 광학 이성질체를 분리한 기체 크로마토그램.4 is according to the present invention Gas chromatogram of halogenated alkane optical isomers separated using a -CD derivative.

본 발명은-시클로덱스트린(이하, "-CD"라 한다.) 유도체에 관한 것이며, 보다 상세하게는 광학 이성질체 분리에 유용한, 알킬실란기를 갖는-시클로덱스트린 유도체 및 그 이용에 관한 것이다.The present invention Cyclodextrin (hereinafter, " -CD ".), More particularly having an alkylsilane group, useful for optical isomer separation -Cyclodextrin derivatives and their use.

Angewandte Chemie, 29, pp. 939-1076(1990)등에 의하면 모세관 기체 크로마토그래피(이하, "CGC"라고 한다.) 에 고정상으로-CD 유도체를 사용하는 경우, 라세미 광학이성질체 뿐만 아니라 구조 이성질체를 용이하게 분리할 수 있는 것으로 알려져 있다. 이와같이 이성질체 분리에 유용한-CD 관련하여 종래 많은 연구가 행하여져 왔으며 그 예로는 미국특허 제 5,064,944, 5,154,738 및 5,198,429 등을 들 수 있다. 상기 특허 제 5,064,944 및 5,154,783 은-CD을 구성하는 글루코스의 2번, 3번 및 6번 위치의 히드록시기를 프로필 에테르도 유도체화(propylation)하고 반응 되지 않은 히드록시기는 메틸에테르로 유도체화한 것으로 순수한 물질이 아닌 이성질체가 섞여 있는 혼합물이다.Angewandte Chemie, 29, pp. 939-1076 (1990), etc., as a stationary phase in capillary gas chromatography When -CD derivatives are used, it is known that not only racemic optical isomers but also structural isomers can be easily separated. Thus useful for isomer separation Many studies have been done with respect to CDs and examples thereof include US Pat. Nos. 5,064,944, 5,154,738 and 5,198,429. The patents 5,064,944 and 5,154,783 -The hydroxy group at the 2nd, 3rd and 6th position of glucose constituting the CD is also propylated, and the unreacted hydroxy group is derivatized with methyl ether and is a mixture of isomers, not pure substances. .

또한, 상기 특허 제 5,198,429는-CD를 구성하는 글루코스의 2번, 3번 및 6번 위치의 히드록시기를 모두 펜틸에테르로 유도체화한 것 및 한편으로는 2번 6번 위치의 히드록시기를 펜틸에테르로 유도체화하고 3번 위치의 히드록시기는 아세틸화한 것으로 혼합물이 아닌 순수한 물질이다.In addition, the patent 5,198,429 -Derivatives of the hydroxy groups at the 2nd, 3rd and 6th position of glucose constituting the CD with pentyl ether, and on the other hand, the hydroxyl groups at the 2nd and 6th positions are derivatized with pentyl ether and the hydroxy groups at the 3rd position Is acetylated and is a pure substance, not a mixture.

본 발명자는 우수한 광학선택성을 나타내는 시클로덱스트린 화합물을 얻기 위하여 연구 해온 결과 종래의 시클로덱스트린 유도체와는 화학적 구조가 상이하면서 그 광학선택성이 보다 우수한 새로운-CD 유도체를 발견하였다.The present inventors have studied to obtain a cyclodextrin compound exhibiting excellent optical selectivity, and as a result, the chemical structure is different from that of a conventional cyclodextrin derivative, and its optical selectivity is better. -CD derivative was found.

이에 본 발명의 목적은 새로은-CD 유도체 화합물 및 이를 이용한 광학 이성질체 분리 방법을 제공하는데 있다.The purpose of the present invention is A CD derivative compound and an optical isomer separation method using the same are provided.

본 발명의 제1견지에 의하면 하기 식(Ⅰ)의-CD 유도체 화합물이 제공된다.According to the first aspect of the present invention, the following formula (I) -CD derivative compounds are provided.

본 발명자는 우수한 광학 선택성을 갖는 시클로덱스트린을 얻기 위하여 글루코스의 히드록실기를 여러 가지 치환체로 치환시켜 시험한 결과 상기 식(Ⅰ)의 화합물을 CGC컬럼의 정지상으로 사용하는 경우 라세미(racemic) 광학활성물질의 분리에 매우 유용하다는 것을 발견하였다.In order to obtain a cyclodextrin having excellent optical selectivity, the inventors have tested the hydroxyl group of glucose with various substituents and found that when the compound of formula (I) is used as a stationary phase of a CGC column, racemic optics are used. It has been found to be very useful for the separation of actives.

상기 식(Ⅰ)의 화합물은 글루코스의 2번과 3번 탄소위치의 히드록실기를 에틸화하고 6번 탄소위치의 히드록실기를 tert-부틸디메틸화 시킨 6-tert-부틸디메틸 실릴-2, 3-디에틸 알파 시클로덱스트린으로써, 이를 CGC 컬럼에 정지상으로 사용시 라세미 광활성물질, 특히, 고리형 알킬 알코올 화합물, 니트로기 및 페닐기를 갖는 알코올 및, 이차 알코올, 1, 2-헥산디올과 같은 디올, 1, 2, 4 트라히드록시부탄과 같은 트리올의 광학이성질체 분리에 효과적이다. 상기 고리형 알킬알코올 화합물로는 2-시클로헥센-1-올, trans-1, 2-시클로헥산디올, (cis & trans) 1, 4-시클로헥산디올, 니트로기를 갖는 알코올로는 (cis & trans) 3-니트로-2-부탄올을 페닐기를 갖는 알코올로는 sec-펜에틸 알코올, 1-페닐-1-프로판올 등을 그리고, 이차 알코올로는 2-헥산올, 3-헥산올, 3-헵탄올들을 들 수 있다. 상기 본 발명에 의한-CD 유도체는 종래 고정상에 사용되는 물질과 혼합하여 사용할 수 있으며, 이를 사용하여 고리형 알코올, 이차 알코올, 니트로기 및 페닐기를 갖는 알코올 및 디올, 할로겐화 알칸등을 분리하는 경우 우수한 분리 선택성()을 나타낸다.The compound of formula (I) is 6-tert-butyldimethyl silyl-2 obtained by ethylating the hydroxyl group at the 2nd and 3rd carbon positions of glucose and tert-butyldimethylated at the 6th position of the hydroxyl group, 3-diethyl alpha cyclodextrin, when used as a stationary phase in a CGC column, racemic photoactive substances, in particular alcohols having cyclic alkyl alcohol compounds, nitro groups and phenyl groups, and diols such as secondary alcohols, 1, 2-hexanediol It is effective for the separation of optical isomers of triols, such as 1, 2, 4 trihydroxybutane. As the cyclic alkyl alcohol compound, 2-cyclohexen-1-ol, trans-1, 2-cyclohexanediol, (cis & trans) 1, 4-cyclohexanediol, and alcohol having nitro group (cis & trans ) 3-nitro-2-butanol as sec-phenethyl alcohol, 1-phenyl-1-propanol as an alcohol having a phenyl group, 2-hexanol, 3-hexanol, 3-heptanol as a secondary alcohol Can be heard. According to the present invention -CD derivatives can be used in combination with materials used in conventional stationary phases, and excellent separation selectivity when separating alcohols and diols and halogenated alkanes having cyclic alcohols, secondary alcohols, nitro groups and phenyl groups using ).

또한, 상기 본 발명의-CD 유도체는 하기 식(Ⅰ)의-CD 화합물과 tert-부틸디메틸실릴 클로라이드를 반응시켜 하기 식(2)의 6-tert-부틸디메틸실릴--CD를 얻은 다음 이를 요오드화 에탄과 알킬화반응시켜 얻을 수 있다.In addition, of the present invention -CD derivatives of the formula (I) 6-tert-butyldimethylsilyl of the following formula (2) by reacting a CD compound with tert-butyldimethylsilyl chloride -CD can be obtained and then alkylated with ethane iodide.

하기 식(2)의 실란유도체를 형성하는 반응은 0-실온의 온도 범위에서 피리딘과 같은 염기존재하에서 반응을 수행하며, 이때 피리딘은 용매의 역할도 수행한다. 또한 상기 알킬화 반응에서는 용매로 디메틸 포름알데히드 혹은 테트라하이드로 푸란을 사용하여 수소화나트륨(NaH) 염기 존재하의 상온에서 알킬화한다.The reaction for forming the silane derivative of the following formula (2) is 0 In the temperature range of room temperature, the reaction is carried out in the presence of a base such as pyridine, where pyridine also plays the role of a solvent. In addition, the alkylation reaction uses dimethyl formaldehyde or tetrahydrofuran as a solvent to alkylate at room temperature in the presence of sodium hydride (NaH) base.

상기 방법을 도식화하면 다음과 같다.Schematic of the method is as follows.

본 발명의 제2견지에 의하면 상기 방법에 따라 제조된 식(Ⅰ)의-CD 유도체 화합물을 이용한 광학 이성질체 분리방법이 제공되며, 이 방법은,According to the second aspect of the present invention, the formula (I) A method for separating optical isomers using a -CD derivative compound is provided.

정지상(stationary phase)과 혼합물을 접촉시켜 혼합물로부터 광학이성질체를 분리하는 기체크로마토그래피 분리방법에 있어서,In the gas chromatography separation method of separating the optical isomer from the mixture by contacting the mixture with a stationary phase,

정지상으로서 상기 식(1)의 화합물을 사용함을 특징으로 한다.It is characterized by using the compound of Formula (1) as a stationary phase.

이 방법은 이성질체인 고리형 알코올 광학 이성질체의 분리에 유용하며 그 구체적인 예로는 2-헥산올, 3-헥산올, 3-헵탄올, 3-니트로-2-부탄올 등을 들 수 있다.This method is useful for the separation of isocyclic cyclic alcohol optical isomers, and specific examples thereof include 2-hexanol, 3-hexanol, 3-heptanol, 3-nitro-2-butanol and the like.

이하, 본 발명의 실시예에 대하여 상세히 설명한다.Hereinafter, embodiments of the present invention will be described in detail.

[실시예 1 : 6tert-부틸디메틸 실릴-2, 3-디에틸--CD(식(Ⅰ)의 화합물)의 제조]Example 1 6 tert-Butyldimethyl silyl-2, 3-diethyl- Preparation of CD (Compound of Formula (I))]

(1) 6tert-부틸디메틸실릴--CD(식(Ⅲ)의 화합물)의 합성(1) 6tert-butyldimethylsilyl- -Synthesis of CD (Compound of Formula (III))

상기 식(1)의-CD 2.31g을 녹인 피리딘 용액 30ml 에 tert-부틸디메틸실릴 클로라이드 2.27g을 녹인 피리딘 20을 0에서 천천히 가한 후 실온에서 8시간 동안 교반한 다음 0에서 물 50을 첨가하였다. 이때 생성한 고체를 여과, 건조하고 남은 고체 혼합물을 실리카겔 컬럼 크로마토그래피(용출용매, 메탄올 : 염화 메틸렌=1:10)로 분리 정제하여 순수한 표제화합물(2.1g)을 흰색 고체로 얻었다.Of formula (1) Pyridine 20 dissolved 2.27 g of tert-butyldimethylsilyl chloride in 30 ml of pyridine solution containing 2.31 g of -CD 0 Slowly at room temperature and stirred for 8 hours at room temperature Water 50 Was added. The resulting solid was filtered and dried and the remaining solid mixture was separated and purified by silica gel column chromatography (eluent, methanol: methylene chloride = 1: 10) to obtain pure title compound (2.1 g) as a white solid.

1H-NMR(300MHz, CDCl3) :0.03(s, 36H), 0.87(s, 54H), 3.50-4.04(m, 36H), 4.86(d, 6H, J=3.3Hz), 5.23(s, 6H), 6.67(s, 6H) 1 H-NMR (300 MHz, CDCl 3 ): 0.03 (s, 36H), 0.87 (s, 54H), 3.50-4.04 (m, 36H), 4.86 (d, 6H, J = 3.3 Hz), 5.23 (s, 6H), 6.67 (s, 6H)

13C-NMR(75.13MHz, CDCl3) : -5.2, -5.1, 18.3, 25.9, 61.7, 72.6, 73.4, 73.7, 81.8, 102.1 ppm 13 C-NMR (75.13 MHz, CDCl 3 ): -5.2, -5.1, 18.3, 25.9, 61.7, 72.6, 73.4, 73.7, 81.8, 102.1 ppm

(2) 6-tert-부틸디메틸실릴-2, 3-디에틸--CD(식(Ⅰ)의 화합물)의 합성(2) 6-tert-butyldimethylsilyl-2, 3-diethyl- -Synthesis of CD (Compound of Formula (I))

수소화나트륨(NaH) 120을 디메틸 포름아미드 5에 녹인 용액에 6-tert-부틸디메틸실릴-CD 200을 0에서 첨가하고 상온에서 30분간 수소발생이 종결될 때까지 교반하였다. 그 후 주사기로 요오드화 에탄 1을 천천히 주입하고 4시간 동안 교반하였다. 반응 혼합물에 소량의 메탄올을 가하여 반응을 종결시키고 물 20와 각각 에틸아세테이트 20로 3번 추출하고 감압하에 농축하였다. 그 후 실리카겔 컬럼 크로마토그래피(용출용매, 에틸아세테이트 : 헥산=1:10)로 분리 정제하여 무색고체의 표제화합물 180을 얻었다.Sodium hydride (NaH) 120 Dimethyl Formamide 5 6-tert-butyldimethylsilyl- in solution CD 200 0 The mixture was added at and stirred at room temperature for 30 minutes until hydrogen evolution was terminated. Iodine iodide with a syringe after that 1 Was injected slowly and stirred for 4 h. A small amount of methanol was added to the reaction mixture to terminate the reaction and water 20 And ethyl acetate 20 Extracted three times and concentrated under reduced pressure. Then purified by silica gel column chromatography (eluent, ethyl acetate: hexane = 1: 10) to give the title compound 180 as a colorless solid. Got.

1H-NMR(300MHz, CDCl3) :0.002(2 x S, 36H), 0.86(s, 54H), 1.16-1.25(m, 36H), 3.10(dd, 6H, J=3.3Hz, 9.9Hz), 3.52-3.86(m, 42H), 4.02-4.17(m, 12H), 5.12(d, 6H, J=3.4Hz) 1 H-NMR (300 MHz, CDCl 3 ): 0.002 (2 x S, 36H), 0.86 (s, 54H), 1.16-1.25 (m, 36H), 3.10 (dd, 6H, J = 3.3 Hz, 9.9 Hz), 3.52-3.86 (m, 42H), 4.02 -4.17 (m, 12H), 5.12 (d, 6H, J = 3.4 Hz)

13C-NMR(75.47MHz, CDCl3) : -5.0, -4.7, 15.8, 18.2, 25.9, 62.4, 66.4, 68.8, 72.4, 77.7, 80.1, 80.4, 98.0 ppm 13 C-NMR (75.47 MHz, CDCl 3 ): -5.0, -4.7, 15.8, 18.2, 25.9, 62.4, 66.4, 68.8, 72.4, 77.7, 80.1, 80.4, 98.0 ppm

[실시예 2 :-CD 유도체를 이용한 광학이성질체 분리]Example 2 Separation of Optical Isomers Using -CD Derivatives]

(1)모세관 기체 크로마토그래피의 고정상 준비(1) Preparation of stationary phase of capillary gas chromatography

코팅되지 않은 용융 실리카 모세관 컬럼(fused silica capillary column, 30m x 0.25mm)을 사용하였으며 Alltech사(미국)에서 구입하였다. 본 발명에 의한 식(Ⅰ)의-CD 유도체와 시판되고 있는 폴리실록산을 1:1 중량비로 혼합한 후, 이를 염화 메틸렌(CH2Cl2)과 노르말 펜탄이 1:1 부피비로 혼합된 용액에 0.33%가 되도록 녹였다. 상기 폴리실록산은 극성에 따라 0V-1(100% 메틸 폴리실록산), SE-54(3-5% 페닐, 1% 비닐, 94-96% 메틸 폴리실록산), PS-086(12-15% 페닐, 7% 시아노프로필, 86% 메틸 폴리실록산), 0V-1701(7% 페닐, 7% 시아노프로필, 86% 메틸 폴리실록산)등을 들 수 있으며, 폴리실록산으로 0V-1701을 사용하는 것이 가장 바람직하다. 그후, J.Bouche와 M.Verzele 가 J.Gas Chromatogr. 6(1968) 501에 발표한 정적(static) 코팅 방법에 따라 상기 용액으로 모세관 컬럼을 코팅하여 고정상을 준비하였다.Uncoated fused silica capillary column (30m x 0.25mm) was used and was purchased from Alltech (USA). Of formula (I) according to the present invention -CD derivative and commercially available polysiloxane were mixed in a 1: 1 weight ratio, and then dissolved in a solution containing methylene chloride (CH 2 Cl 2 ) and normal pentane in a 1: 1 volume ratio to 0.33%. The polysiloxanes are 0V-1 (100% methyl polysiloxane), SE-54 (3-5% phenyl, 1% vinyl, 94-96% methyl polysiloxane), PS-086 (12-15% phenyl, 7% depending on polarity) Cyanopropyl, 86% methyl polysiloxane), 0V-1701 (7% phenyl, 7% cyanopropyl, 86% methyl polysiloxane), and the like, with 0V-1701 being most preferred as the polysiloxane. J. Bouche and M. Verzele then published J. Gas Chromatogr. A fixed phase was prepared by coating a capillary column with the solution according to the static coating method disclosed in 6 (1968) 501.

(2) 라세미 광학이성질체의 분리(2) Separation of racemic optical isomers

기체 크로마토그래피의 검출기는 불꽃이온화 검출기(flame ionization detector, FID)를 그리고 상기 제조된 컬럼을 고정상으로 사용하고 시료주입기의 온도는 250검출기의 온도는 300로 하여 이성질체를 분리하였다. 분리하려는 시료 10을 염화 메틸렌 1l 에 녹여서 1로 주입하였으며, 시료 주입시 시료주입비율은 1:30 으로 하였다. 운반 기체로는 헬륨을 사용하였으며, 입구의 압력은 14psi 였다.Gas chromatography detector uses a flame ionization detector (FID) and the prepared column as a stationary phase and the temperature of the sample injector is 250 Detector temperature is 300 Isomers were separated. Sample to be separated 10 Methylene chloride 1 dissolved in l 1 Was injected into the sample, and the sample injection ratio was 1:30. Helium was used as the carrier gas and the inlet pressure was 14 psi.

하기 표 1의 온도조건하에 각 시료의 라세미 광학 이성질체를 분리하였다.The racemic optical isomers of each sample were separated under the temperature conditions shown in Table 1 below.

본 발명의-CD 유도체를 고정상으로 사용하여 만든 모세관 컬럼으로 상기 각 라세미 광학 이성질체인 고리형 알코올, 이차 알코올, 니트로기 및 페닐기르 갖는 알코올 및 디올, 할로겐화 알칸을 분리한 결과를 각 제1도-제4도에 나타냈다.Of the present invention -Capillary column made using a CD derivative as a stationary phase, and the results of separating the racemic optical isomers of the cyclic alcohol, secondary alcohol, nitro group and phenyl group alcohol, diol and halogenated alkanes Shown in the figure.

또한, 문헌에 발표된[HRC, 16(vol), 693(1993)] 종래의 6-t-부틸디메틸실릴-2, 3-디메틸--시클로덱스트린(TB--CD)과 본 발명의 화합물(Ⅰ)을 사용하여 얻은 광학선택성 값(value)의 비교치를 하기 표 2에 나타냈다. 표 2의 결과에 의하면 본 발명의 화합물을 사용하여 만든 컬럼으로 라세미 광학 이성질체를 분리할 경우 할로겐화 알칸화합물의 분리선택성이 저조하게 나타나지만 페닐기를 갖는 화합물의 분리 선택성은 보다 우수함을 알 수 있다.See also in the literature [HRC, 16 (vol), 693 (1993)] conventional 6-t-butyldimethylsilyl-2, 3-dimethyl- Cyclodextrin (TB- -CD) and the optical selectivity obtained using the compound (I) of the present invention ( value) is shown in Table 2 below. The results of Table 2 show that the separation selectivity of the halogenated alkanes is poor when the racemic optical isomer is separated by a column made using the compound of the present invention, but the separation selectivity of the compound having a phenyl group is better.

* 4개의 이설질체가 존재함.* 4 isomers are present.

또한 상기 시험 결과로부터 본 발명에 의한-CD 유도체는 광학 이성질체의 분리 선택성이 매우 우수하며 특히-CD 유도체는 공동의 크기가 작음으로 분자가 작은 사슬형 알킬 알코올 그리고 니트로기를 갖는 알코올의 광학 이성질체 분리에 유용함을 알 수 있다.In addition, according to the present invention from the test results -CD derivatives have very good separation selectivity of the optical isomers, especially It can be seen that the -CD derivative is useful for optical isomer separation of small alkyl chains and alcohols having nitro groups due to their small size.

Claims (4)

하기 구조식(Ⅰ)을 갖는 광학 이성질체분리에 고정상으로 유용한 6-tert-부틸디메틸실릴-2, 3-디에틸--시클로 덱스트린 화합물.6-tert-butyldimethylsilyl-2, 3-diethyl- useful as a stationary phase for optical isomer separation having the structural formula (I) Cyclodextrin compounds. 정지상과 혼합물을 접촉시켜 광학이성질체를 분리하는 기체크로마토그래피 분리 방법에 있어서, 상기 정지상으로 청구범위 제1항의 식(Ⅰ)의 시클로덱스트린 유도체를 사용함을 특징으로 하는 방법.A gas chromatography separation method for separating an optical isomer by contacting a stationary phase with a mixture, wherein the stationary phase uses a cyclodextrin derivative of formula (I) of claim 1. 제2항에 있어서, 상기 광학 이성질체는 알코올 화합물임을 특징으로 하는 방법.The method of claim 2, wherein the optical isomer is an alcohol compound. 제3항에 있어서, 상기 알코올은 2-헥산올, 3-헥산올, 3-헵탄올, 3-니트로-2-부탄올로 구성되는 그룹에서 선택됨을 특징으로 하는 방법.The method of claim 3 wherein the alcohol is selected from the group consisting of 2-hexanol, 3-hexanol, 3-heptanol, 3-nitro-2-butanol.
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