JPH04169595A - Oligosaccharide derivative and separatory agent therefor - Google Patents
Oligosaccharide derivative and separatory agent thereforInfo
- Publication number
- JPH04169595A JPH04169595A JP29781790A JP29781790A JPH04169595A JP H04169595 A JPH04169595 A JP H04169595A JP 29781790 A JP29781790 A JP 29781790A JP 29781790 A JP29781790 A JP 29781790A JP H04169595 A JPH04169595 A JP H04169595A
- Authority
- JP
- Japan
- Prior art keywords
- oligosaccharide
- derivative
- derivatives
- oligosaccharide derivative
- synthesized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001542 oligosaccharide Polymers 0.000 title claims abstract description 32
- 150000002482 oligosaccharides Chemical class 0.000 title claims abstract description 29
- 125000000524 functional group Chemical group 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 4
- -1 oligosaccharide compound Chemical class 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 9
- SBTVLCPCSXMWIQ-UHFFFAOYSA-N (3,5-dimethylphenyl) carbamate Chemical class CC1=CC(C)=CC(OC(N)=O)=C1 SBTVLCPCSXMWIQ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 2
- DZSGDHNHQAJZCO-UHFFFAOYSA-N 1-isocyanato-3,5-dimethylbenzene Chemical compound CC1=CC(C)=CC(N=C=O)=C1 DZSGDHNHQAJZCO-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 238000000926 separation method Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000000921 elemental analysis Methods 0.000 description 8
- 229920000856 Amylose Polymers 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000004676 glycans Chemical class 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 229920001282 polysaccharide Polymers 0.000 description 4
- 239000005017 polysaccharide Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GHPYJLCQYMAXGG-WCCKRBBISA-N (2R)-2-amino-3-(2-boronoethylsulfanyl)propanoic acid hydrochloride Chemical compound Cl.N[C@@H](CSCCB(O)O)C(O)=O GHPYJLCQYMAXGG-WCCKRBBISA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- ZPZDIFSPRVHGIF-UHFFFAOYSA-N 3-aminopropylsilicon Chemical compound NCCC[Si] ZPZDIFSPRVHGIF-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- AKZWRTCWNXHHFR-PDIZUQLASA-N [(3S)-oxolan-3-yl] N-[(2S,3S)-4-[(5S)-5-benzyl-3-[(2R)-2-carbamoyloxy-2,3-dihydro-1H-inden-1-yl]-4-oxo-3H-pyrrol-5-yl]-3-hydroxy-1-phenylbutan-2-yl]carbamate Chemical compound NC(=O)O[C@@H]1Cc2ccccc2C1C1C=N[C@](C[C@H](O)[C@H](Cc2ccccc2)NC(=O)O[C@H]2CCOC2)(Cc2ccccc2)C1=O AKZWRTCWNXHHFR-PDIZUQLASA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- LUEWUZLMQUOBSB-ZLBHSGTGSA-N alpha-maltotetraose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)O[C@H](O[C@@H]2[C@H](O[C@H](O[C@@H]3[C@H](O[C@H](O)[C@H](O)[C@H]3O)CO)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-ZLBHSGTGSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、光学分割を行う機能材料として極めて有用な
少糖誘導体及び該誘導体から成る分離剤に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to oligosaccharide derivatives that are extremely useful as functional materials for optical resolution, and to separation agents comprising the derivatives.
〔従来の技術及び発明が解決しようとする課題〕従来、
多糖誘導体を用いた分離剤は、液体クロマトグラフィー
用の固定相として多種多様のラセミ体化合物に対して優
れた分割能力を示しているが、分割には多糖誘導体の高
次構造がラセミ体化合物の構造に良好に適合し、両者の
間で種々の吸着的相互作用が効果的に働くことが重要と
考えられている。しかし、分割能力に優れている多糖誘
導体を用いても分割することが難しい化合物が存在する
のも事実である。本発明者らは、かかる分割することが
難しい化合物を分割し得る分離剤について鋭意研究し、
多糖誘導体と同じ繰り返し単位の構造を有するが、繰り
返し単位数が少ない少糖誘導体について着目して少糖誘
導体の合成と分割能について鋭意研究した結果、本発明
を完成するに到った。[Problems to be solved by conventional techniques and inventions] Conventionally,
Separating agents using polysaccharide derivatives have shown excellent resolution ability for a wide variety of racemic compounds as stationary phases for liquid chromatography, but separation agents require the higher-order structure of the polysaccharide derivatives to resolve racemic compounds. It is believed that it is important that the structure be well matched and that various adsorption interactions can work effectively between the two. However, it is also true that there are compounds that are difficult to split even using polysaccharide derivatives that have excellent splitting ability. The present inventors have conducted intensive research on separation agents that can separate such difficult-to-separate compounds, and
Focusing on oligosaccharide derivatives that have the same repeating unit structure as polysaccharide derivatives but with a smaller number of repeating units, the present invention was completed as a result of intensive research into the synthesis and resolution ability of oligosaccharide derivatives.
即ち本発明は、下記の一般式（１）で表されるＤ−グル
コピラノシドを繰り返し単位とする少糖類化合物の水酸
基の一部又は全部を、原子数４〜３０の官能基で置換し
た化合物からなる少糖誘導体及びこれを主成分とする分
離剤に係るものである。That is, the present invention consists of a compound in which part or all of the hydroxyl groups of an oligosaccharide compound having D-glucopyranoside as a repeating unit represented by the following general formula (1) are substituted with a functional group having 4 to 30 atoms. This invention relates to oligosaccharide derivatives and separation agents containing them as main components.
（式中ｎは１〜９の整数である。）
〈少 糖〉
本発明における少糖とは、繰り返し単位数が１〜９、好
ましくは３〜９の光学活性体で、繰り返し単位がＤ−グ
ルコピラノシド構造を有する化合物であり、結合形態は
α位が置換されるα−１，４−グルコシド又はβ位が置
換されるβ−１，４−グリコシドの何れでも構わない。(In the formula, n is an integer of 1 to 9.) <Oligose> The oligosaccharide in the present invention is an optically active substance having 1 to 9 repeating units, preferably 3 to 9, and the repeating unit is D- It is a compound having a glucopyranoside structure, and the bond form may be either an α-1,4-glucoside substituted at the α-position or a β-1,4-glycoside substituted at the β-position.
具体的に例示するならば、次の如き化合物があげられる
。Specific examples include the following compounds.
＾） α−１，４−グリコシド類
繰り返し単位数ｎ＝３の場合
Ｂ） β−１，４−グリコシド類
繰り返し単位数ｎ＝３の場合
〈官 能 基〉
導入する官能基としては、少糖類の水酸基との反応によ
り得られる原子数が４〜３０の官能基であれば如何なる
ものでも構わない。^) When the number of α-1,4-glycoside repeating units n = 3 B) When the number of β-1,4-glycoside repeating units n = 3 <Functional group> The functional group to be introduced is an oligosaccharide. Any functional group having 4 to 30 atoms obtained by reaction with a hydroxyl group may be used.
代表的な官能基を例示するならば次の様なものがあげら
れる。The following are examples of typical functional groups.
＾） エステル誘導体
Ｒは原子数１〜２８のグループで、具体的にはメチル（
−ＣＨ３）、エチル（−Ｃ，Ｈ５） 、フェニルある。^) Ester derivative R is a group having 1 to 28 atoms, specifically methyl (
-CH3), ethyl (-C,H5), and phenyl.
Ｂ） カルバメート誘導体
Ｒ′は原子数１〜２５のグループで、具体的になどがあ
る。B) Carbamate derivative R' is a group having 1 to 25 atoms, and specifically includes the following.
Ｃ） エーテル誘導体
Ｒ”は原子数４〜２９のグループで、具体的にどがある
。C) Ether derivative R'' is a group having 4 to 29 atoms, and there are specific examples.
官能基の導入率は、８０％〜１００％、好ましくは９０
％以上である。The introduction rate of functional groups is 80% to 100%, preferably 90%.
% or more.
（合成方法〉
１） エステル誘導体
本発明に係るエステル誘導体の合成は、対応するカルボ
ン酸を塩化チオニノペオキサリルクロリドなどを用いて
酸クロリドとした後、ピリジン溶媒中で、対応する少糖
と前記酸りロリドとを反応させることにより、容易に得
られる。(Synthesis method> 1) Ester derivative The ester derivative according to the present invention is synthesized by converting the corresponding carboxylic acid into an acid chloride using thioninopeoxalyl chloride or the like, and then converting the corresponding oligosaccharide with the above-mentioned oligosaccharide in a pyridine solvent. It can be easily obtained by reacting with an acid loride.
２） カルバメート誘導体
本発明に係るカルバメート誘導体の合成には、通常のア
ルコールとイソシアナートからウレタンを生ずる反応を
そのまま適用できる。2) Carbamate derivatives For the synthesis of carbamate derivatives according to the present invention, a conventional reaction for producing urethane from alcohol and isocyanate can be applied as is.
例えば、適当な溶媒中で三級アミン等のルイス塩基、又
は錫化合物等のルイス酸を触媒として、対応するイソシ
アナートと少糖とを反応させることにより得ることがで
きる。また、イソシアナートの合成は、例えば、対応す
るアニリン誘導体のアミノ基にホスゲンを作用させるこ
とにより、容易に得ることができる。For example, it can be obtained by reacting the corresponding isocyanate and oligosaccharide in an appropriate solvent using a Lewis base such as a tertiary amine or a Lewis acid such as a tin compound as a catalyst. Furthermore, isocyanates can be easily synthesized by, for example, allowing phosgene to act on the amino groups of the corresponding aniline derivatives.
３） エーテル誘導体
本発明に係るエーテル誘導体の合成は、対応するハロゲ
ン化物と、例えばジオキサン又はピリジン溶媒中で、塩
基として水酸化カリウム、カリウムｔ−ブトキシドを用
いて、相当する少糖とを反応させることにより得られる
。3) Ether derivatives The ether derivatives according to the present invention are synthesized by reacting the corresponding halide with the corresponding oligosaccharide in a dioxane or pyridine solvent, for example, using potassium hydroxide or potassium t-butoxide as a base. It can be obtained by
く分 離 剤〉
本発明の少糖誘導体は、機能材料として極めて有用な物
質であり、特に光学分割用充填剤、即ち分離剤として有
用なものである。Separating Agent> The oligosaccharide derivative of the present invention is an extremely useful substance as a functional material, and is particularly useful as a filler for optical resolution, that is, as a separating agent.
本発明の少糖誘導体を分離剤として、化合物の混合物や
光学異性体混合物を分離する目的に使用するには、本発
明による少糖誘導体を充填したカラムを用いるガスクロ
マトグラフィー、液体クロマトグラフィー及び薄層クロ
マトグラフィーなどのクロマトグラフィー法を用いるの
が一般的であるが、この他、本発明による少糖誘導体を
含む膜を成形し、この成形膜を用いて膜分離を行うこと
もできる。In order to use the oligosaccharide derivative of the present invention as a separation agent for the purpose of separating a mixture of compounds or a mixture of optical isomers, gas chromatography, liquid chromatography, Although it is common to use a chromatography method such as layer chromatography, it is also possible to form a membrane containing the oligosaccharide derivative according to the present invention and perform membrane separation using this formed membrane.
少糖誘導体を担体に担持させるには、化学的方法でも物
理的方法でもどちらの方法を用いてもよい。物理的方法
としては、少糖誘導体を可溶性の溶剤に溶解させ、担体
と良く混合した後、減圧又は加温下で、気流により溶剤
を留去させる方法や、少糖誘導体を可溶性の溶剤に溶解
させ、担体と良く混合した後、少糖誘導体に対して不溶
性である溶剤を用いて、可溶性溶剤を拡散させてしまう
方法もある。この様にして得られた分離剤は、加熱、溶
媒の添加、洗浄などの適当な処理を行うことによって、
その分離能を改善することも可能である。To support the oligosaccharide derivative on a carrier, either a chemical method or a physical method may be used. Physical methods include dissolving the oligosaccharide derivative in a soluble solvent, mixing well with the carrier, and then distilling off the solvent with air flow under reduced pressure or heating; or dissolving the oligosaccharide derivative in a soluble solvent. There is also a method in which the oligosaccharide derivative is thoroughly mixed with the carrier, and then a soluble solvent is diffused using a solvent that is insoluble in the oligosaccharide derivative. The separation agent obtained in this way can be treated with appropriate treatments such as heating, adding a solvent, and washing.
It is also possible to improve its resolution.
用いる担体としては、多孔質有機担体又は多孔質無機担
体があり、好ましくは多孔質無機担体である。多孔質有
機担体として適当なものは、ポリスチレン、ポリアクリ
ルアミド、ポリアクリレート等からなる高分子物質があ
げられる。The carrier used may be a porous organic carrier or a porous inorganic carrier, preferably a porous inorganic carrier. Suitable porous organic carriers include polymeric substances such as polystyrene, polyacrylamide, and polyacrylate.
多孔質無機担体として適当なものは、シリカ、アルミナ
、マグネシア、ガラス、カオリン、酸化チタン、ケイ酸
塩などであり、またカルバメート誘導体との親和性を良
くしたり、担体自体の表面の特性を改質するために、前
記多孔質無機担体の表面に処理を施したものを用いても
良い。表面処理の方法としては、有機シラン化合物によ
るシラン化処理やプラズマ重合による表面処理方法等が
ある。Suitable porous inorganic carriers include silica, alumina, magnesia, glass, kaolin, titanium oxide, and silicate. The surface of the porous inorganic carrier may be treated in order to improve its quality. Examples of surface treatment methods include silanization using an organic silane compound and surface treatment using plasma polymerization.
また、化学結合による担持の場合には、例えば少糖の水
酸基の一部とシラン処理されたシリカゲルとを、多官能
のイソシアナート誘導体を介して化学結合させた後、少
糖の水酸基の残部に置換基を導入する方法などがある（
特開昭６２−２７０６０２）。In addition, in the case of supporting by chemical bonding, for example, a part of the hydroxyl groups of the oligosaccharide and silane-treated silica gel are chemically bonded via a polyfunctional isocyanate derivative, and then the remaining hydroxyl groups of the oligosaccharide are bonded to the silane-treated silica gel. There are methods such as introducing substituents (
Japanese Patent Publication No. 62-270602).
液体クロマトグラフィーあるいは薄層クロマトグラフィ
ーを行う場合の展開溶媒としては、少糖誘導体を溶解さ
せたり、又はこれと反応するものを除いて特に制約はな
い。There are no particular restrictions on the developing solvent used in liquid chromatography or thin layer chromatography, as long as it dissolves or reacts with the oligosaccharide derivative.
以下に実施例について本発明を具体的に説明するが、本
発明はこれらの実施例に限定されるものではない。The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples.
合成例（少糖の３．５−ジメチルフェニルカルバメート
誘導体の合成）
所定量の少糖をピリジンに懸濁溶解させ、当量以上の３
，５−ジメチルフェニルイソシアナートを加えた後、窒
素雰囲気下で、８０℃で１０〜２４時間攪拌した。前記
反応物を室温まで冷却した後、減圧下でピリジンを蒸発
させることにより除去した。得られた残渣をｎ−ヘキサ
ンで洗浄後、乾燥し、次にＮ、Ｎ−ジメチルアセトアミ
ドあるいはテトラヒドロフランに懸濁溶解し、不溶部を
遠心分離によって除去した。Synthesis example (synthesis of 3,5-dimethylphenyl carbamate derivative of oligosaccharide) A predetermined amount of oligosaccharide is suspended and dissolved in pyridine,
, 5-dimethylphenylisocyanate, and then stirred at 80° C. for 10 to 24 hours under a nitrogen atmosphere. After the reaction was cooled to room temperature, the pyridine was removed by evaporation under reduced pressure. The obtained residue was washed with n-hexane and dried, then suspended and dissolved in N,N-dimethylacetamide or tetrahydrofuran, and the insoluble portion was removed by centrifugation.
可溶部を、混合比が４：１であるメタノール−水混合溶
媒へ注ぎ入れて再沈殿させることによって得られた析出
物をグラスフィルターで濾別した後、６０℃で減圧乾燥
した。The soluble portion was poured into a mixed solvent of methanol and water at a mixing ratio of 4:1 to cause reprecipitation, and the resulting precipitate was filtered through a glass filter and then dried under reduced pressure at 60°C.
実施例１
上記合成例に基づいて、ｎ（繰り返し単位数）が２であ
るアミロースオリゴマーの３．５−ジメチルフェニルカ
ルバメート誘導体を合成した。Example 1 Based on the above synthesis example, a 3,5-dimethylphenyl carbamate derivative of amylose oligomer having n (number of repeating units) of 2 was synthesized.
得られた化合物の元素分析値は以下の通りである。The elemental analysis values of the obtained compound are as follows.
０％ ８％ Ｎ％
実測値 ６７．６７ ６．２４ ７．６８計算値
６６．３９ ６．２３ ７．３７実施例２
上記合成例に基づいて、ｎが３であるアミロースオリコ
マ−の３．５−ジメチルフェニルカルバメート誘導体を
合成した。0% 8% N% Actual value 67.67 6.24 7.68 Calculated value
66.39 6.23 7.37 Example 2 Based on the above synthesis example, a 3,5-dimethylphenyl carbamate derivative of amylose oligomer in which n is 3 was synthesized.
元素分析値は以下の通りである。The elemental analysis values are as follows.
０％ ８％ Ｎ％
実測値 ６５．９５ ６．２２ ７．３６計算値
６６．１８ ６．２２ ７．２６実施例３
上記合成例に基づいて、ｎが４であるアミロースオリゴ
マーの３．５−ジメチルフェニルカルバメート誘導体を
合成した。0% 8% N% Actual value 65.95 6.22 7.36 Calculated value
66.18 6.22 7.26 Example 3 Based on the above synthesis example, a 3,5-dimethylphenyl carbamate derivative of amylose oligomer in which n is 4 was synthesized.
元素分析値は以下の通りである。The elemental analysis values are as follows.
０％ ８％ Ｎ％
実測値 ６５．７０ ６．２０ ７．１７計算値
６６．０７ ６．２１ ７．１９実施例４
上記合成例に基づいて、ｎが５であるアミロースオリゴ
マーの３．５−ジメチルフェニルカルバメート誘導体を
合成した。0% 8% N% Actual value 65.70 6.20 7.17 Calculated value
66.07 6.21 7.19 Example 4 Based on the above synthesis example, a 3,5-dimethylphenyl carbamate derivative of amylose oligomer in which n is 5 was synthesized.
元素分析値は以下の通りである。The elemental analysis values are as follows.
０％ ８％ Ｎ％
実測値 ６５．４８ ６゜１４ ７．１６計算値
６５．９９ ６．２０ ７．１５実施例５
上記合成例に基づいて、ｎが６であるアミロースオリゴ
マーの３．５−ジメチルフェニルカルバメート誘導体を
合成した。0% 8% N% Actual value 65.48 6゜14 7.16 Calculated value
65.99 6.20 7.15 Example 5 Based on the above synthesis example, a 3.5-dimethylphenyl carbamate derivative of amylose oligomer in which n is 6 was synthesized.
元素分析値は以下の通りである。The elemental analysis values are as follows.
０％ ８％ Ｎ％
実測値 ６６．４０ ６．２２ ７．４１計算値
６５．９４ ６．２０ ７．１２実施例６
上記合成例に基づいて、ｎが７であるアミロースオリゴ
マーの３．５−ジメチルフェニルカルバメート誘導体を
合成した。0% 8% N% Actual value 66.40 6.22 7.41 Calculated value
65.94 6.20 7.12 Example 6 Based on the above synthesis example, a 3.5-dimethylphenyl carbamate derivative of amylose oligomer in which n is 7 was synthesized.
元素分析値は以下の通りである。The elemental analysis values are as follows.
０％ ８％ Ｎ％
実測値 ６６．１４ ６．２９ ７．４１− 計
算値 ６５．９０ ６．２０ ７．１０実施例７
上記合成例に基づいて、ｎが２であるセルロースオリゴ
マー（セロビオース）の３．５−ジメチルフェニルカル
バメート誘導体を合成した。0% 8% N% Actual value 66.14 6.29 7.41- Calculated value 65.90 6.20 7.10 Example 7 Based on the above synthesis example, cellulose oligomer (cellobiose) where n is 2 A 3.5-dimethylphenylcarbamate derivative was synthesized.
元素分析値は以下の通りである。The elemental analysis values are as follows.
０％ ８％ Ｎ％
実測値 ６６．７３ ６．３０ ７．５０計算値
６６．３９ ６．２３ ７．３７実施例８
上記合成例に基づいて、ｎが４であるセルロースオリゴ
マー（セロテトラオース）の３，５−ジメチルフェニル
カルバメート誘導体を合成した。0% 8% N% Actual value 66.73 6.30 7.50 Calculated value
66.39 6.23 7.37 Example 8 Based on the above synthesis example, a 3,5-dimethylphenyl carbamate derivative of cellulose oligomer (cellotetraose) in which n is 4 was synthesized.
元素分析値は以下の通りである。The elemental analysis values are as follows.
０％ ８％ Ｎ％
実測値 ６６．８５ ６．２８ ７．４９計算値
６６．０７ ６．２１ ７．１９応用例
実施例１〜８で得られた少糖のカルバメート誘導体０．
７５ ｇを溶媒に溶解しく実施例１〜６で得られた前記
誘導体はＮ、 Ｎ’−ジメチルアセトアミドに、実施例
７，８で得られた前記誘導体テトラヒドロフランに、そ
れぞれ溶解した）、この溶解液と、アミノプロピルシラ
ン処理を施したシリカゲル３ｇとを混和させた後、前記
溶媒を除去して分離用の充填剤を得た。0% 8% N% Actual value 66.85 6.28 7.49 Calculated value
66.07 6.21 7.19 Application Examples Carbamate derivatives of oligosaccharides obtained in Examples 1 to 8 0.
75 g of the derivatives obtained in Examples 1 to 6 were dissolved in N,N'-dimethylacetamide and the derivatives obtained in Examples 7 and 8 were dissolved in tetrahydrofuran, respectively), and this solution was dissolved. and 3 g of silica gel treated with aminopropylsilane were mixed, and the solvent was removed to obtain a separation filler.
上記充填剤をメタノールを用いるスラリー法により、内
径０．４６ｃｍ、長さ２５ｃｍのステンレス製カラムに
充填した。The above-mentioned packing material was packed into a stainless steel column with an inner diameter of 0.46 cm and a length of 25 cm by a slurry method using methanol.
この分離剤を用いて下記に示す種々のラセミ体化合物ユ
〜ｊを分離した。その結果を表１及び表２に示す。Using this separating agent, various racemic compounds U to J shown below were separated. The results are shown in Tables 1 and 2.
尚、表中の容量比（ｋ″）及び分離係数（α）はそれぞ
れ下式により定義される。Incidentally, the capacity ratio (k″) and separation coefficient (α) in the table are defined by the following formulas, respectively.
容量比（ｋ’）＝ デッドタイム 分離係数（α）＝ ラセミ体化合物１〜５Capacity ratio (k’)= dead time Separation coefficient (α) = Racemic compounds 1-5
Claims (1)
ドを繰り返し単位とする少糖類化合物の水酸基の一部又
は全部を、原子数４〜３０の官能基で置換した化合物か
らなる少糖誘導体。 ▲数式、化学式、表等があります▼……（１） （式中ｎは１〜９の整数である。） ２ 請求項１記載の少糖誘導体からなる分離剤。[Scope of Claims] 1. A compound in which part or all of the hydroxyl groups of an oligosaccharide compound having D-glucopyranoside as a repeating unit represented by the following general formula (1) are substituted with a functional group having 4 to 30 atoms. A oligosaccharide derivative consisting of ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (1) (In the formula, n is an integer from 1 to 9.) 2. A separating agent comprising the oligosaccharide derivative according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29781790A JP2971938B2 (en) | 1990-11-01 | 1990-11-01 | Separating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29781790A JP2971938B2 (en) | 1990-11-01 | 1990-11-01 | Separating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04169595A true JPH04169595A (en) | 1992-06-17 |
| JP2971938B2 JP2971938B2 (en) | 1999-11-08 |
Family
ID=17851548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29781790A Expired - Fee Related JP2971938B2 (en) | 1990-11-01 | 1990-11-01 | Separating agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2971938B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997015549A1 (en) * | 1995-10-26 | 1997-05-01 | Tokyo Tanabe Company Limited | PHENYLETHANOLAMINE COMPOUNDS USEFUL AS β3 AGONIST, PROCESS FOR PRODUCING THE SAME, AND INTERMEDIATES IN THE PRODUCTION OF THE SAME |
| JP2011183361A (en) * | 2010-03-11 | 2011-09-22 | Daicel Chemical Industries Ltd | Separator having fixed cyclic oligosaccharide and method for producing the same |
-
1990
- 1990-11-01 JP JP29781790A patent/JP2971938B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997015549A1 (en) * | 1995-10-26 | 1997-05-01 | Tokyo Tanabe Company Limited | PHENYLETHANOLAMINE COMPOUNDS USEFUL AS β3 AGONIST, PROCESS FOR PRODUCING THE SAME, AND INTERMEDIATES IN THE PRODUCTION OF THE SAME |
| US6069176A (en) * | 1995-10-26 | 2000-05-30 | Mitsubishi-Tokyo Pharmaceuticals, Inc. | Phenylethanolamine compounds useful as β 3 agonists, process for producing the same, and intermediates in the production of the same |
| JP2011183361A (en) * | 2010-03-11 | 2011-09-22 | Daicel Chemical Industries Ltd | Separator having fixed cyclic oligosaccharide and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2971938B2 (en) | 1999-11-08 |
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