JPS59228936A - Separating and extracting agent for carbonyl compound - Google Patents
Separating and extracting agent for carbonyl compoundInfo
- Publication number
- JPS59228936A JPS59228936A JP58103903A JP10390383A JPS59228936A JP S59228936 A JPS59228936 A JP S59228936A JP 58103903 A JP58103903 A JP 58103903A JP 10390383 A JP10390383 A JP 10390383A JP S59228936 A JPS59228936 A JP S59228936A
- Authority
- JP
- Japan
- Prior art keywords
- cyclodextrin
- group
- immobilized
- amino group
- react
- 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
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
Abstract
Description
【発明の詳細な説明】
本発明はカルボニル化合物の分離、抽出用剤に関するも
のでｓｂ詳しくは、シクロデキストリンの７級水酸基の
一部が７Ｍアミノ基を有する基で置換されたシクロデキ
ストリンを含む不溶性樹脂よ〕なるカルボニル化合物の
分ｍ、抽出用剤に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an agent for separating and extracting carbonyl compounds.Specifically, the present invention relates to an agent for separating and extracting carbonyl compounds. It relates to extractants of carbonyl compounds such as resins.
従来、化学物質の分離法の一つとして、イオン交換クロ
マトグラフィー、分配クロマトグラいる。Conventionally, ion exchange chromatography and partition chromatography have been used as methods for separating chemical substances.
これらは化学伸質のイオンとしての性質、化学物質の移
動相と固定相への分配比の差異１分子サイズの大小関係
等を利用するものである。These methods utilize the ionic properties of chemical elongation, the difference in the distribution ratio of chemical substances between the mobile phase and the stationary phase, and the size relationship of one molecule.
又近時は包接化合物の分離、抽出剤としての利用も注目
され、シクロデキストリンを含む各種の樹脂が合成さり
、カラムクロマトグラフィーの分離剤への応用が検討さ
れてｂる。Recently, the separation of clathrate compounds and their use as extractants have also attracted attention, and various resins containing cyclodextrins have been synthesized, and their applications as separation agents for column chromatography are being considered.
これらはシクロデキストリンの環状疎水性空孔が適当な
太き式の疎水性分子を包接するというものであり１分子
サイズの大、小関係を利用するものである。In these methods, the cyclic hydrophobic pores of cyclodextrin enclose a hydrophobic molecule of an appropriate thickness, and utilize the relationship between large and small molecule sizes.
本発明者らは、シクロデキストリンによる化学物質の分
離剤としての新規な利用について鋭意検討した結果、シ
クロデキストリンの／級水酸基側に導入したアミノ基は
、アルデヒド十ケトンと反応してカルビノールアミン又
はシッフ塩基を形成するが、この反応は平衡反応であシ
、平衡に到達する速度も充分に大である、とｂう不溶性
樹脂は、シクロデキストリン部分による疎水認識と、ア
ミノ基による官能基認識の機能とを併せ持った特殊な樹
脂として、カルボニル化合物の分離剤に利用し得ること
を見出した。As a result of intensive studies on the novel use of cyclodextrin as a separation agent for chemical substances, the present inventors found that the amino group introduced into the /class hydroxyl group side of cyclodextrin reacts with aldehyde decaketone to form carbinolamine or Although a Schiff base is formed, this reaction is an equilibrium reaction, and the speed at which equilibrium is reached is sufficiently high.b.The insoluble resin has hydrophobic recognition by the cyclodextrin moiety and functional group recognition by the amino group. We have discovered that this special resin can be used as a separating agent for carbonyl compounds.
不発Ｆ！Ａハ上記の知見をもとに完成されたものでアシ
、その安上はシクロデキストリンの７級水酸基の一部が
／ｉアミノ基を有する基で置換存する。Misfire F! A was completed on the basis of the above knowledge, and in this case, a part of the 7th-class hydroxyl group of cyclodextrin is substituted with a group having an /i amino group.
以下本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の分離抽出用樹脂は、溶媒に不溶性の樹脂に固定
化でれたシクロデキストリンの７級を
水酸基０１ｌｌＶｃ／蕨アミノ基が導入され？なるもの
である。The separation/extraction resin of the present invention has a hydroxyl group 01llVc/warabi amino group introduced into the 7th class of cyclodextrin immobilized on a solvent-insoluble resin. It is what it is.
かかる物質は従来公知の固定化シクロデキストリンのデ
キストリン部の７級水酸基の一部を７級アミノ基を有す
る各種の置換基で置換する方法や、アミノ置換シクロデ
キストリンを各種の方法で不溶性樹脂に固定化する方法
で製造される。Such substances can be obtained by substituting some of the 7th-class hydroxyl groups of the dextrin moiety of conventionally known immobilized cyclodextrins with various substituents having a 7th-class amino group, or by immobilizing amino-substituted cyclodextrins on insoluble resins by various methods. Manufactured using a method that
本発明の樹脂のシクロデキストリン環からアミン基まで
の置換基の長さは分離対象物質に応じて適宜選択変更さ
れる。The length of the substituent from the cyclodextrin ring to the amine group in the resin of the present invention is appropriately selected and changed depending on the substance to be separated.
又シクロデキストリンにはα−シクロデキストリン、β
−シクロデキストリン、γ−シクロデキストリン吟があ
るが１分離対象物質に応じて適宜なシクロデキストリン
が利用される。In addition, cyclodextrin includes α-cyclodextrin, β-cyclodextrin,
-Cyclodextrin and γ-cyclodextrin are available, and an appropriate cyclodextrin is used depending on the substance to be separated.
固定化シクロテキスト１ノンとしては、シクロデキスト
リンとエピクロルヒドリンとの共重合体、ポリビニルア
ルコールとシクロデキストリンのビス（エポキシグロビ
ル）エーテルによる架橋ポリマー、ポリ（アクリロイル
−β−シクロデキストリン）、／、４ｔ−ブタンジオー
ルグリシジルエーテルを用いてアガロースへ結合させた
ゲル、ジイソシアネートとシクロデキストリンのポリウ
レタン等が利用できる。The immobilized cyclotext 1non includes a copolymer of cyclodextrin and epichlorohydrin, a crosslinked polymer of polyvinyl alcohol and bis(epoxyglobyl) ether of cyclodextrin, poly(acryloyl-β-cyclodextrin), /, 4t- Gels bonded to agarose using butanediol glycidyl ether, polyurethanes of diisocyanates and cyclodextrin, etc. can be used.
例えば、これらの固定化シクロデキストリンを膨潤させ
、かつ、ｐ−トルエンスルホン酸クロライドと不活性な
溶媒中で、固定化シクロデキストリン、！＝ｐ−）ルエ
ンスルホン酸クロライドとを反応させて、シクロデキス
トリン部分の／＠水酸基の一部をｐ−トルエンスルホン
酸エステルに変化はせ、次いで、エチレンシアミンやア
ミノエタンチオール、アンモニア等ト反応させ、更にカ
セイソーダ水溶液等のアルカリ性の水浴液で洗浄するこ
とによって、固定化シクロデキストリンに７級アミノ基
を導入することができる。For example, by swelling these immobilized cyclodextrins and p-toluenesulfonic acid chloride in an inert solvent, the immobilized cyclodextrins,! =p-) to react with toluenesulfonic acid chloride to change a part of the /@hydroxyl group of the cyclodextrin moiety into p-toluenesulfonic acid ester, and then react with ethylenecyamine, aminoethanethiol, ammonia, etc. By washing the immobilized cyclodextrin with an alkaline water bath solution such as a caustic soda aqueous solution, a 7th-class amino group can be introduced into the immobilized cyclodextrin.
或いは７級アミノ基を導入したシクロデキストリンを不
溶性の高分子物質と反応させて、シクロデキストｖ’、
ｍ不溶性高分子物質に結合させることによっても本発明
の分離、抽出用樹脂が製造できる。例えばビス−（β−
アミノエチルスルフェニル）ジクロデキストリントカル
ボキシエステル基を有する不溶性高分子物質とを縮合さ
せることによって製造できる。Alternatively, cyclodextrin into which a 7th-class amino group has been introduced is reacted with an insoluble polymer substance to form cyclodext v',
The separation and extraction resin of the present invention can also be produced by binding it to an m-insoluble polymeric substance. For example, bis-(β-
It can be produced by condensing dichlorodextrin (aminoethylsulfenyl) with an insoluble polymeric substance having a tocarboxyester group.
エステル基を有する不溶性高分子物質としては架橋ポリ
アクリル酸メチル、架橋ポリアクリル酸エチル、架橋ポ
リメタクリル酸メチル、架橋ポリメタクリル酸エチル、
アクリロニトリルとアクリル酸エステルとの共重合物等
が挙げられる。Examples of insoluble polymeric substances having ester groups include crosslinked polymethyl acrylate, crosslinked polyethyl acrylate, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate,
Examples include copolymers of acrylonitrile and acrylic esters.
縮合反応はピリジン、キノリン、ピコリン等の反応に不
活性で、不溶性高分子物質とビス−（β−アミノエチル
スルフェニル）シクロデキストリンの両者に対する良溶
媒中でおこ々われる。The condensation reaction takes place in a solvent that is inert to the reaction of pyridine, quinoline, picoline, etc. and is good for both the insoluble polymeric substance and bis-(β-aminoethylsulfenyl)cyclodextrin.
本発明の分離、抽出用樹脂はシクロデキストリンの疎水
空孔による疎水認識と、アミン基による官能基認識とが
協同して働くいわゆる分子二重８Ｒの原理を利用するも
のであシ、各種の疎水性のカルボニル化合物の分離、抽
出に適用できる。The separation and extraction resin of the present invention utilizes the principle of so-called molecular double 8R, in which hydrophobic recognition by the hydrophobic pores of cyclodextrin and functional group recognition by the amine group work together. It can be applied to the separation and extraction of carbonyl compounds.
特に、以下の表−／に示すような生理活性アルデヒド（
ケトン）化合物に対し高い分離効率表−／
本発明の分離、抽出用樹脂は、例えば力２ムに充填して
カラムクロマドグ２フイーによって。In particular, bioactive aldehydes (
Table of high separation efficiency for (ketone) compounds - / The separation and extraction resin of the present invention can be packed, for example, in a column chroma dog 2 column.
カルボニル化合物の分離、抽出に使用される。Used for separation and extraction of carbonyl compounds.
本発明の樹脂を充填したカラムに疎水性のカルボニル化
合物を含有する試料溶液を注入して、展開させると、他
の化合物にくらべてカルボニル化合物の溶出時間が大と
なシ、これを精度よく分離、抽出し得る。When a sample solution containing a hydrophobic carbonyl compound is injected into a column packed with the resin of the present invention and allowed to develop, the elution time of the carbonyl compound is longer than that of other compounds, allowing it to be separated with precision. , can be extracted.
展開の際の移動相としては、水あるいは、メチルアルコ
ール、エチルアルコール等の含水アルコールが使用され
るが、アルコール含量を変えることによって溶出時間を
調節することができる。Water or a hydrous alcohol such as methyl alcohol or ethyl alcohol is used as the mobile phase during development, and the elution time can be adjusted by changing the alcohol content.
以下本発明を実施例によって更に詳細に舵明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
ビス−（β−アミノエチルスルフェニル）−β−シクロ
デキストリンλ？ （／、ｊ ！ ｍｍｏＪ−）をピリ
ジン−水（／：／ｖ／ｖ）ｊθゴに溶解し、これに、ア
クリロニトリル−アクリル酸メチル共重合体（アクリロ
ニトリル：アクリル酸メチル＝グ”、０．３９ｊモル）
θ、に２を加え、トリエチルアミンの共存下、Ｎ、置換
して７００℃。Bis-(β-aminoethylsulfenyl)-β-cyclodextrin λ? (/, j ! mmoJ-) was dissolved in pyridine-water (/:/v/v)jθgo, and acrylonitrile-methyl acrylate copolymer (acrylonitrile: methyl acrylate=g”, 0.39j mole)
2 was added to θ, and N was substituted in the presence of triethylamine at 700°C.
ｔｏ時間加熱した。The mixture was heated for to hours.
次いで、反応溶液に／θθｄの水を加えて樹脂をヂ取し
、これを水、エタノール、エーテル各！０−で順次洗浄
したのち、減圧乾燥（Ｏ９／ｍ’１ｌｒＨｆ、室温、７
日）して本発明の樹脂を得た。Next, /θθd of water was added to the reaction solution to remove the resin, and this was mixed with water, ethanol, and ether! After sequentially washing with 0-, dry under reduced pressure (O9/m'1lrHf, room temperature, 7
1) to obtain the resin of the present invention.
上記樹脂の収量は、Ｏ６♂２であり ＫＢｒ ｄｉｓｃ
法による工Ｒスペクトルの特性ビーク（ｃ−’ ）は次
の通りであった。The yield of the above resin is O6♂2 and KBr disc
The characteristic peak (c-') of the engineering R spectrum obtained by the method was as follows.
３ｇθθ−３θθθ、 ２りθθ、 ／４６１．
／１６θ、 ／ダ！θ、 ／りθθ／３６０． ／２
２θ、 ／／４ｔＯ，／θｇθ、 ／θ３θ、 ９グ
Ｏ，フグθ実施例／
製造例で得た本発明樹脂ｉｏｏｗｇ（粒径Ｏ２０コ〜θ
、４ｔｍｉ＋）を水で膨潤させたのち、内径！朋、長さ
３０Ｉｔのガラスカラムに充填し、蒸留水を／ ｋｇ／
ｃｓｌＧの圧力で十分流通させた。3gθθ−3θθθ, 2 θθ, /461.
/16θ, /Da! θ, /riθθ/360. /2
2θ, //4tO, /θgθ, /θ3θ, 9gO, pufferfish θ Example/Resin of the present invention obtained in the production example ioowg (particle size O20~θ
, 4tmi+) after swelling with water, the inner diameter! Me, I packed a glass column with a length of 30It and added distilled water/kg/
The pressure of cslG allowed for sufficient circulation.
次−で、カラム上部へベンズアルデヒドのエチルアルコ
ール溶液ｏ、ｏ ｒ−を注入して展開を行った。Next, development was carried out by injecting an ethyl alcohol solution of benzaldehyde into the upper part of the column.
ベンズアルデヒドは、へグーの保持容量の７ラクシヨン
を中心として溶出した。溶出曲線を第７図中に（−）と
して示す。また１本発明樹脂の分離を相対保持容量（Δ
Ｖ／Ｖｏ）として表−一に示した。Benzaldehyde was eluted around the 7 lactation of Hegu's retention volume. The elution curve is shown as (-) in FIG. In addition, the relative retention capacity (Δ
V/Vo) is shown in Table 1.
なお、上記カラムのホールドアツプ量は。Furthermore, the hold up amount of the above column is as follows.
Ｎａ０Ｊ水溶液を試料として求めたところ、約０、ｊｄ
であった。When a Na0J aqueous solution was used as a sample, it was found that approximately 0,jd
Met.
参考例／及びコ
実施例／で用いた本発明樹脂によって同一条件下でベン
ジルアルコールと安息香酸ナトリウムの各エチルアルコ
ール溶液の展開を行った。Ethyl alcohol solutions of benzyl alcohol and sodium benzoate were developed under the same conditions using the resin of the present invention used in Reference Example and Co-Example.
各溶出曲線を第１図中に（ｂ） （Ｃ）として示した。Each elution curve is shown in FIG. 1 as (b) and (C).
また、相対保持容量を表−２に示した。Further, the relative retention capacity is shown in Table-2.
実施例コーグ
実施例／で用いた本発明樹脂によって同一条件下で、ア
セトフェノ／、ヘプタナール、プラムバキンの各エチル
アルコール溶液の展開ヲ行った。EXAMPLE Ethyl alcohol solutions of acetophenol, heptanal, and plumbaquin were developed using the resin of the present invention used in KOG Example 1 under the same conditions.
相対保持容量の結果を表−，２に示した。The results of relative retention capacity are shown in Table 2.
物のアルデヒド（ケトン）に対して１本発明の樹脂はそ
の保持容量を特異的に遅くする効果を有し、従って１本
発明の樹脂は、特に、実用的価値の高し生理活性アルデ
ヒド（ケトン）を。The resin of the present invention has the effect of specifically slowing down the retention capacity of aldehydes (ketones), and therefore the resins of the present invention are particularly suitable for bioactive aldehydes (ketones) of high practical value. )of.
他の物質との混合物から或いは粗抽出液から／過程で簡
単に分離、抽出し得る優れた能力を持つ。It has excellent ability to be easily separated and extracted from a mixture with other substances or from a crude extract.
表−λ （Ｖｏ＝Ｖｉ （ＮａＯｊ）−０，！ ）Table - λ (Vo=Vi (NaOj)-0,!)
第１図は％溶出曲線を示すグラフでおり、横軸は溶出′
Ｊｌ（＃Ｉ／）を縦軸は吸光度を示す。
図中、（ａ）はベンズアルデヒド、 （ｂ）はベンジル
アルコール、（０）は安息香酸ナトリウムの溶出曲線で
あり、破線は標準物質として用い九ＮａＧｊの溶出曲線
である。
出 願 人 三菱化成工業株式会社
代 理 人 弁理士 長谷用 −
（ほか７名）Figure 1 is a graph showing the % elution curve, and the horizontal axis is the elution '
The vertical axis represents absorbance of Jl (#I/). In the figure, (a) is the elution curve of benzaldehyde, (b) is the elution curve of benzyl alcohol, (0) is the elution curve of sodium benzoate, and the broken line is the elution curve of 9-NaGj used as a standard substance. Applicant Mitsubishi Chemical Industries, Ltd. Agent Patent Attorney Hase - (and 7 others)
Claims (1)
を有する基で置換されたシフロブキス）ＩＪンを含む不
溶性樹脂よシなる疎水性のカルボニル化合物の分離・抽
出用剤An agent for separating and extracting hydrophobic carbonyl compounds such as an insoluble resin containing cyclodextrin, in which a portion of the 7th-class hydroxyl group is substituted with a group having a 7th-class amino group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58103903A JPS59228936A (en) | 1983-06-10 | 1983-06-10 | Separating and extracting agent for carbonyl compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58103903A JPS59228936A (en) | 1983-06-10 | 1983-06-10 | Separating and extracting agent for carbonyl compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59228936A true JPS59228936A (en) | 1984-12-22 |
| JPH0442062B2 JPH0442062B2 (en) | 1992-07-10 |
Family
ID=14366381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58103903A Granted JPS59228936A (en) | 1983-06-10 | 1983-06-10 | Separating and extracting agent for carbonyl compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59228936A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014087838A1 (en) * | 2012-12-07 | 2014-06-12 | ダイキン工業株式会社 | Organic fluorine-based-compound adsorbent comprising cyclodextrin-supporting polymer |
| CN105418380A (en) * | 2015-12-21 | 2016-03-23 | 广西大学 | Acetophenone and 1-phenethyl alcohol separation method |
-
1983
- 1983-06-10 JP JP58103903A patent/JPS59228936A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014087838A1 (en) * | 2012-12-07 | 2014-06-12 | ダイキン工業株式会社 | Organic fluorine-based-compound adsorbent comprising cyclodextrin-supporting polymer |
| US9308519B2 (en) | 2012-12-07 | 2016-04-12 | Daikin Industries, Ltd. | Adsorbent for organic fluoro-compound comprising cyclodextrin-supported polymer |
| JP6034403B2 (en) * | 2012-12-07 | 2016-11-30 | ダイキン工業株式会社 | Organofluorine compound adsorbent comprising cyclodextrin-supported polymer |
| CN105418380A (en) * | 2015-12-21 | 2016-03-23 | 广西大学 | Acetophenone and 1-phenethyl alcohol separation method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0442062B2 (en) | 1992-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6042723A (en) | Mono- and di-derivatives of cyclodextrins, synthesis thereof and purification and use thereof in a support | |
| Betzenbichler et al. | Chiral stationary phases and applications in gas chromatography | |
| CA2450448A1 (en) | Block copolymer reduced in impurity content, polymeric carrier, pharmaceutical preparations in polymeric form and process for the preparation of the same | |
| CN102775564B (en) | Preparation method of temperature sensitive type monolithic column with chiral molecule recognition function | |
| Lee et al. | Synthesis of a vinyl monomer containing β‐cyclodextrin and grafting onto cotton fiber | |
| EP4331701A1 (en) | Modified macroporous adsorption resin, preparation method therefor and use thereof | |
| Li et al. | Thioether bridged cationic cyclodextrin stationary phases: Effect of spacer length, selector concentration and rim functionalities on the enantioseparation | |
| CN102133519A (en) | Limiting chiral chromatography stationary phase material and preparation method thereof | |
| Zhou et al. | A cationic cyclodextrin clicked bilayer chiral stationary phase for versatile chiral separation in HPLC | |
| JP5775072B2 (en) | Compositions and methods for cyclofructans as separating agents | |
| Kubota et al. | Chromatographic enantioseparation by cycloalkylcarbamate derivatives of cellulose and amylose | |
| Kasal et al. | Chiral Nafion membranes prepared by strong electrostatic binding of multiply positively charged β-cyclodextrin derivatives for tryptophan racemic mixtures’ separation | |
| JPS59228936A (en) | Separating and extracting agent for carbonyl compound | |
| CN111944195B (en) | Cellulose aerogel modified by polyion liquid as well as preparation method and application thereof | |
| CN103316642B (en) | Chitosan-derived calixarene [4] bonded silica gel stationary phase and its preparation method and application thereof | |
| Nagy et al. | Synthesis and Applications of Cinchona Squaramide‐Modified Poly (Glycidyl Methacrylate) Microspheres as Recyclable Polymer‐Grafted Enantioselective Organocatalysts | |
| Yashima et al. | Enantioseparation on 4‐halogen‐substituted phenylcarbamates of amylose as chiral stationary phases for high‐performance liquid chromatography | |
| KR20080007427A (en) | Bead for optical-isomer resolution and process for producing the same | |
| JPS59227906A (en) | Immobilized cyclodextrin amino derivative and its production | |
| CN112588215B (en) | Coating type cellulose high cross-linked polymer microsphere chiral stationary phase and preparation method and application thereof | |
| JP2005501920A (en) | Derivatized macrocycles for covalent bonding to substrates and methods for their preparation and use | |
| CN104130419B (en) | Regioselective beta-cyclodextrin derivative chiral stationary phase as well as preparation method and application thereof | |
| CN105601940B (en) | A kind of chitosan derivative cup [4] aromatic hydrocarbons bonded silica gel stationary phase and its production and use | |
| US7067640B1 (en) | Cross-linked chiral compounds and methods of making thereof | |
| JPH04106101A (en) | Cyclodextrin polymer and its production |