JPH0680081B2 - Polysaccharide derivative - Google Patents
Polysaccharide derivativeInfo
- Publication number
- JPH0680081B2 JPH0680081B2 JP59072173A JP7217384A JPH0680081B2 JP H0680081 B2 JPH0680081 B2 JP H0680081B2 JP 59072173 A JP59072173 A JP 59072173A JP 7217384 A JP7217384 A JP 7217384A JP H0680081 B2 JPH0680081 B2 JP H0680081B2
- Authority
- JP
- Japan
- Prior art keywords
- cellulose
- polysaccharide derivative
- polysaccharide
- optically active
- acid
- 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.)
- Expired - Lifetime
Links
Description
【発明の詳細な説明】 本発明は新規な多糖類誘導体に関するものであり、詳し
くは光学活性なカルボン酸の多糖類エステルに関するも
のである。TECHNICAL FIELD The present invention relates to a novel polysaccharide derivative, and more particularly to a polysaccharide ester of an optically active carboxylic acid.
多糖類のカルボン酸エステルは種々の化合物が知られて
いるが、カルボン酸が光学活性であるような多糖類カル
ボン酸エステルは、カルボン酸がアミノ酸である場合を
除き殆ど知られていない。Although various compounds of carboxylic acid esters of polysaccharides are known, almost no carboxylic acid ester of polysaccharides in which a carboxylic acid is optically active are known except when the carboxylic acid is an amino acid.
多糖類の光学活性を有するカルボン酸とのエステルは、
特にそれが多糖類分子中の水酸基の50％以上が置換され
た高置換度エステルの場合は、一般に有機溶剤に可溶性
であり、クロマトグラフイー用担体、液晶物質等として
利用できる可能性が高いが、特に光学活性物質の分離剤
として有用であると考えられる。Esters with carboxylic acids having optical activity of polysaccharides,
In particular, when it is a highly substituted ester in which 50% or more of the hydroxyl groups in the polysaccharide molecule are substituted, it is generally soluble in organic solvents and is likely to be usable as a chromatographic carrier, liquid crystal substance, etc. In particular, it is considered to be useful as a separating agent for optically active substances.
本発明の多糖類誘導体の合成に用いる光学活性なカルボ
ン酸とは、一対の光学対掌体が存在し実質的にその一方
のみからなる光学活性なＬ−メントキシ酢酸である。ま
た、本発明の多糖類誘導体の合成に用いる多糖類はセル
ロースである。The optically active carboxylic acid used for the synthesis of the polysaccharide derivative of the present invention is an optically active L-menthoxyacetic acid having a pair of optical antipodes and consisting essentially of only one of them. The polysaccharide used for the synthesis of the polysaccharide derivative of the present invention is cellulose.
セルロースをエステル化し、本発明の誘導体に導くため
の反応試薬は、対応するカルボン酸無水物又はカルボン
酸ハライドを用いれば良く、反応触媒としては硫酸、過
塩素酸のようなプレンステツド酸、塩化亜鉛のようなル
イス酸、ピリジン、トリエチルアミン、４−ジメチルア
ミノピリジン等の塩基が適宜使用できる。As a reaction reagent for esterifying cellulose and leading to the derivative of the present invention, a corresponding carboxylic acid anhydride or carboxylic acid halide may be used, and as a reaction catalyst, sulfuric acid, prensted acid such as perchloric acid, or zinc chloride. A Lewis acid, a base such as pyridine, triethylamine, or 4-dimethylaminopyridine can be appropriately used.
本発明の多糖類誘導体の合成にあたり、原料多糖類とし
ては、一旦水或いは蟻酸などの溶媒に溶解させたものを
別種の溶媒中に沈澱させて乾燥したもの、水溶液を直接
凍結乾燥したもの、或いは酢酸エステルのような多糖類
エステルを加水分解して得たものなどを原料とすると、
反応に対する活性が大きく有利に使用できる。In synthesizing the polysaccharide derivative of the present invention, as the raw material polysaccharide, what is once dissolved in a solvent such as water or formic acid is precipitated in another solvent and dried, or an aqueous solution is directly freeze-dried, or If the raw material is obtained by hydrolyzing a polysaccharide ester such as acetate ester,
It has a large activity for the reaction and can be advantageously used.
多糖類の種類、重合度によつて反応性は異るが、反応条
件の選択により多糖類誘導体の置換度は調節が可能であ
る。The reactivity varies depending on the type of the polysaccharide and the degree of polymerization, but the degree of substitution of the polysaccharide derivative can be adjusted by selecting the reaction conditions.
本発明の多糖類誘導体は種々の形態で利用できる。例え
ば、フイルム状、繊維状、粒子状などに成型して使用す
る。この場合には、重合度が比較的高いもの、例えば60
以上のものが、成型品の物理的強度などの点で好まし
い。The polysaccharide derivative of the present invention can be used in various forms. For example, it is used after being formed into a film shape, a fiber shape, a particle shape, or the like. In this case, the degree of polymerization is relatively high, for example 60
The above is preferable in terms of physical strength of the molded product.
又、微小シリカゲルに担持して使用するような場合に
は、重合度の比較的低いもの、例えば10〜80程度のもの
の方が、コーテイング性などの点で有利である。Further, in the case of being used by being supported on fine silica gel, those having a relatively low degree of polymerization, for example, those having a degree of polymerization of about 10 to 80 are more advantageous in terms of coating property and the like.
本発明の多糖類誘導体は、置換度が高い方、例えば分子
中の水酸基の50％以上をカルボン酸エステル化したもの
の方が、有機溶剤溶解性、及び種々の機能に優れている
傾向がみられる。The polysaccharide derivative of the present invention has a high degree of substitution, for example, one in which 50% or more of the hydroxyl groups in the molecule are carboxylic acid esterified, and it tends to be excellent in organic solvent solubility and various functions. .
本発明に係るセルロースのＬ−メントキシ酢酸エステル
は、本来光学活性なセルロースに光学活性なＬ−メント
キシ酢酸をエステル結合せしめたものであり、このよう
に２種の光学活性体が結合する時、それらは所謂ジアス
テレオマーを形成し、もはや単独の光学活性化合物とは
異なったものとなる。従って、本発明に係るセルロース
のＬ−メントキシ酢酸エステルは光学活性物質の新規な
分離剤として有用である。The L-menthoxyacetic acid ester of cellulose according to the present invention is essentially an optically active cellulose obtained by ester-bonding an optically active L-menthoxyacetic acid, and when two kinds of optically active substances are bound together, Forms a so-called diastereomer, which is different from the optically active compound alone. Therefore, the L-menthoxyacetic acid ester of cellulose according to the present invention is useful as a novel separating agent for optically active substances.
以下に実施例を挙げて本発明を説明するが、本発明はこ
れに限定されるものではない。The present invention will be described below with reference to examples, but the present invention is not limited thereto.
実施例１ 三酢酸セルロースをヒドラジンでケン化しセルロースと
し、良く水洗した後、アセトンで置換し真空乾燥した。
こうして得られたセルロース1.5g、ピリジン70ml、トリ
エチルアミン7.7mg、ジメチルアミノピリジン50mgを撹
拌棒、冷却コンデンサーのついた３つ口フラスコに入
れ、常温でＬ−メントキシアセチルクロリド18.2gを加
えた後、100℃で５時間撹拌した。得られた反応物を500
mlのエタノールに撹拌しながら加えた。沈澱物が得ら
れ、これをグラスフイルターで過し、エタノールで良
く洗浄した。得られた固体は乾燥させた後、塩化メチレ
ンに溶解させて、エタノールに再沈澱し、過後エタノ
ールで洗浄をくりかえし、次で真空乾燥した。Example 1 Cellulose triacetate was saponified with hydrazine to give cellulose, which was thoroughly washed with water, replaced with acetone, and vacuum dried.
1.5 g of cellulose thus obtained, 70 ml of pyridine, 7.7 mg of triethylamine, and 50 mg of dimethylaminopyridine were placed in a three-necked flask equipped with a stirring bar and a cooling condenser, and 18.2 g of L-menthoxyacetyl chloride was added at room temperature. The mixture was stirred at 100 ° C for 5 hours. The reaction product obtained is 500
Add to ml of ethanol with stirring. A precipitate was obtained, which was filtered through a glass filter and washed well with ethanol. The obtained solid was dried, dissolved in methylene chloride, reprecipitated in ethanol, repeatedly washed with ethanol, and then vacuum dried.
塩化メチレンに溶解し、食塩セルに塗布し、乾燥した後
得られた赤外吸収スペクトルは第１図の通りであり、特
徴的な吸収帯は次の通りである。The infrared absorption spectrum obtained after dissolving in methylene chloride, coating on a sodium chloride cell, and drying was as shown in FIG. 1, and the characteristic absorption bands are as follows.
2850〜2930cm-1 メチル基、メチレン基Ｃ−Ｈ伸縮振動 1750〜1770cm-1 カルボン酸エステルのＣ＝Ｏ伸縮振動 1450〜1470cm-1 メチル基Ｃ−Ｈ逆対称変角振動 メチレン基はさみ振動 1130cm-1 メントキシ基Ｃ−Ｏ−Ｃの伸縮振動 1040〜1200cm-1 セルロースのＣ−Ｏ−Ｃの伸縮振動 920cm-1 gem−ジメチル基Ｃ−Ｈ変角振動 セルロースのOHに基づく3450cm-1付近の吸収はほとんど
認められず、ほぼ３置換体であることを示す。又CDCl3
中で測定したプロトンNMRスペクトルの特徴的な吸収は
次の通りである。2850～2930Cm -1 methyl group, methylene group C-H stretching vibration 1750~1770cm -1 carboxylic acid ester C = O stretching vibration 1450～1470Cm -1 methyl C-H antisymmetric bending vibration methylene scissor vibration 1130 cm - 1 Stretching vibration of mentoxy group C-O-C 1040 to 1200 cm -1 Stretching vibration of C-O-C of cellulose 920 cm -1 gem-Dimethyl group C-H bending vibration Absorption of cellulose near 3450 cm -1 based on OH Is hardly observed, indicating that the compound is almost a 3-substituted product. Also CDCl 3
The characteristic absorptions of the proton NMR spectrum measured in are as follows.
3.8〜4.4ppm カルボキシメチル基のメチレンプロトン 0.2〜3.3ppm メントキシ基に含まれる 〜6ppm セルロース環及び６位のメチレンのプロトン これらの結果から、生成物は置換度約3.0のセルロース
−Ｌ−メントキシ酢酸エステルであると認められる。3.8-4.4ppm Methylene proton of carboxymethyl group 0.2-3.3ppm ~ 6ppm contained in menthoxy group Proton of cellulose ring and methylene at 6-position From these results, the product is cellulose-L-menthoxyacetic acid ester with substitution degree of about 3.0. Is recognized as
得られたセルロース−Ｌ−メントキシ酢酸エステルをジ
クロルメタンに溶解し、ジフェニルシラン処理したシリ
カゲルに担持（シリカゲルに対して15重量％）して、充
填剤を製造した。この充填剤をカラム（長さ25cm、内径
0.46cm）に充填し、ヘキサン／イソプロピルアルコール
＝9/1（v/v）を溶離液として、トランス−2,3−ジフェ
ニルオキシラン及び２−フェニルシクロヘキサノンに対
する分離能を旋光検出器を用いてチェックした。その結
果、トランス−2,3−ジフェニルオキシランではピーク
が先ずマイナス側にふれ、２−フェニルシクロヘキサノ
ンではピークが先ずプラス側にふれ、光学分割能が確認
された。The obtained cellulose-L-menthoxyacetic acid ester was dissolved in dichloromethane and supported on silica gel treated with diphenylsilane (15% by weight based on silica gel) to prepare a filler. This packing material is applied to the column (length 25 cm, inner diameter
0.46 cm) and using hexane / isopropyl alcohol = 9/1 (v / v) as an eluent, the resolution for trans-2,3-diphenyloxirane and 2-phenylcyclohexanone was checked using a polarimetric detector. . As a result, the peak of trans-2,3-diphenyloxirane was first shifted to the negative side, and the peak of 2-phenylcyclohexanone was first shifted to the positive side, confirming the optical resolution.
第１図は実施例１の多糖類誘導体の赤外吸収スペクトル
を示す図である。FIG. 1 is a diagram showing an infrared absorption spectrum of the polysaccharide derivative of Example 1.
Claims (2)
からなる多糖類誘導体。1. A polysaccharide derivative comprising L-menthoxyacetic acid ester of cellulose.
−メントキシ酢酸で置換されている特許請求の範囲第１
項記載の多糖類誘導体。2. At least 50% of the hydroxyl groups in the cellulose molecule are L
-Claims 1 substituted with mentoxyacetic acid
Item 6. The polysaccharide derivative according to the item.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59072173A JPH0680081B2 (en) | 1984-04-11 | 1984-04-11 | Polysaccharide derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59072173A JPH0680081B2 (en) | 1984-04-11 | 1984-04-11 | Polysaccharide derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60217201A JPS60217201A (en) | 1985-10-30 |
| JPH0680081B2 true JPH0680081B2 (en) | 1994-10-12 |
Family
ID=13481567
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59072173A Expired - Lifetime JPH0680081B2 (en) | 1984-04-11 | 1984-04-11 | Polysaccharide derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0680081B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5264422A (en) * | 1986-06-30 | 1993-11-23 | Fidia S.P.A. | Esters of alginic acid with steroidal alcohols |
| IT1203814B (en) * | 1986-06-30 | 1989-02-23 | Fidia Farmaceutici | ESTERS OF ALGINIC ACID |
| JP2669554B2 (en) * | 1989-01-20 | 1997-10-29 | ダイセル化学工業株式会社 | Novel polysaccharide derivatives and separating agents |
| JP2648516B2 (en) * | 1989-07-27 | 1997-09-03 | ダイセル化学工業株式会社 | Separation of stereoisomers |
| JP4534024B2 (en) * | 2004-07-02 | 2010-09-01 | 農工大ティー・エル・オー株式会社 | Compound separation carrier and compound separation method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5232086A (en) * | 1975-09-06 | 1977-03-10 | Fujikura Kasei Kk | Process for preparing a photochromic polymer |
| JPS5738801A (en) * | 1980-08-21 | 1982-03-03 | Chisso Corp | Production of porous spherical cellulose particle |
-
1984
- 1984-04-11 JP JP59072173A patent/JPH0680081B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| 「バイオメディカルクロマトグラフィー第１集」化学の領域増刊１３２号、南江堂（１９８１）Ｐ．１７１〜１９８ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60217201A (en) | 1985-10-30 |
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