JPH0699482B2 - Polysaccharide derivative - Google Patents
Polysaccharide derivativeInfo
- Publication number
- JPH0699482B2 JPH0699482B2 JP59076291A JP7629184A JPH0699482B2 JP H0699482 B2 JPH0699482 B2 JP H0699482B2 JP 59076291 A JP59076291 A JP 59076291A JP 7629184 A JP7629184 A JP 7629184A JP H0699482 B2 JPH0699482 B2 JP H0699482B2
- Authority
- JP
- Japan
- Prior art keywords
- polysaccharide
- cinnamic acid
- mannan
- amylose
- product
- 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
- 229920001282 polysaccharide Polymers 0.000 title claims description 21
- 239000005017 polysaccharide Substances 0.000 title claims description 21
- 150000004676 glycans Chemical class 0.000 title claims description 20
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid group Chemical group C(C=CC1=CC=CC=C1)(=O)O WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 13
- 229920000856 Amylose Polymers 0.000 claims description 9
- 229920000057 Mannan Polymers 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000000047 product Substances 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000009102 absorption Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 229930016911 cinnamic acid Natural products 0.000 description 7
- 235000013985 cinnamic acid Nutrition 0.000 description 7
- -1 cinnamic acid ester Chemical class 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WOGITNXCNOTRLK-VOTSOKGWSA-N (e)-3-phenylprop-2-enoyl chloride Chemical compound ClC(=O)\C=C\C1=CC=CC=C1 WOGITNXCNOTRLK-VOTSOKGWSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 241000202427 Phytelephas aequatorialis Species 0.000 description 1
- 235000012541 Phytelephas macrocarpa Nutrition 0.000 description 1
- FXEDRSGUZBCDMO-PHEQNACWSA-N [(e)-3-phenylprop-2-enoyl] (e)-3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1/C=C/C(=O)OC(=O)\C=C\C1=CC=CC=C1 FXEDRSGUZBCDMO-PHEQNACWSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- FXEDRSGUZBCDMO-UHFFFAOYSA-N cinnamic acid anhydride Natural products C=1C=CC=CC=1C=CC(=O)OC(=O)C=CC1=CC=CC=C1 FXEDRSGUZBCDMO-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000311 mannosyl group Chemical group C1([C@@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
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
くは多糖類の桂皮酸エステルに関するものである。The present invention relates to novel polysaccharide derivatives, and more particularly to cinnamic acid esters of polysaccharides.
従来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、カルボン酸が桂皮酸又は置換桂皮酸であ
るものは、セルロース桂皮酸エステルを除き、ほとんど
知られていない。Conventionally, various compounds of carboxylic acid esters of polysaccharides have been known, but those in which the carboxylic acid is cinnamic acid or substituted cinnamic acid are almost unknown except for the cellulose cinnamic acid ester.
セルロース桂皮酸エステルについては、置換度が3.0に
近い高置換度のものまで合成されている（Vysokemol,So
edim,Ser,A.９（４）826〜31（1967））。この物質は感
光性高分子としての機能があり、波長2537Åの光での架
橋反応について研究されている（J.Appl.Polym.Sci.15
（３）1743（1971））。しかしながらセルロース以外の
多糖類の桂皮酸エステルについては報告されていない。
また、セルロースを含む多糖類の置換基を有する桂皮酸
エステルについても報告されていない。多糖類の桂皮酸
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媒
に可溶性であり、感光性樹脂のほか吸着剤、酵素担体、
クロマトグラフイー用担体、光学異性体分離剤、液晶物
質等として利用できる可能性が高い。Cellulose cinnamates have been synthesized up to a high degree of substitution close to 3.0 (Vysokemol, So
edim, Ser, A. 9 (4) 826-31 (1967)). This substance has a function as a photopolymer, and the cross-linking reaction with light of wavelength 2537Å has been studied (J.Appl.Polym.Sci.15).
(3) 1743 (1971)). However, cinnamic acid esters of polysaccharides other than cellulose have not been reported.
In addition, cinnamic acid esters having a substituent of polysaccharides containing cellulose have not been reported. The cinnamic acid ester of a polysaccharide is generally soluble in an organic solvent, especially when it is a highly substituted ester in which 50% or more of the hydroxyl groups in the polysaccharide molecule are substituted, and it is generally soluble in organic solvents.
It is highly possible to be used as a chromatographic carrier, optical isomer separating agent, liquid crystal substance, and the like.
本発明者等は種々研究の結果、多糖類の新規な桂皮酸エ
ステルを見出して、本発明に到ったものである。即ち本
発明は、アミロース及びマンナンから選ばれた多糖類分
子中の水酸基の50％以上が桂皮酸基で置換されており且
つ有機溶剤可溶性である多類類誘導体に係わるものであ
り、特にそれらの三置換体を提供するものである。As a result of various studies, the present inventors have found a novel cinnamic acid ester of a polysaccharide and arrived at the present invention. That is, the present invention relates to a polycide derivative in which 50% or more of the hydroxyl groups in a polysaccharide molecule selected from amylose and mannan are substituted with cinnamic acid groups and which are soluble in an organic solvent. It provides a tri-substituted product.
上記の多糖類をエステル化し、本発明の誘導体に導くた
めの反応試薬は、桂皮酸無水物又は桂皮酸ハライドを用
いれば良く、反応触媒としては硫酸、過塩素酸のような
ブレンステツド酸、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 the above-mentioned polysaccharide and leading to the derivative of the present invention, cinnamic acid anhydride or cinnamic acid halide may be used, and the reaction catalyst is sulfuric acid, Bronsted acid such as perchloric acid, zinc chloride. A Lewis acid, a base such as pyridine, triethylamine, 4-dimethylaminopyridine or the like 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 the synthesis of the polysaccharide derivative of the present invention, the raw material polysaccharide is once dissolved in a solvent such as water or formic acid and then precipitated in another solvent and dried, an aqueous solution is directly freeze-dried, or an acetic acid ester. When a material obtained by hydrolyzing such a polysaccharide ester as described above is used as a raw material, 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
件の選択により誘導体の置換度は調節が可能である。The reactivity varies depending on the type of polysaccharide and the degree of polymerization, but the degree of substitution of the 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は比較的高いもの、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。
また、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。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, a polymer having a relatively high degree of polymerization, for example, a polymer having a degree of polymerization of 60 or more is preferable in terms of physical strength of the molded product.
Further, when 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 properties and the like.
本発明の多糖類誘導体は、アミロース又はマンナン分子
の水酸基の50％以上、好ましくは全部が桂皮酸基でエス
テル化されており、有機溶剤溶解性を有し、吸着剤、酵
素担体、クロマトグラフィー用担体、光学異性体分離
体、液晶物質等として利用し得る有用な物質である。The polysaccharide derivative of the present invention has 50% or more, preferably all of the hydroxyl groups of the amylose or mannan molecule esterified with a cinnamic acid group, has organic solvent solubility, is an adsorbent, an enzyme carrier, and for chromatography. It is a useful substance that can be used as a carrier, an optical isomer separation product, a liquid crystal substance and the like.
以下に実施例をあ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 is described below with reference to examples, but the present invention is not limited thereto.
実施例１ 試薬として市販されているアミロース1gに脱水したピリ
ジン47ml、脱水したトリエチルアミン5.2ml、ジメチル
アミノピリジン33.3mlを加え、撹拌しながら桂皮酸クロ
リド9.3gを加え100℃で５時間撹拌反応した。生成物を4
00mlのエタノールに加え、沈殿させた。沈殿物はグラス
フイルターで過し、エタノールで良く洗浄した。生成
物は乾燥後20mlの塩化メチレンに溶解し、400mlのエタ
ノールに再沈殿した後、エタノールで洗浄をくりかえし
た後、真空乾燥した。Example 1 47 g of dehydrated pyridine, 5.2 ml of dehydrated triethylamine and 33.3 ml of dimethylaminopyridine were added to 1 g of amylose commercially available as a reagent, and 9.3 g of cinnamic acid chloride was added with stirring to carry out a reaction at 100 ° C. for 5 hours with stirring. 4 products
It was added to 00 ml of ethanol and precipitated. The precipitate was passed through a glass filter and washed thoroughly with ethanol. The product was dried, dissolved in 20 ml of methylene chloride, reprecipitated in 400 ml of ethanol, repeatedly washed with ethanol, and then vacuum dried.
生成物の塩化メチレン溶液を食塩セルに塗布し、乾燥
し、赤外吸収スペクトルの測定に付した。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。A methylene chloride solution of the product was applied to a sodium chloride cell, dried, and subjected to infrared absorption spectrum measurement. The obtained infrared absorption spectrum is as shown in FIG. 1, and the characteristic absorption bands are as follows.
3050cm-1付近 オレフイン性Ｃ−Ｈ伸縮振動 1730cm-1 カルボン酸エステルのＣ＝Ｏ伸縮振動 1640cm-1 Ｃ＝Ｃ伸縮振動 1580,1500,1450cm-1 ベンゼン環内炭素と炭素間の伸縮
による骨格振動 1250cm-1 エステルのC-O伸縮振動 1030〜1160cm-1 アミロースのC-O-Cの伸縮振動 990cm-1 オレフイン性C-H変角振動 675〜900cm-1 ベンゼン環の面外変角振動 アミロースのOHに基づく3450cm-1付近の吸収はほとんど
認められず、ほぼ三置換体であることがわかる。またCD
Cl3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。Around 3050 cm -1 Olefinic C-H stretching vibration 1730 cm -1 C = O stretching vibration of carboxylic acid ester 1640 cm -1 C = C stretching vibration 1580,1500,1450 cm -1 Skeletal vibration due to stretching between carbon in benzene ring and carbon 1250 cm -1 around 3450 cm -1 based on the OH stretching vibration 990 cm -1 olefinic CH deformation vibration 675～900Cm -1 plane deformation vibration amylose of the benzene ring of the COC ester CO stretching vibration 1030～1160Cm -1 amylose Almost no absorption was observed, indicating that it is almost a tri-substituted product. Also CD
The characteristic absorptions of the proton NMR spectrum measured in Cl 3 are:
6.0〜8.0ppm 桂皮酸部分のベンゼン環及び二重結合の
プロトン 3.8ppm アミロースのグルコース環および６位のメチレ
ンのプロトン この吸収強度比は3:1であつた。6.0-8.0 ppm Proton of benzene ring and double bond of cinnamic acid moiety 3.8 ppm Glucose ring of amylose and proton of methylene at 6-position This absorption intensity ratio was 3: 1.
これにより生成物はグルコース単位あたりの置換度が約
3.0であるアミロース桂皮酸エステルと推定される。This gives the product a degree of substitution per glucose unit of approximately
It is presumed to be amylose cinnamate, which is 3.0.
実施例２ 象牙ヤシの種子のはい乳を文献記載〔G.O.Aspinall,eta
l;J.Chem.Soc.,3184（1953）〕の方法で処理し、高分子
量画分のマンナンＢを得た。このマンナンＢの粉末を原
料とする以外は実施例１とまつたく同様にして合成し生
成物を得た。生成物の塩化メチレン溶液を、食塩セルに
塗布し乾燥し、赤外吸収スペクトル分析に付した。得ら
れた赤外吸収スペクトルは第２図の通りであり、特徴的
な吸収帯は次の通りである。Example 2 Endodon of ivory palm seeds is described in the literature [GO Aspinall, eta.
1; J. Chem. Soc., 3184 (1953)], to obtain a high molecular weight fraction of mannan B. A product was obtained by synthesis in the same manner as in Example 1 except that this mannan B powder was used as the raw material. A methylene chloride solution of the product was applied to a sodium chloride cell, dried and subjected to infrared absorption spectrum analysis. The obtained infrared absorption spectrum is as shown in FIG. 2, and the characteristic absorption bands are as follows.
3050cm-1付近 オレフイン性C-H伸縮振動 1730cm-1 カルボン酸エステルのＣ＝Ｏ伸縮振動 1640cm-1 Ｃ＝Ｃ伸縮振動 1580,1500,1450cm-1 ベンゼン環内の炭素と炭素間の伸
縮による骨格振動 1250cm-1 エステルのC-O伸縮振動 1050〜1170cm-1 マンナンのC-O-Cの伸縮振動 990cm-1 オレフイン性C-H変角振動 675〜900cm-1 ベンゼン環の面外変角振動 マンナンのOHに基づく3450cm-1付近の吸収はほとんど認
められずほぼ三置換体であることがわかる。また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。Approximately 3050 cm -1 Olefin CH stretching vibration 1730 cm -1 C = O stretching vibration of carboxylic acid ester 1640 cm -1 C = C stretching vibration 1580,1500,1450 cm -1 Skeletal vibration due to stretching between carbon in benzene ring 1250 cm -1 esters CO stretching vibration 1050～1170Cm -1 mannan COC stretching vibration 990 cm -1 olefinic CH deformation vibration 675～900Cm -1 around 3450 cm -1 based on the OH of the out-of-plane deformation vibration mannan benzene ring of the Almost no absorption was observed, indicating that the compound is almost trisubstituted. Also CDCl 3
The characteristic absorptions of the proton NMR spectrum measured in are as follows.
６〜8.3ppm 桂皮酸部分のベンゼン環及び二重結合のプ
ロトン ３〜5.8ppm マンナンのマンノース環および６位のメチ
レンのプロトン この吸収強度比は3:1であつた。6 to 8.3 ppm Proton of benzene ring and double bond of cinnamic acid moiety 3 to 5.8 ppm Proton of mannose ring of mannan and methylene at 6-position This absorption intensity ratio was 3: 1.
これにより生成物はマンノース当りの置換度が約3.0で
あるマンナン桂皮酸エステルと推定される。From this, it is estimated that the product is a mannan cinnamic acid ester having a degree of substitution per mannose of about 3.0.
応用例 実施例１で得られたアミローストリシンナメートをシリ
カゲルに担持した粉末状の担持物について、液体クロマ
トグラフィーにより、表１に示すセラミ体の分離実験を
行った。結果を表１に示す。Application Example The powdery carrier of amylose tricinnamate obtained in Example 1 on silica gel was subjected to liquid chromatography to perform a separation experiment of the cerami body shown in Table 1. The results are shown in Table 1.
液体クロマトグラフィーの条件は以下の通りである。The conditions of liquid chromatography are as follows.
溶離液：ヘキサン/2−プロパノール＝9/1の混合液 流速:0.5ml/min 温度:20〜25℃ 表１から明らかなように、本発明の多糖類誘導体は優れ
た光学異性体分離能を有していることがわかる。Eluent: Hexane / 2-propanol = 9/1 mixed liquid Flow rate: 0.5 ml / min Temperature: 20-25 ° C As is clear from Table 1, the polysaccharide derivative of the present invention has excellent optical isomer separation ability.
【図面の簡単な説明】 第１図及び第２図は夫々実施例１及び２の多糖誘導体の
赤外吸収スペクトルである。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 and FIG. 2 are infrared absorption spectra of the polysaccharide derivatives of Examples 1 and 2, respectively.
フロントページの続き (56)参考文献 特開 昭50−77103（ＪＰ，Ａ) 特公 昭40−20188（ＪＰ，Ｂ１) 特公 昭49−13565（ＪＰ，Ｂ１) 特公 昭56−14969（ＪＰ，Ｂ２) 米国特許3519382（ＵＳ，Ａ) Ｖｙｓｏｋｅｍｏｉ，Ｓｏｅｄｉｍ，Ｓ ｅｒ，Ａ．９（４）826〜31（1967) Ｊ．Ａｐｐｌ．Ｐｏｌｙｍ．Ｓｃｉ．15 （３）1743（1971)Continuation of the front page (56) References Japanese Patent Publication No. 50-77103 (JP, A) Japanese Patent Publication No. 40-20188 (JP, B1) Japanese Patent Publication No. 49-13565 (JP, B1) Japanese Patent Publication No. 56-14969 (JP) , B2) U.S. Pat. No. 3519382 (US, A) Vysokemoi, Soedim, Ser, A .; 9 (4) 826-31 (1967) J. Appl. Polym. Sci. 15 (3) 1743 (1971)
Claims (1)
類分子中の水酸基の50％以上が桂皮酸基で置換されてお
り且つ有機溶剤可溶性である多糖類誘導体。1. A polysaccharide derivative in which 50% or more of the hydroxyl groups in a polysaccharide molecule selected from amylose and mannan are substituted with cinnamic acid groups and which are soluble in organic solvents.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59076291A JPH0699482B2 (en) | 1984-04-16 | 1984-04-16 | Polysaccharide derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59076291A JPH0699482B2 (en) | 1984-04-16 | 1984-04-16 | Polysaccharide derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60219202A JPS60219202A (en) | 1985-11-01 |
| JPH0699482B2 true JPH0699482B2 (en) | 1994-12-07 |
Family
ID=13601230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59076291A Expired - Lifetime JPH0699482B2 (en) | 1984-04-16 | 1984-04-16 | Polysaccharide derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0699482B2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1203814B (en) * | 1986-06-30 | 1989-02-23 | Fidia Farmaceutici | ESTERS OF ALGINIC ACID |
| US5264422A (en) * | 1986-06-30 | 1993-11-23 | Fidia S.P.A. | Esters of alginic acid with steroidal alcohols |
| US5679323A (en) * | 1986-07-03 | 1997-10-21 | Advanced Magnetics, Inc. | Hepatocyte-specific receptor-mediated endocytosis-type compositions |
| US5554386A (en) * | 1986-07-03 | 1996-09-10 | Advanced Magnetics, Inc. | Delivery of therapeutic agents to receptors using polysaccharides |
| US5352432A (en) * | 1986-07-03 | 1994-10-04 | Advanced Magnetics, Inc. | Hepatocyte specific composition and their use as diagnostic imaging agents |
| JP2855307B2 (en) * | 1992-02-05 | 1999-02-10 | 生化学工業株式会社 | Photoreactive glycosaminoglycans, cross-linked glycosaminoglycans and methods for producing them |
| IL106581A (en) * | 1993-08-04 | 2000-08-31 | Yissum Res Dev Co | Removal of cholesterol from edibles |
| WO2002060971A1 (en) * | 2001-01-31 | 2002-08-08 | Seikagaku Corporation | Crosslinked polysaccharide sponge |
| US7008476B2 (en) * | 2003-06-11 | 2006-03-07 | Az Electronic Materials Usa Corp. | Modified alginic acid of alginic acid derivatives and thermosetting anti-reflective compositions thereof |
| CN102603910B (en) * | 2012-02-29 | 2013-11-13 | 合肥学院 | Preparation method of pachyman sulfate |
| JP7751826B2 (en) * | 2020-10-30 | 2025-10-09 | 国立大学法人東京農工大学 | Modified polysaccharide, material for forming gas separation membrane, film, gas separation membrane, gas separation membrane module, and gas separation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3519382A (en) | 1968-02-06 | 1970-07-07 | Us Agriculture | High energy radiation stabilization of cellulose obtained by esterifying with benzoyl chloride |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4913565A (en) * | 1972-05-19 | 1974-02-06 | ||
| JPS5614969B2 (en) * | 1973-11-12 | 1981-04-07 | ||
| JPS5614969A (en) * | 1979-07-18 | 1981-02-13 | Toshiba Corp | Ultrasonic image device |
-
1984
- 1984-04-16 JP JP59076291A patent/JPH0699482B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3519382A (en) | 1968-02-06 | 1970-07-07 | Us Agriculture | High energy radiation stabilization of cellulose obtained by esterifying with benzoyl chloride |
Non-Patent Citations (2)
| Title |
|---|
| Ｊ．Ａｐｐｌ．Ｐｏｌｙｍ．Ｓｃｉ．１５（３）１７４３（１９７１） |
| Ｖｙｓｏｋｅｍｏｉ，Ｓｏｅｄｉｍ，Ｓｅｒ，Ａ．９（４）８２６〜３１（１９６７） |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60219202A (en) | 1985-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4201832B2 (en) | Photochemically cross-linked polysaccharide derivatives as supports for chromatographic resolution of enantiomers. | |
| JPH0699482B2 (en) | Polysaccharide derivative | |
| JPH0533210B2 (en) | ||
| JPS60226829A (en) | Separating agent consisting of polysaccharide derivative | |
| CA2147224C (en) | Partially acylated .beta.-cyclodextrins | |
| JPS60226830A (en) | Separating agent consisting of 1,3-glucan | |
| US7049434B2 (en) | Derivatives of hyaluronan | |
| CN101484801B (en) | Filler for optical isomer separation | |
| CN1196062A (en) | Photochemically crosslinked polysaccharide derivatives without photopolymerizable functional groups | |
| AU2002312970A1 (en) | New derivatives of hyaluronan | |
| US4487926A (en) | Fluorine-containing cellulose derivatives | |
| KR20080007312A (en) | Chitosan Derivatives and Manufacturing Methods | |
| JP2000086702A (en) | Crosslinked polymer including derivatives of bis-silane, bis-thioether, bis-sulfoxide, bis-sulfone and butanediyl of polysaccharide and oligosaccharide as base and its molding as support material | |
| JPH0680081B2 (en) | Polysaccharide derivative | |
| JPS62195395A (en) | Production of low-molecular-weight cellulose derivative having narrow molecular weight distribution | |
| JPS60108751A (en) | Separating agent | |
| JPH0655764B2 (en) | Cellulose derivative | |
| JPS6017444B2 (en) | Carboxymethyl cellulose ester and its production method | |
| JPH0647604B2 (en) | Polysaccharide derivative | |
| JPS60219201A (en) | Polysaccharide derivative | |
| JPH0655765B2 (en) | Cellulose derivative | |
| EP0626388A2 (en) | 14Alpha-hydroxy-4-androstene-3,6,17-trione hydrate crystal and process for producing same | |
| Heinze et al. | Synthesis and characterization of the novel cellulose derivative dansyl cellulose | |
| JPS61171702A (en) | Fluorine-containing cellulose ether derivative | |
| JPH0680082B2 (en) | Aromatic carbamate derivatives of polysaccharides |