JPH0643441B2 - Polysaccharide derivative - Google Patents
Polysaccharide derivativeInfo
- Publication number
- JPH0643441B2 JPH0643441B2 JP59076290A JP7629084A JPH0643441B2 JP H0643441 B2 JPH0643441 B2 JP H0643441B2 JP 59076290 A JP59076290 A JP 59076290A JP 7629084 A JP7629084 A JP 7629084A JP H0643441 B2 JPH0643441 B2 JP H0643441B2
- Authority
- JP
- Japan
- Prior art keywords
- glucan
- polysaccharide
- polysaccharide derivative
- thiophene ring
- cellulose
- 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 19
- 239000005017 polysaccharide Substances 0.000 title claims description 19
- 150000004676 glycans Chemical class 0.000 title 1
- 150000004804 polysaccharides Chemical class 0.000 claims description 16
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 15
- 229920002678 cellulose Polymers 0.000 claims description 10
- 239000001913 cellulose Substances 0.000 claims description 10
- 229920000057 Mannan Polymers 0.000 claims description 9
- 229920001503 Glucan Polymers 0.000 claims description 6
- 229920002670 Fructan Polymers 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 claims description 2
- LUEWUZLMQUOBSB-FSKGGBMCSA-N (2s,3s,4s,5s,6r)-2-[(2r,3s,4r,5r,6s)-6-[(2r,3s,4r,5s,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5s,6r)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol 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](OC3[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-FSKGGBMCSA-N 0.000 claims description 2
- SATHPVQTSSUFFW-UHFFFAOYSA-N 4-[6-[(3,5-dihydroxy-4-methoxyoxan-2-yl)oxymethyl]-3,5-dihydroxy-4-methoxyoxan-2-yl]oxy-2-(hydroxymethyl)-6-methyloxane-3,5-diol Chemical compound OC1C(OC)C(O)COC1OCC1C(O)C(OC)C(O)C(OC2C(C(CO)OC(C)C2O)O)O1 SATHPVQTSSUFFW-UHFFFAOYSA-N 0.000 claims description 2
- 229920001817 Agar Polymers 0.000 claims description 2
- 229920000856 Amylose Polymers 0.000 claims description 2
- 229920000189 Arabinogalactan Polymers 0.000 claims description 2
- 239000001904 Arabinogalactan Substances 0.000 claims description 2
- 229920002498 Beta-glucan Polymers 0.000 claims description 2
- 229920002101 Chitin Polymers 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 229920002558 Curdlan Polymers 0.000 claims description 2
- 239000001879 Curdlan Substances 0.000 claims description 2
- 229920002307 Dextran Polymers 0.000 claims description 2
- 229920000926 Galactomannan Polymers 0.000 claims description 2
- 229920002581 Glucomannan Polymers 0.000 claims description 2
- 229920001202 Inulin Polymers 0.000 claims description 2
- 229920001491 Lentinan Polymers 0.000 claims description 2
- 229920001218 Pullulan Polymers 0.000 claims description 2
- 239000004373 Pullulan Substances 0.000 claims description 2
- 239000008272 agar Substances 0.000 claims description 2
- 239000000783 alginic acid Substances 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- 229960001126 alginic acid Drugs 0.000 claims description 2
- 150000004781 alginic acids Chemical class 0.000 claims description 2
- 235000019312 arabinogalactan Nutrition 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 235000019316 curdlan Nutrition 0.000 claims description 2
- 229940078035 curdlan Drugs 0.000 claims description 2
- 229940046240 glucomannan Drugs 0.000 claims description 2
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 claims description 2
- 229940029339 inulin Drugs 0.000 claims description 2
- 229940115286 lentinan Drugs 0.000 claims description 2
- AIHDCSAXVMAMJH-GFBKWZILSA-N levan Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@@H]1[C@@H](O)[C@H](O)[C@](CO)(CO[C@@H]2[C@H]([C@H](O)[C@@](O)(CO)O2)O)O1 AIHDCSAXVMAMJH-GFBKWZILSA-N 0.000 claims description 2
- 235000019423 pullulan Nutrition 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 229920001221 xylan Polymers 0.000 claims description 2
- 150000004823 xylans Chemical class 0.000 claims description 2
- 239000000047 product Substances 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- -1 polysaccharide ester Chemical class 0.000 description 8
- 230000009102 absorption Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 150000002772 monosaccharides Chemical class 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QIQITDHWZYEEPA-UHFFFAOYSA-N thiophene-2-carbonyl chloride Chemical compound ClC(=O)C1=CC=CS1 QIQITDHWZYEEPA-UHFFFAOYSA-N 0.000 description 2
- QERYCTSHXKAMIS-UHFFFAOYSA-M thiophene-2-carboxylate Chemical compound [O-]C(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-M 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 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
- 229920003043 Cellulose fiber Polymers 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
- 239000002841 Lewis acid Substances 0.000 description 1
- 241000202427 Phytelephas aequatorialis Species 0.000 description 1
- 235000012541 Phytelephas macrocarpa Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis 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
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder 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
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- QTWBEVAYYDZLQL-UHFFFAOYSA-N thiophene-3-carbonyl chloride Chemical compound ClC(=O)C=1C=CSC=1 QTWBEVAYYDZLQL-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 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
くはチオフエン環又はその縮合環に直結したカルボキシ
ル基を有するカルボン酸の多糖類エステルに関するもの
である。The present invention relates to a novel polysaccharide derivative, and more particularly to a polysaccharide ester of a carboxylic acid having a carboxyl group directly linked to a thiophene ring or a condensed ring thereof.
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、カルボン酸がチオフエン環に直結したカル
ボキシル基を有するものである場合ごく限られたものし
か知られていない。即ち、セルロース繊維の改質を目的
として合成した例が報告されている〔S.Singh etal,Car
bohydr.Res.,１７ ３５３−３６３（1971）〕が、生成
物はグルコース単位あたりの置換度は1.0以下であり、
一般的な溶媒に溶解しないものである。しかるに本発明
者等は多糖類分子中の水酸基の50％以上がチオフェン環
又はその縮合環に直結したカルボキシル基で置換された
高置換度エステルが、有機溶剤に可溶性であり、吸着
剤、酸素担体、クロマトグラフィー用担体、光学異性体
分離剤、液晶物質等として利用し得る有用な物質である
ことを見出した。Conventionally, various compounds of carboxylic acid esters of polysaccharides are known, but only a very limited number of carboxylic acid esters are known when the carboxylic acid has a carboxyl group directly linked to a thiophene ring. That is, an example of synthesis for the purpose of modifying cellulose fibers has been reported [S. Singh et al.
bohydr.Res., 17 353-363 (1971)], but the product has a degree of substitution per glucose unit of 1.0 or less,
It does not dissolve in common solvents. However, the present inventors have found that a highly substituted ester in which 50% or more of the hydroxyl groups in the polysaccharide molecule are substituted with a carboxyl group directly linked to a thiophene ring or a condensed ring thereof is soluble in an organic solvent, is an adsorbent, and is an oxygen carrier. It was found that they are useful substances that can be used as a carrier for chromatography, an optical isomer separating agent, a liquid crystal substance and the like.
即ち本発明は、多糖類分子中の水酸基の50％以上が次式 （式中Ｒはチオフェン環、又はチオフェン環を含む芳香
族縮合環を表わす） で表わされる基で置換されており且つ有機溶剤可溶性で
ある多糖類誘導体に係るものであり、その吸着剤、分離
剤としての機能の優れたものである。That is, in the present invention, 50% or more of the hydroxyl groups in the polysaccharide molecule are represented by the following formula (Wherein R represents a thiophene ring or an aromatic condensed ring containing a thiophene ring) and is related to a polysaccharide derivative which is substituted with a group and is soluble in an organic solvent. It is an excellent one.
多糖類としては種々の単糖類を構成単位としたものを対
象とすることができるが、直鎖状分子構造を有するも
の、又は分岐を有していても比較的分岐度の小さいもの
が有用である。また構成単位である単糖類の種類、及び
その結合形式もせいぜい２種類程度以下の、比較的単純
な構造のものが特に有用である。それらを例示すればセ
ルロースを含むβ−1,4−グルカン、アミロース、プル
ランを含むα−1,4−グルカン、デキストランを含むα
−1,6−グルカン、カードラン、パキマン、レンチナン
を含むβ−1,3−グルカン、イヌリンを含むβ−2,1−フ
ルクタン、レバンを含むβ−2,6−フルクタン、寒天を
含むガラクタン、アルギン酸を含むポリウナロイド、キ
チン、キトサンを含むグルコサミナン、及びマンナン、
キシランならびにグルコマンナン、ガラクトマンナン、
アラビノガラクタンを含むヘテログリカンなどである。As the polysaccharide, those having various monosaccharides as structural units can be targeted, but those having a linear molecular structure, or those having a relatively small branching degree even if they have a branch are useful. is there. Further, it is particularly useful that the type of monosaccharide which is a constitutional unit, and the binding form thereof is about 2 or less at most, and that the structure is relatively simple. Examples of them include β-1,4-glucan containing cellulose, amylose, α-1,4-glucan containing pullulan, α containing dextran.
-1,6-glucan, curdlan, pachyman, β-1,3-glucan containing lentinan, β-2,1-fructan containing inulin, β-2,6-fructan containing levan, galactan containing agar, Polyunaloids containing alginic acid, chitin, glucosaminonan containing chitosan, and mannan,
Xylan and glucomannan, galactomannan,
Examples include heteroglycans containing arabinogalactan.
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、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、例えばチオフエン−２−
カルボニルクロリド、チオフエン−３−カルボニルクロ
リドなどがある。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, a corresponding carboxylic acid anhydride or carboxylic acid halide may be used. For example, thiophene-2-
Carbonyl chloride, thiophene-3-carbonyl chloride and the like. As the reaction catalyst, sulfuric acid, Bronsted acid such as perchloric acid, Lewis acid such as zinc chloride, and bases such as pyridine, triethylamine and 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 acetic acid. When a material obtained by hydrolyzing a polysaccharide ester such as an ester 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, the degree of polymerization is relatively high, for example 60
The above is preferable in terms of physical strength of the molded product. 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 properties 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 酢酸セルロースをヒドラジンでケン化し、アセトンで洗
浄後乾燥してセルロースを得た。上記セルロース1.5ｇ
に脱水したピリジン７０ml、脱水したトリエチルアミン
7.7ml、４−ジメチルアミノピリジン５０mgを加え、攪
拌しながらチオフエン２−カルボニルクロリド12.2ｇを
添加し、１００゜Cで５時間攪拌反応した。冷却後エタノ
ール４００mlに生成物を攪拌しながら加えて沈殿させ、
グラスフイルターで過後エタノールで良く洗浄した。
真空乾燥した後、塩化メチレン３０mlに溶解し、不溶物
を除いた後４００mlのエタノールに再沈澱した。沈澱を
過後、エタノールで洗浄し、脱液、乾燥した。生成物
の糖製収量は3.9ｇであつた。生成物を塩化メチレンに
溶解後、食塩セルに塗布し、乾燥して赤外吸収スペクト
ル分析に付した。得られた赤外吸収スペクトルは第１図
の通りであり、特徴的な吸収帯は次の通りである。Example 1 Cellulose acetate was saponified with hydrazine, washed with acetone and dried to obtain cellulose. 1.5 g of the above cellulose
70 ml of dehydrated pyridine and dehydrated triethylamine
7.7 ml and 4-dimethylaminopyridine 50 mg were added, and thiophene 2-carbonyl chloride 12.2 g was added with stirring, and the mixture was reacted at 100 ° C. for 5 hours with stirring. After cooling, add the product to 400 ml of ethanol with stirring to precipitate,
After passing through a glass filter, it was thoroughly washed with ethanol.
After vacuum drying, it was dissolved in 30 ml of methylene chloride, the insoluble material was removed, and the precipitate was reprecipitated in 400 ml of ethanol. After passing through the precipitate, it was washed with ethanol, drained and dried. The sugar yield of the product was 3.9 g. The product was dissolved in methylene chloride, applied to a sodium chloride cell, dried and subjected to infrared absorption spectrum analysis. The obtained infrared absorption spectrum is as shown in FIG. 1, and the characteristic absorption bands are as follows.
3100cm-1 芳香族Ｃ−Ｈ伸縮振動 1720cm-1 カルボン酸エステルのＣ＝Ｏ伸縮振動 1360,1420,1520cm-1 チオフエン環伸縮振動 1260cm-1 エステルのＣ−Ｏ伸縮振動 1060〜1160cm-1 セルロースのＣ−Ｏ−Ｃの伸縮振動 860cm-1 ２置換チオフエンのＣ−Ｈ面外変角 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。3100cm -1 Aromatic C-H stretching vibration 1720cm -1 Carboxyl ester C = O stretching vibration 1360,1420,1520cm -1 Thiophene ring stretching vibration 1260cm -1 Ester C-O stretching vibration 1060 to 1160cm -1 Cellulose Stretching vibration of C-O-C 860 cm -1 2 C-H out-of-plane bending angle of 2-substituted thiophene Absorption around 3450 cm -1 based on OH of cellulose was hardly observed, indicating that the compound is almost a tri-substituted product. The characteristic absorptions of the proton NMR spectrum measured in CDCl 3 are as follows.
6.8〜7.8ppmチオフエン環プロトン 2.8〜5.4ppmセルロースの環及び６位のメチレンのプロ
トン チオフエン環プロトンとセルロースのプロトンの比はほ
ぼ９：７であり、三置換体と一致する。6.8 to 7.8 ppm Thiophene ring proton 2.8 to 5.4 ppm Cellulose ring and methylene proton at the 6-position The ratio of thiophene ring proton to cellulose proton is approximately 9: 7, which is in agreement with the tri-substituted product.
また硫黄の元素分析を行なつたところ硫黄含量は19.40
％であり、これらを総合して生成物は置換度約3.0のセ
ルロースチオフエン２−カルボキシレートであると推定
される。In addition, elemental analysis of sulfur revealed that the sulfur content was 19.40.
Taken together, it is estimated that the product is a cellulose thiophene 2-carboxylate with a degree of substitution of about 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。セルロースの代りにこのマンナ
ンＢの粉末を使用する以外は実施例１とまつたく同様に
行なつた。この結果２ｇの反応生成物をえた。この生成
物を塩化メチレンに溶解し、食塩セルに塗布し、乾燥し
て赤外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. The same procedure as in Example 1 was repeated except that this mannan B powder was used instead of cellulose. As a result, 2 g of a reaction product was obtained. The product was dissolved in methylene chloride, applied to a sodium chloride cell, dried and subjected to infrared spectrum measurement. The obtained infrared absorption spectrum is as shown in FIG. 2, and the characteristic absorption bands are as follows.
3100cm-1 方法族Ｃ−Ｈ伸縮振動 1730cm-1 カルボン酸エステルのＣ＝Ｏ伸縮振動 1360,1420,1530cm-1 チオフエン環環伸縮振動 1260cm-1 エステルのＣ−Ｏ伸縮振動 1060〜1180cm-1 マンナンのＣ−Ｏ−Ｃの伸縮振動 860cm-1 ２置換チオフエンのＣ−Ｈ面外変角 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の特徴的な吸収は次の通
りである。3100cm -1 Method group C-H stretching vibration 1730cm -1 Carboxylic ester C = O stretching vibration 1360,1420,1530cm -1 Thiophene ring ring stretching vibration 1260cm -1 Ester C-O stretching vibration 1060-1180cm -1 Mannan Stretching vibration of C-O-C of 860 cm -1 2 C-H out-of-plane bending angle of 2-substituted thiophene Absorption around 3450 cm -1 based on OH of mannan is hardly recognized, and it is found that the compound is almost trisubstituted. Also
The characteristic absorptions of proton NMR measured in CDCl 3 are as follows.
6.8〜8.2ppmチオフエン環のプロトン 3.0〜5.8ppmマンナンの環および６位のメチレンのプロ
トン チオフエン環プロトンとマンナンのプロトンの比はほぼ
９：７であり三置換体と一致する。この結果、生成物は
マンノースあたりの置換度3.0のマンナン２−チオフエ
ンカルボキシレートと推定される。6.8 to 8.2 ppm Proton of thiophene ring 3.0 to 5.8 ppm Proton of mannan ring and methylene at the 6-position The ratio of thiophene ring proton to proton of mannan is approximately 9: 7, which is in agreement with the tri-substituted product. As a result, the product is estimated to be mannan 2-thiophenecarboxylate having a degree of substitution of 3.0 per mannose.
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。1 and 2 are infrared absorption spectra of the polysaccharide derivatives of Examples 1 and 2, respectively.
Claims (2)
族縮合環を表わす） で表わされる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. 50% or more of hydroxyl groups in a polysaccharide molecule are represented by the following formula: (In the formula, R represents a thiophene ring or an aromatic condensed ring containing a thiophene ring) and a polysaccharide derivative which is substituted with a group and is soluble in an organic solvent.
ルカン、アミロース、プルランを含むα−１，４−グル
カン、デキストランを含むα−１，６−グルカン、カー
ドラン、パキマン、レンチナンを含むβ−１，３−グル
カン、イヌリンを含むβ−２，１−フルクタン、レバン
を含むβ−２，６−フルクタン、寒天を含むガラクタ
ン、アルギン酸を含むポリウナロイド、キチン、キトサ
ンを含むグルコサミナン、及びマンナン、キシランなら
びにグルコマンナン、ガラクトマンナン、アラビノガラ
クタンを含むヘテログリカンからなる化合物群から選ば
れたものである特許請求の範囲第１項記載の多糖類誘導
体。2. Polysaccharides include β-1,4-glucan containing cellulose, amylose, α-1,4-glucan containing pullulan, α-1,6-glucan containing dextran, curdlan, pakiman and lentinan. Β-1,3-glucan containing, β-2,1-fructan containing inulin, β-2,6-fructan containing levan, galactan containing agar, polyunaloid containing alginic acid, glucosaminonan containing chitin and chitosan, and mannan. The polysaccharide derivative according to claim 1, which is selected from the group of compounds consisting of heteroglycans including xylan, glucomannan, galactomannan, and arabinogalactan.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59076290A JPH0643441B2 (en) | 1984-04-16 | 1984-04-16 | Polysaccharide derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59076290A JPH0643441B2 (en) | 1984-04-16 | 1984-04-16 | Polysaccharide derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60219201A JPS60219201A (en) | 1985-11-01 |
| JPH0643441B2 true JPH0643441B2 (en) | 1994-06-08 |
Family
ID=13601196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59076290A Expired - Lifetime JPH0643441B2 (en) | 1984-04-16 | 1984-04-16 | Polysaccharide derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0643441B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US5882520A (en) * | 1995-10-26 | 1999-03-16 | The University Of Montana | Use of arabinogalactan in aqueous two phase extractions |
| CN107383225A (en) * | 2017-06-29 | 2017-11-24 | 华东师范大学 | A kind of anti-tumor drug levulan carboxylate and its synthetic method |
-
1984
- 1984-04-16 JP JP59076290A patent/JPH0643441B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| Ｓ．Ｓｉｎｇｈｅｔａｌ，Ｃａｒｂｏｈｙｄｒ．Ｒｅｓ．，１７，ｐ３５３−３６３（１９７１） |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60219201A (en) | 1985-11-01 |
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