JPS60219201A - Polysaccharide derivative - Google Patents
Polysaccharide derivativeInfo
- Publication number
- JPS60219201A JPS60219201A JP7629084A JP7629084A JPS60219201A JP S60219201 A JPS60219201 A JP S60219201A JP 7629084 A JP7629084 A JP 7629084A JP 7629084 A JP7629084 A JP 7629084A JP S60219201 A JPS60219201 A JP S60219201A
- Authority
- JP
- Japan
- Prior art keywords
- polysaccharide
- glucan
- thiophene ring
- degree
- compound
- 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
- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 22
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 22
- 150000004676 glycans Chemical class 0.000 title 1
- 150000004804 polysaccharides Chemical class 0.000 claims abstract description 18
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001913 cellulose Substances 0.000 claims abstract description 11
- 229920002678 cellulose Polymers 0.000 claims abstract description 11
- 229920001503 Glucan Polymers 0.000 claims abstract description 9
- 229920000057 Mannan Polymers 0.000 claims abstract description 9
- -1 polysaccharide ester Chemical class 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 229920000856 Amylose Polymers 0.000 claims abstract description 3
- 229920001218 Pullulan Polymers 0.000 claims abstract description 3
- 239000004373 Pullulan Substances 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 235000019423 pullulan Nutrition 0.000 claims abstract description 3
- 229920002670 Fructan Polymers 0.000 claims description 4
- 229920002581 Glucomannan Polymers 0.000 claims description 4
- 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 3
- 229940046240 glucomannan Drugs 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
- 229920001817 Agar Polymers 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
- 229920000926 Galactomannan Polymers 0.000 claims description 2
- 229920001202 Inulin Polymers 0.000 claims description 2
- 229920001491 Lentinan Polymers 0.000 claims description 2
- 239000008272 agar Substances 0.000 claims description 2
- 239000000783 alginic acid Substances 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- 229960001126 alginic acid Drugs 0.000 claims description 2
- 150000004781 alginic acids Chemical class 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
- 229930192474 thiophene Natural products 0.000 claims description 2
- 229920002558 Curdlan Polymers 0.000 claims 1
- 239000001879 Curdlan Substances 0.000 claims 1
- 229920001353 Dextrin Polymers 0.000 claims 1
- 239000004375 Dextrin Substances 0.000 claims 1
- 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 1
- 235000019316 curdlan Nutrition 0.000 claims 1
- 229940078035 curdlan Drugs 0.000 claims 1
- 235000019425 dextrin Nutrition 0.000 claims 1
- 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 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 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 abstract description 2
- 229920000189 Arabinogalactan Polymers 0.000 abstract description 2
- 239000001904 Arabinogalactan Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 2
- 235000019312 arabinogalactan Nutrition 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 abstract description 2
- 239000000741 silica gel Substances 0.000 abstract description 2
- 229910002027 silica gel Inorganic materials 0.000 abstract description 2
- 229920001221 xylan Polymers 0.000 abstract description 2
- 150000004823 xylans Chemical class 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 239000010408 film Substances 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- 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 7
- 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
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000470 constituent 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
- 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
- 239000002994 raw material Substances 0.000 description 2
- 239000011780 sodium chloride 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
- 150000003577 thiophenes Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- FYGDTMLNYKFZSV-URKRLVJHSA-N (2s,3r,4s,5s,6r)-2-[(2r,4r,5r,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5r,6s)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-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]1OC1[C@@H](CO)O[C@@H](OC2[C@H](O[C@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-URKRLVJHSA-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
- 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
- 229920002307 Dextran Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000237858 Gastropoda Species 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XEIPQVVAVOUIOP-UHFFFAOYSA-N [Au]=S Chemical compound [Au]=S XEIPQVVAVOUIOP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 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
- 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
- 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
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 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
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 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
Abstract
Description
【発明の詳細な説明】
本発明は新規な多糖類誘導体に関フるものであり、詳し
くは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。DETAILED DESCRIPTION OF THE INVENTION 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 bonded 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ェ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。Conventionally, various compounds have been known as carboxylic acid esters of polysaccharides, but only a limited number of compounds are known when the carboxylic acid has a carboxyl group directly connected to a thiophene ring.
ｆｆ１Ｊ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［ ８，８１ｎｇｈθｔａｘ 。An example of synthesis of ff1J for the purpose of modifying cellulose fibers has been reported [8,81nghθtax.
０ａｒｂｏｈｙｄｒ、 Ｒｅｓ、、 １７ ３５３−３
６５（ｔ９７１）〕が、生成物はグルコース単位あたり
の置換度１２１．０以下であり、一般的な溶媒に溶解し
ないものである。多糖類のへテロ芳香族カルボン酸エス
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′；４
３機溶剤に可俗性であり、吸着剤、酵素担体、クロマト
グラフィー用担体、光学異性体分離剤、液晶物質等とし
て利用できる可能性が高い。特に本発明の窒素を環員に
有するカルボン酸エステルは、その吸着剤、分［ＩＪと
しての機能を利用することが期待できる。0arbohydr, Res, 17 353-3
65 (t971)], but the product has a degree of substitution per glucose unit of 121.0 or less and is insoluble in common solvents. Heteroaromatic carboxylic acid esters of polysaccharides, especially when they are highly substituted esters in which 50% or more of the hydroxyl groups in the polysaccharide molecules are substituted, are generally ';4
It is compatible with three solvents, and has a high possibility of being used as an adsorbent, an enzyme carrier, a chromatography carrier, an optical isomer separating agent, a liquid crystal substance, etc. In particular, the carboxylic acid ester of the present invention having nitrogen as a ring member can be expected to utilize its function as an adsorbent.
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、カートラン、バキマン、レンチ
ナンを含むβ−１，５−グルカン、イヌリンを含むβ−
２，１−フルクタン、レバンヲ含む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マンナン、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ヲ含むヘテログリカン
などである。Polysaccharides that have various monosaccharides as constituent units can be used, but those that have a linear molecular structure, or those that have a relatively small degree of branching even if they have branches, are useful. be. In addition, those with relatively simple structures having at most two or less types of monosaccharides as constituent units and their bonding forms are particularly useful. Examples include β-1,4-glucan containing cellulose, amylose, α-1,4-glucan containing pullulan, α-1,6-glucan containing dextran, β-glucan containing curtran, bakiman, and lentinan. β- containing 1,5-glucan and inulin
β-2,6-fructan including 2,1-fructan and lebanon, galactan including agar, polyunaloid including alginic acid, glucomannan including chitin and chitosan, and mannan, xylan, and glucomannan, galactomannan, and arabinogalactan. such as heteroglycans.
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）・ライドを用いれば良く、例えばチオフェン−２
−カルボニルクロリド、チオフェン−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
ようなブレンステッド酸、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 the reaction reagent for esterifying the above polysaccharide to lead to the derivative of the present invention, the corresponding carboxylic acid anhydride or carboxylic acid) ride may be used, for example, thiophene-2
-carbonyl chloride, thiophene-3-carbonyl chloride, etc. As reaction catalysts, Brønsted acids such as sulfuric acid and perchloric acid, Lewis acids such as zinc chloride,
Bases such as pyridine, triethylamine, and 4-dimethylaminopyridine can be used as appropriate.
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 derivatives of the present invention, raw material polysaccharides are those that are once dissolved in a solvent such as water or formic acid and then precipitated in a different type of solvent and dried, those that are directly freeze-dried from an aqueous solution, or those that are directly freeze-dried from an aqueous solution, or those that are directly freeze-dried from an aqueous solution, or those that are directly lyophilized from an aqueous solution. If the raw material is one obtained by hydrolyzing a polysaccharide ester such as ester, it can be advantageously used because it has a large reaction activity.
多糖類の種類、重合度によって反応性は異るが、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。Although reactivity varies depending on the type of polysaccharide and degree of polymerization, the degree of substitution of the derivative can be adjusted by selecting reaction conditions.
本発明の多糖類誘導体は鍾々の形態で利用できる。例え
ば、フィルム状、繊維状、粒子状などに成型して使用す
る。この場合には１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 the form of snails. For example, it is used after being molded into a film, fiber, or particulate form. In this case, the degree of 1 is relatively high, for example 60
The above are preferable in terms of the physical strength of the molded product. Furthermore, when used as supported on microscopic silica gel, those having a relatively low degree of polymerization, for example, about 10 to 80, are more advantageous in terms of coating properties.
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、及び種々の機能にすぐれている傾向がみ
られる。Among the polysaccharide derivatives of the present invention, those with a higher degree of substitution, for example, those in which 50% or more of the hydroxyl groups in the molecule are esterified, tend to have better organic solvent solubility and various functions.
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 will be explained below with reference to Examples, but the present invention is not limited thereto.
実施例１
酢！セルロースをヒト２ジンでケン化し、ア−１＝）ン
で洗浄後乾燥してセルロースをｎ ｆｔｃ。上記セルロ
ース１．５ｇに脱水したピリジン７０ｍ１、脱水したト
リエチルアミン７．７ｍｔ、４−ジメチルアミノピリジ
ン５０〜を加え、攪拌しながらチオフェン２−カルボニ
ルクロリド１２．２９ 全添加し、１００Ｃで５時間攪
拌反応した。冷却後エタノール４００ｆｆｌｌに生成物
を攪拌しながら加えて沈殿させ、グラスフィルターでハ
過後エタノールで良（洗浄した。真空乾燥した後、塩化
メチレン３０麻に溶解し、不溶物を除いた後４００ｍ１
のエタノールに再沈殿した。沈殿をＰ消後、エタノール
で洗浄し、脱液、乾燥した。Example 1 Vinegar! Cellulose was saponified with human 2 gin, washed with Ar-1=), and dried to obtain nftc cellulose. 70 ml of dehydrated pyridine, 7.7 mt of dehydrated triethylamine, and 50~ of 4-dimethylaminopyridine were added to 1.5 g of the above cellulose, and while stirring, 12.29 ml of thiophene 2-carbonyl chloride was added, followed by reaction with stirring at 100 C for 5 hours. . After cooling, the product was added to 400ml of ethanol with stirring to precipitate it, filtered through a glass filter, and then washed with ethanol. After vacuum drying, it was dissolved in 30ml of methylene chloride, and after removing insoluble matter, 400ml of
It was reprecipitated in ethanol. After the precipitate was quenched with P, it was washed with ethanol, dehydrated, and dried.
生成物の糖製収音は６．９９であった。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。The sugar content of the product was 6.99. The product was dissolved in methylene chloride, applied to a saline cell, dried, and subjected to infrared absorption spectroscopy. The obtained infrared absorption spectrum is shown in FIG. 1, and the characteristic absorption bands are as follows.
３１００ｃｍ−’ 芳香族０−Ｈ仲違振動１７２０ｃｍ
−１カルボン酸エステルのｃ；。3100cm-' aromatic 0-H vibration 1720cm
-1 carboxylic acid ester c;.
伸縮振動
１３６０．１４２０，１５２０ｃｒＩＴ−１チオフェン
環伸縮振動
１２６０ｃｍ−’ エステルのａ−ｏ伸縮振動１０６０
〜１１６０ｃｍ−’ セルロースの０−０−Ｑの伸縮振
動
８６０ｔｙｎ−１２置換チオフエンの０−Ｈ面外変角
七ル目−スのＯＨＫ基づ（３４５０ｃｍ−１付近）吸収
はほとんど認められず、はぼ三置換体であることがわか
る。着たＯＤＣ／３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。Stretching vibration 1360.1420,1520crIT-1 Thiophene ring stretching vibration 1260cm-' Ester a-o stretching vibration 1060
~1160 cm-' OHK-based absorption (near 3450 cm-1) of the 0-H out-of-plane bending 7th group of the 0-0-Q stretching vibration of cellulose 860 tyn-12-substituted thiophenes was hardly observed; It can be seen that it is a trisubstituted compound. The characteristic absorption of the proton NMR spectrum measured in the ODC/3 is as follows.
６．８〜７．８ ｐｐｍチオフェン環プ四トン２．８〜
５．４ｐｐＩ１１セルロースの環及び６位のメチレンの
プロトン
チオフェン環プロトンとセルロースのプロトンの比はほ
ぼ？＝７であり、三〇−換体と一致する。6.8~7.8 ppm Thiophene ring tetraton 2.8~
5.4ppI11 Cellulose ring and methylene proton at position 6 What is the approximate ratio of thiophene ring protons to cellulose protons? = 7, which is consistent with 30-transformation.
また硫黄の元素分析を行なったところ硫黄金力；は１
ｊ４０％であり、これらを総合して生成物Ｕｉｍ度約ｓ
、ｏのセルロースチオフェン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 sulfur gold was 1
j40%, and these together give a product Uim degree of about s
, o cellulose thiophene 2-carboxylate.
実施例２ 象牙ヤシの種子のをよい乳を文献記載［Ｇ、Ｏ。Example 2 The good milk of ivory palm seeds has been described in the literature [G, O.
Ａｓｐｉｎａｌｌ、ｅｔａｌ ； Ｊ、Ｃｈｅｍ、Ｓａ
ｃ、５１８４（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とまったぐ同様に
行なった。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、乾繰し
て赤外スペクトルの測定に付した。イｕ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。Aspinall, etal; J, Chem, Sa
C, 5184 (1953)] to obtain a high molecular weight fraction of mannan B. The same procedure as in Example 1 was carried out except that this mannan B powder was used instead of cellulose. As a result, 2 g of reaction product was obtained. This product was dissolved in methylene chloride, applied to a saline cell, dried and subjected to infrared spectroscopy. The obtained infrared absorption spectrum is shown in Figure 2, and the characteristic absorption bands are as follows.
５１００ｃｒｎ 芳香族Ｃ−Ｈ伸縮振動１７３０ｃｙｎ
−’ カルボン酸ニスデルのｃ＝。5100crn Aromatic C-H stretching vibration 1730cyn
-' c= of carboxylic acid Nisder.
伸縮振動
１５６Ｑ、１４２０，１５５０ｃｍ−１ｆオフｘ：ｙ環
環伸縮振動
１２６０ｃｍ−’ エステルのｃ−ｏ伸縮振動１ｏ６ｏ
”−１１８０ｚ−’ −ｒンナ：ｙのａ−ｏ−ｏの伸縮
振動
８６０メ１ ２置換チオフエンの０−Ｈ面外変角
マンナンのＯＨに基づ（３４５０Ｃｒｎ−１付近の吸収
はほとんど認められず、はは三置換体であることがわか
る。また０ＤＯ１５中で測定したプロトンＮ畦の特徴的
な吸収は次の通りである。Stretching vibration 156Q, 1420, 1550cm-1f off x:y ring Ring stretching vibration 1260cm-' Ester c-o stretching vibration 1o6o
``-1180z-' -rner: y ao-o stretching vibration 860m1 Disubstituted thiophene 0-H out-of-plane bending based on OH of mannan (absorption near 3450Crn-1 is almost not observed) It can be seen that zu and ha are trisubstituted products.Furthermore, the characteristic absorption of the proton N ridge measured in 0DO15 is as follows.
６．８〜８．２ ｐｐｍチオフェン環のプロトン３．０
〜５，８ ］）ｐｍマンナンの環および６位のメチレン
のプレトン
チオフェン環プロトンとマンナンのプロトンの比はほぼ
９ニアであり三置換体と一致する。6.8-8.2 ppm Thiophene ring proton 3.0
~5,8 ]) The ratio of the protons of the pretone thiophene ring of the pm mannan ring and methylene at the 6-position to the mannan protons is approximately 9-nia, which is consistent with a trisubstituted product.
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−チオフェンカルボキシレートと推定される
。As a result, the product is estimated to be mannan 2-thiophenecarboxylate with 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ａ誘導体の
赤外吸収スペクトルである〇出願人代理人 古 谷 馨Figures 1 and 2 are infrared absorption spectra of the multi-a derivatives of Examples 1 and 2, respectively.Applicant's agent: Kaoru Furuya
Claims (1)
族縮合環を表わす） で表わされる基で置換されている多糖類誘導体。 ２ 多糖類がセルロースを含む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２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
ヌリンヲ含む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
ルコマンナン、及びマンナン、キシ２ンならびにグルコ
マンナン、ガラクトマンナン、アラビノガラククンを含
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ＷＦ情求範囲第１項記載の多糖類誘導体。 ３ 多糖類分子中の水酸基の５０％以上が置換されてい
る特許請求範囲第１項又は第２項記載の多ｓ！１類訪専
体。[Scope of Claims] 1. A polysaccharide in which the hydroxyl group in the polysaccharide molecule is substituted with a group represented by the following formula % (wherein R represents a thiophene ring or an aromatic condensed ring containing a thiophene ring) derivative. 2 β-1,4-glucan whose polysaccharide includes cellulose,
amylose, α-1,4-glucan containing pullulan, α-1,6-glucan containing dextrin, curdlan,
β-1,3-glucan containing pachyman, lentinan, β-2,1-fructan containing inulin, β containing levan
-A group of compounds consisting of galactans including 2,6-fructan and agar, polyunaloids including alginic acid, glucomannans including chitin and chitosan, and heteroglycans including mannan, xy2ine, and glucomannan, galactomannan, and arabinogalactin. The polysaccharide derivative according to item 1 of the special WF requirements, which is selected from the following. 3. The polys! according to claim 1 or 2, in which 50% or more of the hydroxyl groups in the polysaccharide molecule are substituted. Category 1 Visiting Specialist.
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 true JPS60219201A (en) | 1985-11-01 |
| JPH0643441B2 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) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5352432A (en) * | 1986-07-03 | 1994-10-04 | Advanced Magnetics, Inc. | Hepatocyte specific composition and their use as diagnostic imaging agents |
| US5554386A (en) * | 1986-07-03 | 1996-09-10 | Advanced Magnetics, Inc. | Delivery of therapeutic agents to receptors using polysaccharides |
| US5679323A (en) * | 1986-07-03 | 1997-10-21 | Advanced Magnetics, Inc. | Hepatocyte-specific receptor-mediated endocytosis-type compositions |
| 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.SINGH ETAL,CORBOHYDR.RES=1971 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5352432A (en) * | 1986-07-03 | 1994-10-04 | Advanced Magnetics, Inc. | Hepatocyte specific composition and their use as diagnostic imaging agents |
| US5554386A (en) * | 1986-07-03 | 1996-09-10 | Advanced Magnetics, Inc. | Delivery of therapeutic agents to receptors using polysaccharides |
| US5679323A (en) * | 1986-07-03 | 1997-10-21 | Advanced Magnetics, Inc. | Hepatocyte-specific receptor-mediated endocytosis-type compositions |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0643441B2 (en) | 1994-06-08 |
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