JPH0680082B2 - Aromatic carbamate derivatives of polysaccharides - Google Patents
Aromatic carbamate derivatives of polysaccharidesInfo
- Publication number
- JPH0680082B2 JPH0680082B2 JP60096274A JP9627485A JPH0680082B2 JP H0680082 B2 JPH0680082 B2 JP H0680082B2 JP 60096274 A JP60096274 A JP 60096274A JP 9627485 A JP9627485 A JP 9627485A JP H0680082 B2 JPH0680082 B2 JP H0680082B2
- Authority
- JP
- Japan
- Prior art keywords
- carbamate
- light
- isomerization
- spectrum
- trans
- 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
Landscapes
- Physical Or Chemical Processes And Apparatus (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は新規な多糖の芳香族カルバメート誘導体に関す
る。更に詳しくは芳香族アゾ基を有する光学活性な多糖
の芳香族カルバメート誘導体を提供するものである。TECHNICAL FIELD The present invention relates to a novel aromatic carbamate derivative of polysaccharide. More specifically, the present invention provides an aromatic carbamate derivative of an optically active polysaccharide having an aromatic azo group.
芳香族アゾ化合物、例えばアゾベンゼン〔I〕は光(h
ν)あるいは熱(△)により次式に示す如くその−N=
N−2重結合に関してシス−トランス異性化が可逆的に
起こることが知られている。Aromatic azo compounds, such as azobenzene [I], emit light (h
ν) or heat (△), as shown in the following equation, −N =
It is known that cis-trans isomerization occurs reversibly with respect to the N-2 double bond.
一方、本発明者らは分離剤として使用し得る多糖のフエ
ニルカルバメートについて研究を行なつてきたが、新し
い分離特性を付与し得る化合物について種々検討した結
果、本発明の新規化合物を見出すに到つたものである。 On the other hand, the present inventors have conducted research on a polysaccharide phenylcarbamate that can be used as a separating agent, and as a result of various studies on compounds capable of imparting new separating characteristics, they have found a novel compound of the present invention. It is an ivy.
即ち、本発明はセルローストリス(4−フェニルアゾフ
ェニルカルバメート)又はアミローストリス(4−フェ
ニルアゾフェニルカルバメート)から選ばれる光学活性
な多糖の芳香族カルバメート誘導体に関するものであ
る。That is, the present invention relates to an aromatic carbamate derivative of an optically active polysaccharide selected from cellulose tris (4-phenylazophenyl carbamate) or amylose tris (4-phenylazophenyl carbamate).
本発明の化合物は多糖とイソシアナート基を有する芳香
族アゾ化合物を反応させることにより、多糖残基に対し 結合を介してアゾ化合物を結合させて得ることが出来
る。即ち多糖の官能基であるOHの全部に対し結合し、 が形成される(Rは であるが、ベンゼン環上に置換基を有してもよい)。イ
ソシアナート基を有する芳香族アゾ化合物は、例えば相
当する芳香族アゾ化合物のアミノ基にホスゲンを作用さ
せることにより容易に得られる。The compound of the present invention reacts with a polysaccharide residue by reacting a polysaccharide with an aromatic azo compound having an isocyanate group. It can be obtained by binding an azo compound via a bond. That is, it binds to all of OH, which is a functional group of the polysaccharide, Is formed (R is However, it may have a substituent on the benzene ring). The aromatic azo compound having an isocyanate group can be easily obtained, for example, by reacting phosgene with the amino group of the corresponding aromatic azo compound.
本発明の多糖の芳香族カルバメート誘導体は、光学活性
な糖類に、上記の如く光あるいは熱によつてシス−トラ
ンスの異性化を生ずるアゾ化合物が結合したものである
から、光学分割用の充填剤としての用途が期待される。
さらに、光あるいは熱の作用により、その分離特性に多
様性が発現されることが予想される。また、本発明の芳
香族アゾ基を有する多糖誘導体はそのTHF溶液を石英板
にキヤスト後、遮光下で乾燥して得られた膜に光を照射
してもシス−トランスの異性化が起る。従つて分離膜と
しての応用も期待される。Since the aromatic carbamate derivative of the polysaccharide of the present invention is an optically active saccharide to which an azo compound which causes cis-trans isomerization by light or heat as described above is bound, it is a filler for optical resolution. Is expected to be used.
Furthermore, it is expected that the separation characteristics will be varied due to the action of light or heat. Further, the polysaccharide derivative having an aromatic azo group of the present invention undergoes cis-trans isomerization even if the film obtained by casting the THF solution on a quartz plate and then drying it under light shielding is irradiated with light. . Therefore, application as a separation membrane is also expected.
次に本発明を実施例によつて詳述するが、本発明はこれ
によつて限定されるものではない。Next, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
尚、実施例中のスペクトルの測定は以下の装置を用いて
行なつた。In addition, the measurement of the spectrum in the examples was performed using the following apparatus.
IRスペクトル:JASCO.IR−810 Infrared Spectroscopy. CDスペクトル:JASCO−J−40 Spectropolarimeter 旋光光度計:JASCO,DIP−181 Digital Polarimeter 実施例−1 〔セルローストリス(4−フエニルアゾフエニルカルバ
メート)の合成〕 (1) 4−フエニルアゾフエニルイソシアナートの合
成 フラスコにトルエン約200mlを入れ撹拌しながらトルエ
ン中にホスゲンを送りこむ。フラスコ内がホスゲンで置
換されたところへ、p−アミノアゾベンゼン21.65gのト
ルエン(300ml)溶液を滴下して反応させた。反応フラ
スコを徐々に加温し、室温から約120℃まで上昇させト
ルエン還流下で反応させた。ホスゲンをフラスコ内から
追い出し、反応溶液を油浴中、常圧で加温し、トルエン
を留去した。収量39.6g(但し少量のトルエンを含んで
いる) IRスペクトル(No.562)−N=C=O:2250cm-1 (2) セルローストリス(4−フエニルアゾフエニル
カルバメート)の合成 セルロース0.400g、ピリジン20mlおよび上記(1)で合
成した4−フエニルアゾフエニルイソシアナート6.78g
(トルエンを含む重量)の混合物を約105℃で20時間反
応させた。反応溶液をメタノール300mlに注ぎ生成物を
沈澱させた。沈澱はグラスフイルターで集め、メタノー
ルで洗浄した後、デシケーター中で減圧乾燥し、さらに
60℃で2時間真空乾燥した。生成物は二置換尿素とカル
バメートの混合物であり、収量は2.60gであつた。この
混合物2.51gを酢酸エチル25mlに溶かして溶媒分別した
結果、二置換尿素を不溶部として、カルバメートは可溶
部として得た。両者は遠心分離により分離し、可溶部
は、メタノールに注ぎ入れカルバメートを沈澱させた。
沈澱は再びグラスフイルターで集め、メタノールで洗浄
後、デシケーター中で減圧乾燥し、さらに60℃で2時間
真空乾燥した。収量1.81g、収率91%、生成物は次式で
表わされるセルロースのOH基が全部4−フエニルアゾフ
エルカルバメート基で置換された化合物であると推定さ
れるが、これをIRスペクトル及び元素分析により確認し
た。IR spectrum: JASCO.IR-810 Infrared Spectroscopy. CD spectrum: JASCO-J-40 Spectropolarimeter Optical polarimeter: JASCO, DIP-181 Digital Polarimeter Example-1 [Synthesis of cellulose tris (4-phenylazophenylcarbamate)] (1) Synthesis of 4-phenylazophenyl isocyanate Approximately 200 ml of toluene is placed in a flask and phosgene is fed into toluene while stirring. A solution of 21.65 g of p-aminoazobenzene in toluene (300 ml) was added dropwise to the place where the flask was replaced with phosgene to cause a reaction. The reaction flask was gradually heated, and the temperature was raised from room temperature to about 120 ° C., and the reaction was carried out under reflux of toluene. Phosgene was expelled from the flask, the reaction solution was heated in an oil bath under normal pressure, and toluene was distilled off. Yield 39.6g (but containing a small amount of toluene) IR spectrum (No.562) -N = C = O: 2250cm -1 (2) Synthesis of cellulose tris (4-phenylazophenylcarbamate) 0.400g cellulose 20 ml of pyridine and 6.78 g of 4-phenylazophenyl isocyanate synthesized in (1) above.
The mixture (weight including toluene) was reacted at about 105 ° C. for 20 hours. The reaction solution was poured into 300 ml of methanol to precipitate the product. The precipitate was collected with a glass filter, washed with methanol, and then dried under reduced pressure in a desiccator.
It was vacuum dried at 60 ° C. for 2 hours. The product was a mixture of disubstituted urea and carbamate, and the yield was 2.60 g. As a result of dissolving 2.51 g of this mixture in 25 ml of ethyl acetate and separating the solvent, disubstituted urea was obtained as an insoluble portion and carbamate was obtained as a soluble portion. Both were separated by centrifugation, and the soluble part was poured into methanol to precipitate the carbamate.
The precipitate was collected again with a glass filter, washed with methanol, dried under reduced pressure in a desiccator, and further vacuum dried at 60 ° C. for 2 hours. Yield 1.81 g, 91%, the product is presumed to be a compound in which all the OH groups of the cellulose represented by the following formula are replaced by 4-phenylazofuel carbamate groups. Confirmed by analysis.
IRスペクトル.(No.601)カルバメートのC=O:1730cm
-1 元素分析値, 測定値:C,64.96%;H,4.50%;N,14.95% 計算値:C,64.97%;H,4.48%;N,15.16% 実施例2〔セルローストリス(4−フエニルアゾフエニ
ルカルバメート)のシス−トランス異性化〕 (1) 光による異性化 トランス体セルローストリス(4−フエニルアゾフエニ
ルカルバメート)のテトラヒドロフラン(THF)溶液を
石英セルに入れ、300Wの高圧水銀灯により光を照射し
た。光の波長は東芝硝子製のフイルター,UV−D36CとUV
−35により400nm>λ1>340nmに調節した。この光によ
りトランス体からシス体への異性化を行なつた。また、
フイルターY−47を通過した光によりシス体からトラン
ス体への異性化を行なつた。光の照射はすべて室温で行
ない、溶液の濃度は、約0.1〜0.2mg/mlのものを用い
た。それぞれの異性化に伴う可視紫外吸収スペクトルの
変化を測定した。結果を図−1,及び図−2に示した。IR spectrum. (No.601) Carbamate C = O: 1730cm
-1 Elemental analysis value, Measurement value: C, 64.96%; H, 4.50%; N, 14.95% Calculated value: C, 64.97%; H, 4.48%; N, 15.16% Example 2 [Cis-trans isomerization of cellulose tris (4-phenylazophenyl carbamate)] (1) Isomerization by light Tetrahydrofuran (THF) solution of trans-form cellulose tris (4-phenylazophenyl carbamate) was made into quartz. It was placed in a cell and irradiated with light from a 300 W high-pressure mercury lamp. The wavelength of light is UV-D36C and UV, a filter made by Toshiba Glass.
It was adjusted to 400 nm> λ 1 > 340 nm by -35. This light isomerized the trans form to the cis form. Also,
Isomerization from the cis form to the trans form was carried out by the light passing through the filter Y-47. All the light irradiation was performed at room temperature, and the solution had a concentration of about 0.1 to 0.2 mg / ml. The change in visible-ultraviolet absorption spectrum due to each isomerization was measured. The results are shown in Figures 1 and 2.
(2) 熱による異性化 トランス体のTHF溶液を石英セルに入れ400nm>λ1>34
0nmの光によつてシス体に異性化した。セルを25℃の恒
温水槽に入れ、遮光しておき、各経過時間における可視
紫外吸収スペクトルを測定し、異性化に伴う変化および
異性化の速度について調べた。結果を図−3に示した。(2) Isomerization by heat Put THF solution of trans-form into quartz cell and 400nm> λ 1 > 34
It was isomerized to a cis form by 0 nm light. The cell was placed in a constant temperature water bath at 25 ° C., shielded from light, and the visible-ultraviolet absorption spectrum at each elapsed time was measured to examine the change accompanying isomerization and the rate of isomerization. The results are shown in Figure 3.
実施例3(異性化に伴うCDスペクトルの変化) トランス体のTHF溶液を1mmあるいは1cmの石英セルに入
れ400nm>λ1>340nmの光によりシス体に異性化させ
た。トランス体、シス体および双方を含んだものの吸収
スペクトルならびにCDスペクトルを測定した。また一旦
シス体にした後にλ2>470nmの光によりトランス体に
戻したものについても測定した。CDスペクトルの測定
は、600〜400nmについては1cmのセルを用い、400〜210n
mは1mmのセルを用いて測定した。溶液の濃度は、0.178m
g/mlで行なつた。結果を図−4に示した。Example 3 (Change in CD spectrum due to isomerization) A THF solution of trans isomer was put in a quartz cell of 1 mm or 1 cm to isomerize it to a cis isomer by light of 400 nm> λ 1 > 340 nm. The absorption spectrum and the CD spectrum of the trans form, the cis form, and those containing both were measured. In addition, the cis isomer was once converted into the trans isomer by light having a wavelength of λ 2 > 470 nm. The measurement of the CD spectrum uses a 1 cm cell for 600-400 nm, 400-210 n
m was measured using a 1 mm cell. Solution concentration is 0.178m
It was done in g / ml. The results are shown in Figure 4.
応用例1(光学分割用充填剤への応用) i) 光学分割用カラムの作製 セルローストリス(4−フエニルアゾフエニルカルバメ
ート)のトランス体(750mg)をTHF(10ml)に溶かし、
3−アミノプロピルトリエトキシシラン処理したシリカ
ゲル(3g)にコーテイングした。担持されたポリマーの
シリカゲルに対する重量比は約25%である。用いたシリ
カゲルはMerck社のLi Chrospher SI−4000;粒径10μ
m、孔径4000Å、表面積6m2/gである。調製した充填剤
を25cm×0.46(i.d.)cmのステンレススチール製のカラ
ムにスラリー充填法で充填した。Application Example 1 (Application to filler for optical resolution) i) Preparation of column for optical resolution Dissolve the trans form (750 mg) of cellulose tris (4-phenylazophenylcarbamate) in THF (10 ml),
It was coated on 3-aminopropyltriethoxysilane treated silica gel (3 g). The weight ratio of supported polymer to silica gel is about 25%. The silica gel used was Li Chrospher SI-4000 from Merck; particle size 10μ.
m, pore size 4000 Å, surface area 6 m 2 / g. The prepared packing material was packed in a 25 cm × 0.46 (id) cm stainless steel column by a slurry packing method.
ii) 種々のラセミ体化合物に対する分別結果を次の表
1に示した。ii) The results of fractionation for various racemic compounds are shown in Table 1 below.
実施例4(アミローストリス(4−フエニルアゾフエニ
ルカルバメート)の合成) アミロースと過剰の4−フエニルアゾフエニルイソシア
ナートをピリジン中約100−110℃で反応させ合成した。
生成物の精製および確認はセルロースの場合と同様の方
法をとつた。 Example 4 (Synthesis of amylose tris (4-phenylazophenyl carbamate)) Amylose was synthesized by reacting excess 4-phenylazophenyl isocyanate in pyridine at about 100-110 ° C.
Purification and confirmation of the product were carried out in the same manner as in the case of cellulose.
元素分析値 測定値:C,64.89;H,4.46;N,15.21% 計算値:C,64.97;H,4.48;N,15.16%Elemental analysis value Measured value: C, 64.89; H, 4.46; N, 15.21% Calculated value: C, 64.97; H, 4.48; N, 15.16%
図−1〜図−3は本発明の化合物の可視紫外吸収スペク
トルの図、図−4はCDスペクトルの図である。1 to 3 are diagrams of visible-ultraviolet absorption spectrum of the compound of the present invention, and FIG. 4 is a diagram of CD spectrum.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 G01N 30/48 W 8310−2J ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Office reference number FI technical display location G01N 30/48 W 8310-2J
Claims (1)
ニルカルバメート)又はアミローストリス(4−フェニ
ルアゾフェニルカルバメート)から選ばれる多糖の芳香
族カルバメート誘導体。1. A polysaccharide aromatic carbamate derivative selected from cellulose tris (4-phenylazophenyl carbamate) or amylose tris (4-phenylazophenyl carbamate).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60096274A JPH0680082B2 (en) | 1985-05-07 | 1985-05-07 | Aromatic carbamate derivatives of polysaccharides |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60096274A JPH0680082B2 (en) | 1985-05-07 | 1985-05-07 | Aromatic carbamate derivatives of polysaccharides |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS61254604A JPS61254604A (en) | 1986-11-12 |
JPH0680082B2 true JPH0680082B2 (en) | 1994-10-12 |
Family
ID=14160559
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60096274A Expired - Lifetime JPH0680082B2 (en) | 1985-05-07 | 1985-05-07 | Aromatic carbamate derivatives of polysaccharides |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0680082B2 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2648516B2 (en) * | 1989-07-27 | 1997-09-03 | ダイセル化学工業株式会社 | Separation of stereoisomers |
TW362100B (en) * | 1995-07-21 | 1999-06-21 | Novartis Ag | The preparation and use of photochemically cross-linked polysaccharide derivatives having no photopolymerisable functional groups |
JP2013018851A (en) * | 2011-07-11 | 2013-01-31 | Sumitomo Bakelite Co Ltd | Cellulose fiber, cellulose fiber-containing polymer, resin composition, and molding |
JP2019001876A (en) * | 2017-06-14 | 2019-01-10 | 国立大学法人京都大学 | Fine cellulose fiber, manufacturing method therefor, slurry, and composite |
-
1985
- 1985-05-07 JP JP60096274A patent/JPH0680082B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPS61254604A (en) | 1986-11-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5017290A (en) | Separation agent comprising acyl- or carbamoyl-substituted polysaccharide | |
JP4201832B2 (en) | Photochemically cross-linked polysaccharide derivatives as supports for chromatographic resolution of enantiomers. | |
JP3342482B2 (en) | Separating agent | |
JPH0833380B2 (en) | Filler for liquid chromatography | |
JPH0680082B2 (en) | Aromatic carbamate derivatives of polysaccharides | |
EP0281951B1 (en) | Alkyl-phenylcarbamate derivative of polysaccharide | |
JP2841546B2 (en) | Packing material for liquid chromatography | |
JPH0476976B2 (en) | ||
JPS60108751A (en) | Separating agent | |
JPH0699482B2 (en) | Polysaccharide derivative | |
JPH0653763B2 (en) | Cellulose type carbamate derivative | |
JP2856926B2 (en) | Organosilicon compound | |
Iuliano et al. | Synthesis of four cholic acid-based CSPs containing 2-naphthoyl carbamate and 3, 5-dinitrophenylcarbamate moieties and their evaluation in the HPLC resolution of racemic compounds | |
JPH0693002A (en) | Separating agent consisting of alkoxy-substituted aromatic carbamate derivative of cellulose | |
JP3048085B2 (en) | Method for immobilizing cyclodextrin | |
JP2538618B2 (en) | Separation agent | |
JPS60155968A (en) | Chromatography filler and analysis of enantiomer mixture using the same | |
JPH05239103A (en) | New polysaccharide derivative and separating agent | |
JPH0475208B2 (en) | ||
Oi et al. | Investigation on the chiral discrimination mechanism using an axially asymmetric binaphthalene-based stationary phase for high-performance liquid chromatography | |
JPH08217698A (en) | Agent for optical resolution | |
JP2968319B2 (en) | Chirality discriminating agent and packing material for chromatography | |
JP3059013B2 (en) | Trialkylsilyl-substituted aromatic carbamate derivatives of polysaccharides and separating agents | |
JP3086114B2 (en) | Separating agents for chromatography | |
JPH0478621B2 (en) |