JPH02237982A - Fluorine-containing azacrown ether - Google Patents
Fluorine-containing azacrown etherInfo
- Publication number
- JPH02237982A JPH02237982A JP5819089A JP5819089A JPH02237982A JP H02237982 A JPH02237982 A JP H02237982A JP 5819089 A JP5819089 A JP 5819089A JP 5819089 A JP5819089 A JP 5819089A JP H02237982 A JPH02237982 A JP H02237982A
- Authority
- JP
- Japan
- Prior art keywords
- crown
- monoaza
- fluorine
- ether
- tosylate
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title abstract description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title description 9
- 229910052731 fluorine Inorganic materials 0.000 title description 9
- 239000011737 fluorine Substances 0.000 title description 9
- 239000002555 ionophore Substances 0.000 abstract description 4
- 230000000236 ionophoric effect Effects 0.000 abstract description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000002798 polar solvent Substances 0.000 abstract description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 229910001413 alkali metal ion Inorganic materials 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- -1 alkali metal cations Chemical class 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 2
- 102000003939 Membrane transport proteins Human genes 0.000 description 2
- 108090000301 Membrane transport proteins Proteins 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- VRZVPALEJCLXPR-UHFFFAOYSA-N ethyl 4-methylbenzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=C(C)C=C1 VRZVPALEJCLXPR-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009061 membrane transport Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 238000000023 Kugelrohr distillation Methods 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 108010067973 Valinomycin Proteins 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- FCFNRCROJUBPLU-UHFFFAOYSA-N compound M126 Natural products CC(C)C1NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC(=O)C(C(C)C)NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC(=O)C(C(C)C)NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC1=O FCFNRCROJUBPLU-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- FCFNRCROJUBPLU-DNDCDFAISA-N valinomycin Chemical compound CC(C)[C@@H]1NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC1=O FCFNRCROJUBPLU-DNDCDFAISA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
この発明は、イオノホア（イオン透過担体）として有用
な新規な含フッ素アザクラウンエーテルに関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This invention relates to a novel fluorine-containing azacrown ether useful as an ionophore (ion permeable carrier).
従来の技術
イオン選択的な錯体形成能を有するクラウンエーテル類
は合成化学、分析化学および触媒化学等種々の分野にお
いて汎用されている。BACKGROUND OF THE INVENTION Crown ethers having the ability to form ion-selective complexes are widely used in various fields such as synthetic chemistry, analytical chemistry, and catalytic chemistry.
最近、アルカリ金属イオン等と安定な錯体を形成し、液
膜によるイオン輸送において良好な選択性を示すアザク
ラウンエーテル類は、生体膜におけるアルカリ金属カチ
オンの透過性を誘導するバリノマイシン等の生体系イオ
ノホアのモデル化合物として注目されるようになってい
るが、疎水性および分子間力の点で改良すべき余地が残
こされている。Recently, azacrown ethers, which form stable complexes with alkali metal ions, etc. and exhibit good selectivity in ion transport through liquid membranes, have been developed as ionophores in biological systems such as valinomycin, which induce permeability of alkali metal cations in biological membranes. However, there is still room for improvement in terms of hydrophobicity and intermolecular forces.
即ち、錯体の液膜に対する分配係数に依存するアルカリ
金属イオンの液膜透過性は疎水性が強いほど良好であり
、また、メンプランフィルター等の支持膜に液体を含浸
させた含浸型液膜中での拡散に依存するアルカリ金属イ
オンの液膜透過性は分子間力が小さいほど良好である。In other words, the liquid membrane permeability of alkali metal ions, which depends on the partition coefficient of the complex to the liquid membrane, is better as the hydrophobicity becomes stronger. The liquid membrane permeability of alkali metal ions, which depends on diffusion at , is better as the intermolecular force is smaller.
発明が解決しようとする課題
この発明は、既知のアザクラウンエーテル類に比べて、
疎水性が非常に高く、分子間力が小さいだけでなく、錯
体の安定性の点で全く遜色のない新規なアザクラウンエ
ーテルを提供するためになされたものである。Problems to be Solved by the Invention The present invention has the following problems compared to known aza crown ethers:
This was done in order to provide a new aza crown ether that not only has extremely high hydrophobicity and low intermolecular forces, but also has no inferiority in terms of complex stability.
課題を解決するための手段
即ち本発明は、一般式（Ｉ）；
（式中、ａは１−１２の数を示し、ｍはｌ，２または３
の数を示し、ｎは０、ｌまｔ；は２の数を示す）
で表わされる含フッ素アザクラウンエーテルに関する。Means for solving the problem, that is, the present invention is a general formula (I);
, where n is 0, l or t; is 2).
式（１）において、Ｑは１−１２の数を示し、ｍは１，
２まｔ；は３、好ましくは２の数を示し、ｎは０、ｌま
たは２、好ましくはｌまたは２の数を示す。In formula (1), Q represents a number from 1 to 12, m is 1,
2 represents a number of 3, preferably 2, and n represents a number of 0, 1 or 2, preferably 1 or 2.
含フッ素基Ｃｆ２Ｆ２．２＋１−は直鎖状のものが好ま
しいが、分枝鎖状であってもよい。The fluorine-containing group Cf2F2.2+1- is preferably linear, but may be branched.
分枝鎖状の含フッ素基としては次のものが例示される：
特に好ましい含フッ素アザクラウンエーテルはＮ−（２
−ベルフルオ口ヘキシルエチル）モノアザー１５−クラ
ウン−５およびＮ一（２−ベルフル才口ヘキシルエチル
）モノアザーｌ８−クラウン−６であり、前者はアルカ
リ金属イオンのうちでナトリウムイオンと選択的に錯体
を形成し、後者はカリウムイオンと選択的に錯体を形成
する。Examples of the branched fluorine-containing group include the following: Particularly preferred fluorine-containing azacrown ether is N-(2
-berflurohexylethyl) monoother 15-crown-5 and N-(2-berflurohexylethyl)monoother 18-crown-6, the former selectively forming a complex with sodium ion among alkali metal ions. However, the latter selectively forms complexes with potassium ions.
本発明による含フッ素アザクラウンエーテルの製造方法
は特に限定的ではないが、簡便な方法は、モノアザクラ
ウンエーテル、例えばモノアザー１５−クラウン−５ま
たはモノアザ−１８−クラウン−６を塩基性触媒の存在
下、極性溶媒中において２−ベルフルオ口へキシルアル
キルトシレート、例えば２−ベルフルオロヘキシルエチ
ルトシレートと反応させる方法である。The method for producing the fluorine-containing aza crown ether according to the present invention is not particularly limited, but a simple method is to prepare a monoaza crown ether, such as monoaza 15-crown-5 or monoaza-18-crown-6, in the presence of a basic catalyst. The second method involves reacting with 2-berfluorohexyl ethyl tosylate, such as 2-berfluorohexyl ethyl tosylate, in a polar solvent.
塩基性触媒としてはアルカリ金属やアルカリ土類金属の
炭酸塩、水酸化物および水素化物等が例示される。Examples of the basic catalyst include carbonates, hydroxides, and hydrides of alkali metals and alkaline earth metals.
極性溶媒としてはジオキサン、ジメトキシエタン、ＤＭ
Ｆ，ＤＭＳＯ、Ｎ−メチルピロリドン等が例示される。Dioxane, dimethoxyethane, DM as a polar solvent
Examples include F, DMSO, and N-methylpyrrolidone.
反応温度は通常、８０〜１５０℃である。The reaction temperature is usually 80 to 150°C.
生成する含フッ素アザクラウンエーテルは疎水性が高い
ので、親水性の高い製造原料であるモノアザクラウンエ
ーテルから水洗によって容易に分離精製することができ
る。Since the produced fluorine-containing azacrown ether is highly hydrophobic, it can be easily separated and purified from monoazacrown ether, which is a highly hydrophilic raw material, by washing with water.
以下、本発明を実施例によって説明する。Hereinafter, the present invention will be explained by examples.
実施例ｌ
モノアザ−１５−クラウン−５ ３．ｌＯｇ（１４
． １ ｍａ＋ｏｌ）， ２−ベルフルオロヘキシルエ
チルトシレート７．３ ３９（１ ４．１ｍｍｏｌ）、
Ｎａ２ＣＯ３ ３．０ ０９（２ Ｂ．２ｍｍｏｌ）
およびジオキサン３５ｕＱを反応容器内に入れ、４８時
間還流下で反応をおこなった。反応混合物にベンゼン１
５０ｄを加えた後、水洗によって未反応のモノアザーｌ
５−クラウン＝５を除去し、得られたベンゼン溶液をＭ
ｇＳＯ，を用いる乾燥処理に付し、ベンゼンを除去した
残渣をクーゲルロール蒸留に付すことによってＮ一（２
−ベルフルオロヘキシルエチル）モノアザ−１５−クラ
ウン−５（化合物ｌ）を淡褐色の液体（１１５〜１２０
℃／ ０ ．０ ６ｍｍＨｇ）として４．６３９得た（
収率５８％）。化合物（１）の物性を表−１に示す。Example 1 Monoaza-15-crown-5 3. lOg(14
．． 1 ma+ol), 2-perfluorohexylethyl tosylate 7.3 39 (1 4.1 mmol),
Na2CO3 3.0 09 (2 B.2 mmol)
and 35 uQ of dioxane were placed in a reaction vessel, and the reaction was carried out under reflux for 48 hours. 1 benzene in the reaction mixture
After adding 50d, unreacted monoazal was removed by washing with water.
5-crown=5 was removed and the resulting benzene solution was M
After drying with gSO, and removing benzene, the residue was subjected to Kugelrohr distillation to obtain N-(2
-perfluorohexylethyl) monoaza-15-crown-5 (compound l) as a light brown liquid (115-120
°C/0. 0 6mmHg) and 4.639 was obtained (
yield 58%). The physical properties of compound (1) are shown in Table-1.
実施例２
モノアザ−１５−クラウン−５の代りにモノアヂ−１８
−クラウン−６を使用する以外は、実施例ｌの手順に準
拠して、Ｎ−（２−ベルフルオロヘキシルエチル）モノ
アザ−１８−クラウン−６（化合物２）を淡褐色液体（
１２０〜１２５゜Ｏ／０．０３ｍｍＨｇ）として５．１
２ｇを得た（収率６０％）。生成物の物性を表一１に示
す。Example 2 Monoaji-18 instead of Monoaza-15-crown-5
N-(2-berfluorohexylethyl)monoaza-18-crown-6 (Compound 2) was prepared from a light brown liquid (
120-125°O/0.03mmHg) 5.1
2g was obtained (yield 60%). The physical properties of the product are shown in Table 1.
（以下、余白）
表−１
本発明による含フッ素アザクラウンエーテルは、従来の
フッ素不含アザクラウンエーテル類に比べて、疎水性が
非常に高く、分子間力が小さいだけでなく、アルカリ金
属イオン等の陽イオンとの錆体の安定性の点でも全く遜
色がないので、この種の陽イオンの選択的液膜輸送にお
いてイオノホアとして有効に利用することができ、特に
、水への溶解性は０．１％以下であって、輸送能低下の
一因である担体の液膜からの漏れが非常に少ないので、
低濃度の場合に十分な疎水性が要求される含浸型液膜輸
送の場合に好適である。(The following is a blank space) Table 1 The fluorine-containing azacrown ether according to the present invention not only has extremely high hydrophobicity and small intermolecular force, but also has alkali metal ions compared to conventional fluorine-free azacrown ethers. Since the stability of the rust body is comparable to that of other cations, it can be effectively used as an ionophore in the selective liquid membrane transport of this type of cation. It is less than 0.1%, and leakage from the liquid film of the carrier, which is one of the causes of decreased transport performance, is extremely small.
It is suitable for impregnated liquid membrane transport where sufficient hydrophobicity is required at low concentrations.
また、この種の疎水性の高い含フッ素アザクラウンエー
テルは、親水性の高い製造原料（モノアザクラウンエー
テル）から水洗によって容易に分離精製できるので合成
上も有利である。Furthermore, this type of highly hydrophobic fluorine-containing azacrown ether can be easily separated and purified from a highly hydrophilic production raw material (monoazacrown ether) by washing with water, and is therefore advantageous in terms of synthesis.
Claims (1)
の数を示し、ｎは０、１または２の数を示す） で表わされる含フッ素アザクラウンエーテル。[Claims] 1. General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, l represents a number from 1 to 12, and m represents 1, 2 or 3.
, n is a number of 0, 1 or 2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5819089A JP2700158B2 (en) | 1989-03-10 | 1989-03-10 | Fluorine-containing aza crown ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5819089A JP2700158B2 (en) | 1989-03-10 | 1989-03-10 | Fluorine-containing aza crown ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02237982A true JPH02237982A (en) | 1990-09-20 |
| JP2700158B2 JP2700158B2 (en) | 1998-01-19 |
Family
ID=13077104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5819089A Expired - Fee Related JP2700158B2 (en) | 1989-03-10 | 1989-03-10 | Fluorine-containing aza crown ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2700158B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100372559B1 (en) * | 2000-08-14 | 2003-02-17 | 한국전력공사 | Novel chromogenic calix[4]arene azacrown ether derivatives selectively adsorbing potassium ions |
| WO2008076491A2 (en) * | 2006-09-21 | 2008-06-26 | Medtronic, Inc. | Sensor for implantable medical device |
-
1989
- 1989-03-10 JP JP5819089A patent/JP2700158B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100372559B1 (en) * | 2000-08-14 | 2003-02-17 | 한국전력공사 | Novel chromogenic calix[4]arene azacrown ether derivatives selectively adsorbing potassium ions |
| WO2008076491A2 (en) * | 2006-09-21 | 2008-06-26 | Medtronic, Inc. | Sensor for implantable medical device |
| WO2008076491A3 (en) * | 2006-09-21 | 2008-12-31 | Medtronic Inc | Sensor for implantable medical device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2700158B2 (en) | 1998-01-19 |
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