JPH0369350B2 - - Google Patents
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- Publication number
- JPH0369350B2 JPH0369350B2 JP60213183A JP21318385A JPH0369350B2 JP H0369350 B2 JPH0369350 B2 JP H0369350B2 JP 60213183 A JP60213183 A JP 60213183A JP 21318385 A JP21318385 A JP 21318385A JP H0369350 B2 JPH0369350 B2 JP H0369350B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- crown
- metal ion
- carbon atoms
- formula
- 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
- 229910021645 metal ion Inorganic materials 0.000 claims description 25
- 150000003987 14-crown-4 derivatives Chemical class 0.000 claims description 15
- 238000000605 extraction Methods 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 102000003939 Membrane transport proteins Human genes 0.000 claims description 7
- 108090000301 Membrane transport proteins Proteins 0.000 claims description 7
- 230000009061 membrane transport Effects 0.000 claims description 7
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 24
- -1 N,N-dimethylsulfamoyl group Chemical group 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000002633 crown compound Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229940126062 Compound A Drugs 0.000 description 6
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical group C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000012280 lithium aluminium hydride Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- PVDDBYSFGBWICV-UHFFFAOYSA-N 1,4,8,11-tetraoxacyclotetradecane Chemical compound C1COCCOCCCOCCOC1 PVDDBYSFGBWICV-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 150000003983 crown ethers Chemical group 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- WAUNFWSVXRPCDQ-UHFFFAOYSA-N 1-(bromomethyl)-2-methoxybenzene Chemical compound COC1=CC=CC=C1CBr WAUNFWSVXRPCDQ-UHFFFAOYSA-N 0.000 description 1
- JEQDLQXVZAUQIT-UHFFFAOYSA-N 2-[(2-hydroxyphenyl)diazenyl]-3-phenylphenol Chemical group Oc1ccccc1N=Nc1c(O)cccc1-c1ccccc1 JEQDLQXVZAUQIT-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- YLQHWZKNTNFEPW-UHFFFAOYSA-N COC1=C(CC(CCO)O)C=CC=C1 Chemical compound COC1=C(CC(CCO)O)C=CC=C1 YLQHWZKNTNFEPW-UHFFFAOYSA-N 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000009056 active transport Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005048 flame photometry Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004366 reverse phase liquid chromatography Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Description
〔産業上の利用分野〕
この発明は新規な14−クラウン−４誘導体、こ
れを有効成分として含む金属イオン抽出比色試
薬、および金属イオン液膜輸送剤に関するもので
ある。
〔従来の技術〕
従来よりクラウンエーテル環を有する化合物は
アルカリ金属イオン、アルカリ土類金属イオンそ
の他のカチオン類と錯体を形成するため、これら
イオンの抽出剤として溶媒抽出試薬、相関移動触
媒、カラム充填剤、カチオンの液膜輸送剤、イオ
ン選択性電極などの分野での応用が試みられてい
る。
さらに最近ではこれらクラウン化合物に発色団
を有する非解離型および解離型クラウン化合物が
溶媒抽出比色試薬として種々合成されている。非
解離型クラウン化合物を溶媒抽出試薬として用い
る場合、対アニオンとしてピクリン酸のような有
機相に抽出され易いものが必要であり、さらにク
ラウン化合物の錯体に可視〜紫外部に吸収帯がな
い場合には、さらに炎光光度法などの従来法によ
つて金属イオンを定量しなければならない欠点が
ある。しかし、発色団を有する解離型クラウン化
合物については水層のPHを調節することのみによ
り可視−紫外吸収スペクトルを測定すれば、容易
に金属イオンを定量することができる利点を有し
ている。
このような利点を利用し溶媒抽出比色試薬とし
てナトリウムイオン、カリウムイオン等について
優れた抽出選択性を示し、発色団を有する解離型
クラウン化合物が種々知られている。例えば
Anal.Chem.Acta.139、219（1982）、J.Am.Chem.
Soc.92、386（1970）ではナトリウム、カリウムイ
オンについて優れた選択性を持ち、発色団を有す
る解離型クラウン化合物が報告されており、また
Chem.Lett.1853（1982）、Chem.Lett.1305（1981）
では、リチウム選択性抽出比色試薬として、Ｎ−
（４−メチルアンベリフエロン−８−メチレン）−
モノアザ−15−クラウン５、Ｎ−（２−ヒドロキ
シ−５−ニトロベンジル）−アザ−18−クラウン
６などが記載されている。
〔発明が解決しようとする問題点〕
しかしながら、前述のような公知の金属イオン
選択抽出性を有する発色団を持つ解離型クラウン
化合物ではナトリウム、カリウムイオンについて
は選択性があるものの、リチウムイオンの選択性
は低いものが多く、また従来のリチウム抽出比色
試薬として報告されているクラウン環に窒素原子
を含む化合物では、水が存在すると退色したり、
リチウムに対する選択性が充分でないなどの問題
点があつた。
〔問題点を解決するための手段〕
本発明は上記問題点を解決するためのもので、
新規かつ有用な14−クラウン−４誘導体、金属イ
オン特にリチウムイオンに対して高い選択性を有
する金属イオン抽出比色試薬および金属イオン液
膜輸送剤を提供することを目的としている。
本発明は下記の３発明を含む。
(1) 下記一般式で示される14−クラウン−４誘
導体。
（式中、R1は炭素数１〜20のアルキル基を示
し、R2は
または
の中から選ばれる基を示し、Ｘはニトロ基、
Ｎ，Ｎ−ジメチルスルフアモイル基およびハロ
ゲン基から選ばれる電子吸引性基を示し、ｌは
１または２を示し、ｍ、ｎはそれぞれ３以下の
整数を示す。）
(2) 前記一般式で示される14−クラウン−４誘
導体を含む金属イオン抽出比色試薬。
(3) 前記一般式で示される14−クラウン−４誘
導体を含む金属イオン液膜輸送剤。
第１発明の化合物は前記一般式で示される14
−クラウン−４誘導体で、アルキル基とともに、
アゾ結合を有するフエノールまたはナフトール基
を導入したものである。一般式において、R1
で示される基としては、水素原子、メチル基、エ
チル基、プロピル基、ブチル基、ペンチル基、ヘ
キシル基、ヘプチル基、オクチル基、ノニル基、
デシル基、ドデシル基、テトラデシル基、ヘキサ
デシル基、オクタデシル基、ノナデシル基等があ
げられる。これらの基の中でもR1の基としては
炭素数６〜16のアルキル基が特に金属イオン選択
性が高く好ましいものである。
R2は芳香族環に水酸基およびジアゾ基を有す
るフエノールまたはナフトール基で、発色団を形
成する。Ｘで示される電子吸引性基としては、ニ
トロ基、Ｎ，Ｎ−ジメチルスルフアモイル基また
はハロゲン基などがあげられる。
本発明の化合物は一般式におけるR1、R2の
組合せによる多くの化合物がある。その代表的な
14−クラウン−４誘導体としては、例えば、６−
オクチル−６−〔2′−ヒドロキシ−5′−（フエニル
アゾ）ベンジル〕−１，４，８，11−テトラオキ
サシクロテトラデカン、６−デシル−６−〔2′−
ヒドロキシ−3′−（ｐ−クロルフエニルアゾ）ナ
フチルメチル）−１，４，８，11−テトラオキサ
シクロテトラデカン、６−ドデシル−６−〔2′−
ヒドロキシ−5′−（ｐ−Ｎ，Ｎ−ジメチルスルフ
アモイルフエニルアゾ）ベンジル〕−１，４，８，
11−テトラオキサシクロテトラデカン、６−ドデ
シル−６−〔2′−ヒドロキシ−5′−（ｍ，ｐ−ジニ
トロフエニルアゾ）ベンジル〕−１，４，８，11
−テトラオキサシクロテトラデカン、６−ドデシ
ル−６−〔2′−ヒドロキシ−5′−（フエニルアゾ）
ベンジル〕−１，４，８，11−テトラオキサシク
ロテトラデカン、６−ドデシル−６−〔1′−ヒド
ロキシ−7′−ニトロ−4′−（ｐ，−Ｎ，Ｎ−ジメチ
ルスルフアモイルフエニルアゾ）ナフチルメチ
ル〕−１，４，８，11−テトラオキサシクロテト
ラデカン、６−ドデシル−６−〔2′−ヒドロキシ
−3′−（ｐ−クロルフエニルアゾ）ベンジル〕−
１，４，８，11−テトラオキサシクロテトラデカ
ン、６−ドデシル−６−〔2′，3′−ジヒドロキシ
−5′−（ｐ−ニトロフエニルアゾ）ベンジル〕−
１，４，８，11−テトラオキサシクロテトラデカ
ン、６−ヘキサデシル−６−〔2′−ヒドロキシ−
5′−（ｐ−ニトロフエニルアゾ）ベンジル〕−１，
４，８，11−テトラオキサシクロテトラデカン等
があげられる。
上記14−クラウン−４誘導体の製造方法として
は種々の方法があるが、例えば、芳香族環中の水
酸基をアルコキシド化したR3−CH2BrとR1CH
（CO2Et）2から塩基触媒により
[Industrial Application Field] This invention relates to a novel 14-crown-4 derivative, a metal ion extraction colorimetric reagent containing the same as an active ingredient, and a metal ion liquid membrane transport agent. [Prior art] Conventionally, compounds having a crown ether ring form complexes with alkali metal ions, alkaline earth metal ions, and other cations, so solvent extraction reagents, phase transfer catalysts, and column packing have been used as extractants for these ions. Applications are being attempted in fields such as agents, cation liquid membrane transport agents, and ion-selective electrodes. Furthermore, recently, various non-dissociated and dissociated crown compounds having a chromophore have been synthesized as solvent extraction colorimetric reagents. When using a non-dissociated crown compound as a solvent extraction reagent, a counter anion such as picric acid that is easily extracted into the organic phase is required, and if the crown compound complex does not have an absorption band in the visible to ultraviolet region, The method also has the disadvantage that metal ions must be quantified by conventional methods such as flame photometry. However, dissociated crown compounds having a chromophore have the advantage that metal ions can be easily quantified by measuring visible-ultraviolet absorption spectra only by adjusting the pH of the aqueous layer. Taking advantage of these advantages, various dissociative crown compounds are known that exhibit excellent extraction selectivity for sodium ions, potassium ions, etc. as solvent extraction colorimetric reagents and have chromophores. for example
Anal.Chem.Acta.139, 219 (1982), J.Am.Chem.
Soc.92, 386 (1970) reported a dissociated crown compound with excellent selectivity for sodium and potassium ions and a chromophore.
Chem.Lett.1853 (1982), Chem.Lett.1305 (1981)
Now, as a lithium-selective extraction colorimetric reagent, N-
(4-methylambelliferone-8-methylene)-
Monoaza-15-crown 5, N-(2-hydroxy-5-nitrobenzyl)-aza-18-crown 6, and the like are described. [Problems to be Solved by the Invention] However, although the known dissociated crown compound having a chromophore with metal ion selective extraction property as described above has selectivity for sodium and potassium ions, it has a high selectivity for lithium ions. In addition, compounds containing a nitrogen atom in the crown ring, which have been reported as conventional lithium extraction colorimetric reagents, fade in the presence of water.
There were problems such as insufficient selectivity for lithium. [Means for solving the problems] The present invention is intended to solve the above problems,
The object of the present invention is to provide a new and useful 14-crown-4 derivative, a metal ion extraction colorimetric reagent and a metal ion liquid membrane transport agent having high selectivity for metal ions, particularly lithium ions. The present invention includes the following three inventions. (1) A 14-crown-4 derivative represented by the general formula below. (In the formula, R 1 represents an alkyl group having 1 to 20 carbon atoms, and R 2 is or Indicates a group selected from, X is a nitro group,
It represents an electron-withdrawing group selected from an N,N-dimethylsulfamoyl group and a halogen group, l represents 1 or 2, and m and n each represent an integer of 3 or less. ) (2) A metal ion extraction colorimetric reagent containing a 14-crown-4 derivative represented by the above general formula. (3) A metal ion liquid membrane transport agent containing a 14-crown-4 derivative represented by the above general formula. The compound of the first invention is represented by the general formula 14
-crown-4 derivative, together with an alkyl group,
A phenol or naphthol group having an azo bond is introduced. In the general formula, R 1
Examples of groups represented by include hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Examples include decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, and nonadecyl group. Among these groups, an alkyl group having 6 to 16 carbon atoms is particularly preferable as the group for R 1 because it has high metal ion selectivity. R 2 is a phenol or naphthol group having a hydroxyl group and a diazo group in the aromatic ring, and forms a chromophore. Examples of the electron-withdrawing group represented by X include a nitro group, an N,N-dimethylsulfamoyl group, and a halogen group. The compounds of the present invention include many compounds with combinations of R 1 and R 2 in the general formula. Its representative
As the 14-crown-4 derivative, for example, 6-
Octyl-6-[2'-hydroxy-5'-(phenylazo)benzyl]-1,4,8,11-tetraoxacyclotetradecane, 6-decyl-6-[2'-
Hydroxy-3'-(p-chlorophenylazo)naphthylmethyl)-1,4,8,11-tetraoxacyclotetradecane, 6-dodecyl-6-[2'-
Hydroxy-5'-(p-N,N-dimethylsulfamoylphenylazo)benzyl]-1,4,8,
11-Tetraoxacyclotetradecane, 6-dodecyl-6-[2'-hydroxy-5'-(m,p-dinitrophenylazo)benzyl]-1,4,8,11
-tetraoxacyclotetradecane, 6-dodecyl-6-[2'-hydroxy-5'-(phenylazo)
benzyl]-1,4,8,11-tetraoxacyclotetradecane, 6-dodecyl-6-[1'-hydroxy-7'-nitro-4'-(p, -N,N-dimethylsulfamoylphenyl azo)naphthylmethyl]-1,4,8,11-tetraoxacyclotetradecane, 6-dodecyl-6-[2'-hydroxy-3'-(p-chlorophenylazo)benzyl]-
1,4,8,11-Tetraoxacyclotetradecane, 6-dodecyl-6-[2',3'-dihydroxy-5'-(p-nitrophenylazo)benzyl]-
1,4,8,11-tetraoxacyclotetradecane, 6-hexadecyl-6-[2'-hydroxy-
5′-(p-nitrophenylazo)benzyl]-1,
Examples include 4,8,11-tetraoxacyclotetradecane. There are various methods for producing the above-mentioned 14-crown-4 derivatives. For example, R 3 -CH 2 Br and R 1 CH in which the hydroxyl group in the aromatic ring is alkoxidized.
(CO 2 Et) 2 by base catalyst
【式】
を合成し、さらに還元剤により
Synthesize [Formula] and further use a reducing agent to
本発明の第１発明の14−クラウン−４誘導体は
新規かつ有用である。
また第２発明の金属イオン抽出比色試薬は電子
吸引性基を有するフエニルアゾ基を置換基とする
フエノールまたはナフトール基を持つ解離型クラ
ウンエーテルである14−クラウン−４誘導体を用
いているため、pKaが小さくて対アニオンの影響
を受けず、アルカリ金属、アルカリ土類金属イオ
ンと容易に錯体を形成し、呈色性を示す。特にリ
チウムイオンに対して高い選択性を有し、他の金
属イオンに比してイオン抽出能が著しく高く、リ
チウムイオンと安定な錯体を形成し、リチウム選
択性抽出比色試薬として優れている。
また第３発明の金属イオン液膜輸送剤は多孔質
の高分子体等に含浸させて膜化し、金属イオンの
能動輸送材料として用いることができ、金属イオ
ン、特にリチウムの選択的輸送が可能である。
〔実施例〕
以下、実施例および比較例を挙げてさらに具体
的に本発明を説明する。
実施例 １
フエニルアゾフエノール基を有する14−クラウ
ン−４誘導体の合成
(a) ２−ドデシル−２−（2′−メトキシベンジル）
マロン酸ジエチルエステルの合成
塩化カルシウム管、冷却管および撹拌機を付
した１の３ツ口フラスコ中にドライエタノー
ル300mlおよび金属ナトリウム3.92ｇを加えて
溶解し、60℃に加熱撹拌しながら２−ドデシル
マロン酸ジエチルエステル46.7ｇを加え１時間
加熱還流する。その後２−メトキシベンジルブ
ロマイド34.3ｇを滴下し、20時間加熱還流す
る。反応終了後、エタノールを除去し、水200
mlを加え残渣を溶かし、クロロホルムで抽出す
る。クロロホルム層を水洗し、硫酸マグネシウ
ムで脱水後、クロロホルムを留去して減圧蒸留
し、２−ドデシル−２−（2′−メトキシベンジ
ル）マロン酸ジエチルエステルを収率88.0％で
得た。
(b) ２−ドデシル−２−（2′−メトキシベンジル）
−１，３−プロパンジオールの合成
冷却管および撹拌機を付した500mlの３ツ口
フラスコにヘプタン100mlおよび水素化アルミ
ニウムリチウム2.5ｇを入れて撹拌し、前記(a)
で合成された２−ドデシル−２−（2′−メトキ
シベンジル）マロン酸ジエチルエステル20ｇを
100mlのヘプタン溶液にしたものを系内に滴下
した。さらに室温にて12時間撹拌した後メタノ
ール30mlを加えて過剰の水素化アルミニウムリ
チウムを分解し、ヘプタンおよびメタノールを
除去し、残渣を10％硫酸で溶かしてクロロホル
ムで抽出した。クロロホルム層を10％炭酸ナト
リウム水溶液で洗浄後硫酸マグネシウムで脱水
してクロロホルムを留去し、得られた２−ドデ
シル−２−（2′−メトキシベンジル）−１，３−
プロパンジオールを石油エーテルにより再結晶
して精製した（収率89.2％）。
(c) ６−ドデシル−６−（2′−メトキシベンジル）
−１，４，８，11−テトラオキサシクロテトラ
デカンの合成
塩化カルシウム管および冷却管を付した１
の３ツ口フラスコにドライジオキサン500mlを
入れ、さらに(b)で得られた２−ドデシル−２−
（2′−メトキシベンジル）−１，３−プロパンジ
オール3.64ｇと水素化ナトリウム２ｇを加え、
30分間加熱還流した。その後、過塩素酸リチウ
ムをテンプレートとして２ｇ加えた後、３，７
−ジオキサノナン−１，９−ジオールジトシレ
ート5.04ｇをドライジオキサン70mlに溶解した
ものを滴下し、さらに24時間加熱還流した。さ
らに水を加え過剰の水素化ナトリウムを分解
し、水層を塩酸で酸性にした後クロロホルムで
抽出した。
クロロホルム層を水洗し、クロロホルムを留
去して残渣に石油エーテルを加え未反応の原料
をろ別し、ろ液の石油エーテルを留去し、シリ
カゲルカラムにより不純物を除き、メタノール
により分離精製して収率32.5％で６−ドデシル
−６−（2′−メトキシベンジル）−１，４，８，
11−テトラオキサシクロテトラデカンを得た。
(d) ６−ドデシル−６−（2′−ヒドロキシベンジ
ル）−１，４，８，11−テトラオキサシクロテ
トラデカン（化合物Ａ）の合成
冷却管を付した300mlの３ツ口フラスコ中に
６−ドデシル−６−（2′−メトキシベンジル）−
１，４，８，11−テトラオキサシクロテトラデ
カン100mgをヘプタン70mlに溶かし、さらに水
素化アルミニウムリチウム0.5ｇを添加し15時
間加熱還流させた。反応終了後クロロホルムで
抽出し、クロロホルムを留去した後ODSカラ
ムで分離精製し、収率32.5％で６−ドデシル−
６−（2′−ヒドロキシベンジル）−１，４，８，
11−テトラオキサシクロテトラデカン（化合物
Ａ）を得た。その構造式および分析値を下記に
示す。
マススペクトル（M+＝478）
元素分析 Ｃ Ｈ Ｏ
計算値 72.76 10.53 16.71
分析値 72.46 10.60 −
H1−NMR
δ＝0.88（3H、−（CH2）11−CH3 ）
1.00〜1.50（22H、−（ＣH2 ）11−）
1.56〜1.80（2H、−OCH2 CH2 CH2O−）
2.36（2H、φ−CH2−）
3.20〜3.45（4H、Ｃ−CH2O−）
3.48〜3.70（12H、−CH2 ＯCH2 −）
6.18〜7.10（4H、
The 14-crown-4 derivative of the first aspect of the present invention is novel and useful. Furthermore, since the metal ion extraction colorimetric reagent of the second invention uses a 14-crown-4 derivative, which is a dissociated crown ether having a phenol or naphthol group, which has a phenylazo group having an electron-withdrawing group as a substituent, the pKa It is small and unaffected by counter anions, easily forms complexes with alkali metals and alkaline earth metal ions, and exhibits coloring properties. In particular, it has high selectivity for lithium ions, has significantly higher ion extraction ability than other metal ions, forms stable complexes with lithium ions, and is excellent as a lithium-selective extraction colorimetric reagent. Furthermore, the metal ion liquid membrane transport agent of the third invention can be impregnated into a porous polymer or the like to form a film and used as an active transport material for metal ions, and can selectively transport metal ions, especially lithium. be. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Example 1 Synthesis of 14-crown-4 derivative having phenylazophenol group (a) 2-dodecyl-2-(2'-methoxybenzyl)
Synthesis of malonic acid diethyl ester Add 300 ml of dry ethanol and 3.92 g of sodium metal to a three-necked flask equipped with a calcium chloride tube, a cooling tube, and a stirrer and dissolve the 2-dodecyl ester while stirring at 60°C. Add 46.7 g of malonic acid diethyl ester and heat under reflux for 1 hour. Thereafter, 34.3 g of 2-methoxybenzyl bromide was added dropwise, and the mixture was heated under reflux for 20 hours. After the reaction is complete, remove the ethanol and add 200% water.
ml to dissolve the residue and extract with chloroform. The chloroform layer was washed with water, dried over magnesium sulfate, and then chloroform was distilled off and distilled under reduced pressure to obtain diethyl 2-dodecyl-2-(2'-methoxybenzyl)malonate in a yield of 88.0%. (b) 2-dodecyl-2-(2'-methoxybenzyl)
-Synthesis of 1,3-propanediol 100 ml of heptane and 2.5 g of lithium aluminum hydride were placed in a 500 ml three-necked flask equipped with a condenser and a stirrer and stirred.
20g of 2-dodecyl-2-(2'-methoxybenzyl)malonic acid diethyl ester synthesized in
A 100 ml heptane solution was dropped into the system. After further stirring at room temperature for 12 hours, 30 ml of methanol was added to decompose excess lithium aluminum hydride, heptane and methanol were removed, and the residue was dissolved in 10% sulfuric acid and extracted with chloroform. The chloroform layer was washed with a 10% aqueous sodium carbonate solution, then dehydrated with magnesium sulfate, and the chloroform was distilled off to give 2-dodecyl-2-(2'-methoxybenzyl)-1,3-
Propanediol was purified by recrystallization with petroleum ether (yield 89.2%). (c) 6-dodecyl-6-(2'-methoxybenzyl)
-Synthesis of 1,4,8,11-tetraoxacyclotetradecane 1 with calcium chloride tube and cooling tube
Add 500 ml of dry dioxane to a three-necked flask, and add 2-dodecyl-2- obtained in (b).
Add 3.64 g of (2'-methoxybenzyl)-1,3-propanediol and 2 g of sodium hydride,
The mixture was heated to reflux for 30 minutes. Then, after adding 2g of lithium perchlorate as a template, 3,7
A solution of 5.04 g of -dioxanonan-1,9-diol ditosylate dissolved in 70 ml of dry dioxane was added dropwise, and the mixture was further heated under reflux for 24 hours. Further water was added to decompose excess sodium hydride, and the aqueous layer was made acidic with hydrochloric acid and then extracted with chloroform. The chloroform layer was washed with water, the chloroform was distilled off, petroleum ether was added to the residue, unreacted raw materials were filtered off, the petroleum ether in the filtrate was distilled off, impurities were removed using a silica gel column, and the mixture was separated and purified using methanol. 6-dodecyl-6-(2'-methoxybenzyl)-1,4,8, with a yield of 32.5%.
11-tetraoxacyclotetradecane was obtained. (d) Synthesis of 6-dodecyl-6-(2'-hydroxybenzyl)-1,4,8,11-tetraoxacyclotetradecane (compound A) 6-dodecyl-6-(2'-hydroxybenzyl)-1,4,8,11-tetraoxacyclotetradecane (compound A) Dodecyl-6-(2'-methoxybenzyl)-
100 mg of 1,4,8,11-tetraoxacyclotetradecane was dissolved in 70 ml of heptane, 0.5 g of lithium aluminum hydride was added, and the mixture was heated under reflux for 15 hours. After the reaction was completed, it was extracted with chloroform, and after distilling off the chloroform, it was separated and purified using an ODS column, and 6-dodecyl-
6-(2'-hydroxybenzyl)-1,4,8,
11-tetraoxacyclotetradecane (compound A) was obtained. Its structural formula and analytical values are shown below. Mass spectrum (M + = 478) Elemental analysis C H O Calculated value 72.76 10.53 16.71 Analysis value 72.46 10.60 − H 1 − NMR δ = 0.88 (3H, − (CH 2 ) 11 − CH 3 ) 1.00 to 1.50 (22H, − (C H 2 ) 11 −) 1.56 to 1.80 (2H, −OCH 2 CH 2 CH 2 O−) 2.36 (2H, φ−CH 2 −) 3.20 to 3.45 (4H, C−CH 2 O−) 3.48 to 3.70 (12H, - CH 2 O CH 2 -) 6.18~7.10 (4H,
【式】）
7.88（1H，ＯＨ）
(e) ６−ドデシル−６−〔2′−ヒドロキシ−5′−
（フエニルアゾ）ベンジル〕−１，４，８，11−
テトラオキサシクロテトラデカン（化合物１〜
３）の合成
ｐ−ニトロアニリン、ｐ−Ｎ，N′−ジメチ
メスルフアモイルアニリンおよびｐ−クロルア
ニリンの各アニリン誘導体を用いて前記化合物
Ａをアゾ化する。まず、各アニリン誘導体４ｍ
molを水／THF（１：１）30mlに溶解させ、濃
塩酸を加えて氷冷し、この系にNaNO24ｍmol
を加え約20分間撹拌する。これに、前記14−ク
ラウン−４のフエノール誘導体（化合物Ａ）
0.9ｍmolおよびNaHCO31ｇを水／THF（１：
１）30mlに溶解させた氷冷溶液を加え、氷冷下
に２時間撹拌する。反応終了後THFを留去し、
10％K2CO3水溶液およびCHCl3を加え抽出を行
う。CHCl3層を0.2％酢酸で洗い、CHCl3を留
去すると粗生成物が得られる。その粗生成物を
分取用逆相液体クロマトグラフイーにより分離
精製し油状の生成物（化合物１〜３）を得る。
これらの構造式および分析値を下記に示す。
化合物 １
マススペクトル（M+）＝627）
元素分析 Ｃ Ｈ Ｎ Ｏ
計算値 66.99 8.45 6.70 17.86
分析値 67.3 8.12 6.72 −
H1−NMR
δ＝0.87（3H、−（CH2）11−CH3 ）
1.10〜1.40（22H、−（ＣH2 ）11−）
1.58〜1.72（2H、−OCH2 CH2 CH20−）
2.48（2H、[Formula]) 7.88(1H, OH ) (e) 6-dodecyl-6-[2'-hydroxy-5'-
(phenylazo)benzyl]-1,4,8,11-
Tetraoxacyclotetradecane (compounds 1-
Synthesis of 3) Compound A is azotized using each aniline derivative of p-nitroaniline, p-N,N'-dimethimesulfamoylaniline, and p-chloroaniline. First, each aniline derivative 4m
Dissolve mol in 30 ml of water/THF (1:1), add concentrated hydrochloric acid, cool on ice, and add 4 mmol of NaNO 2 to this system.
Add and stir for about 20 minutes. In addition, the 14-crown-4 phenol derivative (compound A)
0.9 mmol and 1 g of NaHCO 3 in water/THF (1:
1) Add the ice-cooled solution dissolved in 30 ml and stir under ice-cooling for 2 hours. After the reaction is complete, THF is distilled off,
Perform extraction by adding 10% K2CO3 aqueous solution and CHCl3 . The CHCl 3 layer is washed with 0.2% acetic acid and the CHCl 3 is distilled off to obtain the crude product. The crude product is separated and purified by preparative reverse phase liquid chromatography to obtain oily products (compounds 1 to 3).
Their structural formulas and analytical values are shown below. Compound 1 Mass spectrum (M + ) = 627) Elemental analysis C H N O Calculated value 66.99 8.45 6.70 17.86 Analysis value 67.3 8.12 6.72 − H 1 −NMR δ = 0.87 (3H, −(CH 2 ) 11 − CH 3 ) 1.10 to 1.40 (22H, −(CH 2 ) 11 −) 1.58 to 1.72 (2H, −OCH 2 CH 2 CH 2 0−) 2.48 (2H,
【式】） 3.20〜3.71（16H、−ＯCH2 −） 6.87〜8.01（8H、[Formula]) 3.20~3.71 (16H, -O CH 2 -) 6.87~8.01 (8H,
【式】） 8.51（1H、−０Ｈ） 化合物 ２ マススペクトル（M+＝689） 元素分析 Ｃ Ｈ Ｎ Ｏ Ｓ 計算値 64.41 8.62 6.09 16.23 4.65 分析値 64.78 8.72 5.79 − 4.29 H1−NMR δ＝0.87（3H、−（CH2）11−CH3 ） 1.10〜1.40（22H、−（ＣH2 ）11−） 1.57〜1.75（2H、−OCH2 CH2 CH2O−） 2.51（2H、[Formula]) 8.51 (1H, -0H ) Compound 2 Mass spectrum (M + = 689) Elemental analysis C H N O S Calculated value 64.41 8.62 6.09 16.23 4.65 Analyzed value 64.78 8.72 5.79 − 4.29 H 1 −NMR δ=0.87 (3H, −(CH 2 ) 11 − CH 3 ) 1.10 〜1.40(22H, −(CH 2 ) 11 −) 1.57〜1.75(2H, −OCH 2 CH 2 CH 2 O−) 2.51(2H,
【式】） 2.68（6H、−Ｎ（CH3 ）2） 3.15〜3.80、（16H、−ＯCH2 −） 6.84〜7.96（7H，[Formula]) 2.68 (6H, -N( CH 3 ) 2 ) 3.15 to 3.80, (16H, -O CH 2 -) 6.84 to 7.96 (7H,
【式】 8.68（1H、−ＯＨ） 化合物 ３ マススペクトル（M+＝616.5） 元素分析 Ｃ Ｈ Ｎ Ｏ Cl 計算値 68.13 8.60 4.54 12.98 5.75 分析値 68.32 8.55 4.22 H1−NMR δ＝0.87（3H、−（CH2）11−CH 3） 1.10〜1.40（22H、−（CH2 ）11−） 1.55〜1.73（2H、−OCH2 CH2 CH2O−） 2.48（2H、[Formula] 8.68(1H, -OH ) Compound 3 Mass spectrum (M + = 616.5) Elemental analysis C H N O Cl Calculated value 68.13 8.60 4.54 12.98 5.75 Analyzed value 68.32 8.55 4.22 H 1 −NMR δ = 0.87 (3H, −(CH 2 ) 11 − CH 3 ) 1.10 to 1.40 (22H, −( CH 2 ) 11 −) 1.55 to 1.73 (2H, −OCH 2 CH 2 CH 2 O−) 2.48 (2H,
【式】） 3.13〜3.80（16H、−ＯCH2 ） 6.85、7.95（7H、[Formula]) 3.13~3.80 (16H, -O CH 2 ) 6.85, 7.95 (7H,
【式】）
8.65（1H、−ＯＨ）
実施例 ２
上記合成された化合物について、各種金属イオ
ンに対する呈色性を測定した。測定方法は7.5×
10-5Mのクラウン化合物二塩化エチレン溶液４ml
に、LiClO4、NaClO4等の過塩素酸金属塩1Mと
水酸化テトラメチルアンモニウム2.19×10-1Mを
含む水溶液を加え、共栓付セル中で振とう後、可
視−紫外吸収スペクトルを測定することにより測
定した。結果を第１図ないし第３図に示す。各図
が示すように他の金属イオンに比してLi+イオン
に対する抽出、選択性に優れていることが理解さ
れる。
実施例 ３
ポリプロピレン（直径3.3cm）の多孔質膜（細
孔の大きさ0.04×0.4μｍ）を化合物３のｏ−ニト
ロフエノールエーテル溶液に浸漬し、その後過剰
の溶液をろ紙にて除去し、化合物３の液膜を形成
した。この液膜を断面積１cm2で区切られた２相を
有する装置に設置し、一方はPH13でLiOHまたは
NaOHを２×10-2の水溶液20mlを、他方はPH１で
金属水酸化物２×10-2Mおよび塩酸２×10-1Mの
水溶液20mlを入れ、25℃で金属イオンの濃度変化
を調べた。結果を第４図に示す。第４図におい
て、〔M+〕0は初期金属イオン濃度、〔M+〕ｔはｔ
時間後の金属イオン濃度である。第４図よりLi+
に対し優れた選択性を有し、高選択性能動輸送膜
として有効であることが理解される。[Formula]) 8.65 (1H, -OH ) Example 2 The coloring properties of the above-synthesized compounds with respect to various metal ions were measured. The measurement method is 7.5×
4 ml of 10 -5 M crown compound ethylene dichloride solution
An aqueous solution containing 1 M of metal perchlorate such as LiClO 4 or NaClO 4 and 2.19×10 -1 M of tetramethylammonium hydroxide was added to the cell, and after shaking in a cell with a stopper, the visible-ultraviolet absorption spectrum was measured. It was measured by The results are shown in Figures 1 to 3. As shown in each figure, it is understood that extraction and selectivity for Li + ions are superior to other metal ions. Example 3 A porous membrane (pore size 0.04 x 0.4 μm) of polypropylene (diameter 3.3 cm) was immersed in an o-nitrophenol ether solution of compound 3, and then the excess solution was removed with a filter paper, and the compound A liquid film of No. 3 was formed. This liquid film was placed in a device having two phases separated by a cross-sectional area of 1 cm2 , one of which was PH13 and LiOH or
Add 20 ml of an aqueous solution of 2 x 10 -2 NaOH and 20 ml of an aqueous solution of 2 x 10 -2 M metal hydroxide and 2 x 10 -1 M hydrochloric acid at pH 1 to the other, and examine changes in the concentration of metal ions at 25°C. Ta. The results are shown in Figure 4. In Figure 4, [M + ] 0 is the initial metal ion concentration, [M + ] t is t
Metal ion concentration after time. From Figure 4, Li +
It is understood that the membrane has excellent selectivity for the membrane and is effective as a highly selective dynamic transport membrane.
第１図ないし第３図はそれぞれ実施例２の結果
を示すグラフ、第４図は実施例３の結果を示すグ
ラフである。
1 to 3 are graphs showing the results of Example 2, and FIG. 4 is a graph showing the results of Example 3.
Claims (1)
導体。 （式中、R1は炭素数１〜20のアルキル基を示し、
R2は または の中から選ばれる基を示し、Ｘはニトロ基、Ｎ，
Ｎ−ジメチルスルフアモイル基およびハロゲン基
から選ばれる電子吸引性基を示し、ｌは１または
２を示し、ｍ、ｎはそれぞれ３以下の整数を示
す。） ２ R1が炭素数６〜16のアルキル基である特許
請求の範囲第１項記載の14−クラウン−４誘導
体。 ３ 下記一般式で示される14−クラウン−４誘
導体を含む金属イオン抽出比色試薬。 （式中、R1は炭素数１〜20のアルキル基を示し、
R2は または の中から選ばれる基を示し、Ｘはニトロ基、Ｎ，
Ｎ−ジメチルスルフアモイル基およびハロゲン基
から選ばれる電子吸引性基を示し、ｌは１または
２を示し、ｍ、ｎはそれぞれ３以下の整数を示
す。） ４ R1が炭素数６〜16のアルキル基である特許
請求の範囲第３項記載の金属イオン抽出比色試
薬。 ５ 下記一般式で示される14−クラウン−４誘
導体を含む金属イオン液膜輸送剤。 （式中、R1は炭素数１〜20のアルキル基を示し、
R2は または の中から選ばれる基を示し、Ｘはニトロ基、Ｎ，
Ｎ−ジメチルスルフアモイル基およびハロゲン基
から選ばれる電子吸引性基を示し、ｌは１または
２を示し、ｍ、ｎはそれぞれ３以下の整数を示
す。） ６ R1が炭素数６〜16のアルキル基である特許
請求の範囲第５項記載の金属イオン液膜輸送剤。[Claims] 1. A 14-crown-4 derivative represented by the following general formula. (In the formula, R 1 represents an alkyl group having 1 to 20 carbon atoms,
R 2 is or Indicates a group selected from, X is a nitro group, N,
It represents an electron-withdrawing group selected from an N-dimethylsulfamoyl group and a halogen group, l represents 1 or 2, and m and n each represent an integer of 3 or less. 2) The 14-crown-4 derivative according to claim 1, wherein R1 is an alkyl group having 6 to 16 carbon atoms. 3. A metal ion extraction colorimetric reagent containing a 14-crown-4 derivative represented by the following general formula. (In the formula, R 1 represents an alkyl group having 1 to 20 carbon atoms,
R 2 is or Indicates a group selected from, X is a nitro group, N,
It represents an electron-withdrawing group selected from an N-dimethylsulfamoyl group and a halogen group, l represents 1 or 2, and m and n each represent an integer of 3 or less. ) 4 The metal ion extraction colorimetric reagent according to claim 3, wherein R 1 is an alkyl group having 6 to 16 carbon atoms. 5 A metal ion liquid membrane transport agent containing a 14-crown-4 derivative represented by the following general formula. (In the formula, R 1 represents an alkyl group having 1 to 20 carbon atoms,
R 2 is or Indicates a group selected from, X is a nitro group, N,
It represents an electron-withdrawing group selected from an N-dimethylsulfamoyl group and a halogen group, l represents 1 or 2, and m and n each represent an integer of 3 or less. ) The metal ion liquid membrane transport agent according to claim 5, wherein 6 R 1 is an alkyl group having 6 to 16 carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60213183A JPS6272683A (en) | 1985-09-26 | 1985-09-26 | 14-crown-4 derivative, extraction colorimetric reagent for metal ion and liquid membrane transporting reagent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60213183A JPS6272683A (en) | 1985-09-26 | 1985-09-26 | 14-crown-4 derivative, extraction colorimetric reagent for metal ion and liquid membrane transporting reagent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6272683A JPS6272683A (en) | 1987-04-03 |
| JPH0369350B2 true JPH0369350B2 (en) | 1991-10-31 |
Family
ID=16634917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60213183A Granted JPS6272683A (en) | 1985-09-26 | 1985-09-26 | 14-crown-4 derivative, extraction colorimetric reagent for metal ion and liquid membrane transporting reagent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6272683A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5188802A (en) * | 1991-05-28 | 1993-02-23 | Eastman Kodak Company | Dry analytical element for lithium assay |
| US5245021A (en) * | 1991-05-28 | 1993-09-14 | Eastman Kodak Company | 14-crown-4-ether derivatives |
| CN105536707B (en) * | 2015-12-17 | 2018-03-20 | 中国科学院青海盐湖研究所 | A kind of material for separating lithium isotope and its preparation method and application |
| WO2019046616A1 (en) | 2017-08-30 | 2019-03-07 | Cornell University | Fluorinated crown ethers and methods and systems for extraction of lithium using same |
-
1985
- 1985-09-26 JP JP60213183A patent/JPS6272683A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6272683A (en) | 1987-04-03 |
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