JPH0369350B2 - - Google Patents
Info
- 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
Landscapes
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Extraction Or Liquid Replacement (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Description
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[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-
5â²-(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
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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 â H 1 â NMR ÎŽ = 0.88 (3H, â (CH 2 ) 11 â CH 3 ) 1.00 to 1.50 (22H, â (C H 2 ) 11 â) 1.56 to 1.80 (2H, âOCH 2 CH 2 CH 2 Oâ) 2.36 (2H, ÏâCH 2 â) 3.20 to 3.45 (4H, CâCH 2 Oâ) 3.48 to 3.70 (12H, - CH 2 O CH 2 -) 6.18~7.10 (4H,
ãåŒãïŒ
7.88ïŒ1HïŒïŒ¯ïŒšïŒ
(e) ïŒâããã·ã«âïŒâã2â²âããããã·â5â²â
ïŒããšãã«ã¢ãŸïŒãã³ãžã«ãâïŒïŒïŒïŒïŒïŒ11â
ããã©ãªããµã·ã¯ãããã©ãã«ã³ïŒååç©ïŒã
ïŒïŒã®åæ
ïœâãããã¢ããªã³ãïœâïŒNâ²âãžã¡ã
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ããªã³ã®åã¢ããªã³èªå°äœãçšããŠåèšååç©
ãã¢ãŸåããããŸããåã¢ããªã³èªå°äœïŒïœ
molãæ°ŽïŒTHFïŒïŒïŒïŒïŒ30mlã«æº¶è§£ãããæ¿
å¡©é
žãå ããŠæ°·å·ãããã®ç³»ã«NaNO24ïœmol
ãå ãçŽ20åéæ¹æãããããã«ãåèš14âã¯
ã©ãŠã³âïŒã®ããšããŒã«èªå°äœïŒååç©ïŒ¡ïŒ
0.9ïœmolããã³NaHCO31ïœãæ°ŽïŒTHFïŒïŒïŒ
ïŒïŒ30mlã«æº¶è§£ãããæ°·å·æº¶æ¶²ãå ããæ°·å·äž
ã«ïŒæéæ¹æãããåå¿çµäºåŸTHFãçå»ãã
10ïŒ
K2CO3氎溶液ããã³CHCl3ãå ãæœåºãè¡
ããCHCl3å±€ã0.2ïŒ
é
¢é
žã§æŽããCHCl3ãç
å»ãããšç²çæç©ãåŸãããããã®ç²çæç©ã
ååçšéçžæ¶²äœã¯ãããã°ã©ãã€ãŒã«ããåé¢
粟補ãæ²¹ç¶ã®çæç©ïŒååç©ïŒãïŒïŒãåŸãã
ãããã®æ§é åŒããã³åæå€ãäžèšã«ç€ºãã
ååç© ïŒ
ãã¹ã¹ãã¯ãã«ïŒM+ïŒïŒ627ïŒ
å
çŽ åæ    
èšç®å€ 66.99 8.45 6.70 17.86
åæå€ 67.3 8.12 6.72 â
H1âNMR
ÎŽïŒ0.87ïŒ3HãâïŒCH2ïŒ11âCH3 ïŒ
1.10ã1.40ïŒ22HãâïŒïŒ£H2 ïŒ11âïŒ
1.58ã1.72ïŒ2HãâOCH2 CH2 CH20âïŒ
2.48ïŒ2Hã[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 â H 1 âNMR ÎŽ = 0.87 (3H, â(CH 2 ) 11 â CH 3 ) 1.10 to 1.40 (22H, â(CH 2 ) 11 â) 1.58 to 1.72 (2H, âOCH 2 CH 2 CH 2 0â) 2.48 (2H,
ãåŒãïŒ 3.20ã3.71ïŒ16HãâCH2 âïŒ 6.87ã8.01ïŒ8Hã[Formula]) 3.20~3.71 (16H, -O CH 2 -) 6.87~8.01 (8H,
ãåŒãïŒ 8.51ïŒ1HãâïŒïŒšïŒ ååç© ïŒ ãã¹ã¹ãã¯ãã«ïŒM+ïŒ689ïŒ å çŽ åæ      èšç®å€ 64.41 8.62 6.09 16.23 4.65 åæå€ 64.78 8.72 5.79 â 4.29 H1âNMR ÎŽïŒ0.87ïŒ3HãâïŒCH2ïŒ11âCH3 ïŒ 1.10ã1.40ïŒ22HãâïŒïŒ£H2 ïŒ11âïŒ 1.57ã1.75ïŒ2HãâOCH2 CH2 CH2OâïŒ 2.51ïŒ2Hã[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 â 4.29 H 1 âNMR ÎŽ=0.87 (3H, â(CH 2 ) 11 â CH 3 ) 1.10 ã1.40(22H, â(CH 2 ) 11 â) 1.57ã1.75(2H, âOCH 2 CH 2 CH 2 Oâ) 2.51(2H,
ãåŒãïŒ 2.68ïŒ6HãâïŒCH3 ïŒ2ïŒ 3.15ã3.80ãïŒ16HãâCH2 âïŒ 6.84ã7.96ïŒ7HïŒ[Formula]) 2.68 (6H, -N( CH 3 ) 2 ) 3.15 to 3.80, (16H, -O CH 2 -) 6.84 to 7.96 (7H,
ãåŒã 8.68ïŒ1HãâïŒ¯ïŒšïŒ ååç© ïŒ ãã¹ã¹ãã¯ãã«ïŒM+ïŒ616.5ïŒ å çŽ åæ     Cl èšç®å€ 68.13 8.60 4.54 12.98 5.75 åæå€ 68.32 8.55 4.22 H1âNMR ÎŽïŒ0.87ïŒ3HãâïŒCH2ïŒ11âCH 3ïŒ 1.10ã1.40ïŒ22HãâïŒCH2 ïŒ11âïŒ 1.55ã1.73ïŒ2HãâOCH2 CH2 CH2OâïŒ 2.48ïŒ2Hã[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 âNMR ÎŽ = 0.87 (3H, â(CH 2 ) 11 â CH 3 ) 1.10 to 1.40 (22H, â( CH 2 ) 11 â) 1.55 to 1.73 (2H, âOCH 2 CH 2 CH 2 Oâ) 2.48 (2H,
ãåŒãïŒ 3.13ã3.80ïŒ16HãâCH2 ïŒ 6.85ã7.95ïŒ7Hã[Formula]) 3.13~3.80 (16H, -O CH 2 ) 6.85, 7.95 (7H,
ãåŒãïŒ
8.65ïŒ1HãâïŒ
å®æœäŸ ïŒ
äžèšåæãããååç©ã«ã€ããŠãåçš®éå±ã€ãª
ã³ã«å¯Ÿããåè²æ§ã枬å®ããã枬å®æ¹æ³ã¯7.5Ã
10-5Mã®ã¯ã©ãŠã³ååç©äºå¡©åãšãã¬ã³æº¶æ¶²ïŒml
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ãšããŠæå¹ã§ããããšãç解ãããã[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 7.5Ã
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 2.19Ã10 -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 ÎŒm) 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ïŒå³ãªãã第ïŒå³ã¯ããããå®æœäŸïŒã®çµæ
ã瀺ãã°ã©ãã第ïŒå³ã¯å®æœäŸïŒã®çµæã瀺ãã°
ã©ãã§ããã
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)
å°äœã ïŒåŒäžãR1ã¯ççŽ æ°ïŒã20ã®ã¢ã«ãã«åºã瀺ãã
R2㯠ãŸã㯠ã®äžããéžã°ããåºã瀺ããã¯ãããåºãïŒ
âãžã¡ãã«ã¹ã«ãã¢ã¢ã€ã«åºããã³ããã²ã³åº
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ïŒã瀺ããïœãïœã¯ããããïŒä»¥äžã®æŽæ°ã瀺
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è«æ±ã®ç¯å²ç¬¬ïŒé èšèŒã®14âã¯ã©ãŠã³âïŒèªå°
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å°äœãå«ãéå±ã€ãªã³æœåºæ¯è²è©Šè¬ã ïŒåŒäžãR1ã¯ççŽ æ°ïŒã20ã®ã¢ã«ãã«åºã瀺ãã
R2㯠ãŸã㯠ã®äžããéžã°ããåºã瀺ããã¯ãããåºãïŒ
âãžã¡ãã«ã¹ã«ãã¢ã¢ã€ã«åºããã³ããã²ã³åº
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è«æ±ã®ç¯å²ç¬¬ïŒé èšèŒã®éå±ã€ãªã³æœåºæ¯è²è©Š
è¬ã ïŒ äžèšäžè¬åŒã§ç€ºããã14âã¯ã©ãŠã³âïŒèª
å°äœãå«ãéå±ã€ãªã³æ¶²è茞éå€ã ïŒåŒäžãR1ã¯ççŽ æ°ïŒã20ã®ã¢ã«ãã«åºã瀺ãã
R2㯠ãŸã㯠ã®äžããéžã°ããåºã瀺ããã¯ãããåºãïŒ
âãžã¡ãã«ã¹ã«ãã¢ã¢ã€ã«åºããã³ããã²ã³åº
ããéžã°ããé»ååžåŒæ§åºã瀺ããïœã¯ïŒãŸãã¯
ïŒã瀺ããïœãïœã¯ããããïŒä»¥äžã®æŽæ°ã瀺
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è«æ±ã®ç¯å²ç¬¬ïŒé èšèŒã®éå±ã€ãªã³æ¶²è茞éå€ã[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 | äžåœç§åŠé¢éæµ·çæ¹ç 究æ | 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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