JPH0124824B2 - - Google Patents
Info
- Publication number
- JPH0124824B2 JPH0124824B2 JP60210179A JP21017985A JPH0124824B2 JP H0124824 B2 JPH0124824 B2 JP H0124824B2 JP 60210179 A JP60210179 A JP 60210179A JP 21017985 A JP21017985 A JP 21017985A JP H0124824 B2 JPH0124824 B2 JP H0124824B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- general formula
- cyclic polyether
- compound
- mmol
- 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
Links
- 150000001875 compounds Chemical class 0.000 claims description 72
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 34
- 125000004122 cyclic group Chemical group 0.000 claims description 34
- 229920000570 polyether Polymers 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 22
- 125000005843 halogen group Chemical group 0.000 claims description 11
- 229920005992 thermoplastic resin Polymers 0.000 claims description 9
- 125000001188 haloalkyl group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 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 15
- 229910052708 sodium Inorganic materials 0.000 description 15
- 239000011734 sodium Substances 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 125000003118 aryl group Chemical group 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000000862 absorption spectrum Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000004949 mass spectrometry Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 229910001415 sodium ion Inorganic materials 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000004800 polyvinyl chloride Substances 0.000 description 7
- 229920000915 polyvinyl chloride Polymers 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000004292 cyclic ethers Chemical class 0.000 description 6
- -1 pentachloroethyl group Chemical group 0.000 description 6
- 239000001103 potassium chloride Substances 0.000 description 6
- 235000011164 potassium chloride Nutrition 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001639 boron compounds Chemical class 0.000 description 3
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 2
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 2
- OQEBBZSWEGYTPG-UHFFFAOYSA-N 3-aminobutanoic acid Chemical compound CC(N)CC(O)=O OQEBBZSWEGYTPG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010421 standard material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HLQZCRVEEQKNMS-UHFFFAOYSA-N 1-(chloromethyl)-4-phenylbenzene Chemical group C1=CC(CCl)=CC=C1C1=CC=CC=C1 HLQZCRVEEQKNMS-UHFFFAOYSA-N 0.000 description 1
- NBQXYAJLUDQSNV-UHFFFAOYSA-N 1-[(4-methylphenyl)methyl]-5-oxopyrrolidine-3-carboxylic acid Chemical compound C1=CC(C)=CC=C1CN1C(=O)CC(C(O)=O)C1 NBQXYAJLUDQSNV-UHFFFAOYSA-N 0.000 description 1
- 150000003984 12-crown-4 derivatives Chemical class 0.000 description 1
- LHJGJYXLEPZJPM-UHFFFAOYSA-N 2,4,5-trichlorophenol Chemical compound OC1=CC(Cl)=C(Cl)C=C1Cl LHJGJYXLEPZJPM-UHFFFAOYSA-N 0.000 description 1
- GXMWLJKTGBZMBH-UHFFFAOYSA-N 2-(2,4-dichlorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=C(Cl)C=C1Cl GXMWLJKTGBZMBH-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229930191564 Monensin Natural products 0.000 description 1
- GAOZTHIDHYLHMS-UHFFFAOYSA-N Monensin A Natural products O1C(CC)(C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CCC1C(O1)(C)CCC21CC(O)C(C)C(C(C)C(OC)C(C)C(O)=O)O2 GAOZTHIDHYLHMS-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 229940000635 beta-alanine Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229960005358 monensin Drugs 0.000 description 1
- GAOZTHIDHYLHMS-KEOBGNEYSA-N monensin A Chemical compound C([C@@](O1)(C)[C@H]2CC[C@@](O2)(CC)[C@H]2[C@H](C[C@@H](O2)[C@@H]2[C@H](C[C@@H](C)[C@](O)(CO)O2)C)C)C[C@@]21C[C@H](O)[C@@H](C)[C@@H]([C@@H](C)[C@@H](OC)[C@H](C)C(O)=O)O2 GAOZTHIDHYLHMS-KEOBGNEYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- ONVGIJBNBDUBCM-UHFFFAOYSA-N silver;silver Chemical compound [Ag].[Ag+] ONVGIJBNBDUBCM-UHFFFAOYSA-N 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Landscapes
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
ãç£æ¥äžã®å©çšåéã
æ¬çºæã¯ãæ°èŠãªç°ç¶ããªãšãŒãã«ååç©åã³
ç±å¯å¡æ§æš¹èãšãããªããç¹ã«ãããªãŠã ã€ãªã³
éžææ§ã瀺ãç°ç¶ããªãšãŒãã«çµæç©ã«é¢ããã
ãåŸæ¥æè¡åã³çºæã解決ããããšããåé¡ç¹ã
åŸæ¥ããããªãŠã ã€ãªã³ã®åé¢ã»åæçã®ç«å Ž
ããããããªãŠã ã€ãªã³ã«éžæçã«åŒ·ãé
äœãã
ææ©ååç©ãèŠæ±ãããŠããããã®ä»£è¡šçãªç 究
ã«ãã¢ãã³ã·ã³çã®æçç©è³ªããããããããã¯
ä»ã®ã¢ã«ã«ãªéå±ãç¹ã«ã«ãªãŠã ã«å¯Ÿããéžææ§
ãäœããããå®çšã«äŸããããã®ã§ã¯ãªãã€ãã
ä»äžã€ã®ç 究äŸã«äžèšæ§é ã®åŠã12âã¯ã©ãŠã³â
ïŒã®éªšæ Œãæããç°ç¶ããªãšãŒãã«ãç¥ãããŠã
ãã
ïŒä»¥äž12âã¯ã©ãŠã³âïŒã®éªšæ Œã¯
[Industrial Application Field] The present invention relates to a cyclic polyether composition comprising a novel cyclic polyether compound and a thermoplastic resin, and particularly exhibiting sodium ion selectivity. [Prior Art and Problems to be Solved by the Invention] Conventionally, from the standpoint of separation and analysis of sodium ions, organic compounds that selectively and strongly coordinate with sodium ions have been required. Typical research has focused on antibiotics such as monensin, but these have low selectivity toward other alkali metals, especially potassium, and have therefore not been of practical use.
Another example of research is the 12-crown structure shown below.
A cyclic polyether having a skeleton of 4 is known. (Below, the skeleton of 12-Crown-4 is
æ¬çºæè
ãã¯ããããªãŠã ã€ãªã³ã«å¯ŸããŠåªã
ãéžæé
äœèœåãæãããã€çæ°Žçã§ããç°ç¶ã
ãªãšãŒãã«ãåæãã¹ãçš®ã
æ€èšãéããŠããã
ãã®çµæãåèšæ§é åŒ(A)åã³(B)ã«æ¯ããŠãã¯ãã
ã«ãããªãŠã éžæçé
äœèœåã«åªããç°ç¶ããªãš
ãŒãã«ååç©ãåŸãããšã«æåããæ¢ã«ææ¡ãã
ïŒç¹é¡æ60â172287å·ïŒã
æ¬çºæè
ãã¯ãããã«ç 究ãéããçµæãäžèš
äžè¬åŒïŒïŒã§ç€ºãããç°ç¶ããªãšãŒãã«ååç©
ãšç±å¯å¡æ§æš¹èãšãããªãçµæç©ããç¹ã«ãããª
ãŠã é»æ¥µãšããŠæçšãªææã§ããããšãèŠãåº
ããæ¬çºæãå®æããã«è³ã€ãã
ããªãã¡ãæ¬çºæã¯ã
(1) (A) ç±å¯å¡æ§æš¹è100éééš
åã³
(B) äžè¬åŒãã
ãäœããã¯ã
The present inventors have conducted various studies in order to synthesize a cyclic polyether that has excellent selective coordination ability for sodium ions and is hydrophobic.
As a result, we succeeded in obtaining a cyclic polyether compound with far superior sodium-selective coordination ability compared to the structural formulas (A) and (B), which we have already proposed (Japanese Patent Application No. 172-287-1987). issue). As a result of further research, the present inventors discovered that a composition consisting of a cyclic polyether compound represented by the above general formula () and a thermoplastic resin is a particularly useful material as a sodium electrode. The invention was completed. That is, the present invention comprises (1) (A) 100 parts by weight of thermoplastic resin and (B) general formula [] [However, A is
ãåŒããformulaã
ãåŒããformulaã
ãåŒããformulaã
ãåŒããformulaã
ãåŒããformulaã
ãåŒããformulaã
ãåŒããformulaã
ãåŒããformulaã
ãåŒããformulaã
ãåŒããformulaã
ãåŒããformulaã
ãåŒããformulaã
å㯠or
ãåŒãïŒäœãã
ã¯ããã²ã³åååã¯ããã²ãã¢ã«ãã«åºã§ã
ããã¯æ°ŽçŽ åååã¯ã¢ã«ãã«åºã§ãããïœ
ã¯ïŒã20ã®æŽæ°ã§ãããïœã¯ïŒãïŒã®æŽæ°ã§
ãããïŒ
ã瀺ããã¯ïŒâCH2ïŒâlCH2ââCH2âïŒ
[Formula] (where, X is a halogen atom or a halogenoalkyl group, R is a hydrogen atom or an alkyl group, m
is an integer of 0 to 20, and n is an integer of 1 to 5. ), B represents (-CH 2 )- l CH 2 -O-CH 2 -,
ãåŒãâïŒâCH2ïŒâl+1
CH2ââCH2âïŒ
[Formula] âO(âCH 2 ) â l+1 CH 2 âOâCH 2 â,
ãåŒãåã¯[Formula] or
ãåŒã
ïŒäœããïœã¯ïŒãïŒã®æŽæ°ã§ãããïŒã§ç€º
ãããåºã瀺ããã
ã§è¡šããããç°ç¶ããªãšãŒãã«ååç©0.1ã40é
ééšããäž»ãšããŠãªãç°ç¶ããªãšãŒãã«çµæç©ã§
ããã
åèšäžè¬åŒããäžãã§ç€ºãããããã²ã³å
åãšããŠã¯ãããçŽ ãå¡©çŽ ãã·ãŠãŠçŽ ããšãŠçŽ ã®
åååã䜿çšãåŸãããŸããã§ç€ºãããããã²
ãã¢ã«ãã«åºãšããŠã¯ãäžèšã®ããã²ã³ååã«ã
ã€ãŠçœ®æãããã¢ã«ãã«åºãäœãå¶éãªãçšãåŸ
ããç¹ã«ãããªãããã¡ãã«åºããã³ã¿ããããš
ãã«åºãããªã¯ããã¡ãã«åºããã³ã¿ã¯ãããšã
ã«åºçã®ããŒããã²ã³åã¢ã«ãã«åºã奜ãŸããçš
ããããã
åèšäžè¬åŒããäžãã§ç€ºãããããã²ãã¢
ã«ãã«åºåã³ïŒ²ã§ç€ºãããã¢ã«ãã«åºã¯ããã®ç
çŽ æ°ã«éå®ãããªããã奜ãŸããã¯ççŽ æ°ïŒãïŒ
ã®ãã®ã䜿çšãããã
åèšäžè¬åŒããã§ç€ºãããç°ç¶ããªãšãŒãã«
ååç©ããããªãŠã éžææ§é»æ¥µã«äœ¿çšããå Žåã«
ã¯ããããªãŠã ã€ãªã³ã«å¯Ÿããéžææ§ãèæ°Žæ§
ã¯ãäžè¬åŒããäžã®ïŒ¡ã®çš®é¡ã«ãã€ãŠå¹Ÿå圱é¿
ãåããã
ãããªãŠã éžææ§ãèæ°Žæ§ãè¯å¥œã«ããããã«
ã¯ãäžè¬åŒããäžã®ïŒ¡ã¯æ¬¡ã®(1)åã¯(2)ã®ããã
ããæºè¶³ããããšã奜ãŸããã
(1) ïŒå以äžã®è³éŠæ žãæããããšã
(2) è³éŠæ žïŒåãæãã該è³éŠæ žã¯ïŒå以äžã®ã
ãã²ã³åååã¯ããã²ãã¢ã«ãã«åºã«ãã€ãŠçœ®
æãããŠããããšã
ããã«ã¯ãäžè¬åŒããäžã®ïŒ¡ã次ã®(3)ã(5)ã®
ãããããæºè¶³ããååç©ã§ããããšã奜ãŸã
ãã
(3) ïŒå以äžã®è³éŠæ žãæããããšã
(4) ïŒåã®è³éŠæ žãæãããã®ã®äžã§ã
[Formula] (However, l is an integer of 0 to 7.) ] This is a cyclic polyether composition mainly consisting of 0.1 to 40 parts by weight of a cyclic polyether compound represented by: In the general formula [], each of fluorine, chlorine, sulfur, and iodine atoms can be used as the halogen atom represented by X. Further, as the halogenoalkyl group represented by X, the alkyl groups substituted with the above-mentioned halogen atoms can be used without any restriction. In particular, perhalogenated alkyl groups such as trifluoromethyl group, pentafluoroethyl group, trichloromethyl group, and pentachloroethyl group are preferably used. In the general formula [], the halogenoalkyl group represented by X and the alkyl group represented by R are not limited in number of carbon atoms, but preferably have 1 to 4 carbon atoms.
are used. When the cyclic polyether compound represented by the above general formula [] is used in a sodium-selective electrode, the selectivity to sodium ions and water resistance are somewhat affected by the type of A in the general formula []. receive. In order to improve sodium selectivity and water resistance, A in the general formula [] preferably satisfies either (1) or (2) below. (1) Having two or more aromatic nuclei. (2) It has one aromatic nucleus, and the aromatic nucleus is substituted with three or more halogen atoms or halogenoalkyl groups. Furthermore, it is preferable that A in the general formula [] is a compound that satisfies any of the following (3) to (5). (3) Having three or more aromatic nuclei. (4) Among those with two aromatic nuclei,
ãåŒããformulaã
ã®ããããã§ããããšã
(5) è³éŠæ žïŒåãæãã該è³éŠæ žãïŒå以äžã®ã
ãã²ã³åååã¯ããã²ãã¢ã«ãã«åºã«ãã€ãŠçœ®
æãããŠããããšã
åèšäžè¬åŒããã«æŒããã«ã€ããŠã¯ãïœã®
æ°ã倧ããå Žåãåæåã³ç²Ÿè£œã®å°é£ããå¢å€§ã
ããããããªãŠã éžææ§ãè¥å¹²äœäžããå Žåãã
ãã®ã§ã奜ãŸããã¯ïŒä»¥äžãæŽã«å¥œãŸããã¯ïŒä»¥
äžã®æŽæ°ã§ããããšãæãŸããã
æ¬çºæã®åèšäžè¬åŒããã§ç€ºãããç°ç¶ããª
ãšãŒãã«ååç©ã¯æ°èŠãªååç©ã§ãé垞次ã®ãã
ãªæž¬å®ã«ãã€ãŠè©²ååç©ã§ããããšã確èªã§ã
ãã
(1) èµ€å€åžåã¹ãã¯ãã«
12âã¯ã©ãŠã³âïŒã®æ§é ã«åºã¥ãåžåã1140ïŒ
1080ã1020cm-1ä»è¿ã«åŒ·ãçŸãããã
(2) 1Hâæ žç£æ°å
±é³Žã¹ãã¯ãã«
éæ°ŽçŽ åã¯ãããã«ã 溶åªäžã§ãããã©ã¡ãã«
ã·ã©ã³ãåºæºãšããŠæž¬å®ãããšã12âã¯ã©ãŠã³â
ïŒéªšæ Œäžã®âCH2ââã®ïŒšã«ç±æ¥ããããŒã¯ã
3.3ppmã4.2ppmä»è¿ã«ãåãè³éŠç°ã«æ°ŽçŽ åå
ãå«ãŸããå Žåãæ°ŽçŽ ååã®åžåããŒã¯ã
6.6ppmã8.2ppmã«è¡šããããããã®ããŒã¯ã®çž
察匷床æ¯ã¯ãåèšäžè¬åŒããããç®åºãããã
ãããã®åºã«çµåããæ°ŽçŽ ã®æ°ã®æ¯ãšäžèŽããã
(3) 質éåæ
質éåæã®äžææ³ãšããŠé»çè±é¢æ³ïŒä»¥äžFD
æ³ãšç¥ãïŒãçšããããšã«ãã€ãŠãæ¬çºæã®åèš
äžè¬åŒããã§ç€ºãããååç©ã®ååã€ãªã³ããŒ
ã¯ã芳枬ãããã
(4) å
çŽ åæ
åèšäžè¬åŒããããç®åºãããååç©ã®ç
çŽ ãæ°ŽçŽ ãçªçŽ ãããã²ã³ã®éã¯ãã®åæçµæã®
ããããã®å
çŽ éã«ã»ãŒäžèŽããã
åèšã®äžè¬åŒããã§ç€ºãããååç©ã®ä»£è¡šç
ãªæ§ç¶ã瀺ãã°ã次ã®éãã§ããã
(1) æ¬çºæã§çšããç°ç¶ããªãšãŒãã«ååç©ã¯äž
è¬ã«èžçäžå¯èœã§æ確ãªæ²žç¹ãåŸé£ãã
(2) æ¬çºæã§çšããç°ç¶ããªãšãŒãã«ååç©ã¯å®€
æž©äžã«æŒããŠé«ç²çš ã®æ¶²äœã§ããããåèšäžè¬
åŒããäžã®ïŒ¡ã«è³éŠæ žãïŒå以äžããããã¯
ïœã®æ°ãïŒä»¥äžã«ãªããšçœè²ããªããé»çœè²ã®
åºäœãšãªãå Žåãå€ããããã«âïŒïŒ®âãå«
ãŸããæã«ã¯æ©è²ã®åºäœããšãŠçŽ ãå«ãå Žåã«
ã¯ãè€è²ã垯ã³ãããã
åèšäžè¬åŒããã§ç€ºãããç°ç¶ããªãšãŒãã«
ååç©ã®æº¶è§£æ§ã¯ããåã³ïŒ¢ã®çš®é¡ã«ãã€ãŠè¥
å¹²çžç°ããããå¡©åã¡ãã¬ã³ãã¯ãããã«ã ãã
ã³ãŒã³ããã«ãšã³ãã¢ã»ãã³ãããã©ããããã©
ã³ããžãªããµã³ããžã¡ãã«ãã«ã ã¢ãããã¡ã¿ã
ãŒã«ããšã¿ããŒã«çã«ã¯å®€æž©ã§æº¶è§£ãããã®ãå€
ããæ°Žã«ã¯æ®ãã©æº¶è§£ããªãã
ããããåèšæ§ç¶ã«ã€ããŠã¯ã極ããŠå®¹æã«ç¢º
èªã§ããã®ã§ã䜿çšã«å
ç«ã¡ãäºã確èªããã°ã
ãã
æ¬çºæã§çšããåèšäžè¬åŒããã§ç€ºãããç°
ç¶ããªãšãŒãã«ååç©ã®è£œé æ¹æ³ã¯ãç¹ã«éå®ã
ãããã®ã§ã¯ãªããåŠäœãªãæ¹æ³ãæ¡çšããŠãã
ããå·¥æ¥çã«å¥œé©ãªæ¹æ³ãå
·äœçã«äŸç€ºããã°æ¬¡
ã®éãã§ããã
(i) åèšäžè¬åŒããã«æŒããŠããïŒâCH2ïŒâl
CH2ââCH2âïŒ Must be one of the following. (5) It has one aromatic nucleus, and the aromatic nucleus is substituted with four or more halogen atoms or halogenoalkyl groups. Regarding B in the above general formula [], if the number of l is large, the difficulty of synthesis and purification may increase or the sodium selectivity may decrease slightly, so it is preferably 4 or less, more preferably It is desirable that it be an integer of 3 or less. The cyclic polyether compound represented by the general formula [ ] of the present invention is a new compound, and can usually be identified as such by the following measurements. (1) Infrared absorption spectrum The absorption based on the structure of 12-crown-4 is 1140,
It appears strongly around 1080 to 1020 cm -1 . (2) 1 H-Nuclear Magnetic Resonance Spectrum When measured in deuterated chloroform solvent using tetramethylsilane as a standard, 12-crown-
The peak derived from H of -CH 2 -O- in the 4 skeletons is
The absorption peak of hydrogen atoms is around 3.3ppm to 4.2ppm, and when hydrogen atoms are included in the aromatic ring.
It appears at 6.6 ppm to 8.2 ppm, and the relative intensity ratio of these peaks matches the ratio of the number of hydrogens bonded to each group calculated from the above general formula []. (3) Mass spectrometry Field desorption method (hereinafter referred to as FD) is a method of mass spectrometry.
By using this method, the molecular ion peak of the compound represented by the general formula [] of the present invention can be observed. (4) Elemental analysis The amounts of carbon, hydrogen, nitrogen, and halogen in the compound calculated from the above general formula [] almost match the amounts of each element as determined by the analysis. Typical properties of the compound represented by the above general formula [] are as follows. (1) The cyclic polyether compound used in the present invention generally cannot be distilled and it is difficult to obtain a clear boiling point. (2) The cyclic polyether compound used in the present invention is a highly viscous liquid at room temperature, but if A in the general formula [] has 3 or more aromatic nuclei or n has 2 or more In this case, it often becomes a white or yellowish-white solid, and when it contains -N=N-, it becomes an orange solid, and when it contains iodine, it tends to be brownish. The solubility of the cyclic polyether compound represented by the general formula [] differs slightly depending on the types of A and B, but includes methylene chloride, chloroform, benzene, toluene, acetone, tetrahydrofuran, dioxane, dimethylformamide, Many of methanol, ethanol, etc. dissolve at room temperature. Almost insoluble in water. Since these properties can be confirmed very easily, they can be confirmed in advance before use. The method for producing the cyclic polyether compound represented by the general formula [] used in the present invention is not particularly limited, and any method may be employed. Specific examples of industrially suitable methods are as follows. (i) In the above general formula [], B is (-CH 2 ) -l
CH 2 âOâCH 2 â,
ãåŒã
âïŒâCH2ïŒâl+1CH2ââCH2âãåã¯
[Formula] âO(âCH 2 )â l+1 CH 2 âOâCH 2 â, or
ãåŒãã®å Žåã«ã¯ã
äžè¬åŒãã
ã§ç€ºãããååç©ïŒä»¥äžãããããã·ã¡ãã«â
12âã¯ã©ãŠã³âïŒãšãããïŒã«äžèšã®äžè¬åŒ
ããïŒããåã¯ããã®ããããäžçš®ã®åå
ç©ãåå¿ãããããšã«ãã€ãŠåŸãããšãã§ã
ãã
ïŒââCH2ïŒâkïŒâCH2ïŒâlCH2â ãã
ïŒäœããåã³ïœã¯äžè¬åŒãããšåæ§ã§ã
ããã¯ããã²ã³ååã§ãããïœã¯ïŒåã¯ïŒã§
ãããïŒ
ïŒäœããåã³ïœã¯äžè¬åŒãããšåæ§ã§ã
ããã¯ããã²ã³ååã瀺ããïœã¯ïŒåã¯ïŒã§
ãããïŒ
ïŒäœããåã³ïœã¯äžè¬åŒãããšåæ§ã§ã
ããïœã¯ïŒåã¯ïŒã§ãããïŒ
(ii) ãŸããåèšäžè¬åŒããã«æŒããŠãã
In the case of [formula], general formula [] The compound represented by (hereinafter referred to as hydroxymethyl-
12-crown-4) with any one of the following general formulas [], [], or []. A(-O- CH2 ) -k ( -CH2 ) -l CH2 -X [] (However, A and l are the same as the general formula [], X is a halogen atom, and k is 0 or 1.) (However, A and l are the same as in the general formula [], X represents a halogen atom, and k is 0 or 1.) (However, A and l are the same as in the general formula [], and k is 0 or 1.) (ii) Also, in the above general formula [], B is
ãåŒãã§ããå Ž
åã«ã¯ãäžè¬åŒãã
ïŒäœããïœã¯äžè¬åŒãããšåæ§ã§ãããïŒ
ã§ç€ºãããååç©ãäžè¬åŒãã
ïŒäœããã¯äžè¬åŒãããšåæ§ã§ããã
ã¯ããã²ã³ååã§ãããïŒ
ã§ç€ºãããé
žãã©ã€ããšåå¿ãããããšã«ãã€
ãŠåŸãããšãã§ããã
äžèšäžè¬åŒããã§ç€ºãããååç©ã¯ãåèš
äžè¬åŒããã§ç€ºãããããããã·ã¡ãã«â12
âã¯ã©ãŠã³âïŒãšÏâã¢ããã¢ã«ãã«ã«ã«ãã³
é
žãH2NâCH2ïŒâCH2ïŒâlCOOHããšãé
žè§Šåª
ã®ååšäžã«åå¿ãããããšã«ãã€ãŠåŸãããšã
ã§ããã
(iii) ããã«ãåèšäžè¬åŒããã«æŒããŠããïŒâ
CH2ïŒâlCH2ââCH2âïŒ
If [formula], general formula [] (However, l is the same as the general formula [].) The compound represented by the general formula [] (However, A is the same as the general formula [], and X
is a halogen atom. ) can be obtained by reacting with an acid halide shown in The compound represented by the above general formula [] is hydroxymethyl-12 represented by the above general formula []
It can be obtained by reacting -crown-4 and Ï-aminoalkylcarboxylic acid [ H2N - CH2 ( -CH2 ) -lCOOH ] in the presence of an acid catalyst. (iii) Furthermore, in the general formula [], B is (-
CH 2 ) â l CH 2 âOâCH 2 â,
ãåŒãâïŒâCH2ïŒâl+1CH2
ââCH2âåã¯
[Formula] âO(âCH 2 ) â l+1 CH 2 âOâCH 2 â or
æ¬çºæã®ç°ç¶ããªãšãŒãã«çµæç©ã¯ãåèšãã
ããã«ããããªãŠã ã€ãªã³ã«å¯Ÿããéžææ§ã極ã
ãŠè¯å¥œã§ããããããæ圢ããèç¶ç©ã¯ããããª
ãŠã é»æ¥µãæ§æããèç¶ç©ãšããŠçæ³çãªãã®ã§
ãããç¹ã«ãææ©ããŠçŽ ååç©ãå«ãç°ç¶ããªãš
ãŒãã«çµæç©ã¯ããããªãŠã ã€ãªã³ã«å¯Ÿããéžæ
åçåã³æ床ã«åªããŠããããŸããããããããª
ãŠã é»æ¥µãšããŠçšããå Žåã®èä¹
æ§ã«ãåªããŠã
ãããã®ä»æ¬çºæã®ç°ç¶ããªãšãŒãã«ååç©ãå«
æããçµæç©ã¯ããããªãŠã å¡©ã®éžæç茞éèœå
ãããã¯éžæçåžåèœåãæããŠããããããªãŠ
ã å¡©ã®é€å»ãæŽã«ã¯æ¿çž®çãžã®å¿çšãå¯èœã§ã
ãã
以äžã«æ¬çºæãæŽã«å
·äœçã«èª¬æããããã«è£œ
é äŸåã³å®æœäŸãæããããæ¬çºæã¯ãããã®è£œ
é äŸåã³å®æœäŸã«éå®ããããã®ã§ã¯ãªãã
å®æœäŸã«ãããŠãæ¬çºæã®çµæç©ãæ圢ããŠåŸ
ãèç¶ç©ãçšããé»æ¥µã®æ§èœã¯ã以äžã®è£
眮åã³
æ¹æ³ã«ããè©äŸ¡ããã
å®æœäŸïŒãïŒåã³å®æœäŸïŒãïŒã«ã€ããŠã¯ç¬¬ïŒ
ïŒå³ã«ç€ºããèãã«ããŒã«ãèç¶ç©ãè£
çãã第
ïŒïŒå³ã«ç€ºããè£
眮ãçšããŠé»æ¥µæ§èœãè©äŸ¡ã
ããå®æœäŸïŒã«ãããŠã¯ã第ïŒïŒå³ã«ç€ºããåŠã
ã®çœéç·è¡šé¢ã«èç¶ç©ã圢æãããã®ãé»æ¥µãš
ãã第ïŒïŒå³ã®ïŒã®é»æ¥µéšåã«çŽæ¥è£
çããããš
ã«ããé»æ¥µæ§èœãè©äŸ¡ããã
ã«ãªãŠã ã€ãªã³ã«å¯ŸãããããªãŠã ã€ãªã³ã®éž
æåçã®æ±ºå®ã¯ããã€ãªã³éžææ§é»æ¥µãïŒå
±ç«åº
çã1977ïŒç¬¬ïŒç« ïŒç¯ã«èšèŒãããæ··å溶液æ³ã«
ãã€ãŠæ±ãããå
·äœçã«ã¯å¡©åã«ãªãŠã ãšå¡©åã
ããªãŠã ãå«ã氎溶液ã«ãããŠãå¡©åãããªãŠã
ãäžå®æ¿åºŠïŒ10-4MïŒãšããå¡©åã«ãªãŠã ã®æ¿åºŠ
ãå€åãããŠèµ·é»åã枬å®ããããããŠãèµ·é»å
ãšå¡©åã«ãªãŠã æ¿åºŠã®é¢ä¿ããããããããã®å±
æ²ç¹ã«ãããå¡©åã«ãªãŠã æ¿åºŠãå¡©åãããªãŠã
ã®æ¿åºŠã§é€ããå€ããã€ãŠéžæåçãšããããã®
å€ã¯å€§ãªãã»ã©ãããªãŠã é»æ¥µãšããŠåªããŠã
ãã
ãŸããå¡©åãããªãŠã ã®ã¿ã10-1ã10-5Mã®æ¿
床ç¯å²ã§å«ã氎溶液ã®èµ·é»åã枬å®ããŠãèµ·é»å
ãšå¡©åãããªãŠã æ¿åºŠãšã®é¢ä¿ããåŸé
ãå¡©åã
ããªãŠã æ¿åºŠã10åå€åããã«ã€ããŠã®èµ·é»åã®
å€åéãšããŠmVïŒdecadeã®åäœã§æ±ããããã®
å€ã倧ãªãçšé»æ¥µã®æ床ãé«ãããšã瀺ãããŸ
ãããã¹ãŠã®æž¬å®ã¯25âã§è¡ã€ãã
補é äŸ ïŒ
å·åŽç®¡ãä»ããå
容ç©100mlã®ãã¹åãã©ã¹ã³
ã«ãïœâã¯ãã«ã¡ãã«ãããšãã«ãïŒããªã¢ã«å
ã³ããããã·ã¡ãã«â12âã¯ã©ãŠã³âïŒãïŒããª
ã¢ã«åã³æ°Žé
žåã«ãªãŠã ãïŒããªã¢ã«ãä»èŸŒã¿ã
ã¢ã»ãã³äžã§96æéå ç±ç°æµãããåå¿åŸå·åŽ
ããå¡©é
žã§äžåããåŸãçããå¡©ããå¥ãããŒã¿
ãªãŒãšããã¬ãŒã¿ã§æº¶åªãé€å»ãããåŸãããç
æç©ãé
¢é
žãšãã«ãå±é溶åªãšããŠãã·ãªã«ã²ã«
ïŒåååïŒã¯ã³ãŒã²ã«ïŒ£â200ïŒãå
å¡«ããã«ã©ã
ã§åé¢ããæãäžèšæ§é åŒã§ç€ºãããååç©0.78
ïœïŒåç42ïŒ
ïŒã
åŸãã
åŸããããã®ã«ã€ããŠä»¥äžã®åæãè¡ã€ãã
(1) èµ€å€åžåã¹ãã¯ãã«ïŒçµæã第ïŒå³ãšããŠæ·»
ä»ããïŒ
è³éŠç° 3000ã3100cm-1
ç°ç¶ãšãŒãã« 1020ã1160cm-1
(2) 1Hâæ žç£æ°å
±é³Žã¹ãã¯ãã«ïŒçµæã第ïŒå³
ãšããŠæ·»ä»ããïŒ
枬å®æº¶åªïŒéã¯ãããã«ã
æšæºç©è³ªïŒããã©ã¡ãã«ã·ã©ã³ïŒä»¥äžã®å®æœäŸ
ã«ãããŠãåŽå®æº¶åªåã³æšæºç©è³ªã¯æ¬
å®æœäŸãšåãã§ããã®ã§èšè¿°ã¯çç¥ã
ããïŒ
ç©åã«ãã€ãŠåŸãããæ°ŽçŽ éã®æ¯ã¯ç®çç©ã®ã
ãã«äžèŽããã
(3) 質éåæã¹ãã¯ãã«
FDæ³ ïœïŒïœ
ïŒ372 ïŒM+ïŒ
(4) å
çŽ åæ
As mentioned above, the cyclic polyether composition of the present invention has extremely good selectivity for sodium ions, and a film formed from the same is ideal as a film forming a sodium electrode. . In particular, a cyclic polyether composition containing an organic boron compound has excellent selectivity and sensitivity for sodium ions, and also has excellent durability when used as a sodium electrode. In addition, the composition containing the cyclic polyether compound of the present invention has the ability to selectively transport or selectively absorb sodium salts, and can be applied to the removal and even concentration of sodium salts. Production examples and examples are given below to further specifically explain the present invention, but the present invention is not limited to these production examples and examples. In Examples, the performance of an electrode using a film-like material obtained by molding the composition of the present invention was evaluated using the following apparatus and method. For Examples 1 to 4 and Examples 6 to 8, the second
A membrane material was attached to the membrane holder shown in Figure 2, and the electrode performance was evaluated using the apparatus shown in Figure 21. In Example 5, an electrode having a film-like material formed on the surface of a platinum wire as shown in FIG. 23 was used as an electrode, and the electrode performance was evaluated by directly attaching it to the electrode part 1 in FIG. 21. The selectivity of sodium ions over potassium ions was determined by the mixed solution method described in Chapter 2, Section 3 of "Ion Selective Electrodes" (Kyoritsu Shuppan, 1977). Specifically, in an aqueous solution containing potassium chloride and sodium chloride, the electromotive force was measured while keeping the concentration of sodium chloride constant (10 -4 M) and varying the concentration of potassium chloride. Then, the relationship between electromotive force and potassium chloride concentration was plotted, and the value obtained by dividing the potassium chloride concentration at the inflection point by the sodium chloride concentration was determined as the selection magnification. The higher this value, the better the sodium electrode. In addition, we measured the electromotive force of an aqueous solution containing only sodium chloride in the concentration range of 10 -1 to 10 -5 M, and from the relationship between the electromotive force and the sodium chloride concentration, we calculated the slope for a 10-fold change in the sodium chloride concentration. The amount of change in electromotive force was determined in mV/decade. The larger this value is, the higher the sensitivity of the electrode is. Furthermore, all measurements were performed at 25°C. Production Example 1 Into a 100 ml eggplant-shaped flask equipped with a cooling tube, 5 mmol of p-chloromethylbiphenyl, 5 mmol of hydroxymethyl-12-crown-4, and 5 mmol of potassium hydroxide were charged.
The mixture was heated to reflux in acetone for 96 hours. After the reaction was cooled and neutralized with hydrochloric acid, the resulting salt was filtered off, and the solvent was removed using a rotary evaporator. The obtained product was separated using a column packed with silica gel (trade name: Wakogel C-200) using ethyl acetate as a developing solvent, and a compound represented by the following structural formula 0.78
g (yield 42%) was obtained. The following analysis was performed on the obtained product. (1) Infrared absorption spectrum (results are attached as Figure 1) Aromatic ring 3000-3100cm -1 Cyclic ether 1020-1160cm -1 (2) 1 H-nuclear magnetic resonance spectrum (results are attached as Figure 2) ) Measurement solvent: Deuterated chloroform Standard material: Tetramethylsilane (In the following examples, the determination solvent and standard material are the same as in this example, so their description will be omitted.) The ratio of hydrogen amounts obtained by integration agreed with that of the target product. (3) Mass spectrometry spectrum FD method m/e=372 (M + ) (4) Elemental analysis
ãè¡šã
以äžã®æž¬å®çµæãããçæç©ãç®çç©ã§ããã
ãšã確èªãããã
補é äŸ ïŒã29
補é äŸïŒãšåæ§ã®æ¹æ³ã§ãÏâã¯ãã«åºãæã
ãååç©ãšããããã·â12âã¯ã©ãŠã³âïŒããäž
è¬åŒããã§ç€ºãããååç©ãåæãã第ïŒè¡šã«
瀺ããã
補é äŸïŒã29ã«ãã€ãŠåæãããååç©ã¯ã補
é äŸïŒãšåæ§ãªæ¹æ³ã«ãŠç®çååç©ã§ããããšã
確èªããããªããåèãŸã§ã«è£œé äŸïŒã®èµ€å€åžå
ã¹ãã¯ãã«åã³1Hâæ žç£æ°å
±é³Žã¹ãã¯ãã«ãã
ããã第ïŒå³ã第ïŒå³ãšããŠç€ºããã[Table] From the above measurement results, it was confirmed that the product was the desired product. Production Examples 2 to 29 Compounds represented by the general formula [ ] were synthesized from a compound having an Ï-chloro group and hydroxy-12-crown-4 in the same manner as in Production Example 1, and are shown in Table 1. The compounds synthesized in Production Examples 2 to 29 were confirmed to be target compounds in the same manner as Production Example 1. For reference, the infrared absorption spectrum and 1 H-nuclear magnetic resonance spectrum of Production Example 6 are shown in FIGS. 3 and 4, respectively.
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šã
補é äŸ 30
å·åŽç®¡ã«ä»ããå
容ç©100mlã®ãã¹åãã©ã¹ã³
ã«ãããããã·ã¡ãã«12âã¯ã©ãŠã³âïŒïŒïŒããª
ã¢ã«ãããªãšãã«ã¢ãã³ïŒïŒããªã¢ã«ã也ç¥ïŒ®ïŒ
âãžã¡ãã«ãã«ã ã¢ããïŒä»¥äžDMFãšç¥èšã
ãïŒ50mlãä»èŸŒã¿ã次ãã§ïœâã¢ãŸãã³ãŒã³ã«ã«
ãã³é
žã¯ãã©ã€ãïŒããªã¢ã«ãå ããã70âã§48
æéåå¿ãè¡ã€ãåŸãå·åŽããçããæ²æ®¿ããå¥
ããŠãããŒã¿ãªãŒãšããã¬ãŒã¿ã«ããDMFãç
å»ãããçæç©ãé
¢é
žãšãã«ãå±é溶åªãšããŠã
ã·ãªã«ã²ã«ïŒåååïŒã¯ã³ãŒã²ã«ïŒ£â200ïŒãå
å¡«ããã«ã©ã ã§åé¢ç²Ÿè£œããäžèšæ§é åŒã§ç€ºãã
ãååç©1.25ïœïŒåç60ïŒ
ïŒãåŸãã
以äžã«ãã®åæçµæãèšèŒããã
(1) èµ€å€åžåã¹ãã¯ãã«ïŒçµæã第ïŒå³ãšããŠæ·»
ä»ããïŒ
è³éŠç° 3000ã3100cm-1
ç°ç¶ãšãŒãã« 1020ã1160cm-1
ãšã¹ãã« 1720cm-1
(2) 1Hâæ žç£æ°å
±é³Žã¹ãã¯ãã«ïŒçµæã第ïŒå³
ãšããŠæ·»ä»ããïŒ
(3) 質éåæã¹ãã¯ãã«
FDæ³ ïœïŒïœ
ïŒ414
(4) å
çŽ åæ[Table] Production example 30 In a eggplant-shaped flask with an internal volume of 100 ml attached to a cooling tube, add 5 mmol of hydroxymethyl 12-crown-4, 5 mmol of triethylamine, dry N,
50 ml of N-dimethylformamide (hereinafter abbreviated as DMF) was charged, and then 5 mmol of p-azobenzenecarboxylic acid chloride was added. 48 at 70â
After reacting for an hour, the mixture was cooled, the resulting precipitate was filtered off, and DMF was distilled off using a rotary evaporator. The product was extracted using ethyl acetate as a developing solvent.
Separation and purification was performed using a column packed with silica gel (trade name: Wako Gel C-200) to obtain 1.25 g (yield: 60%) of a compound represented by the following structural formula. The analysis results are listed below. (1) Infrared absorption spectrum (results are attached as Figure 5) Aromatic ring 3000~3100cm -1 Cyclic ether 1020~1160cm -1 Ester 1720cm -1 (2) 1 H-nuclear magnetic resonance spectrum (results are attached as Figure 5) attached as a diagram) (3) Mass spectrometry spectrum FD method m/e=414 (4) Elemental analysis
ãè¡šã
以äžã®æž¬å®çµæããçæç©ãç®çç©ã§ããããš
ã確èªã§ããã
補é äŸ 31ã59
補é äŸ30ãšåæ§ã®æ¹æ³ã§ãé
žã¯ãã©ã€ãååç©
ãšããããã·â12âã¯ã©ãŠã³âïŒããäžè¬åŒ
ãã
ã§ç€ºãããååç©ãåæãããçµæã第ïŒè¡šã«ãŸ
ãšããŠèšãããããã®ååç©ã«ã€ããŠã¯è£œé äŸ30
ãšåæ§ãªæ¹æ³ã«ãã€ãŠåæããç®çååç©ã§ãã
ããšã確èªãããåèãŸã§ã«ã補é äŸ32ã®èµ€å€åž
åã¹ãã¯ãã«åã³1Hâæ žç£æ°å
±é³Žã¹ãã¯ãã«ã
ãããã第ïŒå³ã第ïŒå³ãšããŠç€ºããã[Table] From the above measurement results, it was confirmed that the product was the desired product. Production Examples 31-59 In the same manner as Production Example 30, general formula [] was prepared from an acid chloride compound and hydroxy-12-crown-4. The compound shown was synthesized. The results are summarized in Table 2. For these compounds, see Preparation Example 30.
It was analyzed using the same method as above and confirmed to be the target compound. For reference, the infrared absorption spectrum and 1 H-nuclear magnetic resonance spectrum of Production Example 32 are shown in FIGS. 7 and 8, respectively.
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šã
補é äŸ 60
å·åŽç®¡ãæ°Žåå®éååšãä»ãã100mlã®ãã¹å
ãã©ã¹ã³ã«ãã«ãšã³50mlãïŒïŒïŒâãžã¯ããããš
ãã«é
¢é
žïŒããªã¢ã«ãããããã·12âã¯ã©ãŠã³â
ïŒïŒïŒããªã¢ã«ãïœâãã«ãšã³ã¹ã«ãã³é
žïŒæ°Žå
ç©2.5ããªã¢ã«ãä»èŸŒã¿ã96æéå ç±éæµããç
æããæ°Žãå
±æ²žè±æ°Žã«ããé€å»ãããåå¿åŸãæ°Ž
é
žåãããªãŠã ã§äžåããæ°Ž25mlãå ããŠãã«ãš
ã³å±€ãåé¢ããããŒã¿ãªãŒãšããã¬ãŒã¿ãŒã§ãã«
ãšã³ãçå»ãããçæç©ãé
¢é
žãšãã«ã溶åªãšã
ãŠã·ãªã«ã²ã«ïŒã¯ã³ãŒã²ã«ïŒ£â200ïŒãå
å¡«ãã
ã«ã©ã ã§åé¢ç²Ÿè£œããäžèšæ§é åŒã§ç€ºãããåå
ç©
1.01ïœïŒåç51ïŒ
ïŒãåŸããåŸãããååç©ã«
ã€ããŠä»¥äžã®åæãè¡ã€ãã
(1) èµ€å€åžåã¹ãã¯ãã«ïŒçµæã第ïŒå³ãšããŠç€º
ããïŒ
è³éŠç° 3050ã3100cm-1
ç°ç¶ãšãŒãã« 1020ã1160cm-1
ãšã¹ãã« 1740cm-1
(2) 1Hâæ žç£æ°å
±é³Žã¹ãã¯ãã«ïŒçµæã第ïŒïŒ
å³ãšããŠç€ºããïŒ
(3) 質éåæã¹ãã¯ãã«
FDæ³ ïœïŒïœ
ïŒ392ïŒ394ïŒ396ïŒM+ïŒããã
ã¯Cl35 Cl37ã«ããåäœäœã§ããã
(4) å
çŽ åæ[Table] Production example 60 In a 100 ml eggplant-shaped flask equipped with a condenser and a moisture meter, add 50 ml of toluene, 5 mmol of 2,4-dichlorophenylacetic acid, and 12-crown hydroxyl.
4:5 mmol and 2.5 mmol of p-toluenesulfonic acid monohydrate were charged, heated under reflux for 96 hours, and the produced water was removed by azeotropic dehydration. After the reaction, the mixture was neutralized with sodium hydroxide, 25 ml of water was added, the toluene layer was separated, and the toluene was distilled off using a rotary evaporator. The product was separated and purified using a column packed with silica gel (Wako Gel C-200) using ethyl acetate as a solvent, and a compound represented by the following structural formula was obtained. 1.01 g (yield 51%) was obtained. The following analysis was performed on the obtained compound. (1) Infrared absorption spectrum (results are shown in Figure 9) Aromatic ring 3050~3100cm -1 Cyclic ether 1020~1160cm -1 Ester 1740cm -1 (2) 1 H-Nuclear magnetic resonance spectrum (results shown in Figure 9)
Shown as a diagram. ) (3) Mass spectrometry spectrum FD method m/e = 392, 394, 396 (M + ) These are isotopes based on Cl 35 Cl 37 . (4) Elemental analysis
ãè¡šã
以äžã®æž¬å®çµæããçæç©ãç®çç©ã§ããããš
ã確èªã§ããã
補é äŸ 61ã82
補é äŸ60ãšåæ§ã®æ¹æ³ã§ã«ã«ãã³é
žååç©ãšã
ãããã·12âã¯ã©ãŠã³âïŒãããäžè¬åŒããã§
瀺ãããååç©ãåæããã
第ïŒè¡šã«çµæããŸãšããŠèšãããããã®ååç©
ã«ã€ããŠè£œé äŸ60ãšåæ§ã®æ段ã§åæãè¡ããç®
çç©ã§ããããšã確èªããã[Table] From the above measurement results, it was confirmed that the product was the desired product. Production Examples 61-82 Compounds represented by the general formula [] were synthesized from a carboxylic acid compound and hydroxy 12-crown-4 in the same manner as in Production Example 60. Table 3 summarizes the results. These compounds were analyzed using the same method as in Production Example 60, and it was confirmed that they were the desired products.
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šã
補é äŸ 83
å·åŽç®¡ãä»ããå
容ç©200mlã®ãã¹åãã©ã¹ã³
ã«ããã³ã¿ã¯ãã«ããšããŒã«30ããªã¢ã«ãæ°Žé
žå
ã«ãªãŠã 30ããªã¢ã«ãäºèåãšãã¬ã³300ããªã¢
ã«ãå ããã¢ã»ãã³äžã§96æéå ç±ç°æµãããå
å¿åŸãå¡©é
žã§äžåãçæããå¡©ããå¥ããåŸãã
ãŒã¿ãªãŒãšããã¬ãŒã¿ãŒã§ã¢ã»ãã³åã³äœå°ã®äº
èåãšãã¬ã³ãçå»ãããçæç©ãã€ãœãããã«
ã¢ã«ã³ãŒã«ããåçµæ¶ããäžèšæ§é åŒã§ç€ºããã
ååç©4.5ïœïŒåç40ïŒ
ïŒãåŸãã
該ååç©ïŒããªã¢ã«ãåã³ããããã·ã¡ãã«â
12âã¯ã©ãŠã³âïŒ ïŒããªã¢ã«ãåã³æ°Žé
žåã«ãª
ãŠã ïŒããªã¢ã«ãå·åŽç®¡ãä»ããå
容ç©100mlã®
ãã¹åãã©ã¹ã³ã«ä»èŸŒã¿ã96æéå ç±ç°æµãè¡ã€
ããåå¿åŸå¡©é
žã§äžåãçæããå¡©ããå¥ããã
ãŒã¿ãªãŒãšããã¬ãŒã¿ãŒã§æº¶åªãæ¿çž®ããåŸãã·
ãªã«ã²ã«ïŒã¯ã³ãŒã²ã«C200ïŒãå
å¡«ããã«ã©ã
ã§é
¢é
žãšãã«ã溶åªãšããŠåé¢ç²Ÿè£œãè¡ã€ããçµ
æã¯äžèšæ§é åŒã§ç€ºãããååç©0.89ïœïŒåç36
ïŒ
ïŒãåŸãã
åŸãããååç©ã«ã€ããŠä»¥äžã®åæãè¡ã€ãã
(1) èµ€å€åžåã¹ãã¯ãã«ïŒçµæã第ïŒïŒå³ãšããŠ
瀺ãããïŒ
ç°ç¶ãšãŒãã« 1020ã1160cm-1
(2) 1Hâæ žç£æ°å
±é³Žã¹ãã¯ãã«ïŒçµæã第ïŒïŒ
å³ãšããŠç€ºãããïŒ
(3) 質éåæã¹ãã¯ãã«
ïœïŒïœ
ïŒ496ïŒ498ïŒ500ïŒ502ïŒ504ïŒM+ïŒ
ãããã¯Cl35ïŒCl37ã«åºã¥ãåäœäœã§ããã
(4) å
çŽ åæ[Table] Production Example 83 30 mmol of pentachlorophenol, 30 mmol of potassium hydroxide, and 300 mmol of ethylene dibromide were added to a 200 ml eggplant-shaped flask equipped with a cooling tube, and the mixture was heated and refluxed in acetone for 96 hours. After the reaction, the reaction mixture was neutralized with hydrochloric acid, the resulting salt was filtered off, and acetone and excess ethylene dibromide were distilled off using a rotary evaporator. The product was recrystallized from isopropyl alcohol to obtain 4.5 g (yield: 40%) of a compound represented by the following structural formula. 5 mmol of the compound, and hydroxymethyl-
5 mmol of 12-crown-4 and 5 mmol of potassium hydroxide were placed in a 100 ml eggplant-shaped flask equipped with a condenser, and heated under reflux for 96 hours. After the reaction, the reaction mixture was neutralized with hydrochloric acid, the resulting salt was filtered out, and the solvent was concentrated using a rotary evaporator, followed by separation and purification using a column packed with silica gel (Wako Gel C200) using ethyl acetate as a solvent. The result was 0.89g of the compound shown by the following structural formula (yield 36
%) was obtained. The following analysis was performed on the obtained compound. (1) Infrared absorption spectrum (results are shown in Figure 11) Cyclic ether 1020-1160 cm -1 (2) 1 H-nuclear magnetic resonance spectrum (results are shown in Figure 12)
Shown as a diagram. ) (3) Mass spectrometry spectrum m/e = 496, 498, 500, 502, 504 (M + ) These are isotopes based on Cl 35 and Cl 37 . (4) Elemental analysis
ãè¡šã
以äžã®çµæããçæç©ãç®çç©ã§ããããšã確
èªãããã
補é äŸ 84ã164
補é äŸ83ãšåæ§ã®æ¹æ³ã§ãåèšäžè¬åŒïŒïŒã§
瀺ãããç°ç¶ããªãšãŒãã«ååç©ãåæãããçµ
æã第ïŒè¡šã«ãŸãšãããåèãŸã§ã«ã補é äŸ105
ã®èµ€å€åžåã¹ãã¯ãã«åã³ 1Hâæ žç£æ°å
±é³Žã¹ã
ã¯ãã«ããããã第ïŒïŒå³ã第ïŒïŒå³ãšããŠèšèŒ
ããã[Table] The above results confirmed that the product was the desired product. Production Examples 84 to 164 In the same manner as Production Example 83, cyclic polyether compounds represented by the general formula () were synthesized. The results are summarized in Table 4. For reference, manufacturing example 105
The infrared absorption spectrum and 1 H-nuclear magnetic resonance spectrum are shown in FIGS. 13 and 14, respectively.
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šã
補é äŸ 165
å·åŽç®¡ãä»ããå
容ç©200mlã®ãã¹åãã©ã¹ã³
ã«ãïŒïŒïŒïŒïŒâããªã¯ãã«ããšããŒã«30ããªã¢
ã«ãæ°Žé
žåã«ãªãŠã 30ããªã¢ã«ãã¯ãã«é
¢é
žãšã
ã«30ããªã¢ã«ãã¢ã»ãã³100mlãä»èŸŒã¿ã96æé
å ç±ç°æµãããåå¿åŸãå¡©é
žã§äžåããçæãã
å¡©ããå¥ãããŒã¿ãªãŒãšããã¬ãŒã¿ã§æº¶åªãçå»
ãããçæç©ãã¢ã»ãã³100mlãæ°Ž20mlãå¡©é
ž10
mlã®æ··å溶液ã§50âã10æéå ç±ããšã¹ãã«ã®å
æ°Žå解ãè¡ã€ããåå¿åŸã溶åªãçå»ããã«ãšã³
ããåçµæ¶ãè¡ããäžèšäžè¬åŒã§è¡šããããåå
ç©8.3ïœïŒåç92ïŒ
ïŒãåŸãã
ãã®ååç©ïŒããªã¢ã«ãããããã·12âã¯ã©ãŠ
ã³âïŒ ïŒããªã¢ã«ãåã³ïœâãã«ãšã³ã¹ã«ãã³
é
ž2.5ããªã¢ã«ãå·åŽç®¡åã³æ°Žåå®éååšãä»ã
ãå
容ç©100mlã®ãã¹åãã©ã¹ã³ã«ä»èŸŒã¿ããã«
ãšã³äžã§å ç±ç°æµãè¡ããçæããæ°Žãé€å»ã
ããåå¿åŸå·åŽããæ°Ž50mlãå ããŠäžåãææ©å±€
ãååããŠããŒã¿ãªãŒãšããã¬ãŒã¿ã§ãã«ãšã³ã
é€å»ãçæç©ãé
¢é
žãšãã«ã溶åªãšããŠãã·ãªã«
ã²ã«ïŒã¯ã³ãŒã²ã«C200ïŒãå
å¡«ããã«ã©ã ã§å
é¢ç²Ÿè£œããäžèšæ§é åŒã§ç€ºãããååç©1.11ïœ
ïŒåç50ïŒ
ïŒãåŸãã
åŸãããååç©ã«ã€ããŠä»¥äžã®åæãè¡ã€ãã
(1) èµ€å€åžåã¹ãã¯ãã«ïŒçµæã第ïŒïŒå³ãšããŠ
瀺ãããïŒ
è³éŠç° 3100cm-1
ç°ç¶ãšãŒãã« 1020ã1160cm-1
ãšã¹ãã« 1750cm-1
(2) 1Hâæ žç£æ°å
±é³Žã¹ãã¯ãã«ïŒçµæã第ïŒïŒ
å³ãšããŠç€ºãããïŒ
(3) 質éåæã¹ãã¯ãã«
ïœïŒïœ
ïŒ442ïŒ444ïŒ446ïŒ448ãããã¯Cl35ïŒ
Cl37ã«ããåäœäœã§ããã
(4) å
çŽ åæ[Table] Production example 165 A 200 ml eggplant-shaped flask equipped with a cooling tube was charged with 30 mmol of 2,4,5-trichlorophenol, 30 mmol of potassium hydroxide, 30 mmol of ethyl chloroacetate, and 100 ml of acetone, and the mixture was heated for 96 hours. The mixture was heated to reflux. After the reaction, the reaction mixture was neutralized with hydrochloric acid, the resulting salt was filtered off, and the solvent was distilled off using a rotary evaporator. Mix the product with 100ml of acetone, 20ml of water, and 10ml of hydrochloric acid.
ml of the mixed solution was heated at 50°C for 10 hours to hydrolyze the ester. After the reaction, the solvent was distilled off and recrystallization was performed from toluene to obtain 8.3 g (yield: 92%) of a compound represented by the following general formula. 5 mmol of this compound, 5 mmol of hydroxy 12-crown-4, and 2.5 mmol of p-toluenesulfonic acid were placed in a 100 ml eggplant-shaped flask equipped with a condenser and a moisture meter, and heated and refluxed in toluene. , the water produced was removed. After the reaction, cool, add 50 ml of water to neutralize, separate the organic layer and remove toluene using a rotary evaporator, separate and purify the product using ethyl acetate as a solvent and a column packed with silica gel (Wako Gel C200). 1.11g of the compound shown by the following structural formula
(yield 50%). The following analysis was performed on the obtained compound. (1) Infrared absorption spectrum (results are shown in Figure 15) Aromatic ring 3100 cm -1 Cyclic ether 1020 to 1160 cm -1 Ester 1750 cm -1 (2) 1 H-Nuclear magnetic resonance spectrum (results shown in Figure 16)
Shown as a diagram. ) (3) Mass spectrometry spectrum m/e=442, 444, 446, 448 These are Cl 35 ,
It is an isotope due to Cl 37 . (4) Elemental analysis
ãè¡šã
以äžã®çµæãããçæç©ãç®çç©ã§ããããšã
確èªããã
補é äŸ 166ã230
補é äŸ165ãšåæ§ãªæ¹æ³ã§ãšã¹ãã«ååå¿ã«ã
ãåèšäžè¬åŒïŒïŒã§ç€ºãããååç©ãåæã
ããçµæã第ïŒè¡šã«ãŸãšããããããã®åæãã
ãååç©ã«ã€ããŠã¯ã補é äŸ165ãšåæ§ã®åæã«
ãããç®çç©ã§ããããšã確èªããããªããåè
ãŸã§ã«ã補é äŸ177ã®èµ€å€åžåã¹ãã¯ãã«åã³1H
âæ žç£æ°å
±é³Žã¹ãã¯ãã«ããããã第ïŒïŒå³ã第
ïŒïŒå³ãšããŠç€ºããã[Table] From the above results, it was confirmed that the product was the desired product. Production Examples 166-230 Compounds represented by the general formula () were synthesized by esterification reaction in the same manner as in Production Example 165. The results are summarized in Table 5. These synthesized compounds were analyzed in the same manner as in Production Example 165, and were confirmed to be the desired products. For reference, the infrared absorption spectrum and 1 H
- Nuclear magnetic resonance spectra are shown in FIGS. 17 and 18, respectively.
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šã
補é äŸ 231
å·åŽç®¡ãä»ããå
容ç©200mlã®ãã¹åãã©ã¹ã³
ã«ãããããã·ã¡ãã«â12âã¯ã©ãŠã³âïŒ 50ã
ãªã¢ã«ãã°ãªã·ã³50ããªã¢ã«ãåã³ïœâãã«ãšã³
ã¹ã«ãã³é
ž75ããªã¢ã«ãä»èŸŒã¿ããã«ãšã³äžã§12
æéå ç±ç°æµãè¡ã€ããåå¿åŸãå·åŽãæ°Ž100ml
ãå ããŠæ°Žé
žåãããªãŠã ã§äžåããææ©çžãå
åãããã«ãšã³ãçå»ãããçæç©ãã¯ãããã«
ã 100mlãæ°Ž50mlãå ããæ¹æããªããPHã匱塩
åºæ§ã«ãªããŸã§æ°Žé
žåãããªãŠã ãå ãããææ©
çžãåé¢ããŠã¯ãããã«ã ãçå»ããäžèšæ§é åŒ
ã§ç€ºãããååç©8.4ïœïŒåç65ïŒ
ïŒãåŸãã
ãã®ååç©ïŒããªã¢ã«ãšããªãšãã«ã¢ãã³ïŒã
ãªã¢ã«ãå
容ç©100mlã®ãã¹åãã©ã¹ã³ã«ä»èŸŒã¿ã
ã¢ãŸãã³ãŒã³âïœâã«ã«ããã«ã¯ãã©ã€ãïŒããª
ã¢ã«ãå ããŠDMFäžã§ïŒæé宀枩äžã§æ¹æããã
åå¿åŸãçæããå¡©ããå¥ããããŒã¿ãªãŒãšãã
ã¬ãŒã¿ãŒã§ãžã¡ãã«ãã«ã ã¢ãããçå»ãããç
æç©ãé
¢é
žãšãã«ã溶åªãšããŠã·ãªã«ã²ã«ïŒã¯ã³
ãŒã²ã«ïŒ£â200ïŒãå
å¡«ããã«ã©ã ã§åé¢ç²Ÿè£œãã
äžèšæ§é åŒã§è¡šããããååç©0.5ïœïŒåç27ïŒ
ïŒ
ãåŸããåœè©²ããååç©ã«ã€ããŠä»¥äžã®åæãè¡
ã€ãã
(1) èµ€å€åžåã¹ãã¯ãã«ïŒçµæã第ïŒïŒå³ãšããŠ
瀺ãããïŒ
è³éŠç° 3100cm-1
ç°ç¶ãšãŒãã« 1040ã1160cm-1
ã¢ããçµå 1720cm-1
(2) 1Hâæ žç£æ°å
±é³Žã¹ãã¯ãã«ïŒçµæã第ïŒïŒ
å³ãšããŠç€ºãããïŒ
(3) 質éåæã¹ãã¯ãã«
ïœïŒïœ
ïŒ471ïŒM+ïŒ
(4) å
çŽ åæ[Table] Production example 231 In a eggplant-shaped flask with an internal volume of 200 ml equipped with a cooling tube, 50 mmol of hydroxymethyl-12-crown-4, 50 mmol of glycine, and 75 mmol of p-toluenesulfonic acid were charged, and 12 mmol of p-toluenesulfonic acid was added in toluene.
The mixture was heated and refluxed for a period of time. After reaction, cool and add 100ml of water.
was added and neutralized with sodium hydroxide, the organic phase was separated, and toluene was distilled off. To the product, 100 ml of chloroform and 50 ml of water were added, and while stirring, sodium hydroxide was added until the pH became slightly basic. The organic phase was separated and chloroform was distilled off to obtain 8.4 g (yield: 65%) of a compound represented by the following structural formula. 4 mmol of this compound and 4 mmol of triethylamine were placed in an eggplant-shaped flask with an internal volume of 100 ml.
4 mmol of azobenzene-p-carbonyl chloride was added and stirred in DMF for 2 hours at room temperature.
After the reaction, the produced salt was filtered off, and dimethylformamide was distilled off using a rotary evaporator. The product was separated and purified using a column packed with silica gel (Wakogel C-200) using ethyl acetate as a solvent.
0.5g of the compound represented by the following structural formula (yield 27%)
I got it. The following analysis was performed on the compound concerned. (1) Infrared absorption spectrum (results are shown in Figure 19) Aromatic ring 3100cm -1 Cyclic ether 1040-1160cm -1 Amide bond 1720cm -1 (2) 1 H-nuclear magnetic resonance spectrum (results shown in Figure 19)
Shown as a diagram. ) (3) Mass spectrometry spectrum m/e=471 (M + ) (4) Elemental analysis
ãè¡šã
以äžã®çµæããç®çç©ã確èªããã
補é äŸ 232ã280
å®æœäŸ231ãšåæ§ã®æ¹æ³ã§ãããããã·â12â
ã¯ã©ãŠã³âïŒãšÎ²âã¢ã©ãã³ãåã³ïŒâã¢ããé
ª
é
žã®åå¿ã«ãããããã
ãåæããããããã®ååç©ãšçš®ã
ã®é
žã¯ããªã
ãšãåå¿ããããããšã«ãããäžè¬åŒïŒïŒã§ç€º
ãããååç©ãå®æœäŸ231åæ§ã®æ¹æ³ã§åæããã
çµæã第ïŒè¡šã«ç€ºãããåæãããååç©ã«ã€ã
ãŠå®æœäŸ231ãšåæ§ã®åæãè¡ããç®çç©ã§ãã
ããšã確èªããã[Table] The target object was confirmed from the above results. Production Examples 232-280 Hydroxy-12-
By the reaction of crown-4 with β-alanine and 3-aminobutyric acid, respectively was synthesized. By reacting these compounds with various acid chlorides, compounds represented by the general formula () were synthesized in the same manner as in Example 231.
The results are shown in Table 6. The synthesized compound was analyzed in the same manner as in Example 231, and it was confirmed that it was the desired compound.
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šã
å®æœäŸ ïŒ
補é äŸïŒã280ã§åŸãããç°ç¶ããªãšãŒãã«å
åç©20mgãããªå¡©åããã«ïŒå¹³åéå床1100ïŒ
200mgãïœâãããããšãã«ãªã¯ãã«ãšãŒãã«400
mgã10mlã®ããã©ããããã©ã³ã«æº¶è§£ããããã®
溶液ãå¹³æ»ãªã¬ã©ã¹æ¿äžã«æµå»¶ããåŸãããã©ã
ãããã©ã³ãèžçºããããŠçŽ100ÎŒåã®èãåŸãã
ãã®èã第ïŒïŒå³ã«ç€ºãããã«è£
çãã第ïŒïŒå³
ã«ç€ºããè£
眮ãçšããŠé»æ¥µæ§èœãè©äŸ¡ãããçµæ
ã第ïŒè¡šã«ç€ºãã
ãªããæ¯èŒäŸãšããŠãåŸæ¥ã®ãããªãŠã éžææ§
ç©è³ªã§ããäžèšæ§é åŒã§è¡šããããååç©ïŒ¡ïŒïŒ¢
ã«ã€ããŠãåæ§ã®æ¹æ³ã§è©Šéšãè¡ããçµæã第ïŒ
è¡šã«ç€ºããã
[Table] Example 1 20 mg of cyclic polyether compound obtained in Production Examples 1 to 280, polyvinyl chloride (average degree of polymerization 1100)
200mg, o-nitrophenyl octyl ether 400
mg was dissolved in 10 ml of tetrahydrofuran. After this solution was cast onto a smooth glass plate, the tetrahydrofuran was evaporated to obtain a film with a thickness of about 100 ÎŒm.
This membrane was mounted as shown in FIG. 22, and the electrode performance was evaluated using the apparatus shown in FIG. The results are shown in Table 7. In addition, as a comparative example, compounds A and B represented by the following structural formula, which are conventional sodium-selective substances, were used.
The test was conducted in the same manner, and the results were reported in the 7th test.
Shown in the table.
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šã
å®æœäŸ ïŒ
第ïŒè¡šã«ç€ºããç°ç¶ããªãšãŒãã«ååç©20mgãš
ããªïŒãã¹ããšããŒã«ïŒ¡ã«ãŒãããŒãïŒâããª
ïŒãžã¡ãã«ã·ãããµã³ïŒãããã¯å
±éåäœïŒçµæ
49察51ééæ¯ïŒ600mgã20c.c.ã®å¡©åã¡ãã¬ã³ã«æº¶
解ããããã®æº¶æ¶²ãå¹³æ»ãªã¬ã©ã¹æ¿äžã«æµå»¶ãã
åŸãå¡©åã¡ãã¬ã³ãèžçºããããŠãçŽ100ãã¯ã
ã³åã®èç¶ç©ãåŸãããããã®èç¶ç©ãçšããŠæ§
æããé»æ¥µã®æ§èœã第ïŒè¡šã«ç€ºãã[Table] Example 2 20 mg of the cyclic polyether compound shown in Table 8 and poly(bisphenol A carbonate)-poly(dimethylsiloxane) block copolymer (composition
49:51 weight ratio) was dissolved in 20 c.c. of methylene chloride. After this solution was cast on a smooth glass plate, the methylene chloride was evaporated to obtain a film about 100 microns thick. Table 8 shows the performance of electrodes constructed using these membrane materials.
ãè¡šã
å®æœäŸ ïŒ
第ïŒè¡šã«ç€ºããç°ç¶ããªãšãŒãã«ååç©10mgãš
ç±å¯å¡æ§æš¹èåã³å¯å¡å€ã第ïŒè¡šã«ç€ºããçµæã§
10mlã®ããã©ããããã©ã³ã«æº¶è§£ããããã®æº¶æ¶²
ãå¹³æ»ãªã¬ã©ã¹æ¿äžã«æµå»¶ããåŸãããã©ããã
ãã©ã³ãèžçºããããŠãçŽ100ãã¯ãã³åã®èç¶
ç©ãåŸãããããã®èç¶ç©ãçšããŠæ§æããé»æ¥µ
ã®æ§èœã第ïŒè¡šäžã®é»æ¥µæ§èœã«ç€ºãã
ãªãã以äžãç±å¯å¡æ§æš¹èåã³å¯å¡å€ã次ã®ã
ãã«ç¥èšããã
ããªå¡©åããã«ïŒPVC
ããªã¡ãã«ã¡ã¿ã¯ãªã¬ãŒãïŒPMMA
ããªã¹ãã¬ã³ïŒPSt
ããªå¡©åãããªãã³ïŒPVDC
ãªã«ãœãããããšãã«ãªã¯ãã«ãšãŒãã«ïŒ
NPOE
ãžããã«ãã¿ã¬ãŒãïŒDBP
ãžãªã¯ãã«ãã¿ã¬ãŒãïŒDOP
ãžãªã¯ãã«ã¢ãžããŒãïŒDOA
ãžãªã¯ãã«ã»ãã±ãŒãïŒDOS[Table] Example 3 10 mg of the cyclic polyether compound shown in Table 9, a thermoplastic resin, and a plasticizer were used in the composition shown in Table 9.
Dissolved in 10ml of tetrahydrofuran. After this solution was cast on a smooth glass plate, the tetrahydrofuran was evaporated to obtain a film about 100 microns thick. The performance of electrodes constructed using these membrane materials is shown in Table 9. In addition, hereinafter, the thermoplastic resin and plasticizer will be abbreviated as follows. Polyvinyl chloride: PVC Polymethyl methacrylate: PMMA Polystyrene: PSt Polyvinylidene chloride: PVDC Ortho-nitrophenyl octyl ether:
NPOE Dibutyl phthalate: DBP Dioctyl phthalate: DOP Dioctyl adipate: DOA Dioctyl sebacate: DOS
ãè¡šããtableã
ãè¡šã
å®æœäŸ ïŒ
補é äŸïŒã«ãã€ãŠåŸãããååç©20mgãããªå¡©
åããã«200mgããªã«ãœãããããšãã«ãªã¯ãã«
ãšãŒãã«400mgãã¬ã©ã¹è£œå°åã·ã€ãŒã¬ã«å
¥ãã
120âã«å ç±ããç±æ¿äžã§ãã¯ãã¹ããŒãã«ãçš
ããŠååæ··åããåŸã該混åç©ãç±ãã¬ã¹ã«ãã
çŽ70ÎŒïœåã®èç¶ç©ã«æ圢ããããã®èç¶ç©ãçš
ããŠæ§æãããããªãŠã é»æ¥µæ§èœã¯éžæåç40ã
åŸé
51mVïŒdecadeã§ãã€ãã
å®æœäŸ ïŒ
第10è¡šã«ç€ºããç°ç¶ããªãšãŒãã«ååç©20mg
ãšãç±å¯å¡æ§æš¹èåã³å¯å¡å€ã第10è¡šã«ç€ºããçµ
æã§ïŒmlã®ããã©ããããã©ã³ã«æº¶è§£ããããã®
溶液ã«å€åŸ0.5mmã®çœéç·ã10ç§é浞ããããåŸã
溶液ããåãåºã10åéæŸçœ®ãã溶åªã§ãããã
ã©ããããã©ã³ãèžçºããããããã®æäœã10å
ç¹°ãè¿ããçœéç·è¡šé¢ã«èç¶ç©ã圢æããããã
枬å®æ¶²ãšçœéç·ãšã®æ¥è§Šãé¿ããããçœéé²åºéš
åãããã©ãã«ãªããšãã¬ã³è£œããŒãã§è¢«èŠã
ãããã®èç¶ç©è¢«èŠçœéç·ã®æŠç¥ã第ïŒïŒå³ã«ç€º
ãããããèç¶ç©è¢«èŠçœéç·ã®é»æ¥µæ§èœãè©äŸ¡ã
ãããã®çµæã第10è¡šäžã«é»æ¥µæ§èœãšããŠç€ºã
ãã[Table] Example 4 20 mg of the compound obtained in Production Example 9, 200 mg of polyvinyl chloride, and 400 mg of orthonitrophenyl octyl ether were placed in a small glass tray.
After thorough mixing using a micro spatula on a hot plate heated to 120° C., the mixture was formed into a film-like material with a thickness of about 70 Όm by hot pressing. The performance of the sodium electrode constructed using this membrane-like material is that the selection magnification is 40,
The gradient was 51 mV/decade. Example 5 20 mg of the cyclic polyether compound shown in Table 10
The thermoplastic resin and plasticizer were dissolved in 3 ml of tetrahydrofuran with the composition shown in Table 10. After immersing a platinum wire with an outer diameter of 0.5 mm in this solution for 10 seconds,
It was taken out from the solution and left for 10 minutes to evaporate the solvent, tetrahydrofuran. This operation was repeated 10 times to form a film on the surface of the platinum wire.
In order to avoid contact between the measurement solution and the platinum wire, the exposed platinum part was covered with a tape made of tetrafluoroethylene. FIG. 23 shows an outline of this platinum wire coated with a film-like material. The electrode performance of these film-covered platinum wires was evaluated. The results are shown in Table 10 as electrode performance.
ãè¡šããtableã
ãè¡šã
å®æœäŸ ïŒ
第11è¡šã«ç€ºããç°ç¶ããªãšãŒãã«ååç©20mgãš
ç±å¯å¡æ§æš¹è200mgåã³å¯å¡å€300mgåã³äžè¬åŒ
ïŒïŒã§ç€ºãããææ©ããŠçŽ ååç©ãç°ç¶ããªãš
ãŒãã«ååç©ã«å¯ŸããŠæå®ã®ã¢ã«æ¯ã§ïŒïŒïŒâãž
ã¯ãã«ãšã¿ã³10mlã«æº¶è§£ããåŸãã¬ã©ã¹æ¿ã«æµå»¶
ããïŒïŒïŒâãžã¯ãã«ãšã¿ã³ãèžçºããããçŽ
100ÎŒïœåã®èç¶ç©ãåŸããåŸãããèç¶ç©ãçš
ããŠæ§æãããããªãŠã é»æ¥µã®é»æ¥µæ§èœã第11è¡š
ã«ç€ºãã
第11è¡šã«ç€ºãããã«ãææ©ããŠçŽ ååç©ã®æ·»å
ã«ãããéžæåçã10ã40åäžæãããããåŸé
ã58ã60mVãšãã極ããŠé«ãå€ã瀺ããé«æ床
ãªãããªãŠã é»æ¥µãæ§æã§ããããšãæããã§ã
ãã[Table] Example 6 20 mg of the cyclic polyether compound shown in Table 11, 200 mg of the thermoplastic resin, 300 mg of the plasticizer, and the organic boron compound represented by the general formula () were added at a predetermined molar ratio to the cyclic polyether compound. After dissolving in 10 ml of 1,2-dichloroethane, it was cast onto a glass plate, and the 1,2-dichloroethane was evaporated, leaving about
A film-like material with a thickness of 100 ÎŒm was obtained. Table 11 shows the electrode performance of the sodium electrode constructed using the obtained film-like material. As shown in Table 11, addition of an organic boron compound increases the selectivity by 10 to 40 times, and the slope shows an extremely high value of 58 to 60 mV, clearly indicating that a highly sensitive sodium electrode can be constructed. .
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šã
å®æœäŸ ïŒ
補é äŸïŒã®ååç©15mgãããªå¡©åããã«200mgïŒ
ãªã«ãœãããããšãã«ãªã¯ãã«ãšãŒãã«400mgã
[Table] Example 7 15 mg of the compound of Production Example 8, 200 mg of polyvinyl chloride,
Orthonitrophenyl octyl ether 400mg,
ãåŒãã補é äŸïŒã®ååç©ã«å¯ŸããŠ
ã¢ã«æ¯ã§0.1ã®éãã¬ã©ã¹è£œå°åã·ã€ãŒã¬ã«å
¥ãã
120âã«å ç±ããç±æ¿äžã§ãã¯ãã¹ããŒãã«ãçš
ããŠååæ··åããåŸã該混åç©ãç±ãã¬ã¹ã«ãã
çŽ90ÎŒïœåã®èç¶ç©ãåŸãããã®èç¶ç©ãçšããŠ
æ§æãããããªãŠã é»æ¥µã®é»æ¥µãæ§èœã¯ãéžæå
ç50ãåŸé
59mVïŒdecadeã§ãã€ãã
å®æœäŸ ïŒ
å®æœäŸïŒNo.39ã§åŸãèç¶ç©ïŒè£œé äŸ39ã®ååç©
åã³ããªå¡©åããã«åã³ãªã«ãœãããããšãã«ãª
ã¯ãã«ãšãŒãã«ãããªãïŒãçšããŠæ§æãããã
ãªãŠã é»æ¥µãåã³å®æœäŸïŒNo.39ã§åŸãèç¶ç©ïŒè£œ
é äŸ39ã®ååç©åã³ããªå¡©åããã«åã³ãªã«ãœã
ããããšãã«ãªã¯ãã«ãšãŒãã«åã³
[Formula] was added in a molar ratio of 0.1 to the compound of Production Example 8 in a small glass jar,
After thorough mixing using a micro spatula on a hot plate heated to 120° C., the mixture was hot pressed to obtain a film-like material with a thickness of about 90 Όm. The performance of the sodium electrode constructed using this membrane material was a selection factor of 50 and a slope of 59 mV/decade. Example 8 A sodium electrode constructed using the film-like material obtained in Example 1 No. 39 (consisting of the compound of Production Example 39, polyvinyl chloride, and orthonitrophenyl octyl ether), and the membrane material obtained in Example 6 No. 39. film-like substance (compound of Production Example 39 and polyvinyl chloride and orthonitrophenyl octyl ether and
ãåŒããããªãïŒãçšããŠæ§æãã
ãããªãŠã é»æ¥µãïŒã®0.15M NaClïŒ0.003M
KClãå«ã氎溶液ã«30âã«ãŠæµžæŒ¬ããïŒé±éæ¯ã«
åãåºããé»æ¥µæ§èœã枬å®ããäž¡è
ã®é»æ¥µã®èä¹
æ§ã調ã¹ããçµæã第12è¡šã«ç€ºããA sodium electrode constructed using [formula]
The electrodes were immersed in an aqueous solution containing KCl at 30°C and taken out every two weeks to measure electrode performance and examine the durability of both electrodes. The results are shown in Table 12.
第ïŒå³ã第ïŒå³ã第ïŒå³ã第ïŒå³ã第ïŒå³ã第
ïŒïŒå³ã第ïŒïŒå³ã第ïŒïŒå³ã第ïŒïŒå³åã³ç¬¬ïŒ
ïŒå³ã¯ãæ¬çºæã§çšããç°ç¶ããªãšãŒãã«ååç©
ã®èµ€å€åžåã¹ãã¯ãã«ã瀺ãããŸãã第ïŒå³ã第
ïŒå³ã第ïŒå³ã第ïŒå³ã第ïŒïŒå³ã第ïŒïŒå³ã第
ïŒïŒå³ã第ïŒïŒå³ã第ïŒïŒå³åã³ç¬¬ïŒïŒå³ã¯ãæ¬
çºæã®ç°ç¶ããªãšãŒãã«ååç©ã®1Hâæ žç£æ°å
±
鳎ã¹ãã¯ãã«ã瀺ãã第ïŒïŒå³ã¯èµ·é»åã枬å®ã
ãè£
眮ã®èª¬æå³ã§ã第ïŒïŒå³ã¯ç¬¬ïŒïŒå³ã®é»æ¥µïŒ
ã«å
èµãããåçš®æ§æèŠçŽ ã瀺ã説æå³ã§ããã
第ïŒïŒå³ã¯ãæ¬çºæã®ç°ç¶ããªãšãŒãã«ååç©ã
å«ãèç¶ç©ã被èŠããçœéç·ã®æŠç¥å³ã§ããã第
ïŒïŒå³ã第ïŒïŒå³åã³ç¬¬ïŒïŒå³ã®äžã§ãåçªå·ã¯
次ã®å
容ã瀺ãã
ïŒâŠâŠé»æ¥µãïŒâŠâŠæž¬å®æº¶æ¶²ãïŒâŠâŠç£æ°å転
åãïŒâŠâŠç£æ°æ¹ææ©ãïŒâŠâŠ0.1Mé
¢é
žãªããŠ
ã å¡©æ©ãïŒâŠâŠå¡©åã«ãªãŠã 飜å氎溶液ãïŒâŠâŠ
飜åããããé»æ¥µãïŒâŠâŠãšã¬ã¯ããã¡ãŒã¿ãŒ
ïŒåæHEâ103åïŒãïŒïŒâŠâŠã¢ã¯ãªã«è£œèãã«
ããŒãïŒïŒâŠâŠéç·ãïŒïŒâŠâŠè¢«èŠã¬ã©ã¹ç®¡ãïŒ
ïŒâŠâŠéâå¡©åéåéšæšæºé»æ¥µãïŒïŒâŠâŠ10-3M
å¡©åãããªãŠã å
éšæšæºæ¶²ãïŒïŒâŠâŠç°ç¶ããªãš
ãŒãã«ååç©ãå«ãèç¶ç©ãïŒïŒâŠâŠïŒ¯âãªã³
ã°ãïŒïŒâŠâŠçœéç·ãïŒïŒâŠâŠç°ç¶ããªãšãŒãã«
ååç©ãå«ãèç¶ç©ãïŒïŒâŠâŠãããã³è£œããŒ
ãã
Figure 1, Figure 3, Figure 5, Figure 7, Figure 9, Figure 11, Figure 13, Figure 15, Figure 17, and Figure 1.
Figure 9 shows the infrared absorption spectrum of the cyclic polyether compound used in the present invention. Moreover, FIG. 2, FIG. 4, FIG. 6, FIG. 8, FIG. 10, FIG. 12, FIG. 14, FIG. 16, FIG. 18 and FIG. 20 show the cyclic polyether compounds of the present invention. The 1 H-nuclear magnetic resonance spectrum of . FIG. 21 is an explanatory diagram of the device for measuring electromotive force, and FIG. 22 is an explanatory diagram of the device for measuring electromotive force.
FIG. 2 is an explanatory diagram showing various components built into the.
FIG. 23 is a schematic diagram of a platinum wire coated with a film containing the cyclic polyether compound of the present invention. In FIG. 21, FIG. 22, and FIG. 23, each number indicates the following content. DESCRIPTION OF SYMBOLS 1... Electrode, 2... Measurement solution, 3... Magnetic rotor, 4... Magnetic stirrer, 5... 0.1M lithium acetate salt bridge, 6... Potassium chloride saturated aqueous solution, 7...
Saturated electrode, 8... Electrometer (Hokuto HE-103 type), 11... Acrylic membrane holder, 12... Silver wire, 13... Covered glass tube, 1
4...Silver-silver chloride circular standard electrode, 15...10 -3 M
Sodium chloride internal standard solution, 16... Membrane-like material containing a cyclic polyether compound, 17... O-ring, 21... Platinum wire, 22... Membrane-like material containing a cyclic polyether compound, 23... Made of Teflon tape.
Claims (1)
ã¯æ°ŽçŽ åååã¯ã¢ã«ãã«åºã§ãããïœã¯ïŒã
20ã®æŽæ°ã§ãããïœã¯ïŒãïŒã®æŽæ°ã§ãããïŒ ã瀺ããã¯ïŒâCH2ïŒâlCH2ââCH2âïŒ
ãåŒãâïŒâCH2ïŒâl+1CH2 ââCH2âïŒ
ãåŒãå㯠ãåŒã ïŒäœããïœã¯ïŒãïŒã®æŽæ°ã§ãããïŒã§ç€ºã
ããåºã瀺ããã ã§è¡šããããç°ç¶ããªãšãŒãã«ååç©0.1ã40
éééšããäž»ãšããŠãªãç°ç¶ããªãšãŒãã«çµæ
ç©ã ïŒ (A) ç±å¯å¡æ§æš¹è100éééš (B) äžè¬åŒãã ãäœããã¯ãåŒã ãåŒã ãåŒã ãåŒã ãåŒã ãåŒã ãåŒã ãåŒã ãåŒã ãåŒã ãåŒã ãåŒã ãåŒã åã¯ãåŒãïŒäœãã㯠ããã²ã³åååã¯ããã²ãã¢ã«ãã«åºã§ããã
ã¯æ°ŽçŽ åååã¯ã¢ã«ãã«åºã§ãããïœã¯ïŒã
20ã®æŽæ°ã§ãããïœã¯ïŒãïŒã®æŽæ°ã§ãããïŒ ã瀺ããã¯ïŒâCH2ïŒâlCH2ââCH2âïŒ
ãåŒãâïŒâCH2ïŒâl+1CH2 ââCH2âïŒ
ãåŒãå㯠ãåŒã ïŒäœããïœã¯ïŒãïŒã®æŽæ°ã§ãããïŒã§ç€ºã
ããåºã瀺ããã ã§è¡šããããç°ç¶ããªãšãŒãã«ååç©0.1ã40
éééš åã³ (C) äžèš(B)ã®ç°ç¶ããªãšãŒãã«ååç©ã«å¯ŸããŠã¢
ã«æ¯ã§0.01ã0.5ã®éã®äžèšäžè¬åŒãã ïŒãã ããY1ïŒY2ïŒY3åã³Y4ã¯åçš®ãŸãã¯
ç°çš®ã®æ°ŽçŽ ååãããã²ã³ååãã¢ã«ãã«åºãŸ
ãã¯ããã¢ã«ãã«åºã§ãP1ïŒP2ïŒP3åã³P4ã¯
åãããŸãã¯ç°ãªãïŒãïŒã®æŽæ°ã§ãïŒã¯ã¢ã«
ã«ãªéå±ã§ãããïŒ ã§ç€ºãããææ©ããŠçŽ ååç© ããäž»ãšããŠãªãç°ç¶ããªãšãŒãã«çµæç©ã[Claims] 1 (A) 100 parts by weight of thermoplastic resin and (B) General formula [] [However, A is [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] or [Formula] (where X is a halogen atom or a halogenoalkyl group,
R is a hydrogen atom or an alkyl group, m is 0-
It is an integer of 20, and n is an integer of 1 to 5. ), B represents (-CH 2 )- l CH 2 -O-CH 2 -,
[Formula] âO(âCH 2 ) â l+1 CH 2 âOâCH 2 â,
[Formula] or [Formula] (where l is an integer of 0 to 7). ] Cyclic polyether compound represented by 0.1-40
A cyclic polyether composition consisting mainly of parts by weight. 2 (A) 100 parts by weight of thermoplastic resin (B) General formula [] [However, A is [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] or [Formula] (where X is a halogen atom or a halogenoalkyl group,
R is a hydrogen atom or an alkyl group, m is 0-
It is an integer of 20, and n is an integer of 1 to 5. ), B represents (-CH 2 )- l CH 2 -O-CH 2 -,
[Formula] âO(âCH 2 ) â l+1 CH 2 âOâCH 2 â,
[Formula] or [Formula] (where l is an integer of 0 to 7). ] Cyclic polyether compound represented by 0.1-40
Parts by weight and (C) the following general formula [] in an amount of 0.01 to 0.5 in molar ratio to the cyclic polyether compound of (B) above. (However, Y 1 , Y 2 , Y 3 and Y 4 are the same or different hydrogen atoms, halogen atoms, alkyl groups or haloalkyl groups, and P 1 , P 2 , P 3 and P 4 are the same or different 1 to 5, M is an alkali metal.) A cyclic polyether composition mainly consisting of an organoboron compound represented by:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60210179A JPS6270452A (en) | 1985-09-25 | 1985-09-25 | Cyclic polyether composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60210179A JPS6270452A (en) | 1985-09-25 | 1985-09-25 | Cyclic polyether composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6270452A JPS6270452A (en) | 1987-03-31 |
JPH0124824B2 true JPH0124824B2 (en) | 1989-05-15 |
Family
ID=16585084
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60210179A Granted JPS6270452A (en) | 1985-09-25 | 1985-09-25 | Cyclic polyether composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6270452A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5082921A (en) * | 1990-08-27 | 1992-01-21 | The Dow Chemical Company | Benzotrifluoride aryl ether polymer |
US5030252A (en) * | 1990-08-27 | 1991-07-09 | The Dow Chemical Company | Novel benzotrifluoride aryl ether gas separation membranes |
-
1985
- 1985-09-25 JP JP60210179A patent/JPS6270452A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS6270452A (en) | 1987-03-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPH0374337B2 (en) | ||
Kataky et al. | Comparative study of mono-and di-substituted 14-crown-4 derivatives as lithium ionophores | |
JPH0124824B2 (en) | ||
JPH0327551B2 (en) | ||
JP3364313B2 (en) | Porphyrin / indium complex and anion-sensitive membrane | |
US4770759A (en) | Lithium ion-selective membrane electrode | |
EP1096251A1 (en) | Film responsive to bicarbonate ion | |
JP2877682B2 (en) | Calixarene derivatives | |
JP3307687B2 (en) | Ion-selective coordination molecules and ion sensors | |
JPS6345750B2 (en) | ||
JPH06201639A (en) | Ion selective electrode using light responsive calix arene derivative | |
JPH04339251A (en) | Potassium ion selective composition | |
JP2801414B2 (en) | Cyclic polyether diamide compound and calcium ion-selective composition | |
JP3805903B2 (en) | Ammonium ion selective coordination molecules and ion sensors | |
JPH0326192B2 (en) | ||
JP2877731B2 (en) | Sodium ion-selective calixarene derivatives | |
JPH0676512B2 (en) | Cyclic polyether composition | |
JP2889424B2 (en) | Ion-selective calixarene derivatives | |
JP3659756B2 (en) | Ionophore for sodium ion selective electrode | |
JPH01163A (en) | Cyclic polyether composition | |
JPS6345751B2 (en) | ||
JPH0552832B2 (en) | ||
JPH0327550B2 (en) | ||
JPS59196885A (en) | Biscrown ether of schiff base type | |
SU1558913A1 (en) | 4Ñ-tributylcyclohexano-12-crown-4 as selective ionophor of sodium cations in electrochemical liquid membranes |