JPS6411207B2 - - Google Patents
Info
- Publication number
- JPS6411207B2 JPS6411207B2 JP10932984A JP10932984A JPS6411207B2 JP S6411207 B2 JPS6411207 B2 JP S6411207B2 JP 10932984 A JP10932984 A JP 10932984A JP 10932984 A JP10932984 A JP 10932984A JP S6411207 B2 JPS6411207 B2 JP S6411207B2
- Authority
- JP
- Japan
- Prior art keywords
- isothianaphthene
- polymer
- polymerization
- poly
- dihydroisothianaphthene
- 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
- 229920000642 polymer Polymers 0.000 claims description 48
- 238000006116 polymerization reaction Methods 0.000 claims description 33
- LYTMVABTDYMBQK-UHFFFAOYSA-N 2-benzothiophene Chemical group C1=CC=CC2=CSC=C21 LYTMVABTDYMBQK-UHFFFAOYSA-N 0.000 claims description 27
- 239000003792 electrolyte Substances 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910016467 AlCl 4 Inorganic materials 0.000 claims 1
- 229910020366 ClO 4 Inorganic materials 0.000 claims 1
- 229910018286 SbF 6 Inorganic materials 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 25
- -1 tetrafluorethane Chemical compound 0.000 description 25
- 229920000000 Poly(isothianaphthene) Polymers 0.000 description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 12
- 238000000862 absorption spectrum Methods 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 238000010538 cationic polymerization reaction Methods 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 229940075397 calomel Drugs 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 229920001197 polyacetylene Polymers 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229920000123 polythiophene Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- PHXQIAWFIIMOKG-UHFFFAOYSA-N NClO Chemical compound NClO PHXQIAWFIIMOKG-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000002772 conduction electron Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000005670 electromagnetic radiation Effects 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- KGKAYWMGPDWLQZ-UHFFFAOYSA-N 1,2-bis(bromomethyl)benzene Chemical compound BrCC1=CC=CC=C1CBr KGKAYWMGPDWLQZ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 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 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910010277 boron hydride Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000031700 light absorption Effects 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
- LYUARYSAVQUGLK-UHFFFAOYSA-N lithium;triethylborane Chemical compound [Li].CCB(CC)CC LYUARYSAVQUGLK-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000006464 oxidative addition reaction Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000003969 polarography Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
ç£æ¥äžã®å©çšåé
æ¬çºæã¯æ¥µããŠå®å®ã§ããŒãã³ã°ã«ãã極ããŠ
é«ãé»å°æ§ã瀺ãæ°èŠãªé»å°æ§éåäœã«é¢ããæŽ
ã«è©³ããã¯äžè¬åŒ
é«ãé»å°æ§ã瀺ãæ°èŠãªé»å°æ§éåäœã«é¢ããæŽ
ã«è©³ããã¯äžè¬åŒ
ãåŒãåã³ïŒåã¯
ãåŒã
ïŒåŒäžãR1åã³R2ã¯ããããç¬ç«ã«æ°ŽçŽ åã¯ç
çŽ æ°ïŒãïŒã®çåæ°ŽçŽ åºãè¡šãããX-ã¯é»è§£è³ª
ã€ãªã³ãè¡šãããïœã¯ã¢ãããŒïŒã¢ã«åœãã®é°ã€
ãªã³ã®å²åãè¡šãã0.01ãïŒã®æ°ã§ãããïœã¯é
å床ãè¡šããïŒã500ã®æ°ã§ããïŒã§è¡šãããã
ã€ãœãã¢ãããã³æ§é ãæããéåäœã«é¢ããã ãã®éåäœã¯ãé»æ°ã»é»åå·¥æ¥ã®åéã«ãããŠ
é»æ¥µããšã¬ã¯ããã¯ãããã¯è¡šç€ºçŽ åã倪éœé»æ±
ã®è£œé ãé»æ°çæ¥ç¶ãé»ç£ç·ã®åºå®ã»å€æè£ çœ®ã
ãã³å¯éçãªé žåéå ç³»ãšããŠçšããããšãã§ã
ãã åŸæ¥ã®æè¡ è¿å¹Žãé»æ°ã»é»åæ©åšã®è»œéåãè圢åæãã¯
å°ååã®é²æ©ã¯èããããããã«çšããããåçš®
é»å°æ§ææçŽ åçã«ã€ããŠã軜éåãè圢åæã
ã¯å°ååãžã®èŠæã¯åŒ·ããã®ãããã®ã¿ãªããã
ããåªããæ°èŠææã®åºçŸã«åŒ·ãæåŸ ãæãããŠ
ããã ãããã®èŠææãã¯æåŸ ãæºããã¹ããæ°ãã
é»å°æ§é«ååã®éçºãçãã«è¡ãããŠãããäŸã
ã°ããªã¢ã»ãã¬ã³ã¯ãšãŠçŽ æãã¯äºåŒåãçŽ ãªã©
ãããŒãã³ã°ããããšã«ãã102ã103sïŒcmãã®
é«ãé»å°åºŠã瀺ãïŒäŸãã°ã·ã³ã»ãã€ãã¯ã¡ã¿ã«
ãºïŒSynthetic MetalsïŒç¬¬ïŒå·»ïŒå·101é
ïŒ1979ïŒ1980幎åç §ïŒããšãå æŸé»ç¹æ§ãåªããŠ
ããããšããäºæ¬¡é»æ± ã®é»æ¥µææãšããŠæ€èšãã
ãŠããã°ããã§ãªããå ã®åžåç¹æ§ã倪éœå ã®ã
ãã«è¿ãããšãã倪éœé»æ± ææãšããŠãæ€èšãã
ãŠãããããããªãããããªã¢ã»ãã¬ã³ã¯ããèª
äœé žåããæãããŸãããŒãã³ã°ããããªã¢ã»ã
ã¬ã³ã¯æ¹¿æ°ã«å¯ŸããŠã極ããŠææã§ãããšããæ¬
ç¹ãæã€ãŠããã äžæ¹ãããªããªããšã³ã¯ãã®å ±åœ¹æ§é ãã·ã¹å
ããªã¢ã»ãã¬ã³ã«é¡äŒŒããç¡«é»ååãå«ããšãã
ãã®ç¹ç°çãªé»åæ§é ã®æ ã«ãé»å°æ§ææãšããŠ
æãã¯é»æ± é»æ¥µææãšããŠæ€èšãããŠããã®ã¿ãª
ãããããŒãã³ã°ç¶æ ã§ã®å€è²ãå©çšãããšã¬ã¯
ããã¯ãããã¯ææãšããŠãæ€èšãããŠãããäŸ
ãã°ããšãŒã»ãšã ã»ãã«ã€ïŒA.M.DruyïŒçã¯
ïŒïŒ2â²âãããã«ãé»æ°ååŠçã«éåãããšãé
åäœãé žåç¶æ ãéå ç¶æ ã«ãããŠãéè²ãèµ€è²
ãšå€è²ãããããå¯éçã§ããããšãçšããŠããš
ã¬ã¯ããã¯ãããã¯ææãšããŠæçšã§ãããšå ±å
ããŠããïŒãžã€ãŒãã«ã»ãã»ãã€ãžãŒã¯ïŒJ.de
PhysiqueïŒç¬¬44å·»ïŒå·ãC3â595é ïŒ1983幎ïŒïŒã çºæã®ç®ç æ¬çºæè ãã¯äžèšè«žç¹ã«éã¿éææ€èšããçµ
æãã€ãœãã¢ãããã³æ§é ãæããéåäœã空æ°
äžã«ãããŠã極ããŠå®å®ãªååç©ã§ããããšãç¹°
è¿ã䜿çšãååå¯èœãªçšå®å®ã«é žååã¯éå ç¶æ
ã§å¯éçã«å€è²ãåŸããã®ã§ãããéåžžã®ããŒã
ã³ã°å€ã«ãã容æã«10-2sïŒcmããé«ãé»å°åºŠã
æããæ°èŠãªéåäœã§ããããšãèŠåºããŠæ¬çºæ
ãéæããã çºæã®æ§æåã³äœçš å³ã¡æ¬çºæã«ä¿ãéåäœã¯äžè¬åŒ
çŽ æ°ïŒãïŒã®çåæ°ŽçŽ åºãè¡šãããX-ã¯é»è§£è³ª
ã€ãªã³ãè¡šãããïœã¯ã¢ãããŒïŒã¢ã«åœãã®é°ã€
ãªã³ã®å²åãè¡šãã0.01ãïŒã®æ°ã§ãããïœã¯é
å床ãè¡šããïŒã500ã®æ°ã§ããïŒã§è¡šãããã
ã€ãœãã¢ãããã³æ§é ãæããéåäœã«é¢ããã ãã®éåäœã¯ãé»æ°ã»é»åå·¥æ¥ã®åéã«ãããŠ
é»æ¥µããšã¬ã¯ããã¯ãããã¯è¡šç€ºçŽ åã倪éœé»æ±
ã®è£œé ãé»æ°çæ¥ç¶ãé»ç£ç·ã®åºå®ã»å€æè£ çœ®ã
ãã³å¯éçãªé žåéå ç³»ãšããŠçšããããšãã§ã
ãã åŸæ¥ã®æè¡ è¿å¹Žãé»æ°ã»é»åæ©åšã®è»œéåãè圢åæãã¯
å°ååã®é²æ©ã¯èããããããã«çšããããåçš®
é»å°æ§ææçŽ åçã«ã€ããŠã軜éåãè圢åæã
ã¯å°ååãžã®èŠæã¯åŒ·ããã®ãããã®ã¿ãªããã
ããåªããæ°èŠææã®åºçŸã«åŒ·ãæåŸ ãæãããŠ
ããã ãããã®èŠææãã¯æåŸ ãæºããã¹ããæ°ãã
é»å°æ§é«ååã®éçºãçãã«è¡ãããŠãããäŸã
ã°ããªã¢ã»ãã¬ã³ã¯ãšãŠçŽ æãã¯äºåŒåãçŽ ãªã©
ãããŒãã³ã°ããããšã«ãã102ã103sïŒcmãã®
é«ãé»å°åºŠã瀺ãïŒäŸãã°ã·ã³ã»ãã€ãã¯ã¡ã¿ã«
ãºïŒSynthetic MetalsïŒç¬¬ïŒå·»ïŒå·101é
ïŒ1979ïŒ1980幎åç §ïŒããšãå æŸé»ç¹æ§ãåªããŠ
ããããšããäºæ¬¡é»æ± ã®é»æ¥µææãšããŠæ€èšãã
ãŠããã°ããã§ãªããå ã®åžåç¹æ§ã倪éœå ã®ã
ãã«è¿ãããšãã倪éœé»æ± ææãšããŠãæ€èšãã
ãŠãããããããªãããããªã¢ã»ãã¬ã³ã¯ããèª
äœé žåããæãããŸãããŒãã³ã°ããããªã¢ã»ã
ã¬ã³ã¯æ¹¿æ°ã«å¯ŸããŠã極ããŠææã§ãããšããæ¬
ç¹ãæã€ãŠããã äžæ¹ãããªããªããšã³ã¯ãã®å ±åœ¹æ§é ãã·ã¹å
ããªã¢ã»ãã¬ã³ã«é¡äŒŒããç¡«é»ååãå«ããšãã
ãã®ç¹ç°çãªé»åæ§é ã®æ ã«ãé»å°æ§ææãšããŠ
æãã¯é»æ± é»æ¥µææãšããŠæ€èšãããŠããã®ã¿ãª
ãããããŒãã³ã°ç¶æ ã§ã®å€è²ãå©çšãããšã¬ã¯
ããã¯ãããã¯ææãšããŠãæ€èšãããŠãããäŸ
ãã°ããšãŒã»ãšã ã»ãã«ã€ïŒA.M.DruyïŒçã¯
ïŒïŒ2â²âãããã«ãé»æ°ååŠçã«éåãããšãé
åäœãé žåç¶æ ãéå ç¶æ ã«ãããŠãéè²ãèµ€è²
ãšå€è²ãããããå¯éçã§ããããšãçšããŠããš
ã¬ã¯ããã¯ãããã¯ææãšããŠæçšã§ãããšå ±å
ããŠããïŒãžã€ãŒãã«ã»ãã»ãã€ãžãŒã¯ïŒJ.de
PhysiqueïŒç¬¬44å·»ïŒå·ãC3â595é ïŒ1983幎ïŒïŒã çºæã®ç®ç æ¬çºæè ãã¯äžèšè«žç¹ã«éã¿éææ€èšããçµ
æãã€ãœãã¢ãããã³æ§é ãæããéåäœã空æ°
äžã«ãããŠã極ããŠå®å®ãªååç©ã§ããããšãç¹°
è¿ã䜿çšãååå¯èœãªçšå®å®ã«é žååã¯éå ç¶æ
ã§å¯éçã«å€è²ãåŸããã®ã§ãããéåžžã®ããŒã
ã³ã°å€ã«ãã容æã«10-2sïŒcmããé«ãé»å°åºŠã
æããæ°èŠãªéåäœã§ããããšãèŠåºããŠæ¬çºæ
ãéæããã çºæã®æ§æåã³äœçš å³ã¡æ¬çºæã«ä¿ãéåäœã¯äžè¬åŒ
ãåŒãåã³ïŒåã¯
ãåŒã
ïŒåŒäžãR1åã³R2ã¯ããããç¬ç«ã«æ°ŽçŽ åã¯ç
çŽ æ°ïŒãïŒã®çåæ°ŽçŽ åºãè¡šãããX-ã¯é»è§£è³ª
ã®é°ã€ãªã³ãè¡šãããïœã¯ã¢ãããŒïŒã¢ã«åœãã®
é°ã€ãªã³ã®å²åãè¡šãã0.01ãïŒã®æ°ã§ãããïœ
ã¯éå床ãè¡šããïŒã500ã®æ°ã§ããïŒã§è¡šãã
ããã€ãœãã¢ãããã³æ§é åäœãã奜ãŸããã¯
0.1ã100ã¢ã«ïŒ å«æããéåäœã§ããã æ¬çºæã«ä¿ãéåäœã¯çš®ã ã®éåæ¹æ³ã«ãã€ãŠ
容æã«åæããããšãã§ããã äŸãã°ãäžèšäžè¬åŒ ã§è¡šããããïŒïŒïŒâãžãããã€ãœãã¢ãããã³
âïŒâãªãã·ããããã¯ãã®èªå°äœãæ¿ç¡«é žã®ã
ãšããè±æ°Žåã³é žåäœçšããã€æº¶åªäžã§åå¿ãã
ãããšã«ãã€ãŠææã®éåäœãåŸãããšãã§ã
ãã ããã«ã¯äŸãã°äžè¬åŒïœã§è¡šããããååç©
ãã¢ã«ããäžã§è±æ°Žæè¯ãããŠåŸãããäžè¬åŒ ã§è¡šããããã€ãœãã¢ãããã³ãããã¯ãã®èªå°
äœã(1)é»è§£è³ªã®ååšäžãéãããã³æ§æº¶åªäžã§é»
æ°ååŠçã«éåãããã(2)äžè¬åŒïœã§è¡šããã
ãååç©ã溶åªã®ååšäžãããã¯äžåšäžã«ã«ããª
ã³éåãããåŸããããžãããåããªããŒãé žå
å€ã«äœçšãããããšã«ãããè±æ°ŽçŽ ããã(3)äžè¬
åŒïœã§è¡šããããååç©ãé žåéåããçã®æ¹
æ³ã«ãã€ãŠææã®éåäœãåŸãããšãã§ãããã
ããã®äž¡è ãå ±éåãããéã«ã¯ä»»æã®å²åïŒäŸ
ãã°0.1ã99.9ã¢ã«ïŒ ïŒã§å«ãéåäœãåŸãããš
ãã§ããã åèšåéäœã®éåã«éãçšãããã溶åªã¯ãã
ããã®éåæ¹æ³ã«ãã€ãŠé©åœã«éžå®ããããšãã§
ããç¹ã«éå®ã¯ãªããäžè¬çã«èšãã°ãäžè¬åŒ
ïœã§ç€ºãããã€ãœãã¢ãããã³ãããã¯ãã®èªå°
äœãé»è§£è³ªã®ååšäžã«é»æ°ååŠçã«éåããå Žå
ã«ã¯éãããã³æ§æº¶åªãäŸãã°ã¢ã»ããããªã«ã
ãã³ãŸãããªã«ãããããªãããªã«ããžãªããµ
ã³ãããã©ããããã©ã³ãã¹ã«ãã©ã³ããããã¬
ã³ã«ãŒãããŒããªã©ããããããšãã§ããããŸ
ããäžè¬åŒïœã§ç€ºãããã€ãœãã¢ãããã³ãã
ãã¯ãã®èªå°äœãã«ããªã³éåããå Žåã«ã¯ãžã¯
ãã«ã¡ã¿ã³ãã¯ãããã«ã ãåå¡©åççŽ ããžã¯ã
ã«ãšã¿ã³ãããã©ããã«ãšã¿ã³ããããã¡ã¿ã³ã
ããããšã¿ã³ãããããã³ãŒã³ãäºç¡«åççŽ ãªã©
ã®ããšã溶åªããããããšãã§ãããæŽã«äžè¬åŒ
ïœã§ç€ºããããžãããã€ãœãã¢ãããã³âïŒâ
ãªãã·ããããã¯ãã®èªå°äœãè±æ°Žéåããå Žå
ã«ã¯æ¿ç¡«é žãããªãªã³é žãªã©ã®æº¶åªã䜿çšããã
ãšãã§ããããŸãäžè¬åŒïœã§ç€ºãããã€ãœãã¢
ãããã³ãããã¯ãã®èªå°äœãé žåä»å éåãã
å Žåã«ã¯ã«ããªã³éåã§çšãã溶åªãšããªãŒãã«
ã¯ã©ããå觊åªãšãçµåããŠçšããã°ããã ãŸãåèšåéäœã®éåã«éãçšããããéåæž©
床ã¯ãããããã®éåæ¹æ³ã«ãã€ãŠå®ããããã
ã®ã§ããç¹ã«å®ããªããäžè¬ã«ã¯â80âãïŒ200
âã®æž©åºŠç¯å²ã§éåããã®ãæãŸãããéåæé
ã¯éåæ¹æ³åã³éå枩床ãåéäœã®æ§é çã«ãã€
ãŠå®ãããããã®ã§ãããéåžž0.25æéã200æ
éã§éåããã®ãæãŸããã åèšäžè¬åŒïœåã³ïœã§è¡šããããåéäœå
åç©ã¯å ¬ç¥æ¹æ³ã§åæããããšãã§ããäŸãã°ãš
ã ã»ããŒã»ãã€ãïŒM.P.CavaïŒçã®ãžã€ãŒã
ã«ã»ãªãã»ã¢ã¡ãªã«ã³ã»ã±ãã«ã«ã»ãœãµãšãã€ãŒ
ïŒJ.Am.Chem.Soc.ïŒç¬¬81å·»4266é ïŒ1959幎ïŒå
ã³åãããšã ã»ããŒã»ãã€ãçã®ãžã€ãŒãã«ã»ãª
ãã»ãªãŒã¬ããã¯ã»ã±ãã¹ããªãŒïŒJ.Org.
Chem.ïŒç¬¬36å·»25å·3932é ïŒ1971幎ïŒã«å ±åãã
ãŠããæ¹æ³ã§åæããããšãã§ãããæŽã«ãäžé
äœã®ïŒïŒïŒâãžãããã€ãœãã¢ãããã³ã®åçã
äžããããããªããŠã ããªãšãã«ããã³ãã€ãã©
ã€ããšç¡«é»ãåå¿ãããŠåŸãããå¯æº¶åç¡«åãªã
ãŠã ãçšããæ¹æ³ããžãšãŒã»ãšãŒã»ã°ã©ãã€ã¹
ïŒJ.A.GradyszïŒçã®ããã©ãããã³ã¬ã¿ãŒãº
ïŒTetrahadron.Lett.ïŒç¬¬35å·»2329é ïŒ1979幎ïŒã«
ææ¡ãããŠããã çºæã®å¹æ ãã®ããã«ããŠåŸãããæ¬çºæã«ä¿ãéåäœã¯
å šãæ°èŠãªæ§é ãæãããã®ã§ãããããŒãã³ã°
ã«ãã極ããŠé«ãé»å°åºŠã瀺ãã°ããã§ãªããé»
æ°ååŠçã«ãç¹°è¿ãé žåéå ãè¡ãããšãå¯èœã§
äžã€ããããã®ç¶æ ã«ãããŠåºæã®è²ãæããã
æ¬çºæã®ããªïŒã€ãœãã¢ãããã³ïŒã¯æŽã«ååãª
é žåç¶æ ã«ãããŠããéææ§ã倱ããªããšãã極
ããŠèå³ã®ããéåäœã§ãããåŸã€ãŠãæ¬çºæã«
ä¿ãã€ãœãã¢ãããã³æ§é ãæããéåäœã¯ãé»
æ°ã»é»åå·¥æ¥ã®åéã«ãããŠé»æ¥µããšã¬ã¯ããã¯
ãããã¯è¡šç€ºçŽ åã倪éœé»æ± ãé»æ°çæ¥ç¶ãé»ç£
ç·ã®åºå®ã»å€æè£ çœ®ããªãã³ã«å¯éçãªé žåéå
ç³»ãšããŠæ¥µããŠæçšãªãã®ã§ããã å®æœäŸ 以äžã«å®æœäŸã«ããæ¬çºæãæŽã«è©³ãã説æã
ãããæ¬çºæã®æè¡çç¯å²ããããã®å®æœäŸã«ã
ã€ãŠéå®ãããã®ã§ãªãããšã¯ãããŸã§ããªãã
ãªãã以äžã®äŸã«ãããŠãNMRã¹ãã¯ãã«ã¯
TMSãå éšæšæºãšããŠãŽã¢ãªã¢ã³ç€ŸEMâ360A
ã¹ãã¯ããã¡ãŒã¿ãŒãçšã㊠1HâNMRã枬å®
ããèµ€å€åžåã¹ãã¯ãã«ã¯ããŒãã³ãšã«ããŒç€Ÿè£œ
ã¢ãã«281åè£ çœ®ãçšããŠæž¬å®ããã å®æœäŸ ïŒ ïŒïŒïŒâãžãããã€ãœãã¢ãããã³âïŒâãªã
ã·ããæ¿ç¡«é žäžã§åŠçããããšã«ããããªã€ãœ
ãã¢ãããã³ã®è£œé (a) ïŒïŒïŒâãžãããã€ãœãã¢ãããã³âïŒâãª
ãã·ãã®åæ ãªããŠã ããªãšãã«ããã³ãã€ãã©ã€ãã®ïŒ
ã¢ã«ïŒæº¶æ¶²200mlã«å®€æž©ã§ã·ãŠã¬ã³ã¯ãã©ã¹
ã³ã«å ¥ããç²æ«ç¡«é»3.21gïŒ0.1ã¢ã«ïŒãçªçŽ æ°
æµäžã§å ãããåå¿ãçŽã¡ã«èµ·ããç¡«é»ç²æ«ã
溶解ããé»è²ã®æžæ¿æ¶²ãåŸãããããã®æº¶æ¶²ã¯
埮éã®ç©ºæ°ã«è§Šãããšæ·¡é»è²ã®éæãªæº¶æ¶²ãšãª
ã€ãã äžæ¹ãå¥ã«æ»ŽäžããŒããæ¹ææ©ã枩床èšåã³
çªçŽ å°å ¥å£ãä»ããïŒåãå£ãã©ã¹ã³ã«çªçŽ
é°å²æ°äžã§ïœâãã·ãªã¬ã³ãžãããã26.4g
ïŒ0.1ã¢ã«ïŒãç¡æ°Žã®ããã©ããããã©ã³ïŒã«
溶解ããŠãããããã«æ¹æããªããäžèšç¡«åãª
ããŠã ã®ããã©ããããã©ã³æº¶æ¶²ã宀枩ã§1.5
æéãããŠæ»Žäžããããã®åŸãããã©ãããã
ã©ã³ãæžå§ã§çå»ããåŸãæŽã«æ®çç©ãèžçã
ãŠ74ã76âïŒïŒmmHgã®ç¡è²ã®ïŒïŒïŒâãžãã
ãã€ãœãã¢ãããã³10.9gïŒåç80ïŒ ïŒãåŸãã
ãã®ãã®ã®èµ€å€åžåã¹ãã¯ãã«ã¯3060ã3026ã
1582ã1485cm-1ã«ããšãã«åºã«åºã¥ãåžåã
2910ã2840ã1450cm-1ã«ã¡ãã¬ã³åºã«åºã¥ãåž
åã1195cm-1ã«ïŒïŒïŒâ眮æããšãã«ã®é¢å å€
è§åžåã760cm-1ã«ïœâ眮æããšãã«ã®åžåã
740cm-1ã«ãµã«ãã¢ã€ãã®åžåã瀺ããããŸã
TMSãå éšæšæºãšããéæ°ŽçŽ åã¯ãããã«ã
äžã®æ žç£æ°å ±é³Žã¹ãã¯ãã«ïŒ 1HâNMRïŒå
æçµæã¯ä»¥äžã®éãã§ãã€ãã 4.22ïŒïŒ³ã4HïŒã7.20ïŒïœã4HïŒ ãã®ååç©ã¯éåžžã«äžå®å®ã§ãããé®å ã»å¯
æ ä¿åããŠãé»è²ããé»è²ã«å€åããã 次ãã§åŸãããïŒïŒïŒâãžãããã€ãœãã¢ã
ããã³ãäºãçšæããã¡ã¿ãšãŠçŽ é žãããªãŠã
18.6gïŒ0.086ã¢ã«ïŒã溶解ãã450mlã®50ïŒ ã¡ã¿
ããŒã«æ°Žæº¶æ¶²ã«å ãã宀枩ã§12æéæ¹æããã
çæããæ²æ®¿ããå¥ãã50mlã®ã¡ã¿ããŒã«ã§æ®
æ»ãæŽæµãæ¯æ¶²ã«åãããã液ãæžå§äžæ¿çž®
ããçæããé»çœè²åºäœãé ¢é žãšãã«ïŒã·ã¯ã
ãããµã³ããåçµæ¶ããŠå ãã«é»è²ããã€ãçµ
æ¶ãåŸãããã®çµæ¶ã®èç¹ã¯87ã89âã§ãã€
ãã åŸãããçµæ¶ãæŽã«é ¢é žãšãã«ïŒã·ã¯ããã
ãµã³ããåçµæ¶ãããšããã90ã91âã®èç¹ã
瀺ããããã®çµæ¶ã®èµ€å€åžåã¹ãã¯ãã«ã¯ã€ãœ
ãã¢ãããã³ã®åžåã®ä»ã«1035cm-1ã«ã¹ã«ãã
ãµã€ãã®åŒ·ãåžåãèªãããã740cm-1ã®ãµã«
ãã¢ã€ãã®åžåã¯æ¶æ» ããããŸãTMSãéšæš
æºãšããéæ°ŽçŽ åã¯ãããã«ã äžã§ã® 1Hâ
NMRã¹ãã¯ãã«ã¯ä»¥äžã®éãã§ãã€ãã 4.11ïŒïœã2HïŒã4.30ïŒïœã2HïŒã7.20ïŒïœã
4HïŒ äžèšçµæ¶ã®å çŽ åæçµæã¯æ¬¡ã®éãã§ãã€
ãã å®æž¬å€ ïŒ63.08ïŒ ïŒšïŒ5.15ïŒ ïŒ³ïŒ20.87ïŒ èšç®å€ïŒC8H8SOãšããŠïŒ ïŒ63.16ïŒ ïŒšïŒ5.26ïŒ ïŒ³ïŒ21.05ïŒ (b) ïŒïŒïŒâãžãããã€ãœãã¢ãããã³âïŒâãª
ãã·ãïŒåèšåŒïœã§R1ïŒR2ïŒïŒšïŒããã®ã
ãªã€ãœãã¢ãããã³ã®åæ ïŒïŒïŒâãžãããã€ãœãã¢ãããã³âïŒâãª
ãã·ã500mgïŒ3.29ããªã¢ã«ïŒãïŒmlã®æ¿ç¡«é ž
ã«å ãããšããåå¿ç³»ã¯çŽã¡ã«æèµ€è²ãšãªã€
ãã宀枩ã§70æéæŸçœ®ããæ®ãã©åºåããç³»ã
400mlã®ã¡ã¿ããŒã«äžã«æ³šããçæããè€è²ã®
æ²æ®¿ãé å¿åé¢ãã次ãã§ããæ°Žã§æŽæµãã60
âã§ïŒå€ç空也ç¥ãããéåäœããœãã¯ã¹ã¬ãŒ
æœåºåšã«å ¥ãå¡©åã¡ãã¬ã³ã次ãã§ã¯ãã«ãã³
ãŒã³ã§ãããããã12æéãœãã¯ã¹ã¬ãŒæœåº
ãã203mgã®ã¯ãã«ãã³ãŒã³äžæº¶éšãåŸããã
ã®éåäœã®èµ€å€åžåã¹ãã¯ãã«ã¯ç¬¬ïŒå³ã«ç€ºã
éãã§ãã€ãã å çŽ åæçµæã¯ïŒ£ïŒ67.26ïŒ ãïŒ3.12ïŒ ã
ïŒ23.95ïŒ ã§ãããç¹°è¿ãåäœãäžèšæ§é åŒ ãšæšå®ããæã®èšç®å€ïŒïŒ£ïŒ67.19ïŒ ãïŒ
3.32ïŒ ãïŒ23.54ïŒ ïŒãšããäžèŽããã ãã®éåäœã®å®€æž©ã«ãããé»å°åºŠïŒÏRTïŒã
ïŒç«¯ååŒã®é»å°åºŠæž¬å®åšãçšããŠæž¬å®ãããšã
ãÏRTïŒïŒÃ10-2sïŒcmã§ãã€ãã å®æœäŸ ïŒ ã€ãœãã¢ãããã³ãã«ããªã³éåããŠåŸããã
ããªãžãããã€ãœãã¢ãããã³ãé žåå€ãçšã
ãŠé žåããããšã«ããããªã€ãœãã¢ãããã³ã®
補é (a) ã€ãœãã¢ãããã³ïŒäžè¬åŒïœã§R1ïŒR2ïŒ
ïŒã®åæ å®æœäŸïŒ(a)ã«åºã¥ãåæããïŒïŒïŒâãžãã
ãã€ãœãã¢ãããã³âïŒâãªãã·ã300mg
ïŒ1.97ããªã¢ã«ïŒãäžæ§ã¢ã«ãã450mgïŒ4.41ã
ãªã¢ã«ïŒãä¹³é¢äžã§ããç²ç æ··åããåŸãæè¯
åšã«å ¥ãã油济äžã§æžå§ã§å ç±ããã110âïŒ
20mmHgã§æè¯åšå·åŽéšåºéšã«ã€ãœãã¢ããã
ã³ã®çœè²éç¶çµæ¶250mgïŒ1.87ããªã¢ã«ïŒãåŸ
ãããã (b) ããªãžãããã€ãœãã¢ãããã³ã®è£œé ãã®ã¢ãããŒãçŽã¡ã«ç²Ÿè£œè±æ°ããïŒmlã®å¡©
åã¡ãã¬ã³ã«æº¶è§£ãã宀枩ã«ãŠããªãã«ãªãé ¢
é ž10mgãå ããïŒå€æŸçœ®ãããåå¿æ¶²ã50mlã®
ã¡ã¿ããŒã«äžã«æ³šããšãçœè²æ²æ®¿ãåŸãããã
ãã®éåäœã¯ã¯ãããã«ã ãã¯ãã«ãã³ãŒã³ã
ããã©ããããã©ã³ãïŒïŒ®âãžã¡ãã«ãã«ã
ã¢ããã«å¯æº¶ã§ãã€ããéåäœã®èµ€å€åžåã¹ã
ã¯ãã«ã¯ç¬¬ïŒå³ã«ããã㊠1HâNMRã¹ãã¯
ãã«ã¯ç¬¬ïŒå³ã«ç€ºããéãã§ãã€ãã æŽã«ãã®éåäœã®ããã©ããããã©ã³æº¶æ¶²ã®
ã²ã«ããŒããšãŒã·ãšã³ã¯ãããã°ã©ã
ïŒVarian5000ïŒããååéã¯ããªã¹ãã¬ã³æç®
ã§2000ã§ããããšã確ãããããã å®æœäŸïŒãšåæ§ã«ããŠã宀枩ã«ãããé»å°åºŠ
ã枬å®ãããšããÏRTïŒ10-8sïŒcm以äžã§ãã€
ãããŸãå çŽ åæçµæã¯æ¬¡ã®éãã§ãã€ãã å®æž¬å€ ïŒ71.27ïŒ ïŒšïŒ4.54ïŒ ïŒ³ïŒ23.96ïŒ èšç®å€ïŒïŒC8H6SïŒïœãšããŠïŒ ïŒ71.64ïŒ ïŒšïŒ4.48ïŒ ïŒ³ïŒ23.88ïŒ äžèšæ¹æ³ã«ãããŠãããªãã«ãªãé ¢é žã®ä»£ãã
ã«ã¡ã¿ã³ã¹ã«ãã³é žãéåéå§å€ãšããŠçšããå Ž
åãåæ§ã«éåäœãåŸããããã®èµ€å€åžåã¹ãã¯
ãã«ã¯ç¬¬ïŒå³ã®ãã®ãšå®å šã«äžèŽããã ãããã®éåäœãïŒmlã®ã¯ãã«ãã³ãŒã³ã«æº¶è§£
ããïŒåã¢ã«ã®ã¯ãã©ãã«ã§åŠçãããšããé»è²
æ²æ®¿ãçæããããã®éåäœã®å®€æž©ã«ãããé»å°
床ÏRTã¯ïŒÃ10-2sïŒcmã§ããããšãŠçŽ ãããŒãã
ããã®ã®é»å°åºŠã¯ÏRTïŒÃ10-1sïŒcmã§ãã€ããã
ã®ãã®ã®èµ€å€åžåã¹ãã¯ãã«ã¯ç¬¬ïŒå³ã«ç€ºããé
ãã§ãã€ããããŒãåŸã®éåäœã¯å®€æž©äžç©ºæ°äžã«
ïŒé±éæŸçœ®ããŠãããã®é»å°åºŠã«å€åã¯ãªãã€
ãã ã¯ãã©ãã«ã®ä»£ããã«1.1åéã®ïŒ®âã¯ãã«ã³
ãã¯é žã€ãããçšããïŒmlã®ã¯ãããã«ã ãçšã
ãå Žåã«åŸãããéåäœã第ïŒå³ãšå šãåãèµ€å€
åžåã¹ãã¯ãã«ã瀺ãé»è²æ²æ®¿ãåŸãããããã®
éåäœã®é»å°åºŠÏRTã¯2.6Ã10-1sïŒcmã§ãã€ãã å®æœäŸ ïŒ ã€ãœãã¢ãããã³ãé žåéåããããšã«ããã
ãªã€ãœãã¢ãããã³ã®äžæ®µéå äžèšå®æœäŸïŒ(a)ã§èšèŒããæ¹æ³ã§ã€ãœãã¢ãã
ãã³ãåæãããã€ãœãã¢ãããã³250mgãç¡æ°Ž
å¡©åã¡ãã¬ã³ïŒmlãç¡æ°Žå¡©åã¢ã«ãããŠã 134mg
åã³ç¡æ°Žå¡©å第äºé 134mgã枩床35ã37âã§ïŒæ
éåå¿ããããšãããé»è²æ²æ®¿ãçæããããã
ã12æéãã®æž©åºŠã«ä¿æããåŸãæ²æ®¿ç©ãå¡©é žé ž
æ§ã¡ã¿ããŒã«æº¶æ¶²ã§åŠçããåŸãååæ°ŽæŽãã也
ç¥ããã也ç¥éåäœãç±ã¡ã¿ããŒã«ãç±å¡©åã¡ã
ã¬ã³ã次ãã§ç±ã¯ãã«ãã³ãŒã³ã§æ²¹åºãã205mg
ã®é»è²éåäœãåŸãããã®èµ€å€åžåã¹ãã¯ãã«ã¯
第ïŒå³ã«å®å šã«äžèŽããããŸãé»å°åºŠÏRTã¯2.8Ã
10-2sïŒcmã§ãã€ãã å®æœäŸ ïŒ ã€ãœãã¢ãããã³ã®é»æ°ååŠçéåã«ããããª
ã€ãœãã¢ãããã³ã®éå äžèšè¡šïŒã«ç€ºããé»è§£è³ªåã³ã€ãœãã¢ãããã³
ãæå®æ¿åºŠã§æ¥µæ§æº¶åªã«æº¶è§£ãããã®ãé»è§£æ¶²ãš
ããçœéæ¿ãè©Šæ極ãAlæ¿ã察極ãLiïŒLi+ãå
ç §æ¥µãšãã0.75mAïŒcm2ã®å®é»æµå¯åºŠã§æå®æé
宀枩ã§é»æ°ååŠçã«éåããããšãããæ£æ¥µã®çœ
éæ¿äžã«ããªã€ãœãã¢ãããã³ã®ãã€ã«ã ãçæ
ãããå°ãåèšæº¶æ¶²ã¯å°ããšã30åé也ç¥ã¢ã«ãŽ
ã³ã§ãããªã³ã°ããããšã«ããè±é žçŽ åŠçããã
ãã®ãçšãããéåäžã®æ倧é»å§ã¯4.5VïŒvsLiïŒ
Li+ïŒã§ãã€ãã çæãããã€ã«ã ãã¢ã»ããããªã«æ¬¡ãã§å¡©å
ã¡ãã¬ã³ã§ååæŽæµããåŸãç空也ç¥ããŠé»æ°ç
æ§èœã枬å®ãããåŸãããçµæã¯ä»¥äžã®è¡šïŒã«ç€º
ãéãã§ãã€ãã
çŽ æ°ïŒãïŒã®çåæ°ŽçŽ åºãè¡šãããX-ã¯é»è§£è³ª
ã®é°ã€ãªã³ãè¡šãããïœã¯ã¢ãããŒïŒã¢ã«åœãã®
é°ã€ãªã³ã®å²åãè¡šãã0.01ãïŒã®æ°ã§ãããïœ
ã¯éå床ãè¡šããïŒã500ã®æ°ã§ããïŒã§è¡šãã
ããã€ãœãã¢ãããã³æ§é åäœãã奜ãŸããã¯
0.1ã100ã¢ã«ïŒ å«æããéåäœã§ããã æ¬çºæã«ä¿ãéåäœã¯çš®ã ã®éåæ¹æ³ã«ãã€ãŠ
容æã«åæããããšãã§ããã äŸãã°ãäžèšäžè¬åŒ ã§è¡šããããïŒïŒïŒâãžãããã€ãœãã¢ãããã³
âïŒâãªãã·ããããã¯ãã®èªå°äœãæ¿ç¡«é žã®ã
ãšããè±æ°Žåã³é žåäœçšããã€æº¶åªäžã§åå¿ãã
ãããšã«ãã€ãŠææã®éåäœãåŸãããšãã§ã
ãã ããã«ã¯äŸãã°äžè¬åŒïœã§è¡šããããååç©
ãã¢ã«ããäžã§è±æ°Žæè¯ãããŠåŸãããäžè¬åŒ ã§è¡šããããã€ãœãã¢ãããã³ãããã¯ãã®èªå°
äœã(1)é»è§£è³ªã®ååšäžãéãããã³æ§æº¶åªäžã§é»
æ°ååŠçã«éåãããã(2)äžè¬åŒïœã§è¡šããã
ãååç©ã溶åªã®ååšäžãããã¯äžåšäžã«ã«ããª
ã³éåãããåŸããããžãããåããªããŒãé žå
å€ã«äœçšãããããšã«ãããè±æ°ŽçŽ ããã(3)äžè¬
åŒïœã§è¡šããããååç©ãé žåéåããçã®æ¹
æ³ã«ãã€ãŠææã®éåäœãåŸãããšãã§ãããã
ããã®äž¡è ãå ±éåãããéã«ã¯ä»»æã®å²åïŒäŸ
ãã°0.1ã99.9ã¢ã«ïŒ ïŒã§å«ãéåäœãåŸãããš
ãã§ããã åèšåéäœã®éåã«éãçšãããã溶åªã¯ãã
ããã®éåæ¹æ³ã«ãã€ãŠé©åœã«éžå®ããããšãã§
ããç¹ã«éå®ã¯ãªããäžè¬çã«èšãã°ãäžè¬åŒ
ïœã§ç€ºãããã€ãœãã¢ãããã³ãããã¯ãã®èªå°
äœãé»è§£è³ªã®ååšäžã«é»æ°ååŠçã«éåããå Žå
ã«ã¯éãããã³æ§æº¶åªãäŸãã°ã¢ã»ããããªã«ã
ãã³ãŸãããªã«ãããããªãããªã«ããžãªããµ
ã³ãããã©ããããã©ã³ãã¹ã«ãã©ã³ããããã¬
ã³ã«ãŒãããŒããªã©ããããããšãã§ããããŸ
ããäžè¬åŒïœã§ç€ºãããã€ãœãã¢ãããã³ãã
ãã¯ãã®èªå°äœãã«ããªã³éåããå Žåã«ã¯ãžã¯
ãã«ã¡ã¿ã³ãã¯ãããã«ã ãåå¡©åççŽ ããžã¯ã
ã«ãšã¿ã³ãããã©ããã«ãšã¿ã³ããããã¡ã¿ã³ã
ããããšã¿ã³ãããããã³ãŒã³ãäºç¡«åççŽ ãªã©
ã®ããšã溶åªããããããšãã§ãããæŽã«äžè¬åŒ
ïœã§ç€ºããããžãããã€ãœãã¢ãããã³âïŒâ
ãªãã·ããããã¯ãã®èªå°äœãè±æ°Žéåããå Žå
ã«ã¯æ¿ç¡«é žãããªãªã³é žãªã©ã®æº¶åªã䜿çšããã
ãšãã§ããããŸãäžè¬åŒïœã§ç€ºãããã€ãœãã¢
ãããã³ãããã¯ãã®èªå°äœãé žåä»å éåãã
å Žåã«ã¯ã«ããªã³éåã§çšãã溶åªãšããªãŒãã«
ã¯ã©ããå觊åªãšãçµåããŠçšããã°ããã ãŸãåèšåéäœã®éåã«éãçšããããéåæž©
床ã¯ãããããã®éåæ¹æ³ã«ãã€ãŠå®ããããã
ã®ã§ããç¹ã«å®ããªããäžè¬ã«ã¯â80âãïŒ200
âã®æž©åºŠç¯å²ã§éåããã®ãæãŸãããéåæé
ã¯éåæ¹æ³åã³éå枩床ãåéäœã®æ§é çã«ãã€
ãŠå®ãããããã®ã§ãããéåžž0.25æéã200æ
éã§éåããã®ãæãŸããã åèšäžè¬åŒïœåã³ïœã§è¡šããããåéäœå
åç©ã¯å ¬ç¥æ¹æ³ã§åæããããšãã§ããäŸãã°ãš
ã ã»ããŒã»ãã€ãïŒM.P.CavaïŒçã®ãžã€ãŒã
ã«ã»ãªãã»ã¢ã¡ãªã«ã³ã»ã±ãã«ã«ã»ãœãµãšãã€ãŒ
ïŒJ.Am.Chem.Soc.ïŒç¬¬81å·»4266é ïŒ1959幎ïŒå
ã³åãããšã ã»ããŒã»ãã€ãçã®ãžã€ãŒãã«ã»ãª
ãã»ãªãŒã¬ããã¯ã»ã±ãã¹ããªãŒïŒJ.Org.
Chem.ïŒç¬¬36å·»25å·3932é ïŒ1971幎ïŒã«å ±åãã
ãŠããæ¹æ³ã§åæããããšãã§ãããæŽã«ãäžé
äœã®ïŒïŒïŒâãžãããã€ãœãã¢ãããã³ã®åçã
äžããããããªããŠã ããªãšãã«ããã³ãã€ãã©
ã€ããšç¡«é»ãåå¿ãããŠåŸãããå¯æº¶åç¡«åãªã
ãŠã ãçšããæ¹æ³ããžãšãŒã»ãšãŒã»ã°ã©ãã€ã¹
ïŒJ.A.GradyszïŒçã®ããã©ãããã³ã¬ã¿ãŒãº
ïŒTetrahadron.Lett.ïŒç¬¬35å·»2329é ïŒ1979幎ïŒã«
ææ¡ãããŠããã çºæã®å¹æ ãã®ããã«ããŠåŸãããæ¬çºæã«ä¿ãéåäœã¯
å šãæ°èŠãªæ§é ãæãããã®ã§ãããããŒãã³ã°
ã«ãã極ããŠé«ãé»å°åºŠã瀺ãã°ããã§ãªããé»
æ°ååŠçã«ãç¹°è¿ãé žåéå ãè¡ãããšãå¯èœã§
äžã€ããããã®ç¶æ ã«ãããŠåºæã®è²ãæããã
æ¬çºæã®ããªïŒã€ãœãã¢ãããã³ïŒã¯æŽã«ååãª
é žåç¶æ ã«ãããŠããéææ§ã倱ããªããšãã極
ããŠèå³ã®ããéåäœã§ãããåŸã€ãŠãæ¬çºæã«
ä¿ãã€ãœãã¢ãããã³æ§é ãæããéåäœã¯ãé»
æ°ã»é»åå·¥æ¥ã®åéã«ãããŠé»æ¥µããšã¬ã¯ããã¯
ãããã¯è¡šç€ºçŽ åã倪éœé»æ± ãé»æ°çæ¥ç¶ãé»ç£
ç·ã®åºå®ã»å€æè£ çœ®ããªãã³ã«å¯éçãªé žåéå
ç³»ãšããŠæ¥µããŠæçšãªãã®ã§ããã å®æœäŸ 以äžã«å®æœäŸã«ããæ¬çºæãæŽã«è©³ãã説æã
ãããæ¬çºæã®æè¡çç¯å²ããããã®å®æœäŸã«ã
ã€ãŠéå®ãããã®ã§ãªãããšã¯ãããŸã§ããªãã
ãªãã以äžã®äŸã«ãããŠãNMRã¹ãã¯ãã«ã¯
TMSãå éšæšæºãšããŠãŽã¢ãªã¢ã³ç€ŸEMâ360A
ã¹ãã¯ããã¡ãŒã¿ãŒãçšã㊠1HâNMRã枬å®
ããèµ€å€åžåã¹ãã¯ãã«ã¯ããŒãã³ãšã«ããŒç€Ÿè£œ
ã¢ãã«281åè£ çœ®ãçšããŠæž¬å®ããã å®æœäŸ ïŒ ïŒïŒïŒâãžãããã€ãœãã¢ãããã³âïŒâãªã
ã·ããæ¿ç¡«é žäžã§åŠçããããšã«ããããªã€ãœ
ãã¢ãããã³ã®è£œé (a) ïŒïŒïŒâãžãããã€ãœãã¢ãããã³âïŒâãª
ãã·ãã®åæ ãªããŠã ããªãšãã«ããã³ãã€ãã©ã€ãã®ïŒ
ã¢ã«ïŒæº¶æ¶²200mlã«å®€æž©ã§ã·ãŠã¬ã³ã¯ãã©ã¹
ã³ã«å ¥ããç²æ«ç¡«é»3.21gïŒ0.1ã¢ã«ïŒãçªçŽ æ°
æµäžã§å ãããåå¿ãçŽã¡ã«èµ·ããç¡«é»ç²æ«ã
溶解ããé»è²ã®æžæ¿æ¶²ãåŸãããããã®æº¶æ¶²ã¯
埮éã®ç©ºæ°ã«è§Šãããšæ·¡é»è²ã®éæãªæº¶æ¶²ãšãª
ã€ãã äžæ¹ãå¥ã«æ»ŽäžããŒããæ¹ææ©ã枩床èšåã³
çªçŽ å°å ¥å£ãä»ããïŒåãå£ãã©ã¹ã³ã«çªçŽ
é°å²æ°äžã§ïœâãã·ãªã¬ã³ãžãããã26.4g
ïŒ0.1ã¢ã«ïŒãç¡æ°Žã®ããã©ããããã©ã³ïŒã«
溶解ããŠãããããã«æ¹æããªããäžèšç¡«åãª
ããŠã ã®ããã©ããããã©ã³æº¶æ¶²ã宀枩ã§1.5
æéãããŠæ»Žäžããããã®åŸãããã©ãããã
ã©ã³ãæžå§ã§çå»ããåŸãæŽã«æ®çç©ãèžçã
ãŠ74ã76âïŒïŒmmHgã®ç¡è²ã®ïŒïŒïŒâãžãã
ãã€ãœãã¢ãããã³10.9gïŒåç80ïŒ ïŒãåŸãã
ãã®ãã®ã®èµ€å€åžåã¹ãã¯ãã«ã¯3060ã3026ã
1582ã1485cm-1ã«ããšãã«åºã«åºã¥ãåžåã
2910ã2840ã1450cm-1ã«ã¡ãã¬ã³åºã«åºã¥ãåž
åã1195cm-1ã«ïŒïŒïŒâ眮æããšãã«ã®é¢å å€
è§åžåã760cm-1ã«ïœâ眮æããšãã«ã®åžåã
740cm-1ã«ãµã«ãã¢ã€ãã®åžåã瀺ããããŸã
TMSãå éšæšæºãšããéæ°ŽçŽ åã¯ãããã«ã
äžã®æ žç£æ°å ±é³Žã¹ãã¯ãã«ïŒ 1HâNMRïŒå
æçµæã¯ä»¥äžã®éãã§ãã€ãã 4.22ïŒïŒ³ã4HïŒã7.20ïŒïœã4HïŒ ãã®ååç©ã¯éåžžã«äžå®å®ã§ãããé®å ã»å¯
æ ä¿åããŠãé»è²ããé»è²ã«å€åããã 次ãã§åŸãããïŒïŒïŒâãžãããã€ãœãã¢ã
ããã³ãäºãçšæããã¡ã¿ãšãŠçŽ é žãããªãŠã
18.6gïŒ0.086ã¢ã«ïŒã溶解ãã450mlã®50ïŒ ã¡ã¿
ããŒã«æ°Žæº¶æ¶²ã«å ãã宀枩ã§12æéæ¹æããã
çæããæ²æ®¿ããå¥ãã50mlã®ã¡ã¿ããŒã«ã§æ®
æ»ãæŽæµãæ¯æ¶²ã«åãããã液ãæžå§äžæ¿çž®
ããçæããé»çœè²åºäœãé ¢é žãšãã«ïŒã·ã¯ã
ãããµã³ããåçµæ¶ããŠå ãã«é»è²ããã€ãçµ
æ¶ãåŸãããã®çµæ¶ã®èç¹ã¯87ã89âã§ãã€
ãã åŸãããçµæ¶ãæŽã«é ¢é žãšãã«ïŒã·ã¯ããã
ãµã³ããåçµæ¶ãããšããã90ã91âã®èç¹ã
瀺ããããã®çµæ¶ã®èµ€å€åžåã¹ãã¯ãã«ã¯ã€ãœ
ãã¢ãããã³ã®åžåã®ä»ã«1035cm-1ã«ã¹ã«ãã
ãµã€ãã®åŒ·ãåžåãèªãããã740cm-1ã®ãµã«
ãã¢ã€ãã®åžåã¯æ¶æ» ããããŸãTMSãéšæš
æºãšããéæ°ŽçŽ åã¯ãããã«ã äžã§ã® 1Hâ
NMRã¹ãã¯ãã«ã¯ä»¥äžã®éãã§ãã€ãã 4.11ïŒïœã2HïŒã4.30ïŒïœã2HïŒã7.20ïŒïœã
4HïŒ äžèšçµæ¶ã®å çŽ åæçµæã¯æ¬¡ã®éãã§ãã€
ãã å®æž¬å€ ïŒ63.08ïŒ ïŒšïŒ5.15ïŒ ïŒ³ïŒ20.87ïŒ èšç®å€ïŒC8H8SOãšããŠïŒ ïŒ63.16ïŒ ïŒšïŒ5.26ïŒ ïŒ³ïŒ21.05ïŒ (b) ïŒïŒïŒâãžãããã€ãœãã¢ãããã³âïŒâãª
ãã·ãïŒåèšåŒïœã§R1ïŒR2ïŒïŒšïŒããã®ã
ãªã€ãœãã¢ãããã³ã®åæ ïŒïŒïŒâãžãããã€ãœãã¢ãããã³âïŒâãª
ãã·ã500mgïŒ3.29ããªã¢ã«ïŒãïŒmlã®æ¿ç¡«é ž
ã«å ãããšããåå¿ç³»ã¯çŽã¡ã«æèµ€è²ãšãªã€
ãã宀枩ã§70æéæŸçœ®ããæ®ãã©åºåããç³»ã
400mlã®ã¡ã¿ããŒã«äžã«æ³šããçæããè€è²ã®
æ²æ®¿ãé å¿åé¢ãã次ãã§ããæ°Žã§æŽæµãã60
âã§ïŒå€ç空也ç¥ãããéåäœããœãã¯ã¹ã¬ãŒ
æœåºåšã«å ¥ãå¡©åã¡ãã¬ã³ã次ãã§ã¯ãã«ãã³
ãŒã³ã§ãããããã12æéãœãã¯ã¹ã¬ãŒæœåº
ãã203mgã®ã¯ãã«ãã³ãŒã³äžæº¶éšãåŸããã
ã®éåäœã®èµ€å€åžåã¹ãã¯ãã«ã¯ç¬¬ïŒå³ã«ç€ºã
éãã§ãã€ãã å çŽ åæçµæã¯ïŒ£ïŒ67.26ïŒ ãïŒ3.12ïŒ ã
ïŒ23.95ïŒ ã§ãããç¹°è¿ãåäœãäžèšæ§é åŒ ãšæšå®ããæã®èšç®å€ïŒïŒ£ïŒ67.19ïŒ ãïŒ
3.32ïŒ ãïŒ23.54ïŒ ïŒãšããäžèŽããã ãã®éåäœã®å®€æž©ã«ãããé»å°åºŠïŒÏRTïŒã
ïŒç«¯ååŒã®é»å°åºŠæž¬å®åšãçšããŠæž¬å®ãããšã
ãÏRTïŒïŒÃ10-2sïŒcmã§ãã€ãã å®æœäŸ ïŒ ã€ãœãã¢ãããã³ãã«ããªã³éåããŠåŸããã
ããªãžãããã€ãœãã¢ãããã³ãé žåå€ãçšã
ãŠé žåããããšã«ããããªã€ãœãã¢ãããã³ã®
補é (a) ã€ãœãã¢ãããã³ïŒäžè¬åŒïœã§R1ïŒR2ïŒ
ïŒã®åæ å®æœäŸïŒ(a)ã«åºã¥ãåæããïŒïŒïŒâãžãã
ãã€ãœãã¢ãããã³âïŒâãªãã·ã300mg
ïŒ1.97ããªã¢ã«ïŒãäžæ§ã¢ã«ãã450mgïŒ4.41ã
ãªã¢ã«ïŒãä¹³é¢äžã§ããç²ç æ··åããåŸãæè¯
åšã«å ¥ãã油济äžã§æžå§ã§å ç±ããã110âïŒ
20mmHgã§æè¯åšå·åŽéšåºéšã«ã€ãœãã¢ããã
ã³ã®çœè²éç¶çµæ¶250mgïŒ1.87ããªã¢ã«ïŒãåŸ
ãããã (b) ããªãžãããã€ãœãã¢ãããã³ã®è£œé ãã®ã¢ãããŒãçŽã¡ã«ç²Ÿè£œè±æ°ããïŒmlã®å¡©
åã¡ãã¬ã³ã«æº¶è§£ãã宀枩ã«ãŠããªãã«ãªãé ¢
é ž10mgãå ããïŒå€æŸçœ®ãããåå¿æ¶²ã50mlã®
ã¡ã¿ããŒã«äžã«æ³šããšãçœè²æ²æ®¿ãåŸãããã
ãã®éåäœã¯ã¯ãããã«ã ãã¯ãã«ãã³ãŒã³ã
ããã©ããããã©ã³ãïŒïŒ®âãžã¡ãã«ãã«ã
ã¢ããã«å¯æº¶ã§ãã€ããéåäœã®èµ€å€åžåã¹ã
ã¯ãã«ã¯ç¬¬ïŒå³ã«ããã㊠1HâNMRã¹ãã¯
ãã«ã¯ç¬¬ïŒå³ã«ç€ºããéãã§ãã€ãã æŽã«ãã®éåäœã®ããã©ããããã©ã³æº¶æ¶²ã®
ã²ã«ããŒããšãŒã·ãšã³ã¯ãããã°ã©ã
ïŒVarian5000ïŒããååéã¯ããªã¹ãã¬ã³æç®
ã§2000ã§ããããšã確ãããããã å®æœäŸïŒãšåæ§ã«ããŠã宀枩ã«ãããé»å°åºŠ
ã枬å®ãããšããÏRTïŒ10-8sïŒcm以äžã§ãã€
ãããŸãå çŽ åæçµæã¯æ¬¡ã®éãã§ãã€ãã å®æž¬å€ ïŒ71.27ïŒ ïŒšïŒ4.54ïŒ ïŒ³ïŒ23.96ïŒ èšç®å€ïŒïŒC8H6SïŒïœãšããŠïŒ ïŒ71.64ïŒ ïŒšïŒ4.48ïŒ ïŒ³ïŒ23.88ïŒ äžèšæ¹æ³ã«ãããŠãããªãã«ãªãé ¢é žã®ä»£ãã
ã«ã¡ã¿ã³ã¹ã«ãã³é žãéåéå§å€ãšããŠçšããå Ž
åãåæ§ã«éåäœãåŸããããã®èµ€å€åžåã¹ãã¯
ãã«ã¯ç¬¬ïŒå³ã®ãã®ãšå®å šã«äžèŽããã ãããã®éåäœãïŒmlã®ã¯ãã«ãã³ãŒã³ã«æº¶è§£
ããïŒåã¢ã«ã®ã¯ãã©ãã«ã§åŠçãããšããé»è²
æ²æ®¿ãçæããããã®éåäœã®å®€æž©ã«ãããé»å°
床ÏRTã¯ïŒÃ10-2sïŒcmã§ããããšãŠçŽ ãããŒãã
ããã®ã®é»å°åºŠã¯ÏRTïŒÃ10-1sïŒcmã§ãã€ããã
ã®ãã®ã®èµ€å€åžåã¹ãã¯ãã«ã¯ç¬¬ïŒå³ã«ç€ºããé
ãã§ãã€ããããŒãåŸã®éåäœã¯å®€æž©äžç©ºæ°äžã«
ïŒé±éæŸçœ®ããŠãããã®é»å°åºŠã«å€åã¯ãªãã€
ãã ã¯ãã©ãã«ã®ä»£ããã«1.1åéã®ïŒ®âã¯ãã«ã³
ãã¯é žã€ãããçšããïŒmlã®ã¯ãããã«ã ãçšã
ãå Žåã«åŸãããéåäœã第ïŒå³ãšå šãåãèµ€å€
åžåã¹ãã¯ãã«ã瀺ãé»è²æ²æ®¿ãåŸãããããã®
éåäœã®é»å°åºŠÏRTã¯2.6Ã10-1sïŒcmã§ãã€ãã å®æœäŸ ïŒ ã€ãœãã¢ãããã³ãé žåéåããããšã«ããã
ãªã€ãœãã¢ãããã³ã®äžæ®µéå äžèšå®æœäŸïŒ(a)ã§èšèŒããæ¹æ³ã§ã€ãœãã¢ãã
ãã³ãåæãããã€ãœãã¢ãããã³250mgãç¡æ°Ž
å¡©åã¡ãã¬ã³ïŒmlãç¡æ°Žå¡©åã¢ã«ãããŠã 134mg
åã³ç¡æ°Žå¡©å第äºé 134mgã枩床35ã37âã§ïŒæ
éåå¿ããããšãããé»è²æ²æ®¿ãçæããããã
ã12æéãã®æž©åºŠã«ä¿æããåŸãæ²æ®¿ç©ãå¡©é žé ž
æ§ã¡ã¿ããŒã«æº¶æ¶²ã§åŠçããåŸãååæ°ŽæŽãã也
ç¥ããã也ç¥éåäœãç±ã¡ã¿ããŒã«ãç±å¡©åã¡ã
ã¬ã³ã次ãã§ç±ã¯ãã«ãã³ãŒã³ã§æ²¹åºãã205mg
ã®é»è²éåäœãåŸãããã®èµ€å€åžåã¹ãã¯ãã«ã¯
第ïŒå³ã«å®å šã«äžèŽããããŸãé»å°åºŠÏRTã¯2.8Ã
10-2sïŒcmã§ãã€ãã å®æœäŸ ïŒ ã€ãœãã¢ãããã³ã®é»æ°ååŠçéåã«ããããª
ã€ãœãã¢ãããã³ã®éå äžèšè¡šïŒã«ç€ºããé»è§£è³ªåã³ã€ãœãã¢ãããã³
ãæå®æ¿åºŠã§æ¥µæ§æº¶åªã«æº¶è§£ãããã®ãé»è§£æ¶²ãš
ããçœéæ¿ãè©Šæ極ãAlæ¿ã察極ãLiïŒLi+ãå
ç §æ¥µãšãã0.75mAïŒcm2ã®å®é»æµå¯åºŠã§æå®æé
宀枩ã§é»æ°ååŠçã«éåããããšãããæ£æ¥µã®çœ
éæ¿äžã«ããªã€ãœãã¢ãããã³ã®ãã€ã«ã ãçæ
ãããå°ãåèšæº¶æ¶²ã¯å°ããšã30åé也ç¥ã¢ã«ãŽ
ã³ã§ãããªã³ã°ããããšã«ããè±é žçŽ åŠçããã
ãã®ãçšãããéåäžã®æ倧é»å§ã¯4.5VïŒvsLiïŒ
Li+ïŒã§ãã€ãã çæãããã€ã«ã ãã¢ã»ããããªã«æ¬¡ãã§å¡©å
ã¡ãã¬ã³ã§ååæŽæµããåŸãç空也ç¥ããŠé»æ°ç
æ§èœã枬å®ãããåŸãããçµæã¯ä»¥äžã®è¡šïŒã«ç€º
ãéãã§ãã€ãã
å®æœäŸïŒâïŒã§çœéæ¿ã®ä»£ããã«æ£æ¥µãšããŠé
ž
åã€ã³ãžãŠã ãèžçãããå°é»ã¬ã©ã¹ãçšããŠã
é»æ°ååŠçã«å°é»ã¬ã©ã¹äžã«éåäœãæåºãã
ãããã®éåäœã§è¢«èŠãããå°é»ã¬ã©ã¹ãè² æ¥µ
ã«ãçœéç·ãæ£æ¥µã«ãåç §é»æ¥µãšããŠæšæºã«ãã¡
ã«é»æ¥µãçšãã宀枩ã§ããã©ããã«ã¢ã³ã¢ããŠã
ããŒã¯ãã¬ãŒãã®292ããªã¢ã«ïŒã®ã¢ã»ããã
ãªã«æº¶æ¶²äžã§ããŒã©ãã°ã©ãã€ãã¯ã¢ãã©ã€ã¶ãŒ
ïŒEGïŒïŒ§ç€ŸModel 174AåïŒã«ãããµã€ã¯ãªãã¯
ãã«ã¿ã ã枬å®ãããå é»å§æåŒé床ã¯20mVïŒ
secãæåŒç¯å²ã¯ïŒ1.0Vãâ0.7VïŒå¯Ÿæšæºã«ãã¡
ã«é»æ¥µïŒãšãããåŸãããçµæã¯ç¬¬ïŒå³ã«ç€ºãã
éãã§ãã€ãã 第ïŒå³ã«ç€ºãããã«é žåããŒã¯ã¯ïŒ0.58Vãé
å ããŒã¯ã¯â0.5Vã§ããŸãâ0.7VãïŒ0.6Vã®ç¯
å²ã¯æ¿éè²ã§ããïŒ0.6ãïŒ1.0Vã®ç¯å²ã¯ã極ã
ãŠéæãªèãç·è²ã«å€è²ããããã®ããšã¯æ¿éè²
ã®ç¶æ ã¯éåäœãäžæ§ã®ç¶æ ã§ãããé žåããŒã
ã³ã°ã®ç¶æ ã§éææ§ã®é«ãç·è²ã§ããããšã瀺ã
ãŠããã ãé»æ± å®éšã å®æœäŸïŒâïŒã§åŸããã€ã«ã ãå·ŸïŒcmé·ãïŒcm
ã«åããäžç«¯ãå°é»æ§æ¥çå€ãçšãçœéç·ã«æ¥ç
ãããã®ãå寞æ³ã®ãªããŠã ç®ã®äž¡é¢ã«ïŒmmåã®
å€å質ããªãããã¬ã³è£œéèãä»ããŠé»è§£æ¶²ãå
åå«æµžåºæ¥ãããã«ããŠé 眮ãã0.5ã¢ã«ïŒã®
ãªããŠã ããŒã¯ãã¬ãŒãã®ãããã¬ã³ã«ãŒãããŒ
ã溶液ã«æ·±ãïŒcmã«æµžæŒ¬ããããã®ããã«ããŠäœ
補ããããªïŒã€ãœãã¢ãããã³ïŒãæ£æ¥µããªããŠ
ã ç®ãè² æ¥µãšããé»æ± ãçšããã¢ã«ãŽã³é°å²æ°
äžã2.0mAïŒcm2ã§30åéå é»ãè¡ã€ããå é»çµäº
åŸçŽã¡ã«2.0mAïŒcm2ã§æŸé»ãè¡ãªããé»æ± é»å§ã
1Vã«ãªã€ããšããã§å床åèšãšåãæ¡ä»¶ã§å é»
ãè¡ããå é»âæŸé»ã®ç¹°è¿ãè©Šéšãè¡ã€ããšã
ããå ã»æŸé»å¹çã50ïŒ ã«äœäžãããŸã§ã®å æŸé»
ã®ç¹°ãè¿ãåæ°ã¯590åãèšé²ããããŸãç¹°è¿ã
åæ°ïŒåç®ã®å ã»æŸé»å¹çã¯99ïŒ ã§ãã€ãããã
ã«å é»ãããŸãŸã§ã®48æéåŸã®èªå·±æŸé»çã¯3.2
ïŒ ã§ãã€ãã å®æœäŸ ïŒ é»æ°ååŠçéåã«ããããªïŒãžãããã€ãœãã¢
ãããã³ïŒãããã©ãããã³ïŒTetrahedronïŒã
1979幎35å·»2239é ããžãšãŒã»ãšãŒã»ã°ã©ãã€ã¹ã
ïŒJ.A.GladyszïŒçïŒããžã€ãŒãã« ãªã ã¢ã¡ãª
ã«ã³ ã±ãã«ã« ãœãµã€ã¢ãã€ïŒJ.Amer.Chem.
Soe.ïŒã1959幎81å·»4266é ããšã ã»ããŒã»ã«ãŒã
ïŒM.P.CavaïŒçïŒããžã€ãŒãã« ãªã ãªãŒã¬ã
ã㯠ã±ãã¹ããªãŒïŒJ.Org.Chem.ïŒã1971幎36
å·»3932é ããšã ã»ããŒã»ã«ãŒãçã®æç®ã«èšèŒã
ããŠããæé ã«ãã€ãŠã€ãœãã¢ãããã³åéäœã
äœããããã«äœ¿çšããããã®åéäœãäºé»æ¥µãé
宀é»è§£æ§œã«ãããŠé»æ°ååŠçã«é žåããŠããªïŒãž
ãããã€ãœãã¢ãããã³ïŒéåäœãåŸããçœéæ¿
ãéœæ¥µãšããŠçšããé žåé»éãé°æ¥µãšããŠçšã
ããéåã«çšãã溶液ã¯ç¡è²éæã§ãã¢ã»ããã
ãªã«äžã«ã€ãœãã¢ãããã³0.23Mãé»è§£è³ªã§ãã
Bu4NPF6 0.30Mãšå ±ã«å«æãããã®ã§ãã€ãã
ã¢ã»ããããªã«ïŒããªã³ã¯ããã
ïŒMallinckrodtïŒããè³Œå ¥ïŒã¯æŽã«ç²Ÿè£œããã«çŽ
æ¥äœ¿çšãããçŽåã®1.5Vé»æ± ãé»æºãšããŠçšã
ãã å šãŠã®å®éšã也ç¥N2äžã§è¡ã€ãããã®é»è§£æ§œ
ã«4.5Vãæ¥ç¶ãããšããã«ãéœæ¥µã®ä»è¿ã«å€é
ã®çœè²ç²æ«ãçŸããã10ååŸã«é»æ± ãåã€ãŠãšã
ããããªïŒãžãããã€ãœãã¢ãããã³ïŒã§ããã
ã®çœè²ç²æ«ãåžåŒãéã«ããåé¢ããã¢ã»ããã
ãªã«åã³ãžãšãã«ãšãŒãã«ã§æŽæµããç空äžã§ä¹Ÿ
ç¥ããããçæããåºäœãããã©ããããã©ã³â
H2Oããåæ²ãããŠç²Ÿè£œããå çŽ åæãè¡ã€ãã æ°ã«èª¿è£œããã€ãœãã¢ãããã³ã®è©Šæãã
Bu4NClO4åã¯Bu4NBF4ãæ¯æé»è§£è³ªãšããŠã
ã€é žåã¹ãºè¢«èŠã¬ã©ã¹ïŒTOGïŒãéœæ¥µãšããŠçš
ããåé»è§£æ§œã®éœæ¥µå®€ã§é»æ°å解ãããšããã
éœæ¥µå®€ã¯å€éã®çœè²æ²æ®¿ïŒWPïŒã§äžæ¯ã«ãªã€
ãã泚ææ·±ã芳å¯ãããšãããéœæ¥µã¯åãã«ïŒç¬
éçã«ïŒéåžžã«èãéè²ãã€ã«ã ã§ãããããã
ãåŸã«WPã®çæãå§ãŸãããšãããã€ããWP
ã®å€èŠ³ã¯é»æ¥µææã溶åªåã¯æž©åºŠã«é¢ä¿ããªãã€
ããåé¢ãç¹æ§æ±ºå®ïŒèµ€å€ãå çŽ åæïŒåã³ååŠ
æäœïŒäžèšåç §ïŒã«ããWPãããªïŒãžãããã€
ãœãã¢ãããã³ïŒã§ããããšã蚌æããããããª
ããšã³ã¯äžèšã®æ¡ä»¶äžã§éšåé žåããïŒããŒãã³
ã°ããïŒéåäœãã€ã«ã ãšãªããäžæ¹ãã€ãœãã¢
ãããã³ã¯ã極ããŠèãéè²ãã€ã«ã ïŒããŒãã
ãããªïŒã€ãœãã¢ãããã³ïŒãšæãããïŒãä»ç
ããåŸã«ãããªïŒãžãããã€ãœãã¢ãããã³ïŒã«
å€æãããããšã«æ³šç®ãã¹ãã§ããããã®é©ãã¹
ã芳å¯ã«å¯Ÿããå¯äžã®åççãªèª¬æã¯ããªïŒã€ãœ
ãã¢ãããã³ïŒãã€ãœãã¢ãããã³ã®ã«ããªã³é
åã®éå§å€ãšããŠåããšãããã®ã§ãã€ãããã®
ä»®å®ã調ã¹ãããã«ãæ°ã«èª¿è£œããã€ãœãã¢ãã
ãã³ã®æº¶æ¶²ãéåžžã®ã«ããªã³éå§çšè§ŠåªïŒãã¬ã³
ã¹ãããåã³ã«ã€ã¹é žïŒã«é²åãããã€å šãŠãã€
ãœãã¢ãããã³ãçš®ã ã®çšåºŠã«éåãããããšã
èŠåºãããããããããé¢ããŠæãèå³ã®ããçµ
æã¯å¡©åã¡ãã¬ã³äžã®ç¡«é žã®å Žåã§ãã€ãããã
ãã®æ¡ä»¶äžã§ã€ãœãã¢ãããã³ã¯æ°Žåç¡«é žãããŒ
ãããæéè²ç²æ«ç¶ã®ããªïŒã€ãœãã¢ãããã³ïŒ
ã«è»¢åããããé žã觊åªãšããŠã®ã¿ãªããé žåå€
ãšããŠãåããããšã¯æããã§ãããäžèšã®ä»®å®
ã«ã€ããŠåŒ·åºã«ãããåææ§ã®ãè©Šéšã¯ãã¯ãã©
ãã«è±æ°ŽçŽ ã®çæç©ãããªïŒãžãããã€ãœãã¢ã
ããã³ïŒã§ããããã€H2SO4éåã®çæç©ãå
ãèµ€å€ã¹ãã¯ãã«ã瀺ããããšã§ãã€ãããã®èŠ³
å¯ã«å¯Ÿããå¯äžã®åççãªèª¬æã¯ãããŒãããã
ãªïŒã€ãœãã¢ãããã³ïŒã®èµ€å€ã¹ãã¯ãã«ãäŒå°
é»åã«ããåžåã«ãã€ãŠæ¯é ããããã€ååå æ¯
åã«ããåžåãã¹ãã¯ãã«ã®åŒ±ãç¹åŸŽã«ãªããšã
ãããšã§ãããè¿œå ã®å¯Ÿç §å®éšã®ç¡ãå Žåã«ãã
ã®é»è§£è³ªå¹æã説æããããã®è©³çŽ°ãªæ©æ§ã®æšæž¬
ãããããšã¯å°é£ã§ããã H2SO4ããžãããã€ãœãã¢ãããã³ââãª
ãã·ããçŽæ¥ããªïŒã€ãœãã¢ãããã³ïŒã»
ïŒH2SO4ïŒïœã»ïŒH2OïŒïœã«è»¢åãåŸãããšãè
ãåºãããåºäœã®ãžãããã€ãœãã¢ãããã³äžïŒ³
âãªãã·ãã98ïŒ H2SO4ã«å ããŠãäºå®ãææ
ã®éšåããŒãã³ã°ããããªïŒã€ãœãã¢ãããã³ïŒ
ãçæããïŒäžèšã®å³è§£ãåç §ã®ããšïŒã å ããŠãïŒïŒïŒïŒïŒïŒïŒâããã©ã·ã¢ããããž
ã¡ã¿ã³ã¯ã«ããªã³éåçšè§ŠåªãšããŠäœ¿çšããããš
ãã§ãããããããçæç©ã¯ããŒãã³ã°ãããã®
ä»ã®ããªïŒã€ãœãã¢ãããã³ïŒååç©ã®ãããã
ããé«ãé»å°åºŠã瀺ããªãã€ãããã®ããšã¯ãã
ããããå容äœãåºäœã®å°é»çã«å«ãŸããŠããªã
ããšã瀺ãããã®èŠ³å¯ã«å¯ŸããŠïŒã€ã®çç±ãæã
ãããšãã§ããå容äœååã¯ããããããå°ããª
çµæ¶é åå ã«çµã¿èŸŒãŸããŠãããåã³ïŒåã¯å®å š
ãªé»è·ç§»åããããã®ãšæãããã äžèšã®çµæã¯ããªïŒãžãããã€ãœãã¢ããã
ã³ïŒã®çææ¹æ³ã®æ§è³ªã説æãããã€ããªïŒã€ãœ
ãã¢ãããã³ïŒãååŠåæããæ£ããæé ãèŠã€
ããããšãå¯èœã«ãããããŸã ãã€ãœãã¢ããã
ã³ã®é»æ°ååŠçéåã«å ¥ã蟌ããã®ã§ã¯ãªããã
ãã¯ããçºçæã®ãããŒãã³ã°ããããªïŒã€ãœã
ã¢ãããã³ïŒã«ããããªïŒãžãããã€ãœãã¢ãã
ãã³ïŒçæã®è§Šåªäœçšã劚ããæ¹æ³ãèŠåºãããš
ãå¿ èŠãšãããåå¿åªè³ªãã€ãœãã¢ãããã³ãã
ãæ±æ žæ§ã®çš®ãå«æããå Žåã«ã¯ãçé·æ®µéã劚
ããããããšãããã€ããé»æ°å解ããåã«éœæ¥µ
宀ã«ãšãŠåç©ãå ããè©Šéšå®éšã¯ããšãŠåç©ãé»
æ°å解æ¡ä»¶äžã§ç°¡åã«é žåãããããšããå¹æã
äžããªãã€ããããããLiBrãBu4NBråã¯å¥œãŸ
ããã¯Ph4AsClã«ããé»æ°å解ã§ã¯çœéåã¯
TOGäžã«åªãããã€ã«ã ãçæããããã®èŠ³å¯
ã«å¯Ÿããå¯äžã®åççãªèª¬æã¯ãããŒãã³ã°ãã
ããªïŒã€ãœãã¢ãããã³ïŒã®èµ€å€ã¹ãã¯ãã«ãäŒ
å°é»åã«ããåžåã«ãã€ãŠæ¯é ããããã€ååå
æ¯åã«ããåžåãã¹ãã¯ãã«ã®åŒ±ãç¹åŸŽã«ãªããš
ããããšã§ãããè¿œå ã®å¯Ÿç §å®éšã®ç¡ãå Žåã«ã
ãã®é»è§£è³ªå¹æã説æããããã®è©³çŽ°ãªæ©æ§ã®æš
枬ãããããšã¯å°é£ã§ããã åæãïŒC8H6SïŒãšã㊠èšç®ïŒïŒ£ã71.60ïŒïŒšã4.51ïŒïŒ³ã23.89 å®æž¬ïŒïŒ£ã71.27ïŒïŒšã4.54ïŒïŒ³ã23.96 ãã®åå¿ã®å ŽåãLiBF4åã³Bu4NClO4ãé»è§£
質ãšããŠçšããããšãã§ããã æ¬çºæã«ããã°ãå°ããšãïŒã€ã®ç°ãæé ã«ã
ã€ãŠæºå®å®ãªã€ãœãã¢ãããã³ãéåãããŠãã
ç¹æ§ãè¡šããå°é»æ§ã®é«ãéåäœã«ããããšãã§
ããïŒãããã®å ã®ïŒã€ã¯æ±æ žæ§ã¢ããªã³ã®ååš
ã«ãããŠã€ãœãã¢ãããã³ãéåãããããªïŒãž
ãããã€ãœãã¢ãããã³ïŒã®é»æ°ååŠç補æ³ãå
å«ãããæŽã«ããªïŒã€ãœãã¢ãããã³ïŒãããªã
ãªããšã³ãããè¯å¥œãªå°äœã§ããããšãããã€
ãã å®æœäŸ ïŒ ååŠã«ããªã³éåã«ããããªïŒãžãããã€ãœã
ã¢ãããã³ïŒ äºãP2O5ã§ä¹Ÿç¥ãããå¡©åã¡ãã¬ã³10mläžã«
ã€ãœãã¢ãããã³åéäœïŒ396mgã2.96ããªã¢ã«ïŒ
ã溶解ããããã®æº¶æ¶²ã«ã¡ã¿ã³ã¹ã«ãã³é žã®ïŒæ»Ž
ãå ãããšãåå¿æ··åç©ã¯çŽã¡ã«ç¡è²ããèµ€è²ã«
å€åããããã®è²ã¯90ååŸã«ãã€ãªã¬ããè²ã«ãª
ã€ããèžçºã«ãã€ãŠå¡©åã¡ãã¬ã³ãé€ããåŸã«ã
æ®çç©ãããã©ããããã©ã³ã«æº¶è§£ããããã
ãŠããã®æº¶æ¶²ãã¡ã¿ããŒã«äžã«æ³šå ¥ãããšãããª
ïŒãžãããã€ãœãã¢ãããã³ïŒéåäœã溶液ãã
æ²æ®¿ããããããé å¿åé¢ã«ãã€ãŠåé¢ããç空
äžã§ä¹Ÿç¥ããããèµ€å€ã¹ãã¯ãã«ã¯äžèšã®ããª
ïŒãžãããã€ãœãã¢ãããã³ïŒéåäœã®ãã®ãšå
ãã§ãã€ãã 以äžã®å®æœäŸã¯æ¬çºæã®å¥œçµæã®å®æœã«ã€ããŠ
瀺ããã®ã§çºæãå¶éããã€ããã§ã¯ãªãã å®æœäŸ ïŒ é»æ°ååŠçéåã«ããããŒãã³ã°ããããªïŒã€
ãœãã¢ãããã³ïŒ éåæé ã¯å ã«ããªïŒãžãããã€ãœãã¢ããã
ã³ïŒéåäœã«ã€ããŠå®æœäŸïŒã§èª¬æããæé ãšæ¬
質çã«åãã§ãã€ããæãéèŠãªç¹ã¯é»è§£è³ªã§ã
ã€ããèåãªããŠã ãé»è§£è³ªãšããŠçšããå Žå
ã«ã1.5Vé»æ± ã«æ¥ç¶ãããšããã«ããŒãã³ã°ã
ãããªïŒã€ãœãã¢ãããã³ïŒéåäœã®éè²ãã€ã«
ã ãéœæ¥µïŒå°é»æ§ã¬ã©ã¹ïŒäžã«çæããããŸãã
Bu4NBråã³Ph4AsClããã®åå¿çšã®é»è§£è³ªãšã
ãŠäœ¿çšããããšãã§ããã å®æœäŸ ïŒ ç¡«é žãçšããååŠçã«ããªã³é žåéåã«ããã
ãŒãã³ã°ããããªïŒã€ãœãã¢ãããã³ïŒ ç¡«é žïŒïŒmlïŒãã€ãœãã¢ãããã³åéäœïŒ396
mgã2.96ããªã¢ã«ïŒã«å ãããåéäœã®è²ã¯ãçŽ
ã¡ã«ãçœè²ããèµ€è²ããã€ãé»è²ã«å€åãããå
å¿æ··åç©ãã¡ã¿ããŒã«400mläžã«æ³šå ¥ãå€éãæ¹
æããåŸã«ãããŒãã³ã°ããããªïŒã€ãœãã¢ãã
ãã³ïŒéåäœã§ããè€è²ç²æ«ããã®æº¶æ¶²ããæ²æ®¿
ããããããé å¿åé¢ã«ãã€ãŠåé¢ãããã€ãœã
ã¯ã¹ã¬ãŒæœåºåšãçšããŠå¡©åã¡ãã¬ã³åã³ã¯ãã«
ãã³ãŒã³ã§æœåºããåŸã«ç空äžã§ä¹Ÿç¥ããããã
ã®åå¿ã¯ããŸããå¡©åã¡ãã¬ã³äžã®ç¡«é žã®æžæ¿æ¶²
ã«ãã€ãŠãå®æœããããšãã§ããã å®æœäŸ 10 TCNQïŒïŒïŒïŒïŒïŒïŒïŒâããã©ã·ã¢ããããž
ã¡ã¿ã³ïŒãçšããååŠçã«ããªã³é žåéåã«ã
ãããŒãã³ã°ããããªïŒã€ãœãã¢ãããã³ïŒ ã€ãœãã¢ãããã³åéäœïŒ238mgã1.77ããªã¢
ã«ïŒãå¡©åã¡ãã¬ã³ïŒmlã«æº¶è§£ããããã®æº¶æ¶²ã«
TCNQæ°mgãå ããåŸã«ã溶液ã®è²ã¯æ¥µããŠã
ã€ããèµ€è²ã«å€åãããå€éãæ¹æããåŸã«ãã
ã®è²ã¯éè²ããã€ãé»è²ã«ãªã€ãã次ã«ããã®æº¶
液ã«ãæŽã«ã€ãœãã¢ãããã³åéäœã®ã¢ã«éã®ïŒ
åéã®TCNQãå ãããããã110âã«ãŸã§å ç±
ãããã€ïŒæéãã®æž©åºŠãä¿ã€ãããã®åå¿æ··å
ç©ãã¡ã¿ããŒã«äžã«æ³šå ¥ãããšããã®æº¶æ¶²ããç·
è²ããã€ãé»è²ã®ç²æ«ãæ²æ®¿ãããããããœãã¯
ã¹ã¬ãŒæœåºåšãçšããŠã¡ã¿ããŒã«åã³ã¯ãã«ãã³
ãŒã³ã§æŽæµããåŸã«ç空äžã§ä¹Ÿç¥ãããã å®æœäŸ 11 ããªïŒãžãããã€ãœãã¢ãããã³ïŒããã®ããª
ïŒã€ãœãã¢ãããã³ïŒ ããªïŒãžãããã€ãœãã¢ãããã³ïŒéåäœãé»
æ°ååŠçéåã«ãã€ãŠäœããç±ã¯ãã«ãã³ãŒã³ã«
溶解ãããããã¯æ·¡è€è²ã®æº¶æ¶²ã§ãã€ãããã®æº¶
液ã«ããã©âã¯ããâïœâãã³ãŸããã³ïŒã¯ãã©
ãã«ïŒãå ããã溶液ã®è²ã¯ãããã«ãæç·è²ã«
å€åããããã®æº¶æ¶²ãå·åŽãããšç²æ«ãæ²æ®¿ã
ãããããåžåŒãéã«ãã€ãŠåé¢ããã¡ã¿ããŒã«
ã§æŽæµãããã€ç空äžã§ä¹Ÿç¥ããããå®æœäŸïŒã
11ã«èšè¿°ããå šãŠã®ç©è³ªã¯åãèµ€å€ã¹ãã¯ãã«ã
瀺ããã 以äžãããæ¬çºæã¯ããªïŒã€ãœãã¢ãããã³ïŒ
ãžã®ïŒã€ã®å¥çµè·¯ãæäŸããïŒ ïŒ æ±æ žæ§ã¢ããªã³ã®ååšã«ãããã€ãœãã¢ãã
ãã³ã®é»æ°ååŠçéåïŒ ïŒ ã«ããªã³éå觊åªã®ååšã«ãããã€ãœãã¢ã
ããã³åã¯ãžãããã€ãœãã¢ãããã³ââãª
ãã·ãã®ååŠçéåïŒ ïŒ ããªïŒãžãããã€ãœãã¢ãããã³ïŒã®è±æ°Ž
çŽ ã é»å°åºŠæž¬å®ã®äºæž¬çµæãè¡šã«ãŸãšãããããª
ïŒã€ãœãã¢ãããã³ïŒã®ãã³ã端ã¯ãïŒäœãããŒã
ã³ã°ã¬ãã«ã«ãããŠèããã€ã«ã ãéãééçã
ãïŒã1eVïŒ1.1ÎŒïŒã§ãããšæšå®ããããããã¯ã
ããªããªããšã³ã®ãã³ã端ïŒã2eVïŒ620nmïŒã
ãã1eVçšäœãã
åã€ã³ãžãŠã ãèžçãããå°é»ã¬ã©ã¹ãçšããŠã
é»æ°ååŠçã«å°é»ã¬ã©ã¹äžã«éåäœãæåºãã
ãããã®éåäœã§è¢«èŠãããå°é»ã¬ã©ã¹ãè² æ¥µ
ã«ãçœéç·ãæ£æ¥µã«ãåç §é»æ¥µãšããŠæšæºã«ãã¡
ã«é»æ¥µãçšãã宀枩ã§ããã©ããã«ã¢ã³ã¢ããŠã
ããŒã¯ãã¬ãŒãã®292ããªã¢ã«ïŒã®ã¢ã»ããã
ãªã«æº¶æ¶²äžã§ããŒã©ãã°ã©ãã€ãã¯ã¢ãã©ã€ã¶ãŒ
ïŒEGïŒïŒ§ç€ŸModel 174AåïŒã«ãããµã€ã¯ãªãã¯
ãã«ã¿ã ã枬å®ãããå é»å§æåŒé床ã¯20mVïŒ
secãæåŒç¯å²ã¯ïŒ1.0Vãâ0.7VïŒå¯Ÿæšæºã«ãã¡
ã«é»æ¥µïŒãšãããåŸãããçµæã¯ç¬¬ïŒå³ã«ç€ºãã
éãã§ãã€ãã 第ïŒå³ã«ç€ºãããã«é žåããŒã¯ã¯ïŒ0.58Vãé
å ããŒã¯ã¯â0.5Vã§ããŸãâ0.7VãïŒ0.6Vã®ç¯
å²ã¯æ¿éè²ã§ããïŒ0.6ãïŒ1.0Vã®ç¯å²ã¯ã極ã
ãŠéæãªèãç·è²ã«å€è²ããããã®ããšã¯æ¿éè²
ã®ç¶æ ã¯éåäœãäžæ§ã®ç¶æ ã§ãããé žåããŒã
ã³ã°ã®ç¶æ ã§éææ§ã®é«ãç·è²ã§ããããšã瀺ã
ãŠããã ãé»æ± å®éšã å®æœäŸïŒâïŒã§åŸããã€ã«ã ãå·ŸïŒcmé·ãïŒcm
ã«åããäžç«¯ãå°é»æ§æ¥çå€ãçšãçœéç·ã«æ¥ç
ãããã®ãå寞æ³ã®ãªããŠã ç®ã®äž¡é¢ã«ïŒmmåã®
å€å質ããªãããã¬ã³è£œéèãä»ããŠé»è§£æ¶²ãå
åå«æµžåºæ¥ãããã«ããŠé 眮ãã0.5ã¢ã«ïŒã®
ãªããŠã ããŒã¯ãã¬ãŒãã®ãããã¬ã³ã«ãŒãããŒ
ã溶液ã«æ·±ãïŒcmã«æµžæŒ¬ããããã®ããã«ããŠäœ
補ããããªïŒã€ãœãã¢ãããã³ïŒãæ£æ¥µããªããŠ
ã ç®ãè² æ¥µãšããé»æ± ãçšããã¢ã«ãŽã³é°å²æ°
äžã2.0mAïŒcm2ã§30åéå é»ãè¡ã€ããå é»çµäº
åŸçŽã¡ã«2.0mAïŒcm2ã§æŸé»ãè¡ãªããé»æ± é»å§ã
1Vã«ãªã€ããšããã§å床åèšãšåãæ¡ä»¶ã§å é»
ãè¡ããå é»âæŸé»ã®ç¹°è¿ãè©Šéšãè¡ã€ããšã
ããå ã»æŸé»å¹çã50ïŒ ã«äœäžãããŸã§ã®å æŸé»
ã®ç¹°ãè¿ãåæ°ã¯590åãèšé²ããããŸãç¹°è¿ã
åæ°ïŒåç®ã®å ã»æŸé»å¹çã¯99ïŒ ã§ãã€ãããã
ã«å é»ãããŸãŸã§ã®48æéåŸã®èªå·±æŸé»çã¯3.2
ïŒ ã§ãã€ãã å®æœäŸ ïŒ é»æ°ååŠçéåã«ããããªïŒãžãããã€ãœãã¢
ãããã³ïŒãããã©ãããã³ïŒTetrahedronïŒã
1979幎35å·»2239é ããžãšãŒã»ãšãŒã»ã°ã©ãã€ã¹ã
ïŒJ.A.GladyszïŒçïŒããžã€ãŒãã« ãªã ã¢ã¡ãª
ã«ã³ ã±ãã«ã« ãœãµã€ã¢ãã€ïŒJ.Amer.Chem.
Soe.ïŒã1959幎81å·»4266é ããšã ã»ããŒã»ã«ãŒã
ïŒM.P.CavaïŒçïŒããžã€ãŒãã« ãªã ãªãŒã¬ã
ã㯠ã±ãã¹ããªãŒïŒJ.Org.Chem.ïŒã1971幎36
å·»3932é ããšã ã»ããŒã»ã«ãŒãçã®æç®ã«èšèŒã
ããŠããæé ã«ãã€ãŠã€ãœãã¢ãããã³åéäœã
äœããããã«äœ¿çšããããã®åéäœãäºé»æ¥µãé
宀é»è§£æ§œã«ãããŠé»æ°ååŠçã«é žåããŠããªïŒãž
ãããã€ãœãã¢ãããã³ïŒéåäœãåŸããçœéæ¿
ãéœæ¥µãšããŠçšããé žåé»éãé°æ¥µãšããŠçšã
ããéåã«çšãã溶液ã¯ç¡è²éæã§ãã¢ã»ããã
ãªã«äžã«ã€ãœãã¢ãããã³0.23Mãé»è§£è³ªã§ãã
Bu4NPF6 0.30Mãšå ±ã«å«æãããã®ã§ãã€ãã
ã¢ã»ããããªã«ïŒããªã³ã¯ããã
ïŒMallinckrodtïŒããè³Œå ¥ïŒã¯æŽã«ç²Ÿè£œããã«çŽ
æ¥äœ¿çšãããçŽåã®1.5Vé»æ± ãé»æºãšããŠçšã
ãã å šãŠã®å®éšã也ç¥N2äžã§è¡ã€ãããã®é»è§£æ§œ
ã«4.5Vãæ¥ç¶ãããšããã«ãéœæ¥µã®ä»è¿ã«å€é
ã®çœè²ç²æ«ãçŸããã10ååŸã«é»æ± ãåã€ãŠãšã
ããããªïŒãžãããã€ãœãã¢ãããã³ïŒã§ããã
ã®çœè²ç²æ«ãåžåŒãéã«ããåé¢ããã¢ã»ããã
ãªã«åã³ãžãšãã«ãšãŒãã«ã§æŽæµããç空äžã§ä¹Ÿ
ç¥ããããçæããåºäœãããã©ããããã©ã³â
H2Oããåæ²ãããŠç²Ÿè£œããå çŽ åæãè¡ã€ãã æ°ã«èª¿è£œããã€ãœãã¢ãããã³ã®è©Šæãã
Bu4NClO4åã¯Bu4NBF4ãæ¯æé»è§£è³ªãšããŠã
ã€é žåã¹ãºè¢«èŠã¬ã©ã¹ïŒTOGïŒãéœæ¥µãšããŠçš
ããåé»è§£æ§œã®éœæ¥µå®€ã§é»æ°å解ãããšããã
éœæ¥µå®€ã¯å€éã®çœè²æ²æ®¿ïŒWPïŒã§äžæ¯ã«ãªã€
ãã泚ææ·±ã芳å¯ãããšãããéœæ¥µã¯åãã«ïŒç¬
éçã«ïŒéåžžã«èãéè²ãã€ã«ã ã§ãããããã
ãåŸã«WPã®çæãå§ãŸãããšãããã€ããWP
ã®å€èŠ³ã¯é»æ¥µææã溶åªåã¯æž©åºŠã«é¢ä¿ããªãã€
ããåé¢ãç¹æ§æ±ºå®ïŒèµ€å€ãå çŽ åæïŒåã³ååŠ
æäœïŒäžèšåç §ïŒã«ããWPãããªïŒãžãããã€
ãœãã¢ãããã³ïŒã§ããããšã蚌æããããããª
ããšã³ã¯äžèšã®æ¡ä»¶äžã§éšåé žåããïŒããŒãã³
ã°ããïŒéåäœãã€ã«ã ãšãªããäžæ¹ãã€ãœãã¢
ãããã³ã¯ã極ããŠèãéè²ãã€ã«ã ïŒããŒãã
ãããªïŒã€ãœãã¢ãããã³ïŒãšæãããïŒãä»ç
ããåŸã«ãããªïŒãžãããã€ãœãã¢ãããã³ïŒã«
å€æãããããšã«æ³šç®ãã¹ãã§ããããã®é©ãã¹
ã芳å¯ã«å¯Ÿããå¯äžã®åççãªèª¬æã¯ããªïŒã€ãœ
ãã¢ãããã³ïŒãã€ãœãã¢ãããã³ã®ã«ããªã³é
åã®éå§å€ãšããŠåããšãããã®ã§ãã€ãããã®
ä»®å®ã調ã¹ãããã«ãæ°ã«èª¿è£œããã€ãœãã¢ãã
ãã³ã®æº¶æ¶²ãéåžžã®ã«ããªã³éå§çšè§ŠåªïŒãã¬ã³
ã¹ãããåã³ã«ã€ã¹é žïŒã«é²åãããã€å šãŠãã€
ãœãã¢ãããã³ãçš®ã ã®çšåºŠã«éåãããããšã
èŠåºãããããããããé¢ããŠæãèå³ã®ããçµ
æã¯å¡©åã¡ãã¬ã³äžã®ç¡«é žã®å Žåã§ãã€ãããã
ãã®æ¡ä»¶äžã§ã€ãœãã¢ãããã³ã¯æ°Žåç¡«é žãããŒ
ãããæéè²ç²æ«ç¶ã®ããªïŒã€ãœãã¢ãããã³ïŒ
ã«è»¢åããããé žã觊åªãšããŠã®ã¿ãªããé žåå€
ãšããŠãåããããšã¯æããã§ãããäžèšã®ä»®å®
ã«ã€ããŠåŒ·åºã«ãããåææ§ã®ãè©Šéšã¯ãã¯ãã©
ãã«è±æ°ŽçŽ ã®çæç©ãããªïŒãžãããã€ãœãã¢ã
ããã³ïŒã§ããããã€H2SO4éåã®çæç©ãå
ãèµ€å€ã¹ãã¯ãã«ã瀺ããããšã§ãã€ãããã®èŠ³
å¯ã«å¯Ÿããå¯äžã®åççãªèª¬æã¯ãããŒãããã
ãªïŒã€ãœãã¢ãããã³ïŒã®èµ€å€ã¹ãã¯ãã«ãäŒå°
é»åã«ããåžåã«ãã€ãŠæ¯é ããããã€ååå æ¯
åã«ããåžåãã¹ãã¯ãã«ã®åŒ±ãç¹åŸŽã«ãªããšã
ãããšã§ãããè¿œå ã®å¯Ÿç §å®éšã®ç¡ãå Žåã«ãã
ã®é»è§£è³ªå¹æã説æããããã®è©³çŽ°ãªæ©æ§ã®æšæž¬
ãããããšã¯å°é£ã§ããã H2SO4ããžãããã€ãœãã¢ãããã³ââãª
ãã·ããçŽæ¥ããªïŒã€ãœãã¢ãããã³ïŒã»
ïŒH2SO4ïŒïœã»ïŒH2OïŒïœã«è»¢åãåŸãããšãè
ãåºãããåºäœã®ãžãããã€ãœãã¢ãããã³äžïŒ³
âãªãã·ãã98ïŒ H2SO4ã«å ããŠãäºå®ãææ
ã®éšåããŒãã³ã°ããããªïŒã€ãœãã¢ãããã³ïŒ
ãçæããïŒäžèšã®å³è§£ãåç §ã®ããšïŒã å ããŠãïŒïŒïŒïŒïŒïŒïŒâããã©ã·ã¢ããããž
ã¡ã¿ã³ã¯ã«ããªã³éåçšè§ŠåªãšããŠäœ¿çšããããš
ãã§ãããããããçæç©ã¯ããŒãã³ã°ãããã®
ä»ã®ããªïŒã€ãœãã¢ãããã³ïŒååç©ã®ãããã
ããé«ãé»å°åºŠã瀺ããªãã€ãããã®ããšã¯ãã
ããããå容äœãåºäœã®å°é»çã«å«ãŸããŠããªã
ããšã瀺ãããã®èŠ³å¯ã«å¯ŸããŠïŒã€ã®çç±ãæã
ãããšãã§ããå容äœååã¯ããããããå°ããª
çµæ¶é åå ã«çµã¿èŸŒãŸããŠãããåã³ïŒåã¯å®å š
ãªé»è·ç§»åããããã®ãšæãããã äžèšã®çµæã¯ããªïŒãžãããã€ãœãã¢ããã
ã³ïŒã®çææ¹æ³ã®æ§è³ªã説æãããã€ããªïŒã€ãœ
ãã¢ãããã³ïŒãååŠåæããæ£ããæé ãèŠã€
ããããšãå¯èœã«ãããããŸã ãã€ãœãã¢ããã
ã³ã®é»æ°ååŠçéåã«å ¥ã蟌ããã®ã§ã¯ãªããã
ãã¯ããçºçæã®ãããŒãã³ã°ããããªïŒã€ãœã
ã¢ãããã³ïŒã«ããããªïŒãžãããã€ãœãã¢ãã
ãã³ïŒçæã®è§Šåªäœçšã劚ããæ¹æ³ãèŠåºãããš
ãå¿ èŠãšãããåå¿åªè³ªãã€ãœãã¢ãããã³ãã
ãæ±æ žæ§ã®çš®ãå«æããå Žåã«ã¯ãçé·æ®µéã劚
ããããããšãããã€ããé»æ°å解ããåã«éœæ¥µ
宀ã«ãšãŠåç©ãå ããè©Šéšå®éšã¯ããšãŠåç©ãé»
æ°å解æ¡ä»¶äžã§ç°¡åã«é žåãããããšããå¹æã
äžããªãã€ããããããLiBrãBu4NBråã¯å¥œãŸ
ããã¯Ph4AsClã«ããé»æ°å解ã§ã¯çœéåã¯
TOGäžã«åªãããã€ã«ã ãçæããããã®èŠ³å¯
ã«å¯Ÿããå¯äžã®åççãªèª¬æã¯ãããŒãã³ã°ãã
ããªïŒã€ãœãã¢ãããã³ïŒã®èµ€å€ã¹ãã¯ãã«ãäŒ
å°é»åã«ããåžåã«ãã€ãŠæ¯é ããããã€ååå
æ¯åã«ããåžåãã¹ãã¯ãã«ã®åŒ±ãç¹åŸŽã«ãªããš
ããããšã§ãããè¿œå ã®å¯Ÿç §å®éšã®ç¡ãå Žåã«ã
ãã®é»è§£è³ªå¹æã説æããããã®è©³çŽ°ãªæ©æ§ã®æš
枬ãããããšã¯å°é£ã§ããã åæãïŒC8H6SïŒãšã㊠èšç®ïŒïŒ£ã71.60ïŒïŒšã4.51ïŒïŒ³ã23.89 å®æž¬ïŒïŒ£ã71.27ïŒïŒšã4.54ïŒïŒ³ã23.96 ãã®åå¿ã®å ŽåãLiBF4åã³Bu4NClO4ãé»è§£
質ãšããŠçšããããšãã§ããã æ¬çºæã«ããã°ãå°ããšãïŒã€ã®ç°ãæé ã«ã
ã€ãŠæºå®å®ãªã€ãœãã¢ãããã³ãéåãããŠãã
ç¹æ§ãè¡šããå°é»æ§ã®é«ãéåäœã«ããããšãã§
ããïŒãããã®å ã®ïŒã€ã¯æ±æ žæ§ã¢ããªã³ã®ååš
ã«ãããŠã€ãœãã¢ãããã³ãéåãããããªïŒãž
ãããã€ãœãã¢ãããã³ïŒã®é»æ°ååŠç補æ³ãå
å«ãããæŽã«ããªïŒã€ãœãã¢ãããã³ïŒãããªã
ãªããšã³ãããè¯å¥œãªå°äœã§ããããšãããã€
ãã å®æœäŸ ïŒ ååŠã«ããªã³éåã«ããããªïŒãžãããã€ãœã
ã¢ãããã³ïŒ äºãP2O5ã§ä¹Ÿç¥ãããå¡©åã¡ãã¬ã³10mläžã«
ã€ãœãã¢ãããã³åéäœïŒ396mgã2.96ããªã¢ã«ïŒ
ã溶解ããããã®æº¶æ¶²ã«ã¡ã¿ã³ã¹ã«ãã³é žã®ïŒæ»Ž
ãå ãããšãåå¿æ··åç©ã¯çŽã¡ã«ç¡è²ããèµ€è²ã«
å€åããããã®è²ã¯90ååŸã«ãã€ãªã¬ããè²ã«ãª
ã€ããèžçºã«ãã€ãŠå¡©åã¡ãã¬ã³ãé€ããåŸã«ã
æ®çç©ãããã©ããããã©ã³ã«æº¶è§£ããããã
ãŠããã®æº¶æ¶²ãã¡ã¿ããŒã«äžã«æ³šå ¥ãããšãããª
ïŒãžãããã€ãœãã¢ãããã³ïŒéåäœã溶液ãã
æ²æ®¿ããããããé å¿åé¢ã«ãã€ãŠåé¢ããç空
äžã§ä¹Ÿç¥ããããèµ€å€ã¹ãã¯ãã«ã¯äžèšã®ããª
ïŒãžãããã€ãœãã¢ãããã³ïŒéåäœã®ãã®ãšå
ãã§ãã€ãã 以äžã®å®æœäŸã¯æ¬çºæã®å¥œçµæã®å®æœã«ã€ããŠ
瀺ããã®ã§çºæãå¶éããã€ããã§ã¯ãªãã å®æœäŸ ïŒ é»æ°ååŠçéåã«ããããŒãã³ã°ããããªïŒã€
ãœãã¢ãããã³ïŒ éåæé ã¯å ã«ããªïŒãžãããã€ãœãã¢ããã
ã³ïŒéåäœã«ã€ããŠå®æœäŸïŒã§èª¬æããæé ãšæ¬
質çã«åãã§ãã€ããæãéèŠãªç¹ã¯é»è§£è³ªã§ã
ã€ããèåãªããŠã ãé»è§£è³ªãšããŠçšããå Žå
ã«ã1.5Vé»æ± ã«æ¥ç¶ãããšããã«ããŒãã³ã°ã
ãããªïŒã€ãœãã¢ãããã³ïŒéåäœã®éè²ãã€ã«
ã ãéœæ¥µïŒå°é»æ§ã¬ã©ã¹ïŒäžã«çæããããŸãã
Bu4NBråã³Ph4AsClããã®åå¿çšã®é»è§£è³ªãšã
ãŠäœ¿çšããããšãã§ããã å®æœäŸ ïŒ ç¡«é žãçšããååŠçã«ããªã³é žåéåã«ããã
ãŒãã³ã°ããããªïŒã€ãœãã¢ãããã³ïŒ ç¡«é žïŒïŒmlïŒãã€ãœãã¢ãããã³åéäœïŒ396
mgã2.96ããªã¢ã«ïŒã«å ãããåéäœã®è²ã¯ãçŽ
ã¡ã«ãçœè²ããèµ€è²ããã€ãé»è²ã«å€åãããå
å¿æ··åç©ãã¡ã¿ããŒã«400mläžã«æ³šå ¥ãå€éãæ¹
æããåŸã«ãããŒãã³ã°ããããªïŒã€ãœãã¢ãã
ãã³ïŒéåäœã§ããè€è²ç²æ«ããã®æº¶æ¶²ããæ²æ®¿
ããããããé å¿åé¢ã«ãã€ãŠåé¢ãããã€ãœã
ã¯ã¹ã¬ãŒæœåºåšãçšããŠå¡©åã¡ãã¬ã³åã³ã¯ãã«
ãã³ãŒã³ã§æœåºããåŸã«ç空äžã§ä¹Ÿç¥ããããã
ã®åå¿ã¯ããŸããå¡©åã¡ãã¬ã³äžã®ç¡«é žã®æžæ¿æ¶²
ã«ãã€ãŠãå®æœããããšãã§ããã å®æœäŸ 10 TCNQïŒïŒïŒïŒïŒïŒïŒïŒâããã©ã·ã¢ããããž
ã¡ã¿ã³ïŒãçšããååŠçã«ããªã³é žåéåã«ã
ãããŒãã³ã°ããããªïŒã€ãœãã¢ãããã³ïŒ ã€ãœãã¢ãããã³åéäœïŒ238mgã1.77ããªã¢
ã«ïŒãå¡©åã¡ãã¬ã³ïŒmlã«æº¶è§£ããããã®æº¶æ¶²ã«
TCNQæ°mgãå ããåŸã«ã溶液ã®è²ã¯æ¥µããŠã
ã€ããèµ€è²ã«å€åãããå€éãæ¹æããåŸã«ãã
ã®è²ã¯éè²ããã€ãé»è²ã«ãªã€ãã次ã«ããã®æº¶
液ã«ãæŽã«ã€ãœãã¢ãããã³åéäœã®ã¢ã«éã®ïŒ
åéã®TCNQãå ãããããã110âã«ãŸã§å ç±
ãããã€ïŒæéãã®æž©åºŠãä¿ã€ãããã®åå¿æ··å
ç©ãã¡ã¿ããŒã«äžã«æ³šå ¥ãããšããã®æº¶æ¶²ããç·
è²ããã€ãé»è²ã®ç²æ«ãæ²æ®¿ãããããããœãã¯
ã¹ã¬ãŒæœåºåšãçšããŠã¡ã¿ããŒã«åã³ã¯ãã«ãã³
ãŒã³ã§æŽæµããåŸã«ç空äžã§ä¹Ÿç¥ãããã å®æœäŸ 11 ããªïŒãžãããã€ãœãã¢ãããã³ïŒããã®ããª
ïŒã€ãœãã¢ãããã³ïŒ ããªïŒãžãããã€ãœãã¢ãããã³ïŒéåäœãé»
æ°ååŠçéåã«ãã€ãŠäœããç±ã¯ãã«ãã³ãŒã³ã«
溶解ãããããã¯æ·¡è€è²ã®æº¶æ¶²ã§ãã€ãããã®æº¶
液ã«ããã©âã¯ããâïœâãã³ãŸããã³ïŒã¯ãã©
ãã«ïŒãå ããã溶液ã®è²ã¯ãããã«ãæç·è²ã«
å€åããããã®æº¶æ¶²ãå·åŽãããšç²æ«ãæ²æ®¿ã
ãããããåžåŒãéã«ãã€ãŠåé¢ããã¡ã¿ããŒã«
ã§æŽæµãããã€ç空äžã§ä¹Ÿç¥ããããå®æœäŸïŒã
11ã«èšè¿°ããå šãŠã®ç©è³ªã¯åãèµ€å€ã¹ãã¯ãã«ã
瀺ããã 以äžãããæ¬çºæã¯ããªïŒã€ãœãã¢ãããã³ïŒ
ãžã®ïŒã€ã®å¥çµè·¯ãæäŸããïŒ ïŒ æ±æ žæ§ã¢ããªã³ã®ååšã«ãããã€ãœãã¢ãã
ãã³ã®é»æ°ååŠçéåïŒ ïŒ ã«ããªã³éå觊åªã®ååšã«ãããã€ãœãã¢ã
ããã³åã¯ãžãããã€ãœãã¢ãããã³ââãª
ãã·ãã®ååŠçéåïŒ ïŒ ããªïŒãžãããã€ãœãã¢ãããã³ïŒã®è±æ°Ž
çŽ ã é»å°åºŠæž¬å®ã®äºæž¬çµæãè¡šã«ãŸãšãããããª
ïŒã€ãœãã¢ãããã³ïŒã®ãã³ã端ã¯ãïŒäœãããŒã
ã³ã°ã¬ãã«ã«ãããŠèããã€ã«ã ãéãééçã
ãïŒã1eVïŒ1.1ÎŒïŒã§ãããšæšå®ããããããã¯ã
ããªããªããšã³ã®ãã³ã端ïŒã2eVïŒ620nmïŒã
ãã1eVçšäœãã
ãè¡šã
ãè¡šã
å®æœäŸ 11
ïœ ïŒâãã«ãŒãå§çž®æž¬å®
第ïŒå³ã¯ããªïŒã€ãœãã¢ãããã³ïŒã®å¯éé»
æ°ååŠçããŒãã³ã°ã瀺ãããããããã¢ã«ã
ããŠã ãïŒæšæºã«ãã¡ã«åç §é»æ¥µã®å ŽåïŒäžæ¹
ã®é»æ¥µãšããŠçšããããªïŒã€ãœãã¢ãããã³ïŒ
ãä»æ¹ã®é»æ¥µãšããŠçšãããã€ãã«ãªãããŠé ž
ãªããŠã ã®çé žãããã¬ã³æº¶æ¶²ãé»è§£è³ªãšããŠ
çšããã°ãæ¬çºæã®éåäœãé»æ± é»æ¥µãšããŠæ
çšã§ããããšãç解ã§ããã 第ïŒå³ã®å®éšã¯ãæŽã«ãæ¬çºæã®æ°èŠéåäœ
ã®ãšã¬ã¯ããã¯ãããã¯ç¹æ§ãã瀺ãã
æ°ååŠçããŒãã³ã°ã瀺ãããããããã¢ã«ã
ããŠã ãïŒæšæºã«ãã¡ã«åç §é»æ¥µã®å ŽåïŒäžæ¹
ã®é»æ¥µãšããŠçšããããªïŒã€ãœãã¢ãããã³ïŒ
ãä»æ¹ã®é»æ¥µãšããŠçšãããã€ãã«ãªãããŠé ž
ãªããŠã ã®çé žãããã¬ã³æº¶æ¶²ãé»è§£è³ªãšããŠ
çšããã°ãæ¬çºæã®éåäœãé»æ± é»æ¥µãšããŠæ
çšã§ããããšãç解ã§ããã 第ïŒå³ã®å®éšã¯ãæŽã«ãæ¬çºæã®æ°èŠéåäœ
ã®ãšã¬ã¯ããã¯ãããã¯ç¹æ§ãã瀺ãã
第ïŒå³ã¯å®æœäŸïŒã§è£œé ããéåäœã®èµ€å€åžå
ã¹ãã¯ãã«å³ã§ããã第ïŒå³ã¯å®æœäŸïŒã§è£œé ã
ãéåäœã®èµ€å€åžåã¹ãã¯ãã«å³ã§ããã第ïŒå³
ã¯å®æœäŸïŒã§è£œé ããéåäœã®NMRã¹ãã¯ãã«
å³ã§ããã第ïŒå³ã¯å®æœäŸïŒã§è£œé ãã第äžã®é
åäœãã¯ãã©ãã«ã§åŠçããåŸã®éåäœã®èµ€å€åž
åã¹ãã¯ãã«å³ã§ããã第ïŒå³ã¯å®æœäŸïŒã®ãšã¬
ã¯ããã¯ãããã¯ææè©Šéšã§åŸãããéåäœã®ã
ãŒã©ãã°ã©ãåæçµæã瀺ããã€ãŒãå³ã§ããã
第ïŒå³ã¯æšæºã«ãã¡ã«é»æ¥µïŒSCEïŒã«å¯ŸããŠèšé²
ããããªïŒã€ãœãã¢ãããã³ïŒãã€ã«ã ã®é»æ°å
åŠçå¯éæ§ã瀺ãå³ã§ããïŒïŒ0.6VïŒé»è²ãé
æïŒâ0.4VïŒæéè²äžéæïŒé»è§£è³ªïŒçé žãã
ãã¬ã³äžã®LiïŒBF4 -ãæ¬äŸã«ãããé žåéåäœ
ã¯ããŒãã³ã°å€ãšããŠBF4ãå«æããã
ã¹ãã¯ãã«å³ã§ããã第ïŒå³ã¯å®æœäŸïŒã§è£œé ã
ãéåäœã®èµ€å€åžåã¹ãã¯ãã«å³ã§ããã第ïŒå³
ã¯å®æœäŸïŒã§è£œé ããéåäœã®NMRã¹ãã¯ãã«
å³ã§ããã第ïŒå³ã¯å®æœäŸïŒã§è£œé ãã第äžã®é
åäœãã¯ãã©ãã«ã§åŠçããåŸã®éåäœã®èµ€å€åž
åã¹ãã¯ãã«å³ã§ããã第ïŒå³ã¯å®æœäŸïŒã®ãšã¬
ã¯ããã¯ãããã¯ææè©Šéšã§åŸãããéåäœã®ã
ãŒã©ãã°ã©ãåæçµæã瀺ããã€ãŒãå³ã§ããã
第ïŒå³ã¯æšæºã«ãã¡ã«é»æ¥µïŒSCEïŒã«å¯ŸããŠèšé²
ããããªïŒã€ãœãã¢ãããã³ïŒãã€ã«ã ã®é»æ°å
åŠçå¯éæ§ã瀺ãå³ã§ããïŒïŒ0.6VïŒé»è²ãé
æïŒâ0.4VïŒæéè²äžéæïŒé»è§£è³ªïŒçé žãã
ãã¬ã³äžã®LiïŒBF4 -ãæ¬äŸã«ãããé žåéåäœ
ã¯ããŒãã³ã°å€ãšããŠBF4ãå«æããã
Claims (1)
- ãç¹èš±è«æ±ã®ç¯å²ã ïŒ äžè¬åŒ ãåŒãåã³ïŒå㯠ãåŒã ïŒåŒäžãR1åã³R2ã¯ããããç¬ç«ã«æ°ŽçŽ åã¯ç
çŽ æ°ïŒãïŒã®çåæ°ŽçŽ åºãè¡šãããX-ã¯é»è§£è³ª
ã®é°ã€ãªã³ãè¡šãããïœã¯ã¢ãããŒïŒã¢ã«åœãã®
é°ã€ãªã³ã®å²åã瀺ã0.01ãïŒã®æ°ã§ãããïœã¯
éå床ã瀺ãïŒã500ã®æ°ã§ããïŒã§è¡šãããã
ã€ãœãã¢ãããã³æ§é ãæããéåäœã ïŒ åèšäžè¬åŒïŒïœïŒã§è¡šããããã€ãœãã¢ã
ããã³æ§é ã®é»è§£è³ªé°ã€ãªã³X-ãCl-ãBr-ãI-ã
ClO4ãBF4 -ãPF6 -ãAsFb6 -ãSbF6 -ãAlCl4 -ã
AlBr3Cl-ãFeCl4 -ãSnCl3 -åã³CF3SO3 -ããéž
ã°ãããã®ã§ããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒé ã«èšèŒã®
éåäœã
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10932984A JPS6117581A (ja) | 1984-05-31 | 1984-05-31 | ã€ãœãã¢ãããã³æ§é ãæããéåäœ |
| US06/736,984 US4640748A (en) | 1984-05-31 | 1985-05-22 | Polyisothianaphtene, a new conducting polymer |
| CA000482753A CA1248690A (en) | 1984-05-31 | 1985-05-30 | Polyisothianaphthene, a new conducting polymer |
| EP85303864A EP0164974B1 (en) | 1984-05-31 | 1985-05-31 | Polymer having isothianaphthene structure and electrochromic display |
| AT85303864T ATE53046T1 (de) | 1984-05-31 | 1985-05-31 | Polymere mit isothianaphthen-struktur und elektrochromische anzeigevorrichtung. |
| DE8585303864T DE3577860D1 (de) | 1984-05-31 | 1985-05-31 | Polymere mit isothianaphthen-struktur und elektrochromische anzeigevorrichtung. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10932984A JPS6117581A (ja) | 1984-05-31 | 1984-05-31 | ã€ãœãã¢ãããã³æ§é ãæããéåäœ |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6117581A JPS6117581A (ja) | 1986-01-25 |
| JPS6411207B2 true JPS6411207B2 (ja) | 1989-02-23 |
Family
ID=14507462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10932984A Granted JPS6117581A (ja) | 1984-05-31 | 1984-05-31 | ã€ãœãã¢ãããã³æ§é ãæããéåäœ |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6117581A (ja) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0739477B2 (ja) * | 1986-11-06 | 1995-05-01 | æåé»å·¥æ ªåŒäŒç€Ÿ | ã€ãœãã¢ãããã³æ§é ãæããéåäœã®è£œé æ¹æ³ |
| JPH0273826A (ja) * | 1988-09-09 | 1990-03-13 | Toyobo Co Ltd | å°é»æ§éåäœã®è£œé æ¹æ³ |
| JPH0275625A (ja) * | 1988-09-13 | 1990-03-15 | Toyobo Co Ltd | å°é»æ§éåäœ |
| US11136432B2 (en) | 2016-12-28 | 2021-10-05 | Showa Denko K.K. | Method for producing polyisothianaphthene-based electroconductive polymer |
-
1984
- 1984-05-31 JP JP10932984A patent/JPS6117581A/ja active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6117581A (ja) | 1986-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wudl et al. | Poly (isothianaphthene) | |
| JP2777440B2 (ja) | 眮æããªãã§ã³ããããã®ããªãã§ã³ããèªå°ãããå°é»æ§ããªããŒåã³ãããã®è£œé æ¹æ³äžŠã³ã«ãããã®ããªããŒãå«ãè£ çœ® | |
| US5268448A (en) | Conducting polymers derived from fluorinated thiophenes | |
| US4640748A (en) | Polyisothianaphtene, a new conducting polymer | |
| JP4124487B2 (ja) | äºå¡ç°ã¢ããªã³å¡©åã¯ããã©ã¢ã¶ãã³ã¿ã¬ã³èªå°äœãšãã€ãªã³äŒå°æ§ç©è³ªãšããŠã®ãããã®äœ¿çš | |
| US4740436A (en) | Secondary battery | |
| EP0273643B1 (en) | Conducting substituted polyisothianophthenes | |
| US9890230B2 (en) | Tetracyanoanthraquinodimethane polymers and use thereof | |
| JPS63500105A (ja) | å°é»æ§é«åå | |
| US10263280B2 (en) | 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymers and use thereof | |
| JP3234638B2 (ja) | ããçŽ åããªãã§ã³ããããã®ããªãã§ã³ããèªå°ãããããªããŒåã³ãããã®ããªããŒãå«ãå°é»æ§ããªã㌠| |
| JP2892784B2 (ja) | ããçŽ åããªããšã³ããããã®ããªããšã³ããèªå°ãããå°é»æ§ããªããŒããããã®è£œé æ¹æ³åã³ãããã®ããªããŒãå«ãè£ çœ® | |
| US4772940A (en) | Polymer having isothianaphthene structure and electrochromic display | |
| JPH0138808B2 (ja) | ||
| EP0164974B1 (en) | Polymer having isothianaphthene structure and electrochromic display | |
| WO1987003607A1 (fr) | Polymeres ayant une structure isoindole et leur procede de preparation | |
| JPH05314979A (ja) | å¯éæ§é»æ¥µ | |
| CN1023527C (zh) | å¯åå çµçµæ± çµæåé«ååé富çµè | |
| JPH0794538B2 (ja) | æ°èŠãªéåäœããã³ãã®è£œé æ¹æ³ | |
| JPS6117581A (ja) | ã€ãœãã¢ãããã³æ§é ãæããéåäœ | |
| JP2536865B2 (ja) | é»æ± çšæŽ»ç©è³ª | |
| JPH0211614B2 (ja) | ||
| JP2862244B2 (ja) | ãããŒã«èªå°äœããã³ãã®éåäœ | |
| JP2530428B2 (ja) | ããªã¢ããªã³ãé»æ¥µææãšããäºæ¬¡é»æ± | |
| JPH07121983B2 (ja) | ã€ãœãã¢ãããã³æ§é ãæããéåäœã®è£œé æ¹æ³ |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |