TW310329B - - Google Patents
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- TW310329B TW310329B TW084112917A TW84112917A TW310329B TW 310329 B TW310329 B TW 310329B TW 084112917 A TW084112917 A TW 084112917A TW 84112917 A TW84112917 A TW 84112917A TW 310329 B TW310329 B TW 310329B
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- Taiwan
- Prior art keywords
- formula
- acid
- printed
- compound
- hydrogen
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- -1 sulpho Chemical class 0.000 claims abstract description 27
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 16
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 13
- 150000001450 anions Chemical class 0.000 claims abstract description 7
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 6
- 125000001118 alkylidene group Chemical group 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002577 pseudohalo group Chemical group 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001345 alkine derivatives Chemical class 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- KZUKUEXZPFTLAV-UHFFFAOYSA-N [C].[Co].[Co] Chemical compound [C].[Co].[Co] KZUKUEXZPFTLAV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 230000002079 cooperative effect Effects 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002527 isonitriles Chemical class 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 150000002431 hydrogen Chemical class 0.000 claims 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N Vilsmeier-Haack reagent Natural products CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 206010039509 Scab Diseases 0.000 claims 1
- 150000004645 aluminates Chemical class 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical group CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 10
- 125000003118 aryl group Chemical group 0.000 abstract description 6
- 125000003710 aryl alkyl group Chemical group 0.000 abstract description 2
- 125000000753 cycloalkyl group Chemical group 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052772 Samarium Inorganic materials 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 150000002601 lanthanoid compounds Chemical class 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- WDFZWSZNOFELJY-UHFFFAOYSA-N Arene oxide Chemical class C1=CC=CC2OC21 WDFZWSZNOFELJY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- ZQPJZZQRZDOMFD-UHFFFAOYSA-N [amino(methyl)silyl]methane Chemical compound C[SiH](C)N ZQPJZZQRZDOMFD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- ODJKHOBNYXJHRG-UHFFFAOYSA-N 1,3-dimethylimidazole Chemical compound CN1[CH]N(C)C=C1 ODJKHOBNYXJHRG-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 101100328518 Caenorhabditis elegans cnt-1 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000006957 Michael reaction Methods 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 241000218206 Ranunculus Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 235000006085 Vigna mungo var mungo Nutrition 0.000 description 1
- 240000005616 Vigna mungo var. mungo Species 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical class NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- KMFAICDZUONSPP-UHFFFAOYSA-N bis(dimethylsilyl)azanide yttrium(3+) Chemical compound C[SiH]([N-][SiH](C)C)C.C[SiH]([N-][SiH](C)C)C.C[SiH]([N-][SiH](C)C)C.[Y+3] KMFAICDZUONSPP-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002592 krypton Chemical class 0.000 description 1
- 229910021644 lanthanide ion Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- KBPHJBAIARWVSC-RGZFRNHPSA-N lutein Chemical compound C([C@H](O)CC=1C)C(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\[C@H]1C(C)=C[C@H](O)CC1(C)C KBPHJBAIARWVSC-RGZFRNHPSA-N 0.000 description 1
- 229960005375 lutein Drugs 0.000 description 1
- ORAKUVXRZWMARG-WZLJTJAWSA-N lutein Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCCC1(C)C)C=CC=C(/C)C=CC2C(=CC(O)CC2(C)C)C ORAKUVXRZWMARG-WZLJTJAWSA-N 0.000 description 1
- 235000012680 lutein Nutrition 0.000 description 1
- 239000001656 lutein Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 125000003906 silylidene group Chemical group [H][Si]([H])=* 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- KBPHJBAIARWVSC-XQIHNALSSA-N trans-lutein Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2C(=CC(O)CC2(C)C)C KBPHJBAIARWVSC-XQIHNALSSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- FJHBOVDFOQMZRV-XQIHNALSSA-N xanthophyll Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2C=C(C)C(O)CC2(C)C FJHBOVDFOQMZRV-XQIHNALSSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
A 7 B7 經濟部中央搮準局員工消費合作社印製 五、發明説明(1 ) 本發明係關於原子序數57至71的元素(鉅除外)之錯 合物,以雜環碳烯爲錯合配合基。稀土金勝群包括14種元 素,即铈、鐯、钕、鉬、釤、銪、钆、μ、rt、鈥、鋇、 珐、鏡、&|。由於其化學類似性大,故與第三過渡族的金 屬(按照TUPAC 1985推荐,屬第3族),即炕、釔、鑭 ,合稱鑭系元素。 此群17種元素的化學化合物主要爲三價,但鏰系個別 代表形成化合物爲四價(例如铈、Μ )和二價(例如銪、 鐘)。鑭系化學化合物顯示主宰性離子結合和明顯與氧結 合的傾向。鑭系化合物的應用廣泛,第一次槪算是衍自金 屬離子的路易氏酸性,尤其是在較高的氣化狀態,以及可 做爲還原劑和氧化劑的電化學性能。因此,四價铈是強烈 的單電子氧化劑。二價釤做爲選擇性偶合反應劑用於有機 合成。許多鑭系金屬適於摻雜螢光燈材料,因其來自金屬 合金的電子作業功能大降。 幾乎所有_系離子均可溶劑化,即添加路易氏鹸配合 基(例如醚類、胺類)。添加此等鹸常導致鋼系化合物在 有機溶劑內之改進溶解度。同時提高水解安定性,在簡單 的鑭系化合物,諸如鹵化物中,該安定性低。此外,通常 有益的是發生所述金屬離子的路易氏酸性降低。鑑於事實 上許多鑭系化合物可在有機化合物反應中做爲活性觸媒, 則特別需要鑭系金靥反應性之標的控制。在此脈絡中,重 要性是附屬於充分的親核性配合劑,具有安定性,即不形 成與鑭系金屬_子結合的通常解離平衡。同時,在補充時 (請先閱讀背面之注意事項再填艿本茛) •Λ.裝— mV nn I- 订
J 本紙張尺度適用中國國家標準(CNS M4規格(210X297公釐) U0329 五、發明说明(2 ) 要能廣爲變化,使其可以標的方式用做鑭系金屬反應性之 立體電子控制配合劑。此種控制配合劑必須能抗氧化’應 與結合於鑭系金屬離子的其他基反應。此外’此等配合基 必須能提高其所結合鐦系化合物在有機溶劑內之溶解度。 最後,必須不會經歷到鑭系金屬離子超出錯合物形成以上 的任何變化。 由於大部份鑭系離子爲Pearson槪念上的「硬陽離子」 (例如參見R8upp Γ化學百科」1987,第5卷3651頁起) ,此等二價、三價和四價金屬離子在鑭系化學中相對應地 亟需Γ硬鹸」做爲配合基。另方面,電子方面等效性的硫 醚類和膦類,只是附屬的重要性,因做爲「路易氏軟鹸」 係以配位方式結合,遠較稀土金屬離子爲弱。此外,較易 進行氧化製程,以致形成碾類、二氧化硫或氧化膦。 所以,本發明之目的在於提供鋼系金屬錯合物,含有 強烈配位式結合的配合基,可抵抗氧化製程。 此目的是由下式之錯合物達成: 〔LaLnbXc〕n (A) η (I) 經濟部中央標隼局員工消費合作社印製 (請先閲讀背面之注$項再填寫本頁) 其中Ln爲鑭系金屬(元素周期表上原子序數57至71的元素 )氧化態2,3或4之離子(銪和銷除外),做爲中心原 子,X係結合於中心原子的單配位或多配位、帶電荷或不 帶電荷之配合基,而L爲下式之單碳烯類: 〜2〜 本紙張尺度逍用中國國家檬準(CNS ) A4规格(210X297公釐) 五、發明説明(3 )
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c丨R V 同樣結合於中心原子,其中R1 , R2,R3,R4,Rs , R6係相 同或不同,爲直鏈或支鏈、磺化或未磺化之G-r烷基、磺 本紙張尺度逋用中國國家梂準(CNS ) A4规格(210X 297公釐) 經濟部中央標準局員工消費合作社印製 A7 B7 ___五、發明説明(4 ) 化或未磺化之cs-ie脂肪族單環或多環基、磺化或未磺化之 C2-5烯基、磺化或未磺化之芳基、磺化或未磺化之 C7-l9芳烷基,R3,R4,R5,R6亦可爲氫,R3連同R4 ’以及 R5連同Re,各亦可相同或不同熔合而磺化或未磺化Ca- 7基 ,丫爲飽和或不飽和、直鏈或支鏈Cl_4烷叉基、二烷基甲 矽烷叉或四烷基二甲矽烷叉基,八爲單電荷陰離子’或多 電荷陰離子的化學當量,b爲1至4的整數,a爲1至 4xb的整數,c爲0或1至4xb的整數,η爲0或1至 3xb的整數。 迄今文獻只有二件提到鋼系金屬與衍生自雜環碳烯的 配合基之錯合物。碳烯於此結合於分子片_双(V 一五甲 基環戊二烯基)鐵,或双(V —五甲基環戊二烯基)釤。 以戊二烯基的形式,此等錯合物含有強烈電子給予的冗配 合基,在化學和結構方面,與習知金屬鹵化物、醇塩和醯 胺無法比並(Arduengo 等人,J. Am· Chem.· Soe. 1994, 116,7927 頁起,Schnmann 等人,Angew. Chem. 1994, 106,1829 頁起)。 鑑於此前案技術,出乎意外的是衍自氮雜環的碳烯’ 可做爲安定結合的配合基,配位於二價、三價和四價鑭系 金屬離子,而無其他額外有機配合基存在,諸如環戊二烯 基,或五甲基環戊二烯基。 新化合物可溶於有機溶劑,但亦可溶於水,尤其是含 有磺酸根所取代之脂肪族或芳香族基。極具熱安定性,並 具有高度氧化安定性。 (請先閲讀背面之注意事項再填寫本頁) 裝. 訂
L 本紙張尺度適用中國國家榡準(CNS ) A4规格< 210X297公釐) 經濟部中央標準局員工消費合作杜印製 A7 B7 五、發明説明(5 ) 新化合物衍生自元素钪、釔、鋼、铈、鉅、鈸、釤、 虬、铽、她、鈥、鋇、経、鑷、♦魯,氧化態爲二、三或四 。做爲放射性元素,錯排除在本發明目的之鑭系金屬群以 外;銪同樣除外,因該元素極似鍮土金屬錁和鋇。 除碳烯類外可在錯合物內存在的單配位或多配位配合 基,在式(I)中以X表示,有氫或氫_子、鹵素或鹵化物 、假鹵化物、羧酸根離子、磺酸根離子、醵胺基、醇塩基 、乙醯丙酮基、一氧化碳、一氧化氮、膪類、異腈類、單 烯烴或二烯烴類、炔類及7香族基。若錯合分子內有複 數配合基存在,可相同或不同。 在衍自咪唑和表唑或其衍生物而具有式(Π ) (ffl) (F) 和(V)的單碳烯或二碳烯類裡,R1至Re特指甲基、異丙基 、特丁基、年基、三苯基甲基、笨基、二甲苯基、三甲苯 基、金剛烷基,R1和R2最好是甲基、特丁基、苯基、#基 、隣甲苯基,R3和R4最好是氫和甲基。 R3和R4基以及R5和R8基,可連同咪唑環或蟓唑環的二 相_碳原子形成環系。R3和R4基或^和1^最好是(CH)<部 份,可導致形成熔合芳香族六節環、(CH*) *和(CH2)6。 式(F)和(V)二碳烯類的Y所指橋,最好是亞甲、二 甲基亞甲、二苯基亞甲、1,3 —次苯基、乙叉基。含矽橘 當中,以二甲基甲矽烷叉和四甲基二甲矽烷叉基爲佳。 式(I)中,b以1爲佳;A最好是鹵化物、假鹵化物 、四苯基硼酸塩、四氟硼酸塩、六氟磷酸塩’和羧酸根離 子,後者當中尤指乙酸根離子,還有金靥錯合物陰離子, 本紙張尺度逋用中國國家梂準(CNS ) A4规格(210X297公釐) L--^------(裝------訂------^ (請先聞讀背面之注意事項再填寫本育) ΑΊ Β7 經濟部中央標準局員工消費合作社印製 五、發明説明(6 ) 諸如用碳醯鈷酸塩、六氣鉄酸塩(ΠΓ)、四氣鉄酸塩、四氣 鋁酸塩,或四氣鈀酸塩(Π)。 所請求化合物可由各種途徑得之。按照一製法,由相 關偶氮塩利用去質子化所得碳烯,與鋼系化合物反應。碳 烯可預先就此分離或在原位製成。適當鐧系化合物有鹵化 物、羧酸塩、乙醯丙酮化物、Ξί氣甲烷磺酸塩,以及醇塭 、苯氧化物、單烷基醯胺和二烷基醯胺,以及單笨基醯胺 和二苯基醯胺。醇塩和烷基醯胺含Cr-S烷基,以二烷基醯 胺而言,此等基可相同或不同》 製造新錯合物的又一途徑,是鋼系化合物與偶氮塩的 直接反應,即不需由偶氮塩先形成碳烯。鑭系化合物可由 式LnZm ( m = 2,3,4 )說明,其中Z爲鹵化物、假鹵化物 、羧酸塩、乙醯丙酮、醇塩(具有ChS烷基)、苯氧化物 、單烷基醯咹和二烷基醯胺(具有烷基,以二醯胺而 言,可相同或不同),或二甲矽烷基醯胺。偶氮塩相當於 式〔L-H〕Z或〔L-H〕A,其中L、Z和A同上。 鋼系化合物與碳烯,必要時還有配合基的反應,是由 反應物在溶劑內,於低溫(例如-78 °C )、室溫或加溫, 加以混合進行。反應進行快速,常常在數分鐘內即基本上 完成。然而,爲完成反應,宜採用反應時間達幾小時,尤 其是出發物料僅溶於所用媒質者,即由懸浮液反應。 爲製造含磺化配合基的水溶性錯合物,出發物料包含 至少一反應物,其分子或分子片斷經磺化。 爲從反應媒質分離新錯合物,已發現用來除去溶劑, (請先閱讀背面之注意事項再填寫本頁) 裝. 訂
L 本紙張尺度速用中國國家橾率(CNS > A4规格(210X297公釐> 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明(7 ) 宜在高度眞空內進行。粗製生成物可由適當溶劑或溶劑混 合物,利用洗濯和再結晶精製,可在個別情況下由事先實 驗測定。 鑭系金靥一碳烯錯合物I,爲可利用路易氏酸催化之 反應用的觸媒,例如聚丙交酯(爲生物降解性聚合物)之 製造,還有CH、CC、CS i和NC鍵合反應。包含烯烴之 氫氨化、加氫、寡聚合、聚合、烯烴之異構化和氫甲矽烷 化,烯烴和炔類的氫硼化、Michael反應、Diels_ Aider反應 、芳香族之Friedel-Crafts醯化,以及Grignard試劑加成爲 1,3 _二酮類。 茲說明新化合物之製造和性能如下,但本發明不限於 寅施例。 實施例1 三(1,3~二甲基咪唑啉一 2 —烷叉)三氣化鋇 ⑻取在THF內的1,3 —二甲基咪唑啉一2 —烷叉0.14 Μ溶液22.6毫升(相當於3.25毫莫耳碳烯),滴加於懸浮 在50毫升四氫映喃(THF,thf )內的0.508克(1.0毫 莫耳)ErCl3(thf) 3 25 u混合物在室溫攪拌三天,隨即利 用過濾除去溶劑。在0.1 Pa的高度眞空內乾燥5小時後, 得分析級純製黃色生成物〇 . 392克(70 % )。 (b)取 1 莫耳當量 Er〔N( S iMe 3 )〕3 ( Me : -CH3)和 3 莫耳 當量1,3 —二甲基咪唑氣化物,懸浮於50毫升THF內。懸 浮液回流5天。餾除溶劑並在0.1 Pa高度眞空內乾燥6小 時,得分析級純製的黃色生成物。 本紙張尺度逋用中國國家樑準(CNS ) A4规格(210X29*7公釐) (請先閱讀背面之注意事項再填寫本頁) --9 L. 經濟部中央標準局員工消费合作社印製 A7 B7_ 五、發明説明(8 ) 鑑定
Ci5H24Cl3ErNe (562.02) 計算値 C 32.6 Η 4.3 Ν 14.94 Cl 18.92 實測値 C 31.92 Η 4.15 Ν 13.98 Cl 18.98 IR: v = 3153 cm-1 s, 3101 s, 1573 s, 1397 vs, 1313 s, 1221 vs, 1174 s, 1113 s, 1076 m, 1018 m, 1003 m, 972 m, 938 m, 917 m, 894 w, 740 vs, 648 w, 622 m, 609 w, 450 m. MS(EI) : m/2z = 96 a.m.u. (100 %)〔碳烯〕,81 (4) 〔碳烯一Me〕. 實施例2 ( 1,3 —二甲基咪唑啉一2 —烷叉)(四 氫呋喃)三〔双(二甲基甲矽烷基)醯胺 〕釔 取在THF內1,3 —二甲基咪唑啉一2 —烷叉0.3 Μ溶 液4.2毫升(相當於1.2毫莫耳碳烯),緩緩滴加於35毫 升 THF 內的 0.756 克(1.2 毫莫耳)Y(bdsa)3(thf)2,醯胺 (bdsa —双(二甲基甲矽烷基)醯胺)。混合物在室溫攪 拌24小時,餾除溶劑,生成物使用20毫升正己烷萃取。乾 燥後,得0.776克(99%)帶綠生成物,爲分析級純質。 鑑定
CziHssNsOSieY (654.15) 計算値 C 38.56 Η 8.94 Ν 10.71 實測値 C 38.37 Η 8,61 Ν 10.56 IR: ^ = 3169 cnT1 w, 3135 w, 2070 vs, 本紙張尺度逋用中國國家橾牟(CNS ) A4规格(210x297公釐) (請先閲讀背面之注意事項再填寫本頁) 裝. 訂 經濟部中央標率局員工消費合作社印製 A 7 B7 __ __ 五、發明説明(9 ) 1992 (sh)m, 1927 (sh)m, 1773 w, 1540 w, 1401 m, 1316 m, 1243 vs, 1220 m, 1169 w, 1154 w, 1112 m, 1048 (br)vs, 970 vs, 941 vs, 898 (br)vs, 836 vs, 788 vs , 763 vs , 724 s, 682 m, 624 w, 609 w, 446 w, 409 w. XH-NMK (C«De): d = 0.35 ppm (36H, s, SiCHs), 1.41 (4H, d, THF), 3.38 (6H, s, NCHb), 3.56 (4H, d, THF), 5.04 (6H, SiH), 5.79 (2H, s, CH). (CeDe): d = 3.2 ppm (q, SiCH»), 25.7 (t, THF), 37.5 (q, NCHs), 67.9 (t, THF), 121.1 (d, CH), 168.2 (s, NCN). 實施例3 反型双(1,3 —二甲基咪唑啉一 2 —烷叉 )三〔双(二甲基甲矽烷基)醯胺〕釔 取在THF內1,3 —二甲基咪唑啉一2 —烷叉0.3 Μ溶 液8·7毫升(相當於2.4毫莫耳碳烯),緩緩滴加於溶入 35 毫升 THF 內的 0.756 克(1 . 2 毫莫耳)Y ( bds a ) 3 - (thf )2 (bdsa :見實施例2 )。混合物在室溫搅拌24小時,餾狳 溶劑,生成物使用20毫升正己烷萃取。乾燥後,得0 · 805 克(99 % )淡褐色生成物,爲分析級純質。 本紙張尺度適用中國國家梂準(CNS ) A4規格(210X297公釐) I---^------《裝------訂------^ (請先閱讀背面之注意事項再填寫本頁) 310329 a7 B? 五、發明説明(10 ) 鑑定 C22HS8N7SieY (678.18) 計算値 C 38.96 Η 8.62 Ν 14.46 實測値 C 38.78 Η 8.70 Ν 14.50 IR: ν = 3163 cm"1 w, 3X30 w, 2088 m, 2040 (sh)m, 1532 w, 1400 m, 1312 w, 0.26 ppm (1247 s, 1240 s, 1216 m, 1169 w, 1155 w, 1104 w, 1032 s, 969 (sh)m, 936 s, 893 vs, 834 s, 781 s, 760 s, 728 s, 720 s, 693 w, 675 w, 615 w, 602 w, 445 w, 433 w. ^-NMRiCeDe) : d = 0.26 ppm (36H, s, S1CH3), 3.70 (12H, s, NCHa), 5.10 (6H, sep., SiH), 6.03 (4fi, s, CH). 13C-NMR(C6De) : d = 3.S ppm (SiCHs ),38.6 (NCH3 ), 120.7 (CH),未見(NCN). i al—^1 ftn^i Hat t mV —^nl #mT 一°1frfllf mV —HI— m nn (請先閱讀背面之注意事項再填.寫本頁) 經濟部中央標準局買工消費合作社印裝 本紙張尺度適用中國國家揉準(CNS ) Λ4规格(210X 297公釐)
Claims (1)
- 申請專利範園 86.泛· -2 1 邮爷2月H日修正(I) 種下式之錯合物: 〔LaLnbXc〕n (A) η 其中Ln爲鑭系金屬(元素周期表上原子序數57至71的元素 )氧化態2,3或4之離子(銪和鐯除外),做爲中心原 子,X係結合於中心原子的單配位或多配位、帶電荷或不 帶電荷之配合基,而L爲下式之單碳烯類: 诗 先 閲 讀 背 1¾ 之 注 R3 R2I N R3 C C1 C/ \ / R4 NI R1 (Π ) 或下式之二碳烯類: R2I R3 N CI N // R4 1c C1 I i K5 N i R1 (ID) RzI N 訂 CIIc Cl cIIc Cl 線 經濟部中央揉準局負工消費合作社印*. R4R5 •R NIY—N NR、 \ \ CIC IA C R. R. N——Y——N NIC C 5 R \ ,6 C——R V 本紙張尺度逋用中國國家揉率(CNS } A4说格(210X297公釐} tv Μ )8 8 D8 經濟部中央標準局貝工消费合作社印製 六、申請專利範^ΕΞΙΞΞΞΙΤ" 同樣結合於中心原子,其中Ri,R2,R3,R4 , RS,R6係相 同或不同,爲直鏈或支鏈、磺化或未磺化之Cl„e烷基,R3 ,,R6亦可爲氫,Y爲飽和或不飽和、直鏈或支鏈 Ci —院叉基、二烷基甲矽烷叉或四烷基二甲矽烷叉基,A 爲單電荷陰離子,或多電荷陰離子的化學當量,b爲1至 4的整數,a爲1至4xb的整數,c爲0或1至4xb的整 數’ π爲〇或1至3xb的整數,其中式(I)之X爲氫、氫 離子、_素、鹵素離子、假鹵化物、醯胺基、醇塩基、乙 酿丙酮基、腈類、異腈類、單_烴或二烯烴、和炔類者。 2. 如申請專利筘圍第1項之錯合物,其中式({Π (in) (F)和(V)內 R1,R2,R3,,RS,R« 爲甲基、異丙基、 特丁基者。 3. 如申請專利範圍第1或2項之錯合物,其中式(Π) (HI) (F)和(V)內R1和R2爲甲基、特丁基者。 4. 如申請專利範圍第1項之錯合物,其中式(il) (DI) (F)和(V)內R3和R,爲氫和甲基者。 5. 如申請專利範團第1項之銷合物,其中式(1y)和 (V)內Y爲亞甲、二甲基亞甲、二苯基亞甲、乙叉基者。 6. 如申請專利範圍第1項之錯合物,其中式(iy)和 (V)內Y爲二甲基甲矽烷叉和四甲基二甲矽烷叉基者。 7. 如申請專利範圍第1項之錯合物,其中式(n內b 爲1者。 8. 如申請專利範圍第1項之錯合物,其中式(1)內A 爲鹵化物或假鹵化物離子、四苯基硼酸塩、四氟硼酸塩、 |2 本紙張尺度逋用中國國家榡率(CNS } A4规格{ 210X297公釐) ---------痂-- (請先閲讀背面之注意事項再填寫本頁) -* ^1〇329 ^——一一—一 Η __本中 《 日 D8 _____六、申請專利範圍1.^1·^—^六氟磷酸塩、乙酸塩、四碳醯鈷酸塩、六氟鐵酸塩、四氩 鐵酸塩、四氣鋁酸塩,或四氣鈀酸塩離子者。 ---------歉,------訂------線f (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標隼局員工消費合作社印製 13 本紙張尺度逋用中國國家橾準(CNS ) A4规格(210X297公釐)
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DE4447070A DE4447070A1 (de) | 1994-12-29 | 1994-12-29 | Komplexverbindungen der Lanthanoiden mit heterocyclischen Carbenen |
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US (1) | US5705619A (zh) |
EP (1) | EP0721951B1 (zh) |
JP (1) | JP2708735B2 (zh) |
KR (1) | KR960022549A (zh) |
CN (1) | CN1132754A (zh) |
AT (1) | ATE217000T1 (zh) |
AU (1) | AU4069995A (zh) |
BR (1) | BR9505991A (zh) |
CA (1) | CA2165887C (zh) |
DE (2) | DE4447070A1 (zh) |
FI (1) | FI956238A (zh) |
MY (1) | MY131703A (zh) |
PL (1) | PL312034A1 (zh) |
TW (1) | TW310329B (zh) |
ZA (1) | ZA9510929B (zh) |
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FR2778916B1 (fr) | 1998-05-20 | 2000-06-30 | Rhone Poulenc Fibres | Nouveaux complexes organometalliques comprenant des carbenes heterocycliques cationiques et leur procede de preparation |
GB9814282D0 (en) * | 1998-07-01 | 1998-09-02 | Borealis As | Catalysts |
WO2009155170A2 (en) * | 2008-06-20 | 2009-12-23 | Bridgestone Corporation | Catalysts for preparing cis 1,4-polydienes |
-
1994
- 1994-12-29 DE DE4447070A patent/DE4447070A1/de not_active Withdrawn
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1995
- 1995-12-05 TW TW084112917A patent/TW310329B/zh active
- 1995-12-21 ZA ZA9510929A patent/ZA9510929B/xx unknown
- 1995-12-21 BR BR9505991A patent/BR9505991A/pt not_active Application Discontinuation
- 1995-12-21 CA CA002165887A patent/CA2165887C/en not_active Expired - Fee Related
- 1995-12-22 CN CN95120146A patent/CN1132754A/zh active Pending
- 1995-12-22 PL PL95312034A patent/PL312034A1/xx unknown
- 1995-12-22 KR KR1019950054214A patent/KR960022549A/ko not_active Application Discontinuation
- 1995-12-22 FI FI956238A patent/FI956238A/fi not_active Application Discontinuation
- 1995-12-27 DE DE59510191T patent/DE59510191D1/de not_active Expired - Fee Related
- 1995-12-27 JP JP7341364A patent/JP2708735B2/ja not_active Expired - Fee Related
- 1995-12-27 MY MYPI95004111A patent/MY131703A/en unknown
- 1995-12-27 AT AT95120590T patent/ATE217000T1/de not_active IP Right Cessation
- 1995-12-27 EP EP95120590A patent/EP0721951B1/de not_active Expired - Lifetime
- 1995-12-28 AU AU40699/95A patent/AU4069995A/en not_active Abandoned
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AU4069995A (en) | 1996-07-04 |
FI956238A (fi) | 1996-06-30 |
EP0721951B1 (de) | 2002-05-02 |
CA2165887A1 (en) | 1996-06-30 |
JPH08231556A (ja) | 1996-09-10 |
BR9505991A (pt) | 1997-12-23 |
JP2708735B2 (ja) | 1998-02-04 |
US5705619A (en) | 1998-01-06 |
MY131703A (en) | 2007-08-30 |
DE59510191D1 (de) | 2002-06-06 |
ATE217000T1 (de) | 2002-05-15 |
CA2165887C (en) | 1999-07-27 |
EP0721951A1 (de) | 1996-07-17 |
PL312034A1 (en) | 1996-07-08 |
FI956238A0 (fi) | 1995-12-22 |
KR960022549A (ko) | 1996-07-18 |
CN1132754A (zh) | 1996-10-09 |
ZA9510929B (en) | 1996-07-04 |
DE4447070A1 (de) | 1996-07-04 |
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