CN1187359C - 用于制备过渡金属羰基配合物的一氧化碳源 - Google Patents
用于制备过渡金属羰基配合物的一氧化碳源 Download PDFInfo
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- CN1187359C CN1187359C CNB008136548A CN00813654A CN1187359C CN 1187359 C CN1187359 C CN 1187359C CN B008136548 A CNB008136548 A CN B008136548A CN 00813654 A CN00813654 A CN 00813654A CN 1187359 C CN1187359 C CN 1187359C
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- borine
- methyl
- ethyl
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910000085 borane Inorganic materials 0.000 claims abstract description 29
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- 230000002829 reductive effect Effects 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052757 nitrogen Chemical group 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052796 boron Chemical group 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- -1 SnCl 2 Chemical compound 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 230000005595 deprotonation Effects 0.000 claims description 3
- 238000010537 deprotonation reaction Methods 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 3
- 101100347612 Arabidopsis thaliana VIII-B gene Proteins 0.000 claims description 2
- NRUYFUIECQIALQ-UHFFFAOYSA-N C(N)(O)=O.B.N Chemical compound C(N)(O)=O.B.N NRUYFUIECQIALQ-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- 239000000010 aprotic solvent Substances 0.000 claims description 2
- 230000003139 buffering effect Effects 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229960001731 gluceptate Drugs 0.000 claims description 2
- KWMLJOLKUYYJFJ-VFUOTHLCSA-N glucoheptonic acid Chemical group OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O)C(O)=O KWMLJOLKUYYJFJ-VFUOTHLCSA-N 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- 229910052713 technetium Inorganic materials 0.000 claims description 2
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 claims description 2
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- 150000004678 hydrides Chemical class 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract 2
- 239000002879 Lewis base Substances 0.000 abstract 1
- 150000007527 lewis bases Chemical class 0.000 abstract 1
- 150000001721 carbon Chemical group 0.000 description 9
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- 238000002372 labelling Methods 0.000 description 4
- HAEQAUJYNHQVHV-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylbenzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NC2=CC=CC=C2)C=CC=1 HAEQAUJYNHQVHV-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000001301 oxygen Chemical group 0.000 description 2
- 229910052760 oxygen Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FATUQANACHZLRT-KMRXSBRUSA-L calcium glucoheptonate Chemical compound [Ca+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)C([O-])=O FATUQANACHZLRT-KMRXSBRUSA-L 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000002579 carboxylato group Chemical group [O-]C(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- AKMJJGSUTRBWGW-UHFFFAOYSA-N pyridine-2-carboxylic acid Chemical compound OC(=O)C1=CC=CC=N1.OC(=O)C1=CC=CC=N1 AKMJJGSUTRBWGW-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- YQHYMJUDNVWBJN-UHFFFAOYSA-M sodium;2-(hydroxymethyl)benzenesulfonate Chemical compound [Na+].OCC1=CC=CC=C1S([O-])(=O)=O YQHYMJUDNVWBJN-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Carbon And Carbon Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明涉及可新用作一氧化碳源的化合物,并且可选地在过渡金属羰基配合物的制备中用作还原剂。所述化合物通式为(I),其中X1,X2和X3可以相同或不同,可以是Lewis碱或氢化物,Y是σ供电子基团(sigma donatinggroup)。本发明还涉及制备硼烷碳酸盐(borane carbonate)的方法和H3BCO作为还原剂的用途。
Description
本发明涉及可新用作一氧化碳源的化合物,并可任选在过渡金属羰基配合物的制备中用作还原剂。
羰基配合物是含有一氧化碳作为配位基的化合物。一氧化碳在过渡金属化学中是常见配基,这部分是由于其与过渡金属结合键的协同性质。
CO与金属的结合键含有两部分。键第一部分是基于σ供体(σ-donation),碳原子上的孤电子对与所述金属的空的d轨道重叠。第二部分由填充的金属d轨道π反馈作用(π-back-donation)进入CO的碳原子的空的π*轨道。该第二部分称为π-反馈键(pi-backbonding)或π-反馈作用。
如上所述过渡金属羰基配合物的生成对于这些化合物用于标记蛋白,肽和多种其它化合物是关键性的。在多种应用中,借助含有所需试剂的称为标记试剂盒来标记这些分子。当前的试剂盒是以硼氢化物作还原剂为基础的,还含有酒石酸盐,乳糖和硼酸盐缓冲液,pH 11.5,充有CO气体作为CO源。这些已知反应混合物的缺点在于CO溶解进入反应试剂较慢造成羰基配合物产率低;工业上大规模制备填充CO的试剂盒小瓶是不可能的,而且即使小瓶经过严密密封CO还缓慢扩散。此外,pH值相当高,使用不方便。
本发明意图提供CO和硼氢化钠的替代物,它克服了上述的缺点。
已发现通式I的化合物或其盐
其中,X1是-H;
X3和X2是相同或不同的取代基,选自-H,-NHXRY(其中X+Y=3),或-R,其中R是经碳原子分别与氮或硼结合的取代基,优选是烷基或芳基;Y是-OH,-OH2,-OR或-NHR,其中R是经碳原子分别与氮或氧结合的取代基,优选是烷基或芳香基,可用作一氧化碳(CO)源,也可以任选地在水溶液中制备金属羰基配合物中用作还原剂。如果Y是-OH或-OH2,所述化合物是可以被脱去质子的酸(例如用NaOH)。在这种情况下,分离的所述化合物是盐(硼烷碳酸盐(borano carbonate)阴离子R3B-COO2-加上相应的阳离子,例如Li+,Na+,Ca2+,Mg2+及其它)。如果X1,X2,X3中至少有一个是氢原子,则只表现还原剂功能。为了保持稳定,优选X1,X2,X3中有两个是-H。当加热此化合物的水溶液时释放出一氧化碳。
上述化合物的优势如下所述。CO在水性介质中于可控条件(pH,温度)下首次产生。要求保护的金属的羰基配合物可在明确的条件下于水中制备,而不用在有机溶剂中或在高压和高温下制备。由于实际上羰基物的制备总是需要还原作用,单一化合物同时成为CO源和还原剂就是便利的。如果要进行配合的金属是Tc-99m或Re-188/186,生产试剂盒可以不需要用具有毒性和挥发性的CO灌装小瓶。一个主要的具有优势的实施方案是组合不同功能性在一个化合物中的分子上。这样的化合物可用作还原剂以及原位(insitu)CO源,而当质子试剂(如水)或Lewis酸存在时只产生CO。
通过在不同位置进行取代改变,可以得到多种化合物。这些化合物可分为:
1.硼烷碳酸盐化合物,其中X1,X2和X3是-H,Y是-OH2,和/或单或双脱质子化硼烷碳酸根[H3BCO2]2-的对应盐;
2.硼烷氨基酸(氨羧基硼烷),其中X2是NH3,X1和X3是-H,Y是-OH,和/或所述单脱质子化氨络硼烷碳酸根的相应的盐;
3.烷基化硼烷氨基酸(三烷基氨羧基硼烷),其中X2是-NHxRy(x+y=3),R是通过碳原子与氮原子结合的取代基,其优选是烷基或芳基,X1和X3是-H,Y是-OH;
4.通式I的化合物,其中X1是通过碳原子与硼连接的有机取代基,X2和X3是-H,Y是-OH2;
5.通式I的化合物,其中X1和X2是通过碳原子与硼连接的有机取代基,X3是-H,Y是-OH2;
6.硼烷羧酸烷基酯化合物,其中X1,X2和X3如上1-5定义,Y是OR′,其中R′是通过碳原子与氧连接的取代基,例如烷基,更具体地是甲基或乙基。
7.硼烷氨基甲酸酯(borane carbamate)化合物,其中X1,X2和X3如上1-5定义,Y是NH2,NHR″或NR2″,其中R″是通过碳原子与氮连接的取代基,例如烷基,更具体地是甲基或乙基。
这些化合物的具体例子有:硼烷碳酸盐(boranocarbonate)衍生物:
[H3B-COOH2],[H3B-COOH]M,[H3B-COO]M2,Na[H3B-COOCH3],其中M是碱性阳离子;硼烷氨基甲酸盐(boranocarbamates):Na[H3BCONHCH3],M[H3B-CONH2],其中M是碱性阳离子;氨络硼烷碳酸盐(ammine-boranocarbonates):[H3N-BH2-COOH],[H3N-BH2-COO]Li,[(CH3)3N-BH2-COOH],[(CH3)H2N-BH2-COOH],[(CH3)H2N-BH2-COO]Li,[(CH3)H2N-BH2-COOCH3];氨络硼烷氨基甲酸酯(ammine-boranocarbamates):[H3N-BH2-CONH2],[(CH3)2HN-BH2-CONHC2H5]。
本发明的化合物的制备可参照如下方法或类似方法:如Burg等,J.Am.Chem.Soc.59,780(1936)制备BH3CO;如Malone等,Inorg.Chem.6,817(1967)制备M2[H3B-COO]和M[H3B-COOC2H5];如Howe等,Inorg.Chem.10,930(1971)制备M[H3B-CONH2];如Spielvogel等,J.Am.Chem.Soc.102,6343(1980)制备[H3N-BH2-COOH]和[(CH3)3N-BH2-CONHC2H5];如Spielvogel等,Inorg.Chem.23,4322(1984)制备[(CH3)H2N-BH2-COOCH3];如Spielvogel等,Inorg.Chem.23,1776(1984)和J.Am.Chem.Soc.98,5702(1976)制备[H3N-BH2-CONH2],[(CH3)2HN-BH2-CONHC2H5]。
本发明还涉及制备过渡金属羰基配合物的方法,其中如上定义的一种或多种所述化合物用作CO源,并可任选用作还原剂。总的说来此方法包括在水或缓冲液中由于质子迁移和随后进行水解反应从本发明的任一化合物释放CO,具体是所述化合物1-7中的一或多种化合物。同时,用于形成羰基的金属被与硼相连的氢化物取代基还原。本发明的化合物,具体是化合物1-7,溶解于水或缓冲液中,所述金属可以以固体或溶液形式加入。本发明的化合物,具体是化合物1-7的质子化作用和水解作用释放出CO。同时,与硼连接的氢化物(-H)将金属中心还原为某化合价,这样该金属与CO配位。此时,形成了羰基配合物。这样,本发明制备羰基配合物的方法包括将本发明的borano化合物与金属离子或(经)金属化的所述金属的水溶液混合。在本文中的“金属”意图包括所有的金属形式,即也可以是金属离子和(经)金属化的。
本发明的化合物和方法适于生成任何羰基配合物,但具体是那些在羰基金属配合物中的过渡金属是选自V-B到VIII-B族金属。更具体地,本发明适于制备下述过渡金属的羰基配合物:钒(V),铬(Cr),钼(Mo),钨(W),锰(Mn),锝(Tc),铼(Re),铁(Fe),钌(Ru),锇(Os),钴(Co),铑(Rh),铱(Ir)和镍(Ni)和它们的放射性同位素。
此外,本发明提供用于制备过渡金属羰基配合物的试剂盒,其包括本发明的化合物水溶液,稳定剂象酒石酸盐,葡庚糖酸盐(gluco heptonate),乳酸盐,柠檬酸盐和缓冲液系统象硼酸盐或磷酸盐。在一优选实施方案中,本发明的试剂盒包括至少2mg硼烷碳酸盐,优选氮气环境下的无氧环境下硼酸盐缓冲液中(pH 9.1)。优选在加入放射性金属溶液后此溶液的总体积不超过1ml。但是,在特定的情况下也可能采用较大的体积,如2或3ml。合适的温育条件包括加热溶液20分钟到75℃。
根据本发明上述的试剂盒,还包括一种或多种添加的还原剂。根据本发明上述的试剂盒,其中所述添加的还原剂选自氢化硼,连二亚硫酸盐,SnCl2,亚硫酸盐。
本发明的化合物还能用于在水中以可与氢化硼或氰基氢化硼相比的选择性和反应性还原有机化合物。
此外,已发现可从H3B THF连续制备H3BCO,并与氢氧化钾的醇溶液原位反应以产生K2[H3BCO2]。此制备的关键是控制H3BCO和H3B THF之间的平衡:-50℃下从气流中选择性冷凝THF,而被一氧化碳流携带的H3BCO(b.p.-64℃)则得以通过。随后,在-78℃下通过KOH的乙醇溶液对此气体混合物直接鼓泡。[OH-]在H3BCO的高亲电子碳上的亲核子攻击导致K2[H3BCO2]以很高产量形成。如果需要,H3BCO自身可以于-78℃下在冷阱中分离。此制备H3BCO的方法比高压或醚催化方法更为简单和方便,可以放大到几克或更大的量。
因此,本发明的制备硼烷碳酸盐(borano carbonate)的方法包含下列步骤:
a)将H3B THF或THF中类似的加合物或THF和另一有机质子惰性溶剂的混合物与CO反应得到H3BCO;
b)使这样产生的H3BCO通过一价或二价阳离子相反离子(counter ion)的氢氧化物和一种脂肪醇的溶液;并且
c)合适的反应时间之后,加热醇溶液以沉淀硼烷碳酸盐(boranocarbonate)。类似的加合物例如有H3B(Et2O)。氢氧化物例如选自氢氧化钾,氢氧化钠或四烷基氢氧化铵。脂肪醇可选自甲醇,乙醇和异丙醇。
化合物H3BCO也是本发明的一部分。它具有还原特性,可用于此目的,例如在不采用如上所述的高压CO而是在质子惰性或只是弱质子溶剂中制备羰基配合物。也可能在CO鼓泡通过金属的THF溶液产生H3BCO时而原位使用H3BCO,例如用于大量的[TcCl3(CO)3]2或Re类似物的合成。
本发明化合物的应用不仅限于制备羰基配合物,还可应用于需要水溶液中CO源的其它情况。本发明还涉及硼烷碳酸盐(borano carbonate)或其衍生物,如酯、亚胺或醛,在水中作为有机底物的还原剂的应用。这些化合物的还原能力可与BH4-或氰基硼氢化物相比,因此它们可以是大批量工业生产中,例如氰基硼氢化物的替代物。
本发明还在下列实施例中进一步说明,这些实施例仅用于说明目的。
实施例
实施例1
K2H3BCO2的制备
1.BH3CO的合成
真空中(1mbar)剧烈搅拌下经过2小时,将4g NaBH4小心加入到15ml的浓缩H3PO4中(室温下高真空干燥过夜)。将离析出的BH3通过-78℃的冷阱干燥,再在-200℃含70ml无水DME的第二个冷阱中冷凝。第二个冷阱与第一个以及真空管线相脱离。让温度到达-40℃。随后,用1.3bar的干燥CO对此冷阱加压。反应混合物处于-40℃(带乙腈的干冰)冷浴中于1.3bar的CO下搅拌过夜。
2.K2H3BCO2的合成
所述冷阱的气体出口与100ml两口圆底烧瓶(配有气体进口和回流冷却器)相连,其中装有50ml无水乙醇和3g KOH。移去此阱的冷浴,离析出的H3BCO缓慢鼓泡通过0℃的KOH的乙醇溶液。DME溶液缓慢加热到80℃,随后用CO冲洗此阱三遍。在H3BCO停止析出后,回流乙醇30分钟。冷却该溶液到室温,K2H3BCO2沉淀为白色粉末,经烧结玻璃滤器过滤,用冰冷的乙醇(ice cold ethanol)冲洗,并在真空下干燥。
实施例2
采用冻干试剂盒的标记实验
标记试剂盒如下制备,将0.1ml的0.1M PBS,pH7.5中的1mg K2[BH3COO]在已用N2冲洗的管形瓶中冻干。0.1M硼酸缓冲液,pH 8.5可作为替代物使用。
为进行标记,加入1ml发生器洗脱的[99mTcO4]-盐溶液。发现此产量独立于[99mTcO4]-的绝对值。将如此得到溶液加热20分钟到75℃。
pH7.5的产量处于80%到100%之间。
为鉴定所述化合物的成分,向反应液(其中已制备了羰基配合物)中直接加入吡啶甲酸(picolinic acid)。通过与“冷”物质比较,HPLC揭示了所述配合物为[99mTc(OH2)(pic)(CO)3],在本例中,此同样的配合物由“冷”铼制作。“热”物质通过放射性检测仪检测,而“冷”物质用UV探测仪检测。
实施例3
采用称为“湿试剂盒”的标记实验
管形瓶中装有2mg硼烷碳酸盐和一发生器硼酸缓冲液中的高锝酸盐(pertechnetate)洗脱液,pH9.1,总体积1ml,加热20分钟到75℃。如此得到的产物[99mTc(OH2)(CO)3]+的标记产量高于97%。
实施例4
从H3B THF开始制备氢化钾(carboxylato)-三硼氢化物
所用器材由250ml三口圆底烧瓶组成,它通过一个玻璃管与冷阱连接。烧瓶的另两口用橡胶隔片密封。一个用于将气体引入的PTFE管穿入烧瓶。从冷阱的出口,一个PTFE管穿入一个400ml的Schlenk管。从Schlenk管的侧臂通过一个聚乙烯管通向硅油发泡器(bubbler),它将该装置与空气分隔。
此冷阱和Schlenk管浸没在含异丙醇的Dewar烧瓶中。此装置用干燥无氧的氮气吹洗30分钟,同时通过向各Dewar烧瓶加入干冰将冷阱冷却到-50℃,Schlenk管冷却到-78℃。
200ml纯乙醇中含有5.0g氢氧化钾的溶液加入到Schlenk管中,冷却到-78℃。此装置用一氧化碳短暂吹洗,30ml含有1mol dm-3硼烷-四氢呋喃配合物的四氢呋喃溶液引入到圆底烧瓶中。一氧化碳鼓泡进入此溶液中,使每秒约有一个泡通过所述的油鼓泡器离开此装置。通过间歇加入干冰保持中间冷阱温度为-45℃到-55℃之间。
通过一氧化碳2小时后,20ml二甲氧基乙烷引入到圆底烧瓶中,再引入20ml二甲氧基乙烷到中间冷阱。一氧化碳如前通过此装置。一小时后,Schlenk管与该装置其它部分分离,使之回温到室温。回流加热乙醇溶液45分钟。产生的白色沉淀过滤去除,用5ml纯乙醇冲洗两次,真空干燥得到为白色粉末的1.26g产品(43%基于BH3 THF)。发现K,38.85%(以K2Na[Co(NO2)6]重量测定);CH4BKO2需要K为39.9%。δH(200MHz,D2O,25℃)0.80(1:1:1:1quartet,1 J(H-11B)=80Hz;1:1:1:1:1:1:1隔片(septet),1 J(H-10B)=27Hz)。
实施例5
在水中用Boranocarbonate还原有机底物苯甲醛-2-磺酸钠
Boranocarbonate钾(100mg)和苯甲醛-2-磺酸钠(40mg)在水(1ml)中混合,室温下静置30分钟。通过起始物质在δ=10.77的1H-NMR信号的消失和在δ=5.04处产品信号的出现来确定2-(羟甲基)-苯磺酸钠的定量生成。在实验末期的反应混合物无味,表明磺酸盐组分没有被还原。
Claims (25)
1.用作一氧化碳源并在水溶液中制备金属羰基配合物时作为还原剂的通式为I的化合物或它们的盐
其中
X1是-H;
X3和X2是相同或不同的取代基,选自-H、-NHxRy或-R,其中x+y=3,R是分别通过碳原子与氮或硼原子结合的取代基,是甲基或乙基;
Y是-OH、-OH2、-OR′、NH2、-NHR″或NR″2,其中R′是分别通过碳原子与氮或氧原子结合的取代基,是甲基或乙基;NR″是分别通过碳原子与氮或氧原子结合的取代基,是甲基或乙基。
2.权利要求1的化合物或它们的盐,其中所述化合物的盐是硼烷碳酸盐,其中X1,X2和X3是-H,Y是-OH2,或所述化合物的盐是双脱质子硼烷碳酸[H3BCO2]2-的盐。
3.权利要求1的化合物或它们的盐,其中所述化合物是硼烷氨基酸,其中X2是NH3,X1和X3是-H,Y是-OH,或所述化合物的盐是单脱质子化氨络硼烷碳酸[(NH3)H2BCO2]-的盐。
4.权利要求1的化合物或它们的盐,其中所述化合物是烷基化硼烷氨基酸,其中X2是-NHxRy,其中x+y=3,R是通过碳原子与氮原子结合的取代基,为甲基或乙基,X1和X3是-H,Y是-OH。
5.权利要求1的化合物或它们的盐,其中X1,X2和X3是-H,Y是OR′;其中R′为甲基或乙基。
6.权利要求1的化合物或它们的盐,其中X2为NH3,X1和X3是-H,Y是OR′;其中R′是甲基或乙基。
7.权利要求1的化合物或它们的盐,其中X2是-NHxRy,其中,x+y=3,R是甲基或乙基,X1和X3是-H,Y是OR′,其中R′是甲基或乙基。
8.权利要求1的化合物或它们的盐,其中X1,X2和X3是-H,Y是NH2、NHR″或NR″2,其中R″是甲基或乙基。
9.权利要求1的化合物或它们的盐,其中X2是NH3,X1和X3是-H,Y是NH2、NHR″或NR″2,其中R″是甲基或乙基。
10.权利要求1的化合物或它们的盐,其中X2是-NHxRy,其中,x+y=3,R是甲基或乙基,Y是NH2、NHR″或NR″2,其中R″是甲基或乙基。
11.权利要求1的化合物或它们的盐,其选自硼烷碳酸盐的衍生物:[H3B-COOH2],[H3B-COOH]M,[H3B-COO]M2,Na[H3B-COOCH3],其中M是碱性阳离子;硼烷氨基甲酸盐:Na[H3BCONHCH3],M[H3B-CONH2],其中M是碱性阳离子;氨络硼烷碳酸盐:[H3N-BH2-COOH],[H3N-BH2-COO]Li,[(CH3)3N-BH2-COOH],[(CH3)H2N-BH2-COOH],[(CH3)H2N-BH2-COO]Li,[(CH3)H2N-BH2-COOCH3];氨络硼烷氨基甲酸酯:[H3N-BH2-CONH2],[(CH3)2HN-BH2-CONHC2H5]。
12.制备过渡金属羰基配合物的方法,其中权利要求1-11中定义的一种或多种化合物用作CO源。
13.权利要求12的方法,其中所述的一种或多种化合物也用作还原剂。
14.权利要求12或13的方法,其中过渡金属羰基配合物中的过渡金属选自V-B族到VIII-B族金属。
15.权利要求14的方法,其中过渡金属羰基配合物中的过渡金属选自钒,铬,钼,钨,锰,锝,铼,铁,钌,锇,钴,铑,铱和镍。
16.用于制备过渡金属羰基配合物的试剂盒,包括水溶液中的至少一种权利要求1-11的化合物,和缓冲液系统。
17.权利要求16的试剂盒,还包括一种或多种稳定剂。
18.权利要求17的试剂盒,其中所述稳定剂选自葡庚糖酸盐,酒石酸盐,柠檬酸盐,乳酸盐。
19.权利要求16-18之一的试剂盒,还包括一种或多种添加的还原剂。
20.权利要求19的试剂盒,其中所述添加的还原剂选自氢化硼,连二亚硫酸盐,SnCl2,亚硫酸盐。
21.制备硼烷碳酸盐的方法,包括以下步骤:
a)将BH-THF或H3B[Et2O]3在THF中或在THF与另一有机质子惰性溶剂的混合物中的溶液与CO反应产生H3BCO;
b)使这样产生的H3BCO通过一价或二价阳离子相反离子的氢氧化物和脂肪醇的冷溶液;并且
c)合适的反应时间之后,加热醇溶液以沉淀硼烷碳酸盐。
22.权利要求21的方法,其中所述氢氧化物选自氢氧化钾,氢氧化钠或四烷基氢氧化铵。
23.权利要求21的方法,其中所述脂肪醇选自甲醇,乙醇和异丙醇。
24.硼烷碳酸盐在水中作为有机底物的还原剂的用途。
25.权利要求24的用途,其中所述的有机底物为酯,亚胺或醛。
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US6359119B1 (en) * | 2000-05-24 | 2002-03-19 | Mallinckrodt Inc. | Formulation of Tc and Re carbonyl complexes using stannous ion as the reductant for pertechnetate and perrhenate |
GB0111872D0 (en) * | 2001-05-15 | 2001-07-04 | Northwick Park Inst For Medica | Therapeutic agents and methods |
US7968605B2 (en) * | 2002-02-04 | 2011-06-28 | ALFAMA—Investigação e Desenvolvimento de Produtos Farmacêuticos, Lda. | Methods for treating inflammatory disease by administering aldehydes and derivatives thereof |
US20080026984A1 (en) * | 2002-02-04 | 2008-01-31 | Alfama - Investigacao E Desenvolvimento De Productos Farmaceuticos Lda | Methods for treating inflammatory disease by administering aldehydes and derivatives thereof |
RU2004126950A (ru) | 2002-02-04 | 2005-06-27 | АЛФАМА-Инвестигасау и Дезенволвименту де Продутош Фармасеутикуш Лда. (PT) | Использование выделяющих co соединений при изготовлении лекарственного средства для лечения воспалительных заболеваний |
CN100366297C (zh) * | 2002-09-03 | 2008-02-06 | 苏黎世大学 | 通过固相技术经金属辅助的从固体载体上裂解制备m(co)3-配合物的方法 |
GB2395432B (en) * | 2002-11-20 | 2005-09-14 | Northwick Park Inst For Medica | Therapeutic delivery of carbon monoxide to extracorporeal and isolated organs |
US20070207217A1 (en) * | 2003-02-03 | 2007-09-06 | Alfama - Investigacao E Desenvolvimento De Productos Farmaceuticos Lda | Method for treating a mammal by administration of a compound having the ability to release CO |
CA2534415A1 (en) * | 2003-08-04 | 2005-02-17 | Northwick Park Institute For Medical Research | Therapeutic delivery of carbon monoxide |
EP1663868A2 (en) * | 2003-08-08 | 2006-06-07 | Glaxo Group Limited | Process for preparing radiolabelled compounds |
GB0411261D0 (en) * | 2004-05-20 | 2004-06-23 | Northwick Park Inst For Medica | Electrode calibration |
WO2006026855A1 (en) * | 2004-09-07 | 2006-03-16 | Triumf, Operating As A Joint Venture By The Governors Of The University Of Alberta, The University Of British Columbia, Carleton | Synthesis of radiolabeled sugar metal complexes |
GB0601394D0 (en) | 2006-01-24 | 2006-03-01 | Hemocorm Ltd | Therapeutic delivery of carbon monoxide |
GB0623482D0 (en) | 2006-11-24 | 2007-01-03 | Mallinckrodt Inc | Technetium-99m (l) tricarbonyl complexes with tridentate chelators for myocardium imaging |
PT2699242T (pt) | 2011-04-19 | 2018-01-22 | Alfama Inc | Moléculas de libertação de monóxido de carbono e utilizações das mesmas |
EP2734235B1 (en) | 2011-07-21 | 2017-03-22 | Alfama, Inc. | Ruthenium carbon monoxide releasing molecules and uses thereof |
US10676490B2 (en) | 2015-07-07 | 2020-06-09 | Florida Southwestern State College | Use of amine carboxyboranes as therapeutic delivery of carbon monoxide and as general drug delivery system in the presence of reactive oxygen species |
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IL148971A0 (en) | 2002-11-10 |
JP2003511334A (ja) | 2003-03-25 |
CN1377360A (zh) | 2002-10-30 |
IL148971A (en) | 2006-07-05 |
DK1218385T3 (da) | 2009-04-27 |
JP4778654B2 (ja) | 2011-09-21 |
AU783079B2 (en) | 2005-09-22 |
US7053242B1 (en) | 2006-05-30 |
EP1218385A1 (en) | 2002-07-03 |
US20060030722A1 (en) | 2006-02-09 |
HU226659B1 (en) | 2009-06-29 |
RU2256664C2 (ru) | 2005-07-20 |
HUP0203138A3 (en) | 2003-12-29 |
WO2001025243A1 (en) | 2001-04-12 |
CA2385927C (en) | 2011-02-22 |
CZ20021118A3 (cs) | 2003-04-16 |
ATE420093T1 (de) | 2009-01-15 |
ES2320407T3 (es) | 2009-05-22 |
CZ301030B6 (cs) | 2009-10-14 |
EP1218385B1 (en) | 2009-01-07 |
AU1134401A (en) | 2001-05-10 |
CA2385927A1 (en) | 2001-04-12 |
RU2002106404A (ru) | 2004-03-10 |
DE60041344D1 (de) | 2009-02-26 |
US7188725B2 (en) | 2007-03-13 |
HUP0203138A2 (hu) | 2002-12-28 |
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