EP1789426A1 - Procede de production efficace de methyltrioxorhenium(vii) (mto) et d'oxydes d'organorhenium(vii) - Google Patents
Procede de production efficace de methyltrioxorhenium(vii) (mto) et d'oxydes d'organorhenium(vii)Info
- Publication number
- EP1789426A1 EP1789426A1 EP05781750A EP05781750A EP1789426A1 EP 1789426 A1 EP1789426 A1 EP 1789426A1 EP 05781750 A EP05781750 A EP 05781750A EP 05781750 A EP05781750 A EP 05781750A EP 1789426 A1 EP1789426 A1 EP 1789426A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- vii
- reagent
- compound
- functionalized
- prepared
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims description 46
- VZSXFJPZOCRDPW-UHFFFAOYSA-N carbanide;trioxorhenium Chemical compound [CH3-].O=[Re](=O)=O VZSXFJPZOCRDPW-UHFFFAOYSA-N 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 66
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
- 239000003153 chemical reaction reagent Substances 0.000 claims description 43
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 42
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 42
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 31
- 239000011701 zinc Substances 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 24
- 229910052702 rhenium Inorganic materials 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 16
- 238000011065 in-situ storage Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- -1 acyloxy compound Chemical class 0.000 claims description 12
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 9
- BEUQZEAGWZHFJE-UHFFFAOYSA-M C[Zn+].CC([O-])=O Chemical group C[Zn+].CC([O-])=O BEUQZEAGWZHFJE-UHFFFAOYSA-M 0.000 claims description 8
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims description 8
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 claims description 7
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 7
- 150000004820 halides Chemical class 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 7
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 6
- 150000007942 carboxylates Chemical group 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 5
- 150000003751 zinc Chemical class 0.000 claims description 5
- 125000004423 acyloxy group Chemical group 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 125000002577 pseudohalo group Chemical group 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 229940057499 anhydrous zinc acetate Drugs 0.000 claims description 3
- 125000001769 aryl amino group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000000944 Soxhlet extraction Methods 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- SINKOGOPEQSHQD-UHFFFAOYSA-N cyclopentadienide Chemical compound C=1C=C[CH-]C=1 SINKOGOPEQSHQD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical class [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 229910003449 rhenium oxide Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 238000005204 segregation Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 150000003752 zinc compounds Chemical class 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 238000007306 functionalization reaction Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 238000002061 vacuum sublimation Methods 0.000 claims 1
- 239000000047 product Substances 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- NMLXKNNXODLJIN-UHFFFAOYSA-M zinc;carbanide;chloride Chemical compound [CH3-].[Zn+]Cl NMLXKNNXODLJIN-UHFFFAOYSA-M 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 231100000331 toxic Toxicity 0.000 description 5
- 230000002588 toxic effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000002152 alkylating effect Effects 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000001035 methylating effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000000859 sublimation Methods 0.000 description 3
- 230000008022 sublimation Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229960000314 zinc acetate Drugs 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003282 rhenium compounds Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- GFTWDQJSZPFMOZ-UHFFFAOYSA-N acetyl acetate Chemical compound CC(=O)OC(C)=O.CC(=O)OC(C)=O GFTWDQJSZPFMOZ-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005865 alkene metathesis reaction Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- ORVACBDINATSAR-UHFFFAOYSA-N dimethylaluminum Chemical compound C[Al]C ORVACBDINATSAR-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002044 hexane fraction Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000012022 methylating agents Substances 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000006772 olefination reaction Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical class [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 1
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 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
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
Definitions
- the present invention relates to a novel process for the preparation of organorhenium (VII) oxides.
- Methyltrioxorhenium (VII) (abbreviated MTO) as the parent compound of Organorhenium (VII) oxides, was first published in 1979 by /. R Beattie and PJ Jones reports (Inorg Chem., 1979, 18, 2318). It is formed in up to 50% yield from trimethyldioxorhenium (VI) (CH 3 ) 3 ReO 2 or tetramethyloxorhenium (VII) (CH 3 J 4 ReO, the starting compounds having to be exposed to dry air for weeks to effect conversion to MTO.
- MTO Methyltrioxorhenium
- Carboxylic anhydrides and tetraalkyltin compounds implemented.
- halogenated carboxylic anhydrides preferably trifluoroacetic anhydride
- the yields are 80-90%, wherein the separation of the resulting (trialkylstannyl) - carboxylic acid anhydrides from the MTO formed requires many operations and is therefore tedious.
- the described reaction remains limited to the few reactive tin compounds. This limits its synthetic bandwidth.
- Patent: Aventis US Patent 6,180,807, DE 19717178 are inorganic or organometallic perrhenates with a silylation reagent (preferably trimethylsilyl chloride TMS-CI) and an organylating reagent o (usually tetraalkyltin R 4 Sn or dialkylzinc R 2 Zn) to the corresponding organorhenium (VII) oxide implemented.
- a silylation reagent preferably trimethylsilyl chloride TMS-CI
- organylating reagent o usually tetraalkyltin R 4 Sn or dialkylzinc R 2 Zn
- the yield of MTO is 80%.
- the zinc alkyls R 2 Zn - especially (ChU) 2 Zn and (CH 3 CH 2 ) 2 Zn - are spontaneously flammable.
- good yields are rarely achieved, moreover, the reaction must be carried out at very low temperatures (-78 0 C or below), otherwise reduction of the rhenium (VII) precursors to low-valent rhenium compounds occurs.
- the processing of such approaches is cumbersome and tedious. This leads to a significantly increased preparative effort and thus also to higher costs.
- the object has now yet and surprisingly been solved by reacting the rhenium (VII) -containing precursor with a functionalized organylating reagent whose organylating properties are matched by certain substituents to the respective rhenium precursors and reaction conditions.
- a functionalized organylating reagent whose organylating properties are matched by certain substituents to the respective rhenium precursors and reaction conditions.
- An object of the invention is thus a process for the preparation of an organorhenium (VII) oxide from a rhenium (VII) -containing precursor and a dimensionally functionalized organylating reagent.
- halogens such as F, Cl, Br or I
- pseudohalogens such as cyanide and rhodanide (SCN) 1 O-functional
- Alkanesulfanyloxy or arylsulfanyloxy or N-functional groups such as
- the functionalized organylating reagent used is an organometallic compound containing at least one organic radical to be transferred to the rhenium (VII) -containing precursor and at least one functionalizing radical other than that which may also be a Lewis basic solvent ligand (e.g., THF).
- VI rhenium
- THF Lewis basic solvent ligand
- the invention relates to a process for the preparation of compounds of the formula (I)
- a, b and c is such as to satisfy the segregation of rhenium, provided that c is not greater than 4 times b, preferably not greater than 3 times b, and wherein R is the same or different and an aliphatic hydrocarbon radical having 1 to 20 C atoms, preferably having 1 to 10 C atoms, an aromatic hydrocarbon radical having 6 to 20 C atoms, preferably having 6 to 10 C atoms or arylalkyl radical having 7 to 20 C atoms, preferably with 7-13 C atoms, where the radical R may optionally each be independently or differently substituted one or more times and joined to the ligand.
- Substituents on the radical R are preferably selected from halogen, hydroxyl, Ci.i 0 - alkoxy, Cs-1 0 -Aryloxy, Ci -2 o-acyloxy, Ci.io-alkylamino and / or Ce-io-arylamino, wherein alkyl substituents additionally with halogen or / and C 6 -io-
- Aryl and aryl substituents may additionally be substituted by halogen or / and Ci-i O alkyl.
- Particularly preferred examples of R are methyl,
- Lewis basic neutral ligands are pyridine, quinuclidine, pyrazole, tetrahydrofuran, acetonitrile and ⁇ -aromatics, e.g. Toluene.
- Preferred examples of Lewis basic anionic ligands are halides and pseudohalides.
- Suitable rhenium-containing compounds from which the substance class (I) is prepared according to the invention are all compounds having a perrhenyl function "O 3 Re +" , ie compounds of the general formula (II) of the trivalent rhenium:
- L a Lewis basic neutral or anionic ligand
- X any residue with formally single or multiple negative charges.
- Lewis basic neutral ligands are as previously indicated.
- the compound (II) is preferably an ester of perrhenic acid with an alcohol or silanol, a mixed anhydride of perrhenic acid with an organic acid, e.g. a carboxylic acid, an amide of perrhenic acid with ammonia or an amine or a halide of perrhenic acid.
- Preferred examples of negatively charged radicals X are halides, for example Cl " , carboxylates, such as acetate or trifluoroacetate, or perrhenate [ReO 4 ].
- carboxylates such as acetate or trifluoroacetate
- the required rhenium-containing compound of formula (II) is prepared in situ from other rhenium-containing compounds (e.g., dirhenium heptoxide or a perrhenate) with an activating reagent (e.g., an acid anhydride, or a halo-trialkylsilane).
- an activating reagent e.g., an acid anhydride, or a halo-trialkylsilane.
- activating reagents are carboxylic acid anhydrides such as
- the reactivity of the rhenium-containing substrate is adapted to that of the Organyl michsreagenzes.
- the functionalized organylating reagents used are preferably compounds of the formula (III):
- M Al, In, Ga, Cu, Zn, Sc, Y, La, a lanthanoid (eg Ce) or a
- X a halogen, cyclopentadienide, pseudohalogen, alkoxy, aryloxy, siloxy, oxide, sulfide, acyloxy, alkanesulfanyloxy,
- S a coordinated solvent molecule, e.g. tetrahydrofuran,
- R is the same or different and is an aliphatic hydrocarbon group of 1 to 20 carbon atoms, an aromatic hydrocarbon group of 6 to 20 atoms or arylalkyl group Represents 7 to 20 atoms, wherein the radical R may optionally be selected independently of one another and may be substituted identically or differently.
- the functionalized organylating reagents may also be oligomeric or polymeric, for which dimethylaluminum oxide [(CH 3 ) 2 Al-O-] X and [CH 3 Zn-O-] x are typical examples (x> 2).
- X is particularly preferably an acyloxy or halogen group, for example Cl or acetate. Also preferred are alkoxides and amides. Substituent on the group X are preferably selected from Ci-C ⁇ 0 -aryl radicals, for example methyl or ethyl, and C 6 -C, where the alkyl radicals optionally mono- or polysubstituted by halogen, hydroxyl, Ci-C 4 -alkoxy or / and C 6 -C 0 aryl may be substituted and the aryl radicals in turn optionally substituted by halogen, hydroxyl and / or dC 4 alkyl may be substituted.
- Acyloxyreste are preferably the radicals of Ci-C 6 alkyl or C 6 -Cio-Arylcarbonklaren, wherein alkyl and aryl, as indicated above, may be substituted.
- R preferably have the meanings given for the compounds (I). More preferably R is selected from methyl, methyl- [D 3 ], ethyl, propyl, cyclopropyl, phenyl, mesityl, cyclopentadienyl and chloromethyl.
- variable design of the substituent X allows the reactivity and solubility of the alkylating reagent to be adjusted very precisely to the reaction conditions and the respective rhenium precursor.
- the criticality of the exact choice of the alkylating reagent for the synthesis success is shown, for example, by the fact that the reaction of Re 2 O 7 with Zn (CH 3 ) 2 gives known reduced products such as (CH 3 ) 4 Re 2 O 4 , while with CH 3 Zn (OAc) or CH 3 ZnCl exclusively the desired CH 3 ReO 3 (MTO) is formed.
- the organylating reagent [RfMX 9 -Sh] '(III) is prepared in situ from suitable precursors.
- An example which may be mentioned is the / ⁇ -s / fu synthesis of zinc compounds of the formula RZnX, where R and X are as defined above.
- One possibility for this is the treatment of zinc salts of the formula ZnX 2 with an organylating reagent which can transfer the desired R group.
- CH 3 ZnCl The synthesis of CH 3 ZnCl can be carried out, for example, by reacting ZnCl 2 with methylating reagents such as CH 3 Li, (CH 3 ) MgCl or methyl group-containing aluminum reagents, in particular trimethylaluminum or dimethylaluminum chloride.
- methylating reagents such as CH 3 Li, (CH 3 ) MgCl or methyl group-containing aluminum reagents, in particular trimethylaluminum or dimethylaluminum chloride.
- methylzinc compounds CH 3 ZnX can also be prepared by reaction of dimethylzinc with a zinc salt ZnX 2 , according to equation a 1 :
- This manufacturing process is novel. Compared to the production process represented by equation (a), this production process has the advantage of avoiding the loss of methyl groups as methane.
- the comproportionation of dimethylzinc with the corresponding anhydrous zinc salt, for example, zinc (II) acetate, can also be carried out in situ without isolation of the organylating reagent.
- the reaction for the preparation of substance class (I) takes place in a one-pot reaction in organic solvents, in coordinating organic solvents such as acetonitrile, 1,2-dimethyloxyethane, Tetrahydrofuran or diethyl ether, non-coordinating solvents such as n-pentane, n-hexane, toluene, methylene chloride, chlorobenzene or in solvent mixtures.
- the preparation is in donor solvents (eg, tetrahydrofuran, acetonitrile).
- the reaction temperature varies depending on the starting materials used between -115 and +110 0 C, preferably room temperature (25 0 C).
- the reaction is preferably carried out in the absence of water.
- MTO is prepared in the preferred embodiment of the invention from Re 2 O 7 in acetic anhydride, ie from perrhenyl acetate, and a CH 3 Zn (carboxylate) - especially CH 3 Zn (acetate) - preferably at room temperature in acetonitrile as a solvent.
- Another advantage of the synthesis method according to the invention are the very short reaction times, usually less than one hour compared to several hours in the previously known synthesis methods.
- Solvents preferably of CH 3 Zn (OAc), for example, in toluene with O 3 Re (OAc), for example, in acetonitrile quantitatively and in the multikilogram scale feasible.
- OAc CH 3 Zn
- O 3 Re O 3 Re
- the cleaning method can be adapted to the specific procedure of production.
- a perrhenyl compound (II), for example O 3 Re (OAc), with the complex AI (CH 3 ) 3 (THF) at low temperatures in THF, toluene or similar solvents to CH 3 ReO 3 (MTO ) (n 1-3).
- O 3 Re O 3 Re
- MTO CH 3 ReO 3
- the quality of the reagents in particular of the Re 2 O 7 used, has an influence on the purity and yield of the MTO. If CH 3 Zn (OAc) or CH 3 Zn (benzoate) is used as the methylating reagent, it should preferably be added slowly in solution to the rhenium-containing component; otherwise there is a risk of yield reductions.
- Organylzinkcarboxylate are cheap and even air-hand, unlike the Diorganylzink compounds R 2 Zn non-flammable reagents.
- the synthesis of organorhenium (VII) oxide may also be carried out without prior isolation of the organylating reagent of formula (III).
- dirhenium heptoxide in a suitable solvent such as acetonitrile
- a carboxylic anhydride for example with acetic anhydride.
- the molar ratio in this step is about 1: 1.
- the formed O 3 Re-carboxylate, eg O 3 Re-OAc can then be subsequently combined with a solution in which an organylating compound of the formula (III) formed in situ is present.
- a Methylzinkcarboxylat for example CH 3 ZnOAc
- a Zinc carboxylate for example of zinc (II) acetate
- Trimethylaluminum is a very inexpensive methylating agent.
- the Methylzinkcarboxylat generated according to equation (d), for example methylzinc acetate, can be isolated in bulk in a simple manner, but this is not absolutely necessary.
- the organorhenium (VII) oxide synthesized by the process according to the invention does not necessarily have to be worked up, but can be further reacted in situ, for example as a solution. So it may in solution on an inorganic support material, such as Al 2 O 3 , Al 2 O 3 ZSiO 2 , SiO 2 or Nb 2 O 5 or mixtures of these oxides are immobilized.
- an inorganic support material such as Al 2 O 3 , Al 2 O 3 ZSiO 2 , SiO 2 or Nb 2 O 5 or mixtures of these oxides are immobilized.
- the organorhenium (VII) oxide is preferably used as a catalyst.
- Preferred areas for industrial use of organorhenium (VII) oxides include MTO-catalyzed olefin epoxidation and MTO-catalyzed aromatic oxidation (Arco Chemicals U.S. Patent 5,166,372; Hoechst AG DE 3,902,357, EP 90 101 439.9).
- MTO is converted by hydrogen peroxide H 2 O 2 gradually via a mono (peroxo) - into a bis (peroxo) rhenium complex. The latter is the most efficient catalyst for the epoxidation of olefins.
- organorhenium (VII) oxide may also be used to produce high purity rhenium oxides, e.g. be used by a CVD method (Chemical Vapor Deposition).
- the dry ice bath is removed and allowed to continue to warm up with vigorous stirring. If the temperature exceeds the range of -30 0 C to -20 0 C, then begins a violent evolution of gas. When this has subsided (usually after 10 minutes at the latest), the reaction mixture is evaporated in an oil pump vacuum. The product is obtained as a pure white solid in almost quantitative yield (2.74 g, 98%). The yields are typically 95-99%.
- alkyl zinc carboxylates are generally accessible according to 1a) and 1b).
- the formulations under 1a) and 1b) can be easily increased by a factor of 50-100 or more without reducing the yield. In this case, only suitable laboratory equipment should be used and the reaction times, if appropriate also the solvents, suitably adjusted.
- Example 8 The production route under Example 7) can be increased by a factor of 100 or more if the equipment required for this purpose is adapted accordingly (glass flask, stirrer, dosing units, solvents, etc.).
- the work-up of larger amounts of the product CH 3 ReO 3 can alternatively be carried out by Soxhlet extraction, for example with n-pentane.
- the yields are in the range 75-95%.
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Abstract
Applications Claiming Priority (3)
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DE102004041933 | 2004-08-30 | ||
DE102004062246A DE102004062246A1 (de) | 2004-08-30 | 2004-12-23 | Verfahren zur effizienten Herstellung von Methyltrioxorhenium(VII) (MTO) und Organorhenium(VII)-oxiden |
PCT/EP2005/009336 WO2006024493A1 (fr) | 2004-08-30 | 2005-08-30 | Procede de production efficace de methyltrioxorhenium(vii) (mto) et d'oxydes d'organorhenium(vii) |
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EP1789426A1 true EP1789426A1 (fr) | 2007-05-30 |
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EP05781750A Withdrawn EP1789426A1 (fr) | 2004-08-30 | 2005-08-30 | Procede de production efficace de methyltrioxorhenium(vii) (mto) et d'oxydes d'organorhenium(vii) |
Country Status (5)
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US (1) | US20080262256A1 (fr) |
EP (1) | EP1789426A1 (fr) |
JP (1) | JP2008511571A (fr) |
DE (1) | DE102004062246A1 (fr) |
WO (1) | WO2006024493A1 (fr) |
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WO2009036775A1 (fr) * | 2007-09-13 | 2009-03-26 | Süd-Chemie AG | Procédé de production d'oxydes de méthyltrioxorhénium et d'organorhénium (vii) |
DE102008062687A1 (de) | 2008-12-17 | 2010-07-01 | Süd-Chemie AG | Verfahren zur Herstellung von Alkyltrioxorhenium |
DE102008062686A1 (de) * | 2008-12-17 | 2010-07-01 | Süd-Chemie AG | Verfahren zur Herstellung von Methyltrioxorhenium (MTO) |
BR112013015854B1 (pt) * | 2010-12-22 | 2019-07-02 | Ludwig-Maximilians-Universistät München | Processos para produzir reagentes de organozinco e compostos orgânicos, composição de reagentes de organozinco e complexo de coordenação de zinco |
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US5342985A (en) * | 1988-12-10 | 1994-08-30 | Hoechst Ag | Organic derivatives of rhenium oxides and their preparation and use for the metathesis of olefins |
DE19717178A1 (de) * | 1997-04-24 | 1998-10-29 | Hoechst Ag | Direktsynthese von Organorhenium(VII)oxiden aus rheniumhaltigen Verbindungen |
DE19717176A1 (de) * | 1997-04-24 | 1998-10-29 | Hoechst Ag | Verfahren zur katalytischen und selektiven aromatischer Verbindungen |
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- 2005-08-30 EP EP05781750A patent/EP1789426A1/fr not_active Withdrawn
- 2005-08-30 WO PCT/EP2005/009336 patent/WO2006024493A1/fr active Application Filing
- 2005-08-30 JP JP2007528764A patent/JP2008511571A/ja not_active Withdrawn
- 2005-08-30 US US11/661,385 patent/US20080262256A1/en not_active Abandoned
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WO2006024493A1 (fr) | 2006-03-09 |
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