CA1330566C - Organic derivatives of rhenium oxides and their preparation and use for the metathesis of olefins - Google Patents
Organic derivatives of rhenium oxides and their preparation and use for the metathesis of olefinsInfo
- Publication number
- CA1330566C CA1330566C CA000593199A CA593199A CA1330566C CA 1330566 C CA1330566 C CA 1330566C CA 000593199 A CA000593199 A CA 000593199A CA 593199 A CA593199 A CA 593199A CA 1330566 C CA1330566 C CA 1330566C
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- rhenium
- compound
- integer
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 35
- 238000005649 metathesis reaction Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical class [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 title description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 53
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 33
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 32
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 13
- YSZJKUDBYALHQE-UHFFFAOYSA-N rhenium trioxide Chemical compound O=[Re](=O)=O YSZJKUDBYALHQE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002785 ReO3 Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 150000003282 rhenium compounds Chemical class 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 125000001424 substituent group Chemical group 0.000 claims abstract description 4
- NMARTSGFHCLMBT-UHFFFAOYSA-N C[Re]=O Chemical class C[Re]=O NMARTSGFHCLMBT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 3
- 125000004665 trialkylsilyl group Chemical group 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- VZSXFJPZOCRDPW-UHFFFAOYSA-N carbanide;trioxorhenium Chemical compound [CH3-].O=[Re](=O)=O VZSXFJPZOCRDPW-UHFFFAOYSA-N 0.000 claims description 7
- COLOHWPRNRVWPI-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound [CH2]C(F)(F)F COLOHWPRNRVWPI-UHFFFAOYSA-N 0.000 claims description 3
- 150000001925 cycloalkenes Chemical class 0.000 claims description 3
- GJWHXWMUGWZNTO-UHFFFAOYSA-N 2,2-dimethylpropane Chemical compound [CH2]C(C)(C)C GJWHXWMUGWZNTO-UHFFFAOYSA-N 0.000 claims description 2
- AXUSGDAGDBDREJ-UHFFFAOYSA-N CC(C)(C)C[Re](=O)(CC(C)(C)C)CC(C)(C)C Chemical compound CC(C)(C)C[Re](=O)(CC(C)(C)C)CC(C)(C)C AXUSGDAGDBDREJ-UHFFFAOYSA-N 0.000 claims description 2
- VLGNYRMSHKCXPS-UHFFFAOYSA-N C[Re](C)(C)=O Chemical compound C[Re](C)(C)=O VLGNYRMSHKCXPS-UHFFFAOYSA-N 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 239000004480 active ingredient Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 35
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 14
- 229910052681 coesite Inorganic materials 0.000 description 11
- 229910052906 cristobalite Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 235000012239 silicon dioxide Nutrition 0.000 description 11
- 229910052682 stishovite Inorganic materials 0.000 description 11
- 229910052905 tridymite Inorganic materials 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229960005419 nitrogen Drugs 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- -1 allyl halides Chemical class 0.000 description 8
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000012190 activator Substances 0.000 description 6
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 229910009201 Sn(CH3)4 Inorganic materials 0.000 description 5
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 5
- 229940010415 calcium hydride Drugs 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 230000008093 supporting effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000005865 alkene metathesis reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- RMXLHIUHKIVPAB-OWOJBTEDSA-N (e)-1,4-dibromobut-2-ene Chemical compound BrC\C=C\CBr RMXLHIUHKIVPAB-OWOJBTEDSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- FXNFFCMITPHEIT-UHFFFAOYSA-N Ethyl 10-undecenoate Chemical compound CCOC(=O)CCCCCCCCC=C FXNFFCMITPHEIT-UHFFFAOYSA-N 0.000 description 2
- FVKHVICASXTJKB-UHFFFAOYSA-N FC1=C(F)C(F)=C(F)C(F)=C1C[Zn]CC1=C(F)C(F)=C(F)C(F)=C1F Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1C[Zn]CC1=C(F)C(F)=C(F)C(F)=C1F FVKHVICASXTJKB-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical group [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- JRPGMCRJPQJYPE-UHFFFAOYSA-N zinc;carbanide Chemical compound [CH3-].[CH3-].[Zn+2] JRPGMCRJPQJYPE-UHFFFAOYSA-N 0.000 description 2
- AQKQNUNUFNYQFB-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(iodomethyl)benzene Chemical compound FC1=C(F)C(F)=C(CI)C(F)=C1F AQKQNUNUFNYQFB-UHFFFAOYSA-N 0.000 description 1
- SOTWQKWPJWXFPK-UHFFFAOYSA-N 1,4-di(propan-2-yloxy)but-2-ene Chemical compound CC(C)OCC=CCOC(C)C SOTWQKWPJWXFPK-UHFFFAOYSA-N 0.000 description 1
- HOJXZKAICPOWBW-UHFFFAOYSA-N 1,4-diethoxybut-2-ene Chemical compound CCOCC=CCOCC HOJXZKAICPOWBW-UHFFFAOYSA-N 0.000 description 1
- HCHJSQGMAQVHNO-UHFFFAOYSA-N 2-prop-2-enoxypropane Chemical compound CC(C)OCC=C HCHJSQGMAQVHNO-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 1
- GONFBOIJNUKKST-UHFFFAOYSA-N 5-ethylsulfanyl-2h-tetrazole Chemical compound CCSC=1N=NNN=1 GONFBOIJNUKKST-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 101100219382 Caenorhabditis elegans cah-2 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QOIVFFPYOCSTRX-UHFFFAOYSA-N FC(F)(F)C[Zn]CC(F)(F)F Chemical compound FC(F)(F)C[Zn]CC(F)(F)F QOIVFFPYOCSTRX-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101100010166 Mus musculus Dok3 gene Proteins 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- KVXVHMMBCSGZFS-UHFFFAOYSA-N but-3-enyl-[but-3-enyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=CCC[Si](C)(C)O[Si](C)(C)CCC=C KVXVHMMBCSGZFS-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- JFZUABNDWZQLIJ-UHFFFAOYSA-N methyl 2-[(2-chloroacetyl)amino]benzoate Chemical compound COC(=O)C1=CC=CC=C1NC(=O)CCl JFZUABNDWZQLIJ-UHFFFAOYSA-N 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- WQAHWLOKQLDRAG-UHFFFAOYSA-N tetrakis(2,2,2-trifluoroethyl)stannane Chemical compound FC(F)(F)C[Sn](CC(F)(F)F)(CC(F)(F)F)CC(F)(F)F WQAHWLOKQLDRAG-UHFFFAOYSA-N 0.000 description 1
- CGHUMSBZDKNESK-UHFFFAOYSA-N trimethyl(4-trimethylsilyloxybut-2-enoxy)silane Chemical compound C[Si](C)(C)OCC=CCO[Si](C)(C)C CGHUMSBZDKNESK-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 150000003752 zinc compounds Chemical group 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/122—Metal aryl or alkyl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/475—Preparation of carboxylic acid esters by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules
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Abstract
Abstract:
A compound of the general formula R1aRebOc, wherein a is an integer from 1 to 6, b is an integer from 1 to 4 and c is an integer from 1 to 14 and the sum of a, b and c conforms to the 5- to 7-valency of rhenium with the proviso that c does not exceed 3-b, and wherein R1 represents alkyl having from 1 to 9 carbon atoms, cycloalkyl having from 5 to 10 carbon atoms or aralkyl having from 7 to 9 carbon atoms and wherein R1 is unsubstituted or at least partially fluorinated, said compounds containing not more than three groups of more than 6 carbon atoms per rhenium atom and containing a hydrogen atom bound to the carbon atom in .alpha.-position to the rhenium atom, the methylrhenium oxides CH3ReO3 and (CH3)6Re2O3 and pentamethylcyclopentadienyl-rheniumtrioxide (?5-C5(CH3)5)ReO3 being excluded.
The invention further relates to a catalytic composition for the metathesis of olefinic compounds comprising an oxidic carrier charged with a compound of the general formula R1aRebOc, wherein a is an integer from 1 to 6, b is an integer from 1 to 4 and c is an integer from 1 to 14 and the sum of a, b and c conforms to the 5- to 7-valency of rhenium with the proviso that c does not exceed 3?b, and wherein R1 represents alkyl having from 1 to 9 carbon atoms, cycloalkyl having from 5 to 10 carbon atoms or aralkyl having from 7 to 9 carbon atoms and wherein R1 is unsubstituted or at least partially fluorinated, said compounds containing not more than three groups of more than 6 carbon atoms per rhenium atom and containing a hydrogen atom bound to the carbon atom in a-position to the rhenium atom.
The invention also relates to a process for the preparation of a metal organic catalyst as defined hereinbefore, which comprises charging the carrier with the rhenium compound from an anhydrous solvent inert towards the rhenium compounds, and subsequently removing the volatile compounds.
The invention finally relates to a process for the metathesis of olefins which comprises reacting an olefin of the formula YCZ=CZ-(CX2)nR2 (II) wherein n an integer from 1 to 28, X represents H or F, Y represents H or alkyl having from 1 to 10 carbon atoms and Z represents H or a non-aromatic hydrocarbon group having from 1 to 6 carbon atoms and R2 being H, alkyl, halogen, COOR3 or R4, wherein R3 and R4 represent alkyl having from 1 to 15 carbon atoms or phenyl which is unsubstituted or contains from 1 to 3 substituents or wherein R4 is trialkylsilyl R5Si, wherein R5 represents alkyl having from 1 to 5 carbon atoms, at a catalyst comprising an oxidic carrier charged with a rhenium compound as defined hereinbefore.
A compound of the general formula R1aRebOc, wherein a is an integer from 1 to 6, b is an integer from 1 to 4 and c is an integer from 1 to 14 and the sum of a, b and c conforms to the 5- to 7-valency of rhenium with the proviso that c does not exceed 3-b, and wherein R1 represents alkyl having from 1 to 9 carbon atoms, cycloalkyl having from 5 to 10 carbon atoms or aralkyl having from 7 to 9 carbon atoms and wherein R1 is unsubstituted or at least partially fluorinated, said compounds containing not more than three groups of more than 6 carbon atoms per rhenium atom and containing a hydrogen atom bound to the carbon atom in .alpha.-position to the rhenium atom, the methylrhenium oxides CH3ReO3 and (CH3)6Re2O3 and pentamethylcyclopentadienyl-rheniumtrioxide (?5-C5(CH3)5)ReO3 being excluded.
The invention further relates to a catalytic composition for the metathesis of olefinic compounds comprising an oxidic carrier charged with a compound of the general formula R1aRebOc, wherein a is an integer from 1 to 6, b is an integer from 1 to 4 and c is an integer from 1 to 14 and the sum of a, b and c conforms to the 5- to 7-valency of rhenium with the proviso that c does not exceed 3?b, and wherein R1 represents alkyl having from 1 to 9 carbon atoms, cycloalkyl having from 5 to 10 carbon atoms or aralkyl having from 7 to 9 carbon atoms and wherein R1 is unsubstituted or at least partially fluorinated, said compounds containing not more than three groups of more than 6 carbon atoms per rhenium atom and containing a hydrogen atom bound to the carbon atom in a-position to the rhenium atom.
The invention also relates to a process for the preparation of a metal organic catalyst as defined hereinbefore, which comprises charging the carrier with the rhenium compound from an anhydrous solvent inert towards the rhenium compounds, and subsequently removing the volatile compounds.
The invention finally relates to a process for the metathesis of olefins which comprises reacting an olefin of the formula YCZ=CZ-(CX2)nR2 (II) wherein n an integer from 1 to 28, X represents H or F, Y represents H or alkyl having from 1 to 10 carbon atoms and Z represents H or a non-aromatic hydrocarbon group having from 1 to 6 carbon atoms and R2 being H, alkyl, halogen, COOR3 or R4, wherein R3 and R4 represent alkyl having from 1 to 15 carbon atoms or phenyl which is unsubstituted or contains from 1 to 3 substituents or wherein R4 is trialkylsilyl R5Si, wherein R5 represents alkyl having from 1 to 5 carbon atoms, at a catalyst comprising an oxidic carrier charged with a rhenium compound as defined hereinbefore.
Description
13 3 ~ ~ 6 6 HOECHST AKTlENGESELLSCHAFT HOE 88/F 356K Dr.KLR/AP
Description Organic derivatives of rhenium oxides and their prepara-tion and use for the metathesis of olefins The present invention relates to organic derivatives of rhenium oxides and to their preparation and use for the metathesis of olefins as such and also derivatives of olefins. ~-The term metathesis designates, as is known, the cleav-age of olefinic compounds in such a way that the double bond is broken apart and the two fragments combine to form new compounds. In the wider sense, metathesis also includes the ring-opening polymerization of cyclo-olefins. As a result of the invention, an organorhenium compound of definite structure, which can be isolated in an undiluted form, becomes a catalyst for the f;rst time.
It is kno~n that compounds of the element rhenium exhi-bit catalytic activity in the metathesis of olefins, specifically only in the metathesis of olefins as such.
Only if so-called co-catalysts, in particular tetra-alkyltin compounds are added to such rhenium catalystsis the metathesis of derivatives of olefins, ie. ole-fins containing heterofunctions, possible (K.J. Ivin~
Olefin Metathesis, Academic Press, London 1983, 32 -34). Thus the metathesis of olefinically unsaturated carboxylic acid esters and of allyl halides and the like on mu~ti-component catalysts, such as ~Cl6/Sn(CH3)4 or ~-Re207/Sn(CH3)4/Al203 has been described. The last-named system (R.A. Fridman et al., Dokl. Akad.
Nauk. SSSR 2 , (1977), 1354 - 57; R.H.A. Bosma et al., J. Organometal. Chem. 225 (1983) 159 - 171; X. Xiaoding et al., J. Chem. Soc. Chem. Commun. 1985, 631 - 633;
G.C.N. van den Aardweg, loc. cit. 1983, 262 - 263) is the only one containing rhenium which is capable of meta-thesizing olefinically unsaturated organic halides, ~ , ' ~-133~56 esters and the like. Hitherto there has been no know-ledge of the effective catalyst species. The following are practical disadvantages of the rhenium-containing catalyst systems hitherto used:
S a) the necessity of using at the same t;me highly toxic tetraalkyltin compounds as activators in the meta-thesis of derivatives of olefins (J.E. Cremer, ~iochem. J. 68 (1958) 685 - 688; ~.N. Aldridge et al., The Lancet, Sept. 26, 1981, page 692/3), b) low catalyst activity, inacceptable for industrial use, and c) a breadth of application with relatively narrow limits, ie. the catalytic action is only found in the case of simple derivatives of olefins or olefins as such.
It was therefore required to find a non-toxic and effective catalyst system which is as readily acces-sible, simple to handle and stable on storage as possible and which is also adequate without any activa-tor in the metathesis of olefin derivatives.
Considerable interest attaches to the industrial fur-ther processing of the products.
Although some so-called "organorhenium oxides", for example CH3ReO3, (n5-Cs(CH3)s)ReO3 (= penta-methylcyclopentadienylrhenium trioxide), are known as catalyst components for the metathesis of olefins by homogeneous catalysis (W.A. Herrmann et al., Angew.
30 Chem. 100 (1988) 420 - 422, translation in Angew. Chem.
Int. Ed. Engl. 27 (1988) 394 - 396), the concomitant use, as activator, of a Lewis acid which is at least partially soluble in organic solvents was, however, always necessary, preferably aluminum(III) chloride and, in most cases, also the concomitant use of toxic tin tetraalkyls (for example Sn(CH3)4) as further activa-tors. Even then the catalyst systems thus obtainable are completely inactive in respect of the metathesis of derivatives of olefins.
, .. , . , .. . . ... .. --.,,. -- . .. . . . .
~ 13305~6 -It has now been found, surprisingly, that methylrhenium trioxide CH3ReO3 and related compounds of the formula I indicated below are suitable for use as a metathesis catalyst when supported on oxide supporting materials, in particular aluminum oxide supports. The use of additional activator substances ("Co~
catalysts"), which is disadvantageous for many reasons, thus becomes superfluous for the first time.
Thus, according to one aspect, the invention provides a compound of the general formula R aRebOc, wherein a is an integer from 1 to 6, b is an integer from 1 to 4 and c is an integer from ~ -1 to 14 and the sum of a, b and c conforms to the 5- to 7-valency of rhenium with the proviso that c does not exceed 3.b, and wherein R represents alkyl having from 1 to 9 carbon atoms, ;~
cycloalkyl having from 5 to 10 carbon atoms or aralkyl having from 7 to 9 carbon atoms and wherein R1 is unsubstituted or at least ~;;
partially fluorinated, said compounds containing not more than three groups of more than 6 carbon atoms per rhenium atom and containing a hydrogen atom bound to the carbon atom in a-position to the rhenium atom, the methylrhenium oxides CH3ReO3, (CH3)4ReO, (CH ) ReO , [(CH3)3ccH2]3ReO2~ [(CH3)3c CH2]4 2 4' 3 6 2 3 and the pentamethylcyclopentadienyl-rheniumtrioxide (~ -C5(CH3)5)ReO3 being excluded.
According to another aspect, the invention provides a catalytic composition for the metathesis of olefinic compounds .
~ .
~, , 13305~6 comprising an oxidic carrier charged with a rhenium compound of the general formula R1aRebOc, wherein a is an integer from 1 to 6, b is an integer from 1 to 4 and c is an integer from 1 to 14 and the sum of a, b and c conforms to the 5- to 7-valency of rhenium with the proviso that c does not exceed 3.b, and wherein represents alkyl having from 1 to 9 carbon atoms, cycloalkyl having from 5 to 10 carbon atoms or aralkyl having from 7 to 9 carbon atoms and wherein R1 is unsubstituted or at least partially fluorinated, said compounds containing not more than three groups of more than 6 carbon atoms per rhenium atom and containing a :
hydrogen atom bound to the carbon atom in a-position to the rhenium atom. ~:~
According to still another aspect, the invention provides a process for the metathesis of olefins which comprises reacting an olefin of the formula YCZ=CZ-(CX2)nR2 (II) wherein n .';.-~
is an integer from 1 to 28, X represents H or F, . ~.
Y represents H or alkyl having from 1 to 10 carbon atoms and Z represents H or a non-aromatic hydrocarbon group having from 1 to 6 carbon atoms and R2 represents H, alkyl, halogen, CoOR3 or oR4, wherein R3 and R4 represent alkyl having from 1 to 15 carbon atoms or phenyl which is unsubstituted or contains from 1 to 3 substituents or wherein R4 is 1~ .. ,.:
- ~a~ 23221-4607 1330~66 trialkylsilyl R53Si, wherein R5 represents alkyl having from 1 to 5 carbon atoms, ln the pre~ence of a catalytic composition as defined above.
The invention thus relates to the use of compounds of rhenium which have the general formula RlaRebOc tI) ln whlch a is -~
1 to 6, b i~ 1 to 4 and c ls 1 to 14 and the total of a, b and c ls such that lt accords wlth the pentavalency to heptavalency of rhenlum, subject to the provlso that c ls not greater than 3 x b, and whlch are supported on oxlde supportlng materlals, as heterogeneous catalysts for metathesis. In this connection denotes an organlc group attached to the metal rhenlum via a carbon atom to whlch at least one hydrogen atom is stlll attached, speclflcally alkyl radlcals havlng 1 to 9 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, such as cyclohexyl or l-norbornyl, or aralkyl having 7 to 9 carbon atoms, such as benzyl, but preferably methyl. The term~ alkyl and cycloalkyl naturally imply that these groups contaln no multiple bonds. Rl can be at least partially fluorinated. For steric reason3, however, the presence of more than three groups containing more than 6 carbon atoms per rhenium atom is not possible in the compounds; the compound~ preferably contain only one such group at the most. The term metathesis in this context includes the ring-opening polymerization of cycloolefins.
~'' , .
133Q~66 -4b-Of the compounds of the formula mentioned above, CH3ReO3, (CH3)4ReO, (CH3)3ReO2, l(CH3)3CCH2]3ReO2, 3 3 2]4Re204, (CH3)6Re203 and the pentamethylcyclopentadlenyl-rhenlumtrloxlde (~5-C5(CH3)5)ReO3 are admlttedly known, but the catalytlc activlty of these compound~
wlthout the concomltant use of activators, that is to say their sultability as the sole catalyst, was not known and was as unexpected a~ that of the whole class of compound6. Thls -catalytlc actlon ls all the more surprising because (trlmethylstannoxy)-rhenium trioxlde l(CH3)3SnO]ReO3, which ls lsostructural, 1~ catalytlcally lnactive. This show~ the lmportance of the alkyl groups attached to rhenium for the catalytlc actlvity of the compounds according to the inventlon.
In terms of synthesls, the compounds according to the lnventlon can be syntheslzed ln a very slmple manner from Re207 by means of cu~tomary alkylatlng agents. For example, dlrhenlum heptoxlde ls reacted ln an anhydrous solvent whlch is inert towards the rhenlum compounds, at a temperature from O to 60, preferably 10 to 40C, wlth a solutlon of R12Zn ln whlch Rl has the meanlng lndlcated above, and the volatlle constituents are removed. The compounds accordlng to the inventlon are entlrely lnsensltive to alr and molsture. When supported on oxldic supportlng materlals, the rhenium compounds are hlghly active catalysts for the metathesls of oleflns as such and also derlvatlves of oleflns of the type YCZ-CZ-(CX2)nR2 (II) in whlch n ;;
18 an lnteger from 1 to 28, X 18 H or F, Y ls H or alkyl havlng 1 ~-to 10 carbon atoms and Z represents H or a non-aromatlc -~
~D ::
.. -. . ~- . . ~ .
`-13~66 ~ ~
-4c - 23221-4607 hydrocarbon radical having l to 6 carbon atoms, for example ~:
cyclohexyl, but preferably open-chain alkyl having l to 4 carbon a~oms, and the subætituent R2 is H, alkyl, halogen, CoOR3 or oR4 in which R3 is alkyl or aryl and R4 i6 alkyl, aryl or tri~
alkylsilyl R53Si. The alkyl groups in R5 contain l to 5, preferably l to 3 carbon atoms. In R3 and R4 alkyl represents l to 15, preferably l to 6, carbon atoms and aryl represents phenyl ~hlch can also contain one to three substituents on the ring, such as halogen, for example ~ -,. : ~ , . , --., . ~. . .. . . .
~33~6~
fluor;ne, chlorine or bromine, N0z, NR6R7, oR8 and/or alkyl. The radicals R6, R7 and R8 are identical or different and can be hydrogen or alkyl having 1 to 4 carbon atoms. However, the groups YCZ and CZ-(CH2)nR2 S must be different. As halogen, R2 can be fluorine, chlorine, bromine or iodine. If Z is hydrogen and R2 is ~
halogen, the latter is preferably bromine. Examples of -compounds in which at least one X is F are 4-(perfluoro-n-hexyl~but-1-ene, formula (n-C6F13)-CH2-CH2-CH=CH2~
and perfluoropropene C3F6. The number n of units varies, preferably within the range from 1 to 12 and especially up to 8.
The novel catalysts are thus not only active in the case of olefins in which Z = H, but also, for the first time, in the metathesis of partly or completely fluori-nated olefins. They are also suitable for the metathesis of non-terminal olefin derivatives of the formula R9CH=CH-(CH2)nR10 (IV) in which R9 is a branched~ or preferably unbranched, alkyl radical having 1 to 12 carbon atoms, R10 is a carboxyalkyl radi-cal in which the alkyl radical preferably has 1 to 4 carbon atoms, and n represents an integer from 1 to 10.
Methyl oleate (R9 = n-octyl, R10 = C02CH3 and n = 7) may ZS be mentioned as an example.
SiO2/Al203 (for examPle in a ratio by weight of 87:13) and Al203, each of which can be acid, neutral or basic according to its pretreatment, are particularly ~ -suitable as supporting materials. The activity of these catalysts can be increased considerably if the rhenium,compounds are supported on a thoroughly cal- -~-' ~ ; cined, ~ as far as possible anhydrous, support, such as silica/aluminum oxide. This is because if the sup-porting material contains major amounts of moisture,the activity decreases, because the alkyl group attached to rhenium is then partly split off as alkane by means of the water.
1 3 3 ~
The catalytic activity of the catalysts according to the invention for the metathesis of oLefins is higher than that of the rhenium-containing catalyst systems described hitherto. An exemplary proof is afforded by -the systems A1 and V1 (cf. graphs). The system CH3ReO3/
SiO2/Al203 (A1) metathesizes allyl bromide in only 20 minutes to a Q of over 20, peak area of ethylene the ratio Q =
peak area of propane being obtained using propane as predetermined standard and being plotted against time. The shape of the curve provides information on the activity of the particular catalyst system. The standard catalyst NH4tReO4]/SiO2/
Al2/03 (V1) known from the literature is, in contrast, only active in the presence of Sn(CH3)4, and even then only to a comparable extent in 180 minutes. The symbol "r^ 2" is a measure of the agreement between the shape of the curve determined by calculation and the experi-mental values.
The rhenium-containing catalysts hitherto used indus-trially in olefin metathesis are, as a rule, prepared (see ~arwel et al., Chem.-Ztg 1û7 (1983), 115-120) by treating commercially available ammonium perrhenate NH4tReO4] as a solution in dioxane/water with the sup-porting material (as a rule aluminum oxide). The resulting suspension is then evaporated to complete dryness in a water pump vacuum; the dry material is then heated at 550C, first for about 2 hours in a stream of oxygen and then for about 2 hours in a stream of nitrogen. Only the material obtained in this way and cooled to room temperature is employed for catalytic purposes.
For the process according to the invention, on the other hand, it is possible to dispense with these time-consuming and energy-consuming process stages, as a result of ~hich catalysts of better reproducibility are - _ 7 _ 1 3 3 ~
also obtained. For the present process, the catalytically active rhenium compound is applied, pre-ferably at room temperature, from a solvent, preferably a solution of methylene dichloride, to the catalyst 5 support, preferably silica gel/aluminum oxide, and only ~*~
the catalyst support is freed from moisture, before use, for 2 hours at 800C in a stream of nitrogen, in order that the catalyst system may subsequently develop its full activity.
In metathesis using the catalysts according to the invention care must be taken that air and moisture are excluded. The olefins employed must also preferably be dried thoroughly before use. In general, the metathe-sis is carried out at atmospheric pressure and atemperature from 0 to 40C, preferably 10 to 35C. The fact that it is possible to work under such mild reac-tion conditions is a particular advantage of the process according to the invention. It is also pos-sible, however, to use higher temperatures, for exampleup to 100C, or to work under a pressure above or below atmospheric. Usually, however, no advantages are associated there~ith. `~
In the characterization of individual compounds in the following examples "sst" means very strong, "st" means strong, "br" means broad and "EI-MS" means electron -~
impact mass spectrum.
Exa-ples 1-5 - ~etathesis using CH3ReO
In the following tests the olefins employed were dried ~ -over CaH2 and distilled before being used. The catalyst used in these tests was methylrhenium trioxide CH3ReO3 which had been prepared by a simple process in terms of preparation, avoiding toxic tetramethyltin, Sn(CH3)4, as follows:
20 ml of a 0.5-molar solution of dimethylzinc Zn(CH3)2 ~-in tetrahydrofuran were added dropwise at room ... . . . . . ., . ~ .. . . - , . -, ~
- 8 - 1 33 ~
temperature and in the course of 10 minutes to a solution of 4.84 9 (10 mmol) of dirhenium heptoxide Re207 (made by Degussa, 76.9% of Re) in 100 ml of an anhydrous sol-vent, such as tetrahydrofuran, and the mixture was then -stirred for a further 60 minutes at room temperature.
The volatile constituents were then stripped off under an oil pump vacuum into a cold trap. The residue was sublimed in a high vacuum at 40-55C onto a water-cooled sublimation finger. This gave 3.89 9 (78X of theory) of colorless, mostly needle-shaped~ crystals of the catalyst CH3ReO3. The synthesis is also possible using unsublimed Re207, but the yields are then lower. The substance has the following characteristics: Melting point 106. - IR (cm 1, K~r): 1002 sst, 950 sst,br tv(Re=0)].-1H-NMR (CDCl3, 28C): ~tCH3) = 2.61 tsing-let]. - 13C-NMR (CDCl3, 28C): ~(CH3) = 19.03 Cquar-tet, 1J(C,H) = 138 Hz]. - 170-NMR (CDCl3, 28C: (0)=
829 ppm. - EI-MS : m/z = 250 (molecule-ion, with the cor-rect pattern of isotopes 185Re/187Re). - The substance can be stored at room temperature without decomposition.-Elementary analysis: Calculated for CH303Re (249~21):
C 4.82, H 1.20, 0 19.26, Re 74.72; found: C 4.84, H 1.19, 0 19.30, Re 74.78.
In a 30 ml reaction vessel equipped with a septum, a reflux condenser and a mercury pressure relief valve, a solution of 13 mg (0.052 mmol) of methylrhenium tri-oxide CH3ReO3 in 0.5 ml of methylene dichloride was introduced with stirring into a suspension of 1,000 mg of catalyst support tSiO2/Al203, (87:13), particle size below 15 ~m (preparation No. 14-7150 of Strem Chemicals, Newburyport/Mass. 01950 (USA), heated at 800C for 2 hours] in 10 ml of methylene dichloride (dried over calcium hydride and stored under an atmosphere of nitrogen]. The contents of the flask were heated to the boil. After thermal equilibrium had been set up, 5.2 mmol of olefin were injected by means of a syringe through the septum. In order to isolate the product, the mixture was boiled for several hours under reflux .,-.- ~
.,.~
..... .., ~ . , , .. ;
~ 3 3 ~ ~ 6 6 b~ ` ' _ 9 (Table 1), the contact catalyst was filtered off with suction on a frit and was extracted by washing with twice 10 ml of methylene dichloride. The solvent was stripped off under an oil pump vacuum, the product was weighed and its purity was checked by means of a gas chromatograph with coupled mass spectrometer.
TabLe 1: Metathesis of ~-olefin derivatives of the type II with the elimination of ethylene Example/oLefin (*) Time Amount Weight Purity rield (hrs) (mg) (mg) (%) (%_ 1) Allyl bromide4 620100 100 14 2) Ethyl undecenoate 201120 1120 64 64 3) AlLyl isopropyl ether 4 520220 70 30 4) Allyl ethyl ether 5 448 260 50 39 5) Allyl trimethyl-silyl ether 24 680530 88 69 ' ~'~'' (*) Metathesis products~
1) 1,4-Dibromobut-2-ene.
2) Diethyl eicos-10-ene-~,~'-dicarboxylate.
3) 1,4-Bis-(isopropoxy)-but-2-ene.
4) 1,4-Bis-(ethoxy)-but-2-ene.
5) 1,4-Bis-(trimethylsiloxy)-but-2-ene.
Co-parisons In a 30 ml reaction vessel closed with a septum, a solution of 13 mg (0.052 mmol) of methylrhenium tri-oxide CH3ReO3 in 0.5 ml of methylene dichloride was ~ -introduced with stirring into a suspension of 1,000 mg of catalyst support (SiO2/Al203 (weight ratio 87:13, particle size below 15 ~m; kept at 800C for 2 hours)) in 10 ml of methylene dichloride (dried over calcium hyd-ride and stored under an atmoçphere of nitrogen). 0.5 ml of propane was injected as the internal standard.
- ~ 330~66 After stirring for 5 minutes 5 mmol of ole~in were injected (t = 0) and the ethylene content of the gas phase was determined by gas chromatography at the intervals of time evident from graphs A1, A2, V1 and V2 5 (attachments). V1 shows a comparison with A1, A2 shows -the effect of a greater dilution of the catalyst com-pared with A1 and V2 shows a comparison with the rhenium-containing catalyst system hitherto used and known from the literature, as specified by ~arwel et al, l.c. For this purpose 900 mg of neutral aluminum oxide were first impregnated with a solution of 100 mg of ammonium perrhenate NH4CReO4] in 10 ml of dioxane/
water (9+1 parts by volume). The catalyst system was then activated at 550C for 2 hours in a stream of oxygen and then for 2 hours in a stream of nitrogen.
The reaction kinetics tests proceeded analogously to those with methylrhenium trioxide CH3ReO3, but it was necessary for activation to inject 0.005 ml of tetra-methyltin Sn~CH3)4 5 minutes before the addition of olefin, in order to obtain any catalytic effect at all.
A direct comparison was afforded by comparison test V1, j~
in which 14 mg of ammonium perrhenate NH4[ReO4] were absorbed onto 1 9 of SiO2/Al203 and activated in a~ ;~
stream of 2 and N2 as indicated above.
In the metathesis of olefins as such CH3ReO3 on the one hand and NH4CReO4] on the other hand achieved a com- ;~
parable activity on SiO2/Al203. The equilibrium product distribution in the metathesis of a mixture of 50 mol % of 2-pentene + 25 mol % of 2-butene + 25 mol %
of 3-hexene was set up after approx. 5 minutes in both systems, but in the case of NH4CReO4] only after additional activation with tetramethyltin, as can be seen from a comparison of graphs A3 and V3.
Effects arising from the cataLyst support As shown in particular by systems A1 and A2 for the . ,,... . , . . .. ~ ~ . - .. -"~.. , . -3 ~
r~
, ,. j ~ . . . .. -13~0~6~
metathesis of allyl bromide, the activity of the cata-lyst CH3ReO3 increases greatly with dilution (relative to the amount of oxide supporting material): For a reaction time of 300 minutes, 13 mg of CH3ReO3 + 1000 mg of SiO2/Al203 give a value of 30 for Q, while 13 mg of CH3ReO3 + 2000 mg of SiO2/Al203 give a value of 40 for Q.
Exaoples 6-9 - ~etathesis using (CH3)6Re2O3 10 6) In a 30 ml reaction vessel closed with a septum, a ~-solution of 25.5 mg (0.052 mmol) of hexamethyltrioxodi- -rhenium (CH3)6Re203 in 0.5 ml of methylene dichloride was introduced with stirring into a suspension of 1000 mg of catalyst support (SiO2/Al203; weight rat;o 87:13, 15 particle size below 15 ~m; kept at 800C for 2 hours) in - ~ ~;
10 ml of methylene dichloride (dried over calcium hyd-ride and stored under an atmosphere of nitrogen). 0.5 ml of propane were injected as the internal standard. -~
After stirring for 5 minutes 5 mmol of allyl bromide were injected ( t = 0) and the ethylene content of the gas phase was determined by gas chromatography at the intervals of time evident from graph A4 (attachment).
7 - 9) In a 30 ml reaction vessel equipped with a sep-tum, a reflux condenser and a mercury pressure relief valve, a solution of 25.5 mg (0.052 mmol) of hexamethyl- -trioxodirhenium (CH3)6Re203 in 0.5 ml of methylene dichloride was introduced with stirring into a suspen-sion of 1000 mg of catalyst support ~SiO2/Al203 (87:13), 30 particle size below 15 ~m (preparation No. 14-7150 of Strem Chemicals, Newburyport/Mass. 01950 (USA), heated at 800C for 2 hours] in 10 ml of methylene dichloride (dried over calcium hydride and kept under an atmos-phere of nitrogen). The contents of the flask were heated to the boil. After thermal equilibrium had been set up, 5.2 mmol of olefin were injected through the septum by means of a syringe. In order to isolate the product, the mixture was boiled under reflux for sever-al hours (Table 2), the contact catalyst was filtered .,;.: , 133~
off with suction on a frit and was washed with twice 10 mL
of methylene dichLoride. The solvent was stripped off in an oil pump vacuum, the product was weighed and its purity was checked by means of a gas chromatograph with coupled mass spectrometer.
Table 2 Example/olefin (*) Time Amount Weight Purity Yield (hrs) (mg) (mg) (%) (%) 7) Allyl bromide 20 680 72 98 12 8) Ethyl undecenoate 20 1410 840 57 34 9) Allyl trimethyl~
silyl ether 15 705 550 48 41 (*) Metathesis products: ~ 9 7) 1,4-Dibromobut-2-ene.
8) Diethyl eicos-10-ene-1,1'-dicarboxylate.
9) 1,4-~is-(trimethylsiloxy)-but-2-ene.
~.
Example 10 - Metathesîs using (CH3)4Re2O4 In a 30 ml reaction vessel closed by means of a septum, a solution of 25.8 mg (0.052 mmol) of tetramethyltetra-oxodirhenium (CH3)4Re204 in 0.5 ml of methylene dichloride was introduced with stirring into a suspen-sion of 1000 mg of catalyst support (SiO2/Al203; weight ratio 87:13, particle size below 15 ~m; kept at 800C for 2 hours) in 10 ml of methylene dichloride (dried over calcium hydride and kept under an atmosphere of nitro-gen). 0.5 ml of propane were injected as the internal standard. After stirring for 5 minutes 5 mmol of allyl bromide were injected (t = 0) and the ethylene content of the gas phase was determined by gas chromatography at the intervals of time evident from graph A5 (attachment).
Exaoples 11-15 - Co-pounds of the for-ula R1aReb0c 11. Tri-ethYl(oxo)rhenium, (CH3)3ReO :-1 33 0 ?~
a) 2.62 g (10 mmol) of triphenylphosphine P(C6Hs)3 and 10.85 9 (0.1 mol) of trimethylchlorosilane (CH3)3SiCl were added rapidly, successively and at room tempera-ture and with vigorous magnetic stirring to a solution of 4.14 9 (10 mmol) of the compound [(CH3)3SnO]ReO3 in 100 ml of anhydrous tetrahydrofuran. After 3 hours stirring at room temperature a green deposit had formed, l~
consisting of the compound Reocl3[op(c6H5)](oc4H8) (OC4H8 = tetrahydrofuran). Filtering off this preci-10 pitate from the supPrnatant solution, washing it with ~
tetrahydrofuran and drying it ;n an oil pump vacuum -gave 6.19 9 (94% of theory) of this compound in a pure ~-form.
: :: ' 15 b) 3.29 9 (5 mmol) of the compound prepared under a) were suspended in 20 ml of tetrahydrofuran. A 0.2-molar solution of lithiummethyl LiCH3 (altogether 16 mmol) were added dropwise at 0C to this suspension, and the resulting reaction mixture was stirred for a further 3 hours at room temperature. The volatile constituents were then removed in an oil pump vacuum.
The dark brown residue, in most cases somewhat oily, was extracted with approx. 10 ml of toluene. The extract was evaporated to dryness in an oil pump vacuum.
The residue was chromatographed at -60C on a column (40 cm long and 2 cm in diameter) of silanized, cal-cined silica geL (by Merck), the yellow zone of the compound (CH3)3ReO being developed with toluene. The eluate was concentrated under an oil pump vacuum. The residue was then dissolved in 20 ml of n-pentane, and the solution was left to crystallize at -80 to -40C.
This gave 198 mg (16% of theory) of yellow needles of (CH3)3ReO.- :
Characterization: Soluble in the customary anhydrous organic solvents, in particular methylene chloride, tetrahydrofuran and toluene. The substance is solid and, in solution, admittedly only stable undecomposed for some time when stored within the temperature range from -80 to -40C. - IR (cm 1, K~r): 978 sst [v(Re=0)].
133~
- 1H-NMR (270 MHz; 28C, CD2Cl2): ~CH3 = 5.41 (sin- -glet). - FD-mass spectrum: Molecule ion m/z = 248 (187Re), with correct pattern of isotopes 185Re/187Re.
12. Tris(neopentyL)oxorhenium, ReCCH2C(CH3)3~30 ;~
This compound was synthesized analogously to the ins-tructions for Example 11, employing lithiumneopentyl LitCH2C(CH3)3~ instead of lithiummethyl. The product ;~
was worked up analogously. Yield 249 mg (12% of theory).-Characterizat;on: Yellow crystals; stable without de-composition over a prolonged period (approx. 8 days) only at temperatures below -20C. - IR (cm 1, K~r):
975 cm 1 sst [v(Re=0)~ H-NMR (400 MHz, 28C, CDCl3): ~CH3 = 1.12 (singlet, 9H), ~CH2 = 2.21 Csome-what broadened singlet, 2H]. - FD mass spectrum:
Molecule ion m/z = 416 (187Re), with correct pattern of isotopes 185Re/187Re~
13. 2,2,2-TrifLuoroethyLtrioxorhenium, (CF3CH2)ReO3 20 mmol of a 0.5-molar solution of bis-(2,2,2-trifluoro-ethyl)zinc Zn(CH2CF3)2 in tetrahydrofuran was added dropwise at room temperature and in the course of 10 minutes to a solution of 4.84 g (10 mmol) of dirhenium heptoxide Re207 (by Degussa, 76.9% of Re) in 100 ml of an anhydrous solvent such as tetrahydrofuran, and the mix-ture was then stirred for a further 80 minutes at room temperature. The volatile constituents were then stripped off in an oil pump vacuum into a cold trap, cooled with liquid nitrogen. The residue was sublimed in a high vacuum at 40 - 85C onto a water-cooled sub-limation finger. This gave 2.41 9 (38X of theory) of slightly yellowish needle-shaped crystals of the com-pound (CF3CH2)ReO3. The synthesis is also possible using unsublimed Re207, but the yields are then lower (in the range of 10 - 18X).
The substance has the following characteristics:
Soluble in most anhydrous organic solvents, especially 133~5~6 in tetrahydrofuran, methylene chLoride and toluene, forming virtually colorless, light-sensitive solutions.
- IR (cm 1, KBr: 1048 st, 960 sst Cv(Re=0)]. - 1H-NMR
(CDCl3, 28C: ~(CH2) = 2.3û Cquartet~. 170-NMR
(CDCl3, 28C): ~(0) = 590 ppm. - EI-MS: m/z = 318 (mole-cule ion with correct pattern of isotopes 185Re/187Re).
The substance can be kept without decomposition at ice temperature (0C), if care is taken to exclude light.
Elementary analysis: Calculated for C2H2F303Re (317.21): C 7.57, H 0.63, F 17.97, Re 58.70; found:
C 7.60, H 0.70, F 18.00, Re 58.59.
The same compound was obtained in a yield of 40 - 48%
when dirhenium heptoxide Re207 was reacted with an equi-15 molar amount of tetrakis-(2,2,2-trifluoroethyl)-tin Sn(CH2CF3)4 under the conditions mentioned in the pre-ceding instructions, the only difference being that the components were reacted with one another not at room temperature, but in boiling tetrahydrofuran for 1 to 2 20 hours. The product was worked up analogously. ``~
The use of (CH3CH2)ReO3 ~hen this compound is used as a catalyst for olefin metathesis, the procedure is just the same as that des-25 cribed in Examples 1 to 5 for methylrhenium trioxide CH3ReO3.
14. (2,3,4,5,6-pentafluorophenylmethyl)-trioxorheniu-, C6FsCH2ReO3 30 The corresponding Grignard compound C6FsCH2MgI was f;rst prepared from a solution of 6.16 g (20 mmol) of u (2,3,4,5,6-pentafluorophenyl)-methyl iodide C6FsCH2I by a known process by reacting the latter with magnesium turnings in diethyl ether as solvent. 12.3 g (9 mmol) of 35 anhydrous zinc chloride were then added to the resulting solution. The resulting reaction mixture was then boilded under reflux for 5 hours. The compound bis-(2,3,4,5,6-pentafluorophenylmethyl)-zinc Zn(CH2C6Fs)2 thus obtainable could be obtained by filtration from th~
1330~
solution and by recrystaLLization at Low temperatures (-80 to -40C).
- 2.14 9 (5 mmoL) of bis-(2,3,4,5,6-pentafLuorophenyl-methyl)-zinc Zn(CH2C6Fs)z were added at room tempera- ~-ture to a soLution of 4.84 9 (10 mmoL) of dirhen;um heptoxide Re207 (by Degussa, 76.9% of Re) in 100 mL of an anhydrous soLvent such as tetrahydrofuran. The resuLt-ing soLution was stirred for a further 60 m;nutes at room temperature. The voLatiLe constituents were then stripped off in an oiL pump vacuum into a cold trap cooled with liquid air. The residue was extracted with ;~
three times 20 ml of anhydrous toluene, the extract was filtered and the filtrate was then evaporated to dry-ness at 0C under an oil pump vacuum. The residue was recrystallized at -40 to -8C from a solvent mixture composed of equal volumes of n-hexane and toluene. ~ -This gave 581 mg (28% of theory, relative to the zinc compound employed) of slightly yellow octahedral crys-tals of the catalyst (C6FsCH2)ReO3.
The substance has the following characteristics:
Soluble in most of the customary anhydrous organic sol-vents, especially toluene, methylene chloride and tetrahydrofuran. - IR (cm 1, K3r): 1058 st, 958 sst ~v(Re=0)]. - 1H-NMR (CDCl3, 28C): ~(CH2) = 2.39 ppm Csomewhat broadened singlet~. -170-NMR (CDCl3, 28C):
~(0) = 604 ppm. - EI-MS: m/z = 416 (molecule ion with -correct pattern of isotopes 185Re/187Re). - Elementary analysis: Calculated for C6F5CH2ReO3 (415.26):
C 20.25, H 0.48, F 22.87, Re 44.84; found: C 20.20, H 0.50, F 22.60, Re 45.00.
15. ~is-C~-oxo(oxo)dimethylrheniu~(VI)], (CH3)4Re204 2.40 9 of dirhenium heptoxide Re207 (6.60 mmol) were dissolved in 150 ml of anhydrous tetrahydrofuran and cooled to -78C. 0.48 ml of freshly distilled dimethyl-zinc Zn(CH3)2 (6.60 mmol) were added dropwise, with continuous st;rring, to this solution. This must be carried out with exclusion of air and moisture, since ~.. -............ :
1 3 ~
, . .
dimethylzinc burns in the air and is decomposed by water. The soLution was stirred at this temperature for 4 hours and turned a strong yellow color. The reaction temperature was not allowed to exceed -30C.
The solvent was then stripped off at -40C under an oil pump vacuum. The product could be sublimed in a high vacuum in thin yellow needles from the residue which remained. Yield: 1.64 9 (50% of theory). Melting point 120C (without decomposition).
C4H12Re24: Calc.: C 9.64 H 2.41 0 12.85 (476.5) Found: C 9.60 H 2.48 0 12.79 EI mass spectrum: m/e = 498 (molecule ion CM ]), m/e 249 (base peak C1/2 M+]).
Infrared spectrum: (cm 1, K3r): 1017/1007 sst C~ (Re=0)].
H-NMR (CDCl3, 28C); ~(CH3) 2.81 ppm, 13C-NMR (CDCl3, 28C); ~(CH3) 30.36 ppm.
The compound is stable in air and readily soluble in all customary organic solvents.
'~':''' ' ' ~,"
Description Organic derivatives of rhenium oxides and their prepara-tion and use for the metathesis of olefins The present invention relates to organic derivatives of rhenium oxides and to their preparation and use for the metathesis of olefins as such and also derivatives of olefins. ~-The term metathesis designates, as is known, the cleav-age of olefinic compounds in such a way that the double bond is broken apart and the two fragments combine to form new compounds. In the wider sense, metathesis also includes the ring-opening polymerization of cyclo-olefins. As a result of the invention, an organorhenium compound of definite structure, which can be isolated in an undiluted form, becomes a catalyst for the f;rst time.
It is kno~n that compounds of the element rhenium exhi-bit catalytic activity in the metathesis of olefins, specifically only in the metathesis of olefins as such.
Only if so-called co-catalysts, in particular tetra-alkyltin compounds are added to such rhenium catalystsis the metathesis of derivatives of olefins, ie. ole-fins containing heterofunctions, possible (K.J. Ivin~
Olefin Metathesis, Academic Press, London 1983, 32 -34). Thus the metathesis of olefinically unsaturated carboxylic acid esters and of allyl halides and the like on mu~ti-component catalysts, such as ~Cl6/Sn(CH3)4 or ~-Re207/Sn(CH3)4/Al203 has been described. The last-named system (R.A. Fridman et al., Dokl. Akad.
Nauk. SSSR 2 , (1977), 1354 - 57; R.H.A. Bosma et al., J. Organometal. Chem. 225 (1983) 159 - 171; X. Xiaoding et al., J. Chem. Soc. Chem. Commun. 1985, 631 - 633;
G.C.N. van den Aardweg, loc. cit. 1983, 262 - 263) is the only one containing rhenium which is capable of meta-thesizing olefinically unsaturated organic halides, ~ , ' ~-133~56 esters and the like. Hitherto there has been no know-ledge of the effective catalyst species. The following are practical disadvantages of the rhenium-containing catalyst systems hitherto used:
S a) the necessity of using at the same t;me highly toxic tetraalkyltin compounds as activators in the meta-thesis of derivatives of olefins (J.E. Cremer, ~iochem. J. 68 (1958) 685 - 688; ~.N. Aldridge et al., The Lancet, Sept. 26, 1981, page 692/3), b) low catalyst activity, inacceptable for industrial use, and c) a breadth of application with relatively narrow limits, ie. the catalytic action is only found in the case of simple derivatives of olefins or olefins as such.
It was therefore required to find a non-toxic and effective catalyst system which is as readily acces-sible, simple to handle and stable on storage as possible and which is also adequate without any activa-tor in the metathesis of olefin derivatives.
Considerable interest attaches to the industrial fur-ther processing of the products.
Although some so-called "organorhenium oxides", for example CH3ReO3, (n5-Cs(CH3)s)ReO3 (= penta-methylcyclopentadienylrhenium trioxide), are known as catalyst components for the metathesis of olefins by homogeneous catalysis (W.A. Herrmann et al., Angew.
30 Chem. 100 (1988) 420 - 422, translation in Angew. Chem.
Int. Ed. Engl. 27 (1988) 394 - 396), the concomitant use, as activator, of a Lewis acid which is at least partially soluble in organic solvents was, however, always necessary, preferably aluminum(III) chloride and, in most cases, also the concomitant use of toxic tin tetraalkyls (for example Sn(CH3)4) as further activa-tors. Even then the catalyst systems thus obtainable are completely inactive in respect of the metathesis of derivatives of olefins.
, .. , . , .. . . ... .. --.,,. -- . .. . . . .
~ 13305~6 -It has now been found, surprisingly, that methylrhenium trioxide CH3ReO3 and related compounds of the formula I indicated below are suitable for use as a metathesis catalyst when supported on oxide supporting materials, in particular aluminum oxide supports. The use of additional activator substances ("Co~
catalysts"), which is disadvantageous for many reasons, thus becomes superfluous for the first time.
Thus, according to one aspect, the invention provides a compound of the general formula R aRebOc, wherein a is an integer from 1 to 6, b is an integer from 1 to 4 and c is an integer from ~ -1 to 14 and the sum of a, b and c conforms to the 5- to 7-valency of rhenium with the proviso that c does not exceed 3.b, and wherein R represents alkyl having from 1 to 9 carbon atoms, ;~
cycloalkyl having from 5 to 10 carbon atoms or aralkyl having from 7 to 9 carbon atoms and wherein R1 is unsubstituted or at least ~;;
partially fluorinated, said compounds containing not more than three groups of more than 6 carbon atoms per rhenium atom and containing a hydrogen atom bound to the carbon atom in a-position to the rhenium atom, the methylrhenium oxides CH3ReO3, (CH3)4ReO, (CH ) ReO , [(CH3)3ccH2]3ReO2~ [(CH3)3c CH2]4 2 4' 3 6 2 3 and the pentamethylcyclopentadienyl-rheniumtrioxide (~ -C5(CH3)5)ReO3 being excluded.
According to another aspect, the invention provides a catalytic composition for the metathesis of olefinic compounds .
~ .
~, , 13305~6 comprising an oxidic carrier charged with a rhenium compound of the general formula R1aRebOc, wherein a is an integer from 1 to 6, b is an integer from 1 to 4 and c is an integer from 1 to 14 and the sum of a, b and c conforms to the 5- to 7-valency of rhenium with the proviso that c does not exceed 3.b, and wherein represents alkyl having from 1 to 9 carbon atoms, cycloalkyl having from 5 to 10 carbon atoms or aralkyl having from 7 to 9 carbon atoms and wherein R1 is unsubstituted or at least partially fluorinated, said compounds containing not more than three groups of more than 6 carbon atoms per rhenium atom and containing a :
hydrogen atom bound to the carbon atom in a-position to the rhenium atom. ~:~
According to still another aspect, the invention provides a process for the metathesis of olefins which comprises reacting an olefin of the formula YCZ=CZ-(CX2)nR2 (II) wherein n .';.-~
is an integer from 1 to 28, X represents H or F, . ~.
Y represents H or alkyl having from 1 to 10 carbon atoms and Z represents H or a non-aromatic hydrocarbon group having from 1 to 6 carbon atoms and R2 represents H, alkyl, halogen, CoOR3 or oR4, wherein R3 and R4 represent alkyl having from 1 to 15 carbon atoms or phenyl which is unsubstituted or contains from 1 to 3 substituents or wherein R4 is 1~ .. ,.:
- ~a~ 23221-4607 1330~66 trialkylsilyl R53Si, wherein R5 represents alkyl having from 1 to 5 carbon atoms, ln the pre~ence of a catalytic composition as defined above.
The invention thus relates to the use of compounds of rhenium which have the general formula RlaRebOc tI) ln whlch a is -~
1 to 6, b i~ 1 to 4 and c ls 1 to 14 and the total of a, b and c ls such that lt accords wlth the pentavalency to heptavalency of rhenlum, subject to the provlso that c ls not greater than 3 x b, and whlch are supported on oxlde supportlng materlals, as heterogeneous catalysts for metathesis. In this connection denotes an organlc group attached to the metal rhenlum via a carbon atom to whlch at least one hydrogen atom is stlll attached, speclflcally alkyl radlcals havlng 1 to 9 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, such as cyclohexyl or l-norbornyl, or aralkyl having 7 to 9 carbon atoms, such as benzyl, but preferably methyl. The term~ alkyl and cycloalkyl naturally imply that these groups contaln no multiple bonds. Rl can be at least partially fluorinated. For steric reason3, however, the presence of more than three groups containing more than 6 carbon atoms per rhenium atom is not possible in the compounds; the compound~ preferably contain only one such group at the most. The term metathesis in this context includes the ring-opening polymerization of cycloolefins.
~'' , .
133Q~66 -4b-Of the compounds of the formula mentioned above, CH3ReO3, (CH3)4ReO, (CH3)3ReO2, l(CH3)3CCH2]3ReO2, 3 3 2]4Re204, (CH3)6Re203 and the pentamethylcyclopentadlenyl-rhenlumtrloxlde (~5-C5(CH3)5)ReO3 are admlttedly known, but the catalytlc activlty of these compound~
wlthout the concomltant use of activators, that is to say their sultability as the sole catalyst, was not known and was as unexpected a~ that of the whole class of compound6. Thls -catalytlc actlon ls all the more surprising because (trlmethylstannoxy)-rhenium trioxlde l(CH3)3SnO]ReO3, which ls lsostructural, 1~ catalytlcally lnactive. This show~ the lmportance of the alkyl groups attached to rhenium for the catalytlc actlvity of the compounds according to the inventlon.
In terms of synthesls, the compounds according to the lnventlon can be syntheslzed ln a very slmple manner from Re207 by means of cu~tomary alkylatlng agents. For example, dlrhenlum heptoxlde ls reacted ln an anhydrous solvent whlch is inert towards the rhenlum compounds, at a temperature from O to 60, preferably 10 to 40C, wlth a solutlon of R12Zn ln whlch Rl has the meanlng lndlcated above, and the volatlle constituents are removed. The compounds accordlng to the inventlon are entlrely lnsensltive to alr and molsture. When supported on oxldic supportlng materlals, the rhenium compounds are hlghly active catalysts for the metathesls of oleflns as such and also derlvatlves of oleflns of the type YCZ-CZ-(CX2)nR2 (II) in whlch n ;;
18 an lnteger from 1 to 28, X 18 H or F, Y ls H or alkyl havlng 1 ~-to 10 carbon atoms and Z represents H or a non-aromatlc -~
~D ::
.. -. . ~- . . ~ .
`-13~66 ~ ~
-4c - 23221-4607 hydrocarbon radical having l to 6 carbon atoms, for example ~:
cyclohexyl, but preferably open-chain alkyl having l to 4 carbon a~oms, and the subætituent R2 is H, alkyl, halogen, CoOR3 or oR4 in which R3 is alkyl or aryl and R4 i6 alkyl, aryl or tri~
alkylsilyl R53Si. The alkyl groups in R5 contain l to 5, preferably l to 3 carbon atoms. In R3 and R4 alkyl represents l to 15, preferably l to 6, carbon atoms and aryl represents phenyl ~hlch can also contain one to three substituents on the ring, such as halogen, for example ~ -,. : ~ , . , --., . ~. . .. . . .
~33~6~
fluor;ne, chlorine or bromine, N0z, NR6R7, oR8 and/or alkyl. The radicals R6, R7 and R8 are identical or different and can be hydrogen or alkyl having 1 to 4 carbon atoms. However, the groups YCZ and CZ-(CH2)nR2 S must be different. As halogen, R2 can be fluorine, chlorine, bromine or iodine. If Z is hydrogen and R2 is ~
halogen, the latter is preferably bromine. Examples of -compounds in which at least one X is F are 4-(perfluoro-n-hexyl~but-1-ene, formula (n-C6F13)-CH2-CH2-CH=CH2~
and perfluoropropene C3F6. The number n of units varies, preferably within the range from 1 to 12 and especially up to 8.
The novel catalysts are thus not only active in the case of olefins in which Z = H, but also, for the first time, in the metathesis of partly or completely fluori-nated olefins. They are also suitable for the metathesis of non-terminal olefin derivatives of the formula R9CH=CH-(CH2)nR10 (IV) in which R9 is a branched~ or preferably unbranched, alkyl radical having 1 to 12 carbon atoms, R10 is a carboxyalkyl radi-cal in which the alkyl radical preferably has 1 to 4 carbon atoms, and n represents an integer from 1 to 10.
Methyl oleate (R9 = n-octyl, R10 = C02CH3 and n = 7) may ZS be mentioned as an example.
SiO2/Al203 (for examPle in a ratio by weight of 87:13) and Al203, each of which can be acid, neutral or basic according to its pretreatment, are particularly ~ -suitable as supporting materials. The activity of these catalysts can be increased considerably if the rhenium,compounds are supported on a thoroughly cal- -~-' ~ ; cined, ~ as far as possible anhydrous, support, such as silica/aluminum oxide. This is because if the sup-porting material contains major amounts of moisture,the activity decreases, because the alkyl group attached to rhenium is then partly split off as alkane by means of the water.
1 3 3 ~
The catalytic activity of the catalysts according to the invention for the metathesis of oLefins is higher than that of the rhenium-containing catalyst systems described hitherto. An exemplary proof is afforded by -the systems A1 and V1 (cf. graphs). The system CH3ReO3/
SiO2/Al203 (A1) metathesizes allyl bromide in only 20 minutes to a Q of over 20, peak area of ethylene the ratio Q =
peak area of propane being obtained using propane as predetermined standard and being plotted against time. The shape of the curve provides information on the activity of the particular catalyst system. The standard catalyst NH4tReO4]/SiO2/
Al2/03 (V1) known from the literature is, in contrast, only active in the presence of Sn(CH3)4, and even then only to a comparable extent in 180 minutes. The symbol "r^ 2" is a measure of the agreement between the shape of the curve determined by calculation and the experi-mental values.
The rhenium-containing catalysts hitherto used indus-trially in olefin metathesis are, as a rule, prepared (see ~arwel et al., Chem.-Ztg 1û7 (1983), 115-120) by treating commercially available ammonium perrhenate NH4tReO4] as a solution in dioxane/water with the sup-porting material (as a rule aluminum oxide). The resulting suspension is then evaporated to complete dryness in a water pump vacuum; the dry material is then heated at 550C, first for about 2 hours in a stream of oxygen and then for about 2 hours in a stream of nitrogen. Only the material obtained in this way and cooled to room temperature is employed for catalytic purposes.
For the process according to the invention, on the other hand, it is possible to dispense with these time-consuming and energy-consuming process stages, as a result of ~hich catalysts of better reproducibility are - _ 7 _ 1 3 3 ~
also obtained. For the present process, the catalytically active rhenium compound is applied, pre-ferably at room temperature, from a solvent, preferably a solution of methylene dichloride, to the catalyst 5 support, preferably silica gel/aluminum oxide, and only ~*~
the catalyst support is freed from moisture, before use, for 2 hours at 800C in a stream of nitrogen, in order that the catalyst system may subsequently develop its full activity.
In metathesis using the catalysts according to the invention care must be taken that air and moisture are excluded. The olefins employed must also preferably be dried thoroughly before use. In general, the metathe-sis is carried out at atmospheric pressure and atemperature from 0 to 40C, preferably 10 to 35C. The fact that it is possible to work under such mild reac-tion conditions is a particular advantage of the process according to the invention. It is also pos-sible, however, to use higher temperatures, for exampleup to 100C, or to work under a pressure above or below atmospheric. Usually, however, no advantages are associated there~ith. `~
In the characterization of individual compounds in the following examples "sst" means very strong, "st" means strong, "br" means broad and "EI-MS" means electron -~
impact mass spectrum.
Exa-ples 1-5 - ~etathesis using CH3ReO
In the following tests the olefins employed were dried ~ -over CaH2 and distilled before being used. The catalyst used in these tests was methylrhenium trioxide CH3ReO3 which had been prepared by a simple process in terms of preparation, avoiding toxic tetramethyltin, Sn(CH3)4, as follows:
20 ml of a 0.5-molar solution of dimethylzinc Zn(CH3)2 ~-in tetrahydrofuran were added dropwise at room ... . . . . . ., . ~ .. . . - , . -, ~
- 8 - 1 33 ~
temperature and in the course of 10 minutes to a solution of 4.84 9 (10 mmol) of dirhenium heptoxide Re207 (made by Degussa, 76.9% of Re) in 100 ml of an anhydrous sol-vent, such as tetrahydrofuran, and the mixture was then -stirred for a further 60 minutes at room temperature.
The volatile constituents were then stripped off under an oil pump vacuum into a cold trap. The residue was sublimed in a high vacuum at 40-55C onto a water-cooled sublimation finger. This gave 3.89 9 (78X of theory) of colorless, mostly needle-shaped~ crystals of the catalyst CH3ReO3. The synthesis is also possible using unsublimed Re207, but the yields are then lower. The substance has the following characteristics: Melting point 106. - IR (cm 1, K~r): 1002 sst, 950 sst,br tv(Re=0)].-1H-NMR (CDCl3, 28C): ~tCH3) = 2.61 tsing-let]. - 13C-NMR (CDCl3, 28C): ~(CH3) = 19.03 Cquar-tet, 1J(C,H) = 138 Hz]. - 170-NMR (CDCl3, 28C: (0)=
829 ppm. - EI-MS : m/z = 250 (molecule-ion, with the cor-rect pattern of isotopes 185Re/187Re). - The substance can be stored at room temperature without decomposition.-Elementary analysis: Calculated for CH303Re (249~21):
C 4.82, H 1.20, 0 19.26, Re 74.72; found: C 4.84, H 1.19, 0 19.30, Re 74.78.
In a 30 ml reaction vessel equipped with a septum, a reflux condenser and a mercury pressure relief valve, a solution of 13 mg (0.052 mmol) of methylrhenium tri-oxide CH3ReO3 in 0.5 ml of methylene dichloride was introduced with stirring into a suspension of 1,000 mg of catalyst support tSiO2/Al203, (87:13), particle size below 15 ~m (preparation No. 14-7150 of Strem Chemicals, Newburyport/Mass. 01950 (USA), heated at 800C for 2 hours] in 10 ml of methylene dichloride (dried over calcium hydride and stored under an atmosphere of nitrogen]. The contents of the flask were heated to the boil. After thermal equilibrium had been set up, 5.2 mmol of olefin were injected by means of a syringe through the septum. In order to isolate the product, the mixture was boiled for several hours under reflux .,-.- ~
.,.~
..... .., ~ . , , .. ;
~ 3 3 ~ ~ 6 6 b~ ` ' _ 9 (Table 1), the contact catalyst was filtered off with suction on a frit and was extracted by washing with twice 10 ml of methylene dichloride. The solvent was stripped off under an oil pump vacuum, the product was weighed and its purity was checked by means of a gas chromatograph with coupled mass spectrometer.
TabLe 1: Metathesis of ~-olefin derivatives of the type II with the elimination of ethylene Example/oLefin (*) Time Amount Weight Purity rield (hrs) (mg) (mg) (%) (%_ 1) Allyl bromide4 620100 100 14 2) Ethyl undecenoate 201120 1120 64 64 3) AlLyl isopropyl ether 4 520220 70 30 4) Allyl ethyl ether 5 448 260 50 39 5) Allyl trimethyl-silyl ether 24 680530 88 69 ' ~'~'' (*) Metathesis products~
1) 1,4-Dibromobut-2-ene.
2) Diethyl eicos-10-ene-~,~'-dicarboxylate.
3) 1,4-Bis-(isopropoxy)-but-2-ene.
4) 1,4-Bis-(ethoxy)-but-2-ene.
5) 1,4-Bis-(trimethylsiloxy)-but-2-ene.
Co-parisons In a 30 ml reaction vessel closed with a septum, a solution of 13 mg (0.052 mmol) of methylrhenium tri-oxide CH3ReO3 in 0.5 ml of methylene dichloride was ~ -introduced with stirring into a suspension of 1,000 mg of catalyst support (SiO2/Al203 (weight ratio 87:13, particle size below 15 ~m; kept at 800C for 2 hours)) in 10 ml of methylene dichloride (dried over calcium hyd-ride and stored under an atmoçphere of nitrogen). 0.5 ml of propane was injected as the internal standard.
- ~ 330~66 After stirring for 5 minutes 5 mmol of ole~in were injected (t = 0) and the ethylene content of the gas phase was determined by gas chromatography at the intervals of time evident from graphs A1, A2, V1 and V2 5 (attachments). V1 shows a comparison with A1, A2 shows -the effect of a greater dilution of the catalyst com-pared with A1 and V2 shows a comparison with the rhenium-containing catalyst system hitherto used and known from the literature, as specified by ~arwel et al, l.c. For this purpose 900 mg of neutral aluminum oxide were first impregnated with a solution of 100 mg of ammonium perrhenate NH4CReO4] in 10 ml of dioxane/
water (9+1 parts by volume). The catalyst system was then activated at 550C for 2 hours in a stream of oxygen and then for 2 hours in a stream of nitrogen.
The reaction kinetics tests proceeded analogously to those with methylrhenium trioxide CH3ReO3, but it was necessary for activation to inject 0.005 ml of tetra-methyltin Sn~CH3)4 5 minutes before the addition of olefin, in order to obtain any catalytic effect at all.
A direct comparison was afforded by comparison test V1, j~
in which 14 mg of ammonium perrhenate NH4[ReO4] were absorbed onto 1 9 of SiO2/Al203 and activated in a~ ;~
stream of 2 and N2 as indicated above.
In the metathesis of olefins as such CH3ReO3 on the one hand and NH4CReO4] on the other hand achieved a com- ;~
parable activity on SiO2/Al203. The equilibrium product distribution in the metathesis of a mixture of 50 mol % of 2-pentene + 25 mol % of 2-butene + 25 mol %
of 3-hexene was set up after approx. 5 minutes in both systems, but in the case of NH4CReO4] only after additional activation with tetramethyltin, as can be seen from a comparison of graphs A3 and V3.
Effects arising from the cataLyst support As shown in particular by systems A1 and A2 for the . ,,... . , . . .. ~ ~ . - .. -"~.. , . -3 ~
r~
, ,. j ~ . . . .. -13~0~6~
metathesis of allyl bromide, the activity of the cata-lyst CH3ReO3 increases greatly with dilution (relative to the amount of oxide supporting material): For a reaction time of 300 minutes, 13 mg of CH3ReO3 + 1000 mg of SiO2/Al203 give a value of 30 for Q, while 13 mg of CH3ReO3 + 2000 mg of SiO2/Al203 give a value of 40 for Q.
Exaoples 6-9 - ~etathesis using (CH3)6Re2O3 10 6) In a 30 ml reaction vessel closed with a septum, a ~-solution of 25.5 mg (0.052 mmol) of hexamethyltrioxodi- -rhenium (CH3)6Re203 in 0.5 ml of methylene dichloride was introduced with stirring into a suspension of 1000 mg of catalyst support (SiO2/Al203; weight rat;o 87:13, 15 particle size below 15 ~m; kept at 800C for 2 hours) in - ~ ~;
10 ml of methylene dichloride (dried over calcium hyd-ride and stored under an atmosphere of nitrogen). 0.5 ml of propane were injected as the internal standard. -~
After stirring for 5 minutes 5 mmol of allyl bromide were injected ( t = 0) and the ethylene content of the gas phase was determined by gas chromatography at the intervals of time evident from graph A4 (attachment).
7 - 9) In a 30 ml reaction vessel equipped with a sep-tum, a reflux condenser and a mercury pressure relief valve, a solution of 25.5 mg (0.052 mmol) of hexamethyl- -trioxodirhenium (CH3)6Re203 in 0.5 ml of methylene dichloride was introduced with stirring into a suspen-sion of 1000 mg of catalyst support ~SiO2/Al203 (87:13), 30 particle size below 15 ~m (preparation No. 14-7150 of Strem Chemicals, Newburyport/Mass. 01950 (USA), heated at 800C for 2 hours] in 10 ml of methylene dichloride (dried over calcium hydride and kept under an atmos-phere of nitrogen). The contents of the flask were heated to the boil. After thermal equilibrium had been set up, 5.2 mmol of olefin were injected through the septum by means of a syringe. In order to isolate the product, the mixture was boiled under reflux for sever-al hours (Table 2), the contact catalyst was filtered .,;.: , 133~
off with suction on a frit and was washed with twice 10 mL
of methylene dichLoride. The solvent was stripped off in an oil pump vacuum, the product was weighed and its purity was checked by means of a gas chromatograph with coupled mass spectrometer.
Table 2 Example/olefin (*) Time Amount Weight Purity Yield (hrs) (mg) (mg) (%) (%) 7) Allyl bromide 20 680 72 98 12 8) Ethyl undecenoate 20 1410 840 57 34 9) Allyl trimethyl~
silyl ether 15 705 550 48 41 (*) Metathesis products: ~ 9 7) 1,4-Dibromobut-2-ene.
8) Diethyl eicos-10-ene-1,1'-dicarboxylate.
9) 1,4-~is-(trimethylsiloxy)-but-2-ene.
~.
Example 10 - Metathesîs using (CH3)4Re2O4 In a 30 ml reaction vessel closed by means of a septum, a solution of 25.8 mg (0.052 mmol) of tetramethyltetra-oxodirhenium (CH3)4Re204 in 0.5 ml of methylene dichloride was introduced with stirring into a suspen-sion of 1000 mg of catalyst support (SiO2/Al203; weight ratio 87:13, particle size below 15 ~m; kept at 800C for 2 hours) in 10 ml of methylene dichloride (dried over calcium hydride and kept under an atmosphere of nitro-gen). 0.5 ml of propane were injected as the internal standard. After stirring for 5 minutes 5 mmol of allyl bromide were injected (t = 0) and the ethylene content of the gas phase was determined by gas chromatography at the intervals of time evident from graph A5 (attachment).
Exaoples 11-15 - Co-pounds of the for-ula R1aReb0c 11. Tri-ethYl(oxo)rhenium, (CH3)3ReO :-1 33 0 ?~
a) 2.62 g (10 mmol) of triphenylphosphine P(C6Hs)3 and 10.85 9 (0.1 mol) of trimethylchlorosilane (CH3)3SiCl were added rapidly, successively and at room tempera-ture and with vigorous magnetic stirring to a solution of 4.14 9 (10 mmol) of the compound [(CH3)3SnO]ReO3 in 100 ml of anhydrous tetrahydrofuran. After 3 hours stirring at room temperature a green deposit had formed, l~
consisting of the compound Reocl3[op(c6H5)](oc4H8) (OC4H8 = tetrahydrofuran). Filtering off this preci-10 pitate from the supPrnatant solution, washing it with ~
tetrahydrofuran and drying it ;n an oil pump vacuum -gave 6.19 9 (94% of theory) of this compound in a pure ~-form.
: :: ' 15 b) 3.29 9 (5 mmol) of the compound prepared under a) were suspended in 20 ml of tetrahydrofuran. A 0.2-molar solution of lithiummethyl LiCH3 (altogether 16 mmol) were added dropwise at 0C to this suspension, and the resulting reaction mixture was stirred for a further 3 hours at room temperature. The volatile constituents were then removed in an oil pump vacuum.
The dark brown residue, in most cases somewhat oily, was extracted with approx. 10 ml of toluene. The extract was evaporated to dryness in an oil pump vacuum.
The residue was chromatographed at -60C on a column (40 cm long and 2 cm in diameter) of silanized, cal-cined silica geL (by Merck), the yellow zone of the compound (CH3)3ReO being developed with toluene. The eluate was concentrated under an oil pump vacuum. The residue was then dissolved in 20 ml of n-pentane, and the solution was left to crystallize at -80 to -40C.
This gave 198 mg (16% of theory) of yellow needles of (CH3)3ReO.- :
Characterization: Soluble in the customary anhydrous organic solvents, in particular methylene chloride, tetrahydrofuran and toluene. The substance is solid and, in solution, admittedly only stable undecomposed for some time when stored within the temperature range from -80 to -40C. - IR (cm 1, K~r): 978 sst [v(Re=0)].
133~
- 1H-NMR (270 MHz; 28C, CD2Cl2): ~CH3 = 5.41 (sin- -glet). - FD-mass spectrum: Molecule ion m/z = 248 (187Re), with correct pattern of isotopes 185Re/187Re.
12. Tris(neopentyL)oxorhenium, ReCCH2C(CH3)3~30 ;~
This compound was synthesized analogously to the ins-tructions for Example 11, employing lithiumneopentyl LitCH2C(CH3)3~ instead of lithiummethyl. The product ;~
was worked up analogously. Yield 249 mg (12% of theory).-Characterizat;on: Yellow crystals; stable without de-composition over a prolonged period (approx. 8 days) only at temperatures below -20C. - IR (cm 1, K~r):
975 cm 1 sst [v(Re=0)~ H-NMR (400 MHz, 28C, CDCl3): ~CH3 = 1.12 (singlet, 9H), ~CH2 = 2.21 Csome-what broadened singlet, 2H]. - FD mass spectrum:
Molecule ion m/z = 416 (187Re), with correct pattern of isotopes 185Re/187Re~
13. 2,2,2-TrifLuoroethyLtrioxorhenium, (CF3CH2)ReO3 20 mmol of a 0.5-molar solution of bis-(2,2,2-trifluoro-ethyl)zinc Zn(CH2CF3)2 in tetrahydrofuran was added dropwise at room temperature and in the course of 10 minutes to a solution of 4.84 g (10 mmol) of dirhenium heptoxide Re207 (by Degussa, 76.9% of Re) in 100 ml of an anhydrous solvent such as tetrahydrofuran, and the mix-ture was then stirred for a further 80 minutes at room temperature. The volatile constituents were then stripped off in an oil pump vacuum into a cold trap, cooled with liquid nitrogen. The residue was sublimed in a high vacuum at 40 - 85C onto a water-cooled sub-limation finger. This gave 2.41 9 (38X of theory) of slightly yellowish needle-shaped crystals of the com-pound (CF3CH2)ReO3. The synthesis is also possible using unsublimed Re207, but the yields are then lower (in the range of 10 - 18X).
The substance has the following characteristics:
Soluble in most anhydrous organic solvents, especially 133~5~6 in tetrahydrofuran, methylene chLoride and toluene, forming virtually colorless, light-sensitive solutions.
- IR (cm 1, KBr: 1048 st, 960 sst Cv(Re=0)]. - 1H-NMR
(CDCl3, 28C: ~(CH2) = 2.3û Cquartet~. 170-NMR
(CDCl3, 28C): ~(0) = 590 ppm. - EI-MS: m/z = 318 (mole-cule ion with correct pattern of isotopes 185Re/187Re).
The substance can be kept without decomposition at ice temperature (0C), if care is taken to exclude light.
Elementary analysis: Calculated for C2H2F303Re (317.21): C 7.57, H 0.63, F 17.97, Re 58.70; found:
C 7.60, H 0.70, F 18.00, Re 58.59.
The same compound was obtained in a yield of 40 - 48%
when dirhenium heptoxide Re207 was reacted with an equi-15 molar amount of tetrakis-(2,2,2-trifluoroethyl)-tin Sn(CH2CF3)4 under the conditions mentioned in the pre-ceding instructions, the only difference being that the components were reacted with one another not at room temperature, but in boiling tetrahydrofuran for 1 to 2 20 hours. The product was worked up analogously. ``~
The use of (CH3CH2)ReO3 ~hen this compound is used as a catalyst for olefin metathesis, the procedure is just the same as that des-25 cribed in Examples 1 to 5 for methylrhenium trioxide CH3ReO3.
14. (2,3,4,5,6-pentafluorophenylmethyl)-trioxorheniu-, C6FsCH2ReO3 30 The corresponding Grignard compound C6FsCH2MgI was f;rst prepared from a solution of 6.16 g (20 mmol) of u (2,3,4,5,6-pentafluorophenyl)-methyl iodide C6FsCH2I by a known process by reacting the latter with magnesium turnings in diethyl ether as solvent. 12.3 g (9 mmol) of 35 anhydrous zinc chloride were then added to the resulting solution. The resulting reaction mixture was then boilded under reflux for 5 hours. The compound bis-(2,3,4,5,6-pentafluorophenylmethyl)-zinc Zn(CH2C6Fs)2 thus obtainable could be obtained by filtration from th~
1330~
solution and by recrystaLLization at Low temperatures (-80 to -40C).
- 2.14 9 (5 mmoL) of bis-(2,3,4,5,6-pentafLuorophenyl-methyl)-zinc Zn(CH2C6Fs)z were added at room tempera- ~-ture to a soLution of 4.84 9 (10 mmoL) of dirhen;um heptoxide Re207 (by Degussa, 76.9% of Re) in 100 mL of an anhydrous soLvent such as tetrahydrofuran. The resuLt-ing soLution was stirred for a further 60 m;nutes at room temperature. The voLatiLe constituents were then stripped off in an oiL pump vacuum into a cold trap cooled with liquid air. The residue was extracted with ;~
three times 20 ml of anhydrous toluene, the extract was filtered and the filtrate was then evaporated to dry-ness at 0C under an oil pump vacuum. The residue was recrystallized at -40 to -8C from a solvent mixture composed of equal volumes of n-hexane and toluene. ~ -This gave 581 mg (28% of theory, relative to the zinc compound employed) of slightly yellow octahedral crys-tals of the catalyst (C6FsCH2)ReO3.
The substance has the following characteristics:
Soluble in most of the customary anhydrous organic sol-vents, especially toluene, methylene chloride and tetrahydrofuran. - IR (cm 1, K3r): 1058 st, 958 sst ~v(Re=0)]. - 1H-NMR (CDCl3, 28C): ~(CH2) = 2.39 ppm Csomewhat broadened singlet~. -170-NMR (CDCl3, 28C):
~(0) = 604 ppm. - EI-MS: m/z = 416 (molecule ion with -correct pattern of isotopes 185Re/187Re). - Elementary analysis: Calculated for C6F5CH2ReO3 (415.26):
C 20.25, H 0.48, F 22.87, Re 44.84; found: C 20.20, H 0.50, F 22.60, Re 45.00.
15. ~is-C~-oxo(oxo)dimethylrheniu~(VI)], (CH3)4Re204 2.40 9 of dirhenium heptoxide Re207 (6.60 mmol) were dissolved in 150 ml of anhydrous tetrahydrofuran and cooled to -78C. 0.48 ml of freshly distilled dimethyl-zinc Zn(CH3)2 (6.60 mmol) were added dropwise, with continuous st;rring, to this solution. This must be carried out with exclusion of air and moisture, since ~.. -............ :
1 3 ~
, . .
dimethylzinc burns in the air and is decomposed by water. The soLution was stirred at this temperature for 4 hours and turned a strong yellow color. The reaction temperature was not allowed to exceed -30C.
The solvent was then stripped off at -40C under an oil pump vacuum. The product could be sublimed in a high vacuum in thin yellow needles from the residue which remained. Yield: 1.64 9 (50% of theory). Melting point 120C (without decomposition).
C4H12Re24: Calc.: C 9.64 H 2.41 0 12.85 (476.5) Found: C 9.60 H 2.48 0 12.79 EI mass spectrum: m/e = 498 (molecule ion CM ]), m/e 249 (base peak C1/2 M+]).
Infrared spectrum: (cm 1, K3r): 1017/1007 sst C~ (Re=0)].
H-NMR (CDCl3, 28C); ~(CH3) 2.81 ppm, 13C-NMR (CDCl3, 28C); ~(CH3) 30.36 ppm.
The compound is stable in air and readily soluble in all customary organic solvents.
'~':''' ' ' ~,"
Claims (22)
1. A compound of the general formula R1aRebOc, wherein a is an integer from 1 to 6, b is an integer from 1 to 4 and c is an integer from 1 to 14 and the sum of a, b and c conforms to the 5-to 7-valency of rhenium with the proviso that c does not exceed 3.b, and wherein R1 represents alkyl having from 1 to 9 carbon atoms, cycloalkyl having from 5 to 10 carbon atoms or aralkyl having from 7 to 9 carbon atoms and wherein R1 is unsubstituted or at least partially fluorinated, said compounds containing not more than three groups of more than 6 carbon atoms per rhenium atom and containing a hydrogen atom bound to the carbon atom in .alpha.-position to the rhenium atom, the methylrhenium oxides CH3ReO3, (CH3)4ReO, (CH3)3ReO2, [(CH3)3CCH2]3ReO2, [(CH3)3C CH2]4Re2O4, (CH3)6Re2O3 and the pentamethylcyclopentadienyl-rheniumtrioxide (?5-C5(CH3)5)ReO3 being excluded.
2. A catalytic composition for the metathesis of olefinic compounds comprising an oxidic carrier charged with a rhenium compound of the general formula R1aRebOc, wherein a is an integer from 1 to 6, b is an integer from 1 to 4 and c is an integer from 1 to 14 and the sum of a, b and c conforms to the 5- to 7-valency of rhenium with the proviso that c does not exceed 3.b, and wherein R1 represents alkyl having from 1 to 9 carbon atoms, cycloalkyl having from 5 to 10 carbon atoms or aralkyl having from 7 to 9 carbon atoms and wherein R1 is unsubstituted or at least partially fluorinated, said compounds containing not more than three groups of more than 6 carbon atoms per rhenium atom and containing a hydrogen atom bound to the carbon atom in .alpha.-position to the rhenium atom.
3. A compound as claimed in claim 1, in which a is 3, b is 1 and c is 1.
4. The compound trimethyl-(oxo)-rhenium (CH3)3ReO.
5. The compound tris(neopentyl)oxorhenium Re[CH2C(CH3)3]3O.
6. A compound as claimed in claim 1, in which R1 is partially fluorinated.
7. The compound 2,2,2-trifluoroethyl-trioxorhenium (CF3CH2)ReO3.
8. The compound (2,3,4,5,6 pentafluorophenyl-methyl)trioxorhenium C6F5CH2ReO3.
9. The compound (CH3)4Re2O4.
10. A process for the preparation of a catalytic composition as defined in claim 2, which comprises charging the carrier with the rhenium compound from an anhydrous solvent inert towards the rhenium compounds, and subsequently removing the volatile compounds.
11. A process according to claim 10, wherein the rhenium compound is as defined in claim 3.
12. A process for the metathesis of olefins which comprises reacting an olefin of the formula YCZ=CZ-(CX2)nR2 (II) wherein n is an integer from 1 to 28, X represents H or F, Y represents H or alkyl having from 1 to 10 carbon atoms and Z represents H or a non-aromatic hydrocarbon group having from 1 to 6 carbon atoms and R2 represents H, alkyl, halogen, COOR3 or OR4, wherein R3 and R4 represent alkyl having from 1 to 15 carbon atoms or phenyl which is unsubstituted or contains from 1 to 3 substituents or wherein R4 is trialkylsilyl R53Si, wherein R5 represents alkyl having from 1 to 5 carbon atoms, in the presence of a catalytic composition according to claim 2.
13. A process as claimed in claim 12, wherein the olefin of the formula (II) is a functionalized olefin which is subjected to the metathesis reaction.
14. A process as claimed in claim 12, wherein the reaction is carried out in the absence of an activating compound.
15. A process as claimed in claim 12, 13 or 14, wherein R4 is alkyl having from 1 to 6 carbon atoms.
16. A process as claimed in claim 12, 13 or 14, wherein R5 is alkyl having from 1 to 3 carbon atoms.
17. A process as claimed in claim 12, 13 or 14, wherein the olefin of the formula II is a cycloolefin.
18. A process as claimed in claim 12, 13 or 14, wherein the carrier comprises alumina or a combination thereof with silica and has been dried by glowing.
19. A process as claimed in claim 12, 13 or 14, wherein the catalyst contains as the active ingredient methylrhenium trioxide CH3ReO3.
20. A process as claimed in claim 12, 13 or 14, which is carried out at a temperature in the range from 0 to 60°C.
21. A process as claimed in claim 12, 13 or 14, wherein the reaction is carried out at a temperature in the range of from 10 to 30°C.
22. A process as claimed in claim 12, 13 or 14, which is carried out at ambient pressure.
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DEP3841733.2 | 1988-12-10 | ||
DE3841733 | 1988-12-10 | ||
DEP3902787.2 | 1989-01-31 | ||
DE3902787 | 1989-01-31 |
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EP (1) | EP0373488B1 (en) |
JP (2) | JP3021496B2 (en) |
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DE3902357A1 (en) * | 1989-01-27 | 1990-08-02 | Hoechst Ag | USE OF RHENIUM-ORGANIC COMPOUNDS FOR THE OXIDATION OF C-C MULTIPLE-BONDINGS, OXIDATION PROCESSES BASED ON THEM AND NEW RHENIUM-ORGANIC COMPOUNDS |
DE59105881D1 (en) * | 1990-03-28 | 1995-08-03 | Hoechst Ag | USE OF ORGANIC DERIVATIVES OF RHENIUM OXIDES AS CATALYSTS FOR THE ETHENOLYTIC METATHESIS OF OLEFINIC COMPOUNDS AND METHOD FOR THE ETHENOLYTIC METATHESIS OF OLEFINIC COMPOUNDS WITH THE HELP OF THESE CATALYSTS. |
DE4032896A1 (en) * | 1990-10-17 | 1992-04-23 | Hoechst Ag | METHOD OF PARTLY FLUORED HYDROCARBONS |
DE4228887A1 (en) * | 1992-08-29 | 1994-03-03 | Basf Ag | Process for the catalytic isomerization of â-alkenols |
FR2726488B1 (en) | 1994-11-04 | 1996-12-13 | Inst Francais Du Petrole | NOVEL SUPPORTED CATALYSTS CONTAINING RHENIUM AND ALUMINUM, THEIR PREPARATION AND THEIR USE FOR OLEFIN METATHESIS |
DE19717178A1 (en) * | 1997-04-24 | 1998-10-29 | Hoechst Ag | Direct synthesis of organorhenium (VII) oxides from rhenium-containing compounds |
US7002049B2 (en) | 2002-08-19 | 2006-02-21 | Eastman Chemical Company | Process for α,β-dihydroxyalkenes and derivatives |
JP4957105B2 (en) * | 2006-07-20 | 2012-06-20 | 東ソー株式会社 | Method for producing dihalogenononadien |
DE102008062686A1 (en) | 2008-12-17 | 2010-07-01 | Süd-Chemie AG | Process for the preparation of methyltrioxorhenium (MTO) |
DE102008062687A1 (en) | 2008-12-17 | 2010-07-01 | Süd-Chemie AG | Preparation of alkyl trioxo rhenium compound, useful as catalyst e.g. for aromatic oxidation and olefin metathesis, comprises alkylating trioxo rhenium chloride, which is obtained by reacting a rhenium compound with a chlorinating agent |
EP3266758B1 (en) * | 2015-03-03 | 2019-06-19 | AGC Inc. | Production method for fluorine-containing olefin compound |
CN112979436B (en) * | 2019-12-12 | 2022-05-17 | 中国科学院大连化学物理研究所 | Method for preparing 2, 5-hexanedione |
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1989
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EP0373488A2 (en) | 1990-06-20 |
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