DE102017002966A1 - Calcium organic compound and process for its preparation - Google Patents
Calcium organic compound and process for its preparation Download PDFInfo
- Publication number
- DE102017002966A1 DE102017002966A1 DE102017002966.0A DE102017002966A DE102017002966A1 DE 102017002966 A1 DE102017002966 A1 DE 102017002966A1 DE 102017002966 A DE102017002966 A DE 102017002966A DE 102017002966 A1 DE102017002966 A1 DE 102017002966A1
- Authority
- DE
- Germany
- Prior art keywords
- calcium
- bis
- trimethylsilylmethanide
- donor
- trimethylsilylmethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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- -1 Calcium organic compound Chemical class 0.000 title claims abstract description 43
- 239000011575 calcium Substances 0.000 title claims description 31
- 229910052791 calcium Inorganic materials 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title claims description 6
- 230000008569 process Effects 0.000 title claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 230000002776 aggregation Effects 0.000 claims abstract description 5
- 238000004220 aggregation Methods 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- SXPOLNDOTIVFOC-UHFFFAOYSA-N methanidyl(trimethyl)silane Chemical compound C[Si](C)(C)[CH2-] SXPOLNDOTIVFOC-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000002577 pseudohalo group Chemical group 0.000 claims 3
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 230000008022 sublimation Effects 0.000 claims 1
- 238000005292 vacuum distillation Methods 0.000 claims 1
- 238000002061 vacuum sublimation Methods 0.000 claims 1
- 238000010626 work up procedure Methods 0.000 claims 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims 1
- 238000006263 metalation reaction Methods 0.000 abstract description 7
- 150000001412 amines Chemical class 0.000 abstract description 4
- 239000002879 Lewis base Substances 0.000 abstract description 3
- 150000002170 ethers Chemical class 0.000 abstract description 3
- 150000007527 lewis bases Chemical class 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 8
- 239000007983 Tris buffer Substances 0.000 description 8
- 125000002524 organometallic group Chemical group 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 6
- VKNQAYQPRXQKCP-UHFFFAOYSA-M [I-].C[Si](C)(C)C[Ca+] Chemical class [I-].C[Si](C)(C)C[Ca+] VKNQAYQPRXQKCP-UHFFFAOYSA-M 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229940043430 calcium compound Drugs 0.000 description 4
- YBLVILVQEZRPFO-UHFFFAOYSA-N calcium;bis(trimethylsilyl)azanide Chemical compound [Ca+2].C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C YBLVILVQEZRPFO-UHFFFAOYSA-N 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- CQHYRKIZIKFRCN-UHFFFAOYSA-N O1CCCC1.O1CCCC1.[Ca] Chemical compound O1CCCC1.O1CCCC1.[Ca] CQHYRKIZIKFRCN-UHFFFAOYSA-N 0.000 description 3
- 229910000086 alane Inorganic materials 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 150000004795 grignard reagents Chemical class 0.000 description 3
- 238000005649 metathesis reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000006478 transmetalation reaction Methods 0.000 description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- FURJHPORTREKOX-UHFFFAOYSA-N C[Si](C)(C)C[Ca]C[Si](C)(C)C Chemical compound C[Si](C)(C)C[Ca]C[Si](C)(C)C FURJHPORTREKOX-UHFFFAOYSA-N 0.000 description 2
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000010669 acid-base reaction Methods 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 150000001674 calcium compounds Chemical class 0.000 description 2
- ODYJZKDNEJGBSE-UHFFFAOYSA-N calcium;2-methylpropan-2-olate Chemical compound [Ca+2].CC(C)(C)[O-].CC(C)(C)[O-] ODYJZKDNEJGBSE-UHFFFAOYSA-N 0.000 description 2
- ROFABPOLYUJORV-UHFFFAOYSA-N calcium;carbanide Chemical class [CH3-].[CH3-].[Ca+2] ROFABPOLYUJORV-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- BUHVIAUBTBOHAG-FOYDDCNASA-N (2r,3r,4s,5r)-2-[6-[[2-(3,5-dimethoxyphenyl)-2-(2-methylphenyl)ethyl]amino]purin-9-yl]-5-(hydroxymethyl)oxolane-3,4-diol Chemical compound COC1=CC(OC)=CC(C(CNC=2C=3N=CN(C=3N=CN=2)[C@H]2[C@@H]([C@H](O)[C@@H](CO)O2)O)C=2C(=CC=CC=2)C)=C1 BUHVIAUBTBOHAG-FOYDDCNASA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 150000000094 1,4-dioxanes Chemical class 0.000 description 1
- KLIDCXVFHGNTTM-UHFFFAOYSA-N 2,6-dimethoxyphenol Chemical group COC1=CC=CC(OC)=C1O KLIDCXVFHGNTTM-UHFFFAOYSA-N 0.000 description 1
- MCPGMRRGKGTKHO-UHFFFAOYSA-N CC1=CC(C)=CC(C)=C1[Ca]C1=C(C)C=C(C)C=C1C Chemical compound CC1=CC(C)=CC(C)=C1[Ca]C1=C(C)C=C(C)C=C1C MCPGMRRGKGTKHO-UHFFFAOYSA-N 0.000 description 1
- UDOWTRCREXBYQS-UHFFFAOYSA-N CC[Ca]CC Chemical compound CC[Ca]CC UDOWTRCREXBYQS-UHFFFAOYSA-N 0.000 description 1
- VTSFOTYCSHETCQ-UHFFFAOYSA-N C[Si](C)(C)C[Ca] Chemical compound C[Si](C)(C)C[Ca] VTSFOTYCSHETCQ-UHFFFAOYSA-N 0.000 description 1
- AHQMHEHOLXXTEQ-UHFFFAOYSA-N C[Si](C)(C)C[Zn]C[Si](C)(C)C Chemical compound C[Si](C)(C)C[Zn]C[Si](C)(C)C AHQMHEHOLXXTEQ-UHFFFAOYSA-N 0.000 description 1
- PDWNFVUSMMTORE-UHFFFAOYSA-N C[Si](C)(C)[CH-][Si](C)(C)C.[Ca+2].C[Si](C)(C)[CH-][Si](C)(C)C Chemical class C[Si](C)(C)[CH-][Si](C)(C)C.[Ca+2].C[Si](C)(C)[CH-][Si](C)(C)C PDWNFVUSMMTORE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- YMGDMIIYRIYUFO-UHFFFAOYSA-J [Ca+2].[Ca+2].[I-].[I-].[I-].[I-] Chemical compound [Ca+2].[Ca+2].[I-].[I-].[I-].[I-] YMGDMIIYRIYUFO-UHFFFAOYSA-J 0.000 description 1
- BEFKWQGXZOKLFB-UHFFFAOYSA-N [Ca]CC1=CC=CC=C1 Chemical class [Ca]CC1=CC=CC=C1 BEFKWQGXZOKLFB-UHFFFAOYSA-N 0.000 description 1
- OQLLVOGBAKFMIS-UHFFFAOYSA-N [K]CC1=CC=CC=C1 Chemical class [K]CC1=CC=CC=C1 OQLLVOGBAKFMIS-UHFFFAOYSA-N 0.000 description 1
- MYXGYPFZVNSVCB-UHFFFAOYSA-N [bromo(trimethylsilyl)methyl]-trimethylsilane Chemical compound C[Si](C)(C)C(Br)[Si](C)(C)C MYXGYPFZVNSVCB-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000003339 best practice Methods 0.000 description 1
- KKAXNAVSOBXHTE-UHFFFAOYSA-N boranamine Chemical class NB KKAXNAVSOBXHTE-UHFFFAOYSA-N 0.000 description 1
- 150000001669 calcium Chemical class 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- VEONROOWZMTTKR-UHFFFAOYSA-N calcium;bis(trimethylsilyl)methyl-trimethylsilane Chemical compound [Ca+2].C[Si](C)(C)[C-]([Si](C)(C)C)[Si](C)(C)C.C[Si](C)(C)[C-]([Si](C)(C)C)[Si](C)(C)C VEONROOWZMTTKR-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005913 hydroamination reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- VZNYXGQMDSRJAL-UHFFFAOYSA-N iodomethyl(trimethyl)silane Chemical compound C[Si](C)(C)CI VZNYXGQMDSRJAL-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical group [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- KTEKFCJSGSHDBT-UHFFFAOYSA-N potassium;methanidyl(trimethyl)silane Chemical compound [K+].C[Si](C)(C)[CH2-] KTEKFCJSGSHDBT-UHFFFAOYSA-N 0.000 description 1
- AOGFQKQBYCOCBB-UHFFFAOYSA-N potassium;trimethyl(trimethylsilylmethyl)silane Chemical compound [K+].C[Si](C)(C)[CH-][Si](C)(C)C AOGFQKQBYCOCBB-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- QMGBPUMJJYFSTN-UHFFFAOYSA-N trimethyl(phenylmethyl)silane Chemical class C1(=CC=CC=C1)[CH-][Si](C)(C)C QMGBPUMJJYFSTN-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/04—Calcium compounds
-
- 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
- B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
- C08G65/12—Saturated oxiranes characterised by the catalysts used containing organo-metallic compounds or metal hydrides
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/14—Other (co) polymerisation, e.g. of lactides, epoxides
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/23—Calcium
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
Die Erfindung betrifft eine calciumorganische Verbindung mit gebundenen Trimethylsilylmethyl-Gruppen und deren Synthese.
Aufgabe war es, eine in organischen Lösungsmitteln gut lösliche calciumorganische Verbindung zu schaffen, die sich durch hohe Metallierungsstärke auszeichnet und mit möglichst geringem Aufwand in großen Mengen und mit guten Ausbeuten herstellbar ist.
Erfindungsgemäß werden Moleküle gemäß der allgemeinen Formel I vorgeschlagen:
R = Alkyl, Aryl,
D = Donor (jegliche zur Koordination fähige Verbindung, sogenannte aprotische Lewis-Basen wie beispielsweise Ether und/oder Amine),
m = Zahl der Donor-Moleküle (üblicherweise 0 bis 4),
n = jegliches Vielfaches des gezeigten Komplexes (Aggregationsgrad), üblicherweise 1 bis 6 oder ein Aggregationspolymer (n = ∞).The invention relates to a calcium-organic compound having bound trimethylsilylmethyl groups and their synthesis.
Task was to create a readily soluble in organic solvents calcium-organic compound, which is characterized by high metallation and can be produced with the least possible effort in large quantities and with good yields.
According to the invention, molecules according to the general formula I are proposed:
R = alkyl, aryl,
D = donor (any compound capable of coordination, so-called aprotic Lewis bases such as ethers and / or amines),
m = number of donor molecules (usually 0 to 4),
n = any multiple of the complex shown (degree of aggregation), usually 1 to 6 or an aggregation polymer (n = ∞).
Description
Die Erfindung betrifft eine calciumorganische Verbindung mit gebundenen Trimethylsilylmethyl-Gruppen und deren Synthese.The invention relates to a calcium-organic compound having bound trimethylsilylmethyl groups and their synthesis.
Aus dem Stand der Technik sind einige calciumorganische Verbindungen und Synthesewege bekannt.Some calcium-organic compounds and synthetic routes are known from the prior art.
Die Reaktion von Calcium-bis[bis(trimethylsilyl)amid] mit Tris(trimethylsilylmethyl)alan führt zur Bildung des dimeren Calcium-bis(trimethylsilyl)amid-tetrakis(trimethylsilylmethyl)aluminates mit verbrückend zwischen Calcium und Aluminium auftretenden Trimethylsilylmethyl-Gruppen; eine reine und Aluminium-freie Organocalcium-Verbindung lässt sich hieraus nicht isolieren (
Die Transmetallierung von Bis(trimethylsilylmethyl)zink mit Calciummetall in THF führt zu Bildung von Bis(tetrahydrofuran)calcium-bis[tris(trimethylsilylmethyl)zinkat], aus der sich eine reine Organocalcium-Verbindung ebenfalls nicht herstellen lässt (
Durch die Reaktion von aktiviertem Calciummetall und Trimethylsilylmethyliodid/bromid in THF, gefolgt von einem Lösungsmittelwechsel zu Tetrahydropyran (THP), konnten erfolgreich Tetrakis(tetrahydropyran)calcium-(trimethylsilylmethanid)-bromid bzw. -iodid dargestellt werden. Im Gegensatz zu den homologen Organomagnesium-halogeniden (Grignard-Reagenzien) ist hieraus durch Lösungsmittelwechsel nicht einfach eine Halogenid-freie Organocalcium-Verbindung zugänglich (1.
Es sind bereits calciumorganische Verbindungen mit den sterisch deutlich anspruchsvolleren Bis(trimethylsilyl)methyl- und Tris(trimethylsilyl)methyl-Gruppen bekannt, die wegen sterischen Abschirmung der Ca-C-Bindung und wegen elektronischer Rückbindung vom Carbanion zur Trimethylsilylgruppe eine nur geringe chemische Reaktivität aufweisen. Außerdem ist für deren Herstellung ein umständliches und unkomfortables Verfahren erforderlich.There are already known calcium organic compounds with the sterically much more demanding bis (trimethylsilyl) methyl and tris (trimethylsilyl) methyl groups, which have only low chemical reactivity because of steric shielding of the Ca-C bond and because of electronic backbonding of the carbanion to the trimethylsilyl group , In addition, a cumbersome and uncomfortable process is required for their production.
Kokondensation von Calciumdampf und Bis(trimethylsilyl)methylbromid in Tetrahydrofuran (THF) und anschließender Lösungsmittelwechsel zu 1,4-Dioxan erlauben die Isolierung von Bis(dioxan)calcium-bis[bis(trimethylsilyl)methanid].Dieses Verfahren ist zu aufwändig und ungeeignet, um größere Mengen von Calciummethaniden herzustellen (F. G. N. Cloke, P. B. Hitchcock, M.F. Lappert, G. A. Lawless, B. Royo: Lipophilic strontium and calcium alkyls, amides and phenoxides; X-ray structures of the crystalline square-planar [{trans-Sr(NR'2)2(µ-1,4-dioxane)}∞] and tetrahedral [CaR2(1,4-dioxane)2]; R'= SiMe3, R = CH(SiMe3)2], Journal of the Chemical Society, Chemical Communications, 1991, 724-726).Cocond condensation of calcium vapor and bis (trimethylsilyl) methyl bromide in tetrahydrofuran (THF) followed by a solvent switch to 1,4-dioxane allows isolation of bis (dioxane) calcium bis [bis (trimethylsilyl) methanide]. This process is too cumbersome and unsuitable. to prepare larger quantities of calcium methanides (FGN Cloke, PB Hitchcock, MF Lappert, GA Lawless, B. Royo: Lipophilic strontium and calcium alkyls, amides and phenoxides; X-ray structures of the crystalline square-planar [{trans-Sr (NR ' 2 ) 2 (μ-1,4-dioxanes)} ∞ ] and tetrahedral [CaR 2 (1,4-dioxanes) 2 ]; R' = SiMe 3 , R = CH (SiMe 3 ) 2 ], Journal of the Chemical Society, Chemical Communications, 1991, 724-726).
Bis(tetrahydrofuran)calcium-bis[bis(trimethylsilyl)methanid] ist ebenfalls mit Hilfe der Salzmetathese in THF darstellbar, indem Kalium-bis(trimethylsilyl)methanid mit Calciumhalogenid umgesetzt wird (
Diese Methode ist jedoch nicht auf die Herstellung von reinem Calcium-bis(trimethylsilylmethanid) übertragbar. Die Durchführung der Synthese in Benzol statt in THF führt zur Bildung des lösungsmittelfreien Kalium-tris[bis(trimethylsilyl)methyl]-calciates (
Mehreren Arbeitsgruppen gelang lediglich die Darstellung heteroleptischer und sterisch anspruchsvoller Calcium-bis(trimethylsilyl)methanid-Verbindungen mit Hilfe der oben genannten Synthesestrategien, aber es gibt keine Beispiele für die Herstellung von Calcium-Verbindungen mit dem kleineren Trimethylsilylmethyl-Rest (1.
Weiterhin ist donorfreies Calcium-bis[tris(trimethylsilyl)methanid] bekannt, welches mittels der Salzmetathese aus dem entsprechenden Alkylkalium und Calciumdiiodid hergestellt wird (
Neben Bis- und Tris(trimethylsilyl)methyl- Verbindungen des Calciums sind (Trimethylsilyl)(phenyl)methanide bekannt, welche aus den entsprechenden Benzylkaliumverbindungen und Calciumdiiodid dargestellt werden können. Hier nutzt man die Stabilisierung der Verbindung durch Delokalisierung der negativen Ladung in die Phenylgruppe, wodurch die Reaktivität gesenkt und Stabilität erhöht werden (1.
Komplexe mit einem Trimethylsilylmethylcalcium-Grundkörper sind bisher lediglich in heterobimetallischen Verbindungen (1.
Diarylcalcium-Verbindungen lassen sich nur mit sehr schlechten isolierten Ausbeuten und aufwändig durch Kühlen auf sehr niedrige Temperaturen (ca. -90 °C) durch Lösungsmittelwechsel aus den Arylcalcium-halogeniden darstellen (
Zusammenfassend lässt sich feststellen, dass die bisher bekannten Calcium-methanide mindestens eines der folgenden Charakteristika aufweisen:
- 1) Die Methanid-Gruppen weisen mindestens zwei Substituenten auf, wodurch die Metallierungsstärke reduziert wird, aber eine Löslichkeit in unpolaren Lösungsmitteln erreicht wird.
- 2) Es sind nur heterobimetallische Verbindungen mit der kleinen Trimethylsilylmethyl-Gruppe bekannt (Ca/Al; Ca/Zn). Die Anwesenheit des zweiten (elektronegativeren) Metalls führt zu einer deutlichen Reaktivitätsänderung (-erniedrigung) dieser metallorganischen Komplexe.
- 3) Aufwändige Prozesse (Salzmetathese, Kokondensation, Transmetallierung) sind bisher notwendig, um Alkylcalcium-Verbindungen darzustellen.
- 4) Die einzige rein calciumorganische Verbindung, die eine Trimethylsilylmethyl-Gruppe enthält, ist Trimethylsilylmethylcalcium-iodid/bromid, das aber in unpolaren Lösungsmitteln unlöslich ist.
- 1) The methanide groups have at least two substituents, which reduces the metallation strength but achieves solubility in nonpolar solvents.
- 2) Only heterobimetallic compounds with the small trimethylsilylmethyl group are known (Ca / Al, Ca / Zn). The presence of the second (more electronegative) metal leads to a significant change in reactivity (decrease) of these organometallic complexes.
- 3) Elaborate processes (salt metathesis, coccondensation, transmetalation) have been required to date to produce alkylcalcium compounds.
- 4) The only purely organo-calcium compound containing a trimethylsilylmethyl group is trimethylsilylmethylcalcium iodide / bromide, which, however, is insoluble in nonpolar solvents.
Der Erfindung liegt die Aufgabe zu Grunde, eine in organischen Lösungsmitteln gut lösliche calciumorganische Verbindung zu schaffen, die sich durch hohe Metallierungsstärke auszeichnet und mit möglichst geringem Aufwand in großen Mengen und mit guten Ausbeuten herstellbar ist.The invention is based on the object to provide a readily soluble in organic solvents calcium organic compound, which is characterized by high metallation and can be produced with the least possible effort in large quantities and with good yields.
Es werden calciumorganische Verbindungen mit der erfindungsgemäßen allgemeinen Formel I vorgeschlagen:
- R = Alkyl und/oder Aryl
- D = Donor (jegliche zur Koordination fähige Verbindung, sogenannte aprotische Lewis-Basen wie beispielsweise Ether und/oder Amine)
- m = Zahl der Donor-Moleküle (üblicherweise 0 bis 4)
- n = jegliches Vielfaches des gezeigten Komplexes (Aggregationsgrad), üblicherweise 1 bis 6 oder ein Aggregationspolymer (n = ∞)
- R = alkyl and / or aryl
- D = donor (any compound capable of coordination, so-called aprotic Lewis bases such as ethers and / or amines)
- m = number of donor molecules (usually 0 to 4)
- n = any multiple of the complex shown (degree of aggregation), usually 1 to 6 or an aggregation polymer (n = ∞)
Mit der vorgenannten Verbindung wird eine in Kohlenwasserstoffen lösliche calciumorganische Verbindung geschaffen, welche bedingt durch die sterisch wenig abschirmenden Trimethylsilylmethyl-Gruppen eine enorme Metallierungsstärke und Reaktivität aufweist. So lassen sich beispielsweise substituierte Aromaten leicht, schnell und quantitativ metallieren. Als Lösungsmittel werden bevorzugt unpolare, aromatische und/oder aliphatische Kohlenwasserstoffe verstanden.With the abovementioned compound, a calcium-organic compound soluble in hydrocarbons is created which, owing to the sterically less shielding trimethylsilylmethyl groups, has a tremendous metallation strength and reactivity. For example, substituted aromatics can be easily, quickly and quantitatively metallated. The solvents are preferably understood to be nonpolar, aromatic and / or aliphatic hydrocarbons.
Die Koordinationssphäre am Calcium kann durch zusätzliche Lewis-Basen (hier als Donor bezeichnet) abgesättigt werden, so dass Verbindungen des Typus [(Donor)Ca(CH2SiMe3)2] (Donor = jegliche zur Koordination fähige Verbindung, sogenannte aprotische Lewis-Base) sowie dessen Herstellung beschrieben werden. Das Trimethylsilylmethyl-Anion ist ein stark basisches Nukleophil mit hoher Metallierungsstärke und zeigt in Kombination mit Calcium-Ionen neuartige Reaktionen und Eigenschaften.The coordination sphere on the calcium can be saturated by additional Lewis bases (referred to here as donor), so that compounds of the type [(donor) Ca (CH 2 SiMe 3 ) 2 ] (donor = any compound capable of coordination, so-called aprotic Lewis Base) and its preparation are described. The trimethylsilylmethyl anion is a strongly basic nucleophile with high metallation strength and shows in combination with calcium ions novel reactions and properties.
Sie ist verfahrenstechnisch einfach und mit wenig Aufwand nach zwei Methoden unter Normalbedingungen darstellbar (X = Halogenid (bevorzugt Bromid und Iodid, M = Alkalimetall, bevorzugt Kalium):
Die gemäß Formel II beschriebene Synthese der Derivate geschieht in guter Ausbeute und führt selektiv zum gewünschten Produkt. Leicht zugängliches Trimethylsilylmethylcalcium-halogenid bzw. Trimethylsilylmethylcalcium-pseudohalogenid wird mit Metall-(trimethylsilyl)methanid in einem geeigneten Lösungsmittel, beispielsweise Tetrahydrofuran, Tetrahydropyran, Diethylether, Toluol oder Benzol, zur Reaktion gebracht.The synthesis of the derivatives described in accordance with formula II occurs in good yield and leads selectively to the desired product. Easily accessible trimethylsilylmethylcalcium halide or trimethylsilylmethylcalcium pseudohalide is reacted with metal (trimethylsilyl) methanide in a suitable solvent, for example tetrahydrofuran, tetrahydropyran, diethyl ether, toluene or benzene.
Die gemäß Formel III beschriebene Synthese führt zu einer Ausbeute von 50 % bezogen auf eingesetztes Calcium. Dazu werden Trimethylsilylmethylcalcium-halogenid bzw. Trimethylsilylmethylcalcium-pseudohalogenid mit Metall-tert-butanolat in einem geeigneten Lösungsmittel wie beispielsweise Tetrahydrofuran, Tetrahydropyran, Diethylether, Toluol oder Benzol umgesetzt.
Die in Formel IV dargestellte Struktur der Formel I stellt ein repräsentatives Beispiel für ein Donor-stabilisiertes Bis(trimethylsilylmethyl)calcium dar, nämlich Bis(tmeda)calcium-bis(trimethylsilylmethanid). Diese Abbildung zeigt die mit Röntgenbeugungsexperimenten ermittelte Molekülstruktur dieses Komplexes.The structure of Formula I shown in Formula IV represents a representative example of a donor-stabilized bis (trimethylsilylmethyl) calcium, bis (tmeda) calcium bis (trimethylsilylmethanide). This figure shows the molecular structure of this complex determined by X-ray diffraction experiments.
Alle präparativen Arbeiten wurden in einer Sauerstoff- und Wasser-freien Stickstoffatmosphäre unter Normaldruck durchgeführt.All preparative work was carried out in an oxygen and water-free nitrogen atmosphere under atmospheric pressure.
Zur Synthese der Dialkylcalcium-Verbindung wurden 228 mg (1,80 mmol) Kalium-(trimethylsilyl)methanid in 4 mL Tetrahydropyran (THP) gelöst und auf 0 °C gekühlt. Zu dieser Lösung wurden 9 ml einer 0,194 M Lösung von Trimethylsilylmethylcalcium-iodid (1,75 mmol) in THP langsam und bei gleichbleibender Temperatur zugetropft. Die Suspension wurde eine Stunde bei 0 °C gerührt, ehe das Lösungsmittel unter vermindertem Druck abdestilliert wurde. Der Rückstand wurde mit Pentan extrahiert, wobei sich eine Lösung von Tetrakis(tetrahydropyran)calcium-bis(trimethylsilylmethanid) bildet. Die Ausbeute ist typischerweise größer als 80 %. In Folgereaktionen kann der Donor (hier Tetrahydropyran) durch Lösen in anderen Donor-Lösungsmitteln (wie beispielsweise anderen Ethern oder Aminen) substituiert werden.To synthesize the dialkyl calcium compound, 228 mg (1.80 mmol) of potassium (trimethylsilyl) methanide were dissolved in 4 mL of tetrahydropyran (THP) and cooled to 0 ° C. To this solution was added dropwise 9 ml of a 0.194 M solution of trimethylsilylmethylcalcium iodide (1.75 mmol) in THP slowly and at constant temperature. The suspension was stirred for one hour at 0 ° C before the solvent was distilled off under reduced pressure. The residue was extracted with pentane to form a solution of tetrakis (tetrahydropyran) calcium bis (trimethylsilylmethanide). The yield is typically greater than 80%. In subsequent reactions, the donor (here tetrahydropyran) can be substituted by dissolving in other donor solvents (such as other ethers or amines).
1H-NMR-spektroskopische Daten in perdeuteriertem Benzol und Tetrahydrofuran: 1H-NMR (400.129 MHz, 25 °C, [D6]Benzol): δ = -1,38 (s, 4H); 0,43 (s, 18H); 1,31 (bs, 24H); 3.56 (bs, 16H) ppm. 1H-NMR (300.190 MHz, 25 °C, [D8]THF): δ = -1,88 (s, 4H); -0,15 (s, 18H); 1,52 (m, 16H); 1,62 (m, 8H); 3.56 (m, 16H) ppm. 1 H - NMR spectroscopic data in perdeuterated benzene and tetrahydrofuran: 1 H-NMR (400 129 MHz, 25 ° C, [D 6] benzene): δ = -1.38 (s, 4H); 0.43 (s, 18H); 1.31 (bs, 24H); 3.56 (bs, 16H) ppm. 1 H-NMR (300.190 MHz, 25 ° C, [D 8 ] THF): δ = -1.88 (s, 4H); -0.15 (s, 18H); 1.52 (m, 16H); 1.62 (m, 8H); 3.56 (m, 16H) ppm.
ZITATE ENTHALTEN IN DER BESCHREIBUNG QUOTES INCLUDE IN THE DESCRIPTION
Diese Liste der vom Anmelder aufgeführten Dokumente wurde automatisiert erzeugt und ist ausschließlich zur besseren Information des Lesers aufgenommen. Die Liste ist nicht Bestandteil der deutschen Patent- bzw. Gebrauchsmusteranmeldung. Das DPMA übernimmt keinerlei Haftung für etwaige Fehler oder Auslassungen.This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.
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WO2022008838A1 (en) | 2020-07-07 | 2022-01-13 | Compagnie Generale Des Etablissements Michelin | Catalytic system for the stereospecific polymerization of dienes and use thereof in a process for synthesising diene polymers |
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2017
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022008838A1 (en) | 2020-07-07 | 2022-01-13 | Compagnie Generale Des Etablissements Michelin | Catalytic system for the stereospecific polymerization of dienes and use thereof in a process for synthesising diene polymers |
FR3112347A1 (en) | 2020-07-07 | 2022-01-14 | Compagnie Generale Des Etablissements Michelin | Catalytic system for the stereospecific polymerization of dienes and their use in a process for the synthesis of diene polymers |
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