WO2014001291A1 - Method for preparation of a ruthenium indenylidene complex - Google Patents
Method for preparation of a ruthenium indenylidene complex Download PDFInfo
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- WO2014001291A1 WO2014001291A1 PCT/EP2013/063208 EP2013063208W WO2014001291A1 WO 2014001291 A1 WO2014001291 A1 WO 2014001291A1 EP 2013063208 W EP2013063208 W EP 2013063208W WO 2014001291 A1 WO2014001291 A1 WO 2014001291A1
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- Prior art keywords
- catalyst
- thf
- cyclic ether
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- ruthenium
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- 238000000034 method Methods 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052707 ruthenium Inorganic materials 0.000 title abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 79
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 69
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- -1 phenylindenylidene Chemical group 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 33
- 150000004292 cyclic ethers Chemical class 0.000 claims abstract description 23
- 239000011541 reaction mixture Substances 0.000 claims abstract description 18
- 239000012453 solvate Substances 0.000 claims abstract description 13
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000002441 X-ray diffraction Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 claims description 7
- 238000004679 31P NMR spectroscopy Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- ZNOVTXRBGFNYRX-UHFFFAOYSA-N 2-[[4-[(2-amino-5-methyl-4-oxo-1,6,7,8-tetrahydropteridin-6-yl)methylamino]benzoyl]amino]pentanedioic acid Chemical compound C1NC=2NC(N)=NC(=O)C=2N(C)C1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 ZNOVTXRBGFNYRX-UHFFFAOYSA-N 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000002050 diffraction method Methods 0.000 claims 1
- 230000005284 excitation Effects 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 10
- 238000005580 one pot reaction Methods 0.000 abstract description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 62
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 35
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 239000003446 ligand Substances 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000006227 byproduct Substances 0.000 description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 238000005649 metathesis reaction Methods 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000002178 crystalline material Substances 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 125000003963 dichloro group Chemical group Cl* 0.000 description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005865 alkene metathesis reaction Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005686 cross metathesis reaction Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 4
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000006798 ring closing metathesis reaction Methods 0.000 description 4
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 4
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010561 standard procedure Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000001665 trituration Methods 0.000 description 3
- SMCLTAARQYTXLW-UHFFFAOYSA-N 1,1-diphenylprop-2-yn-1-ol Chemical compound C=1C=CC=CC=1C(C#C)(O)C1=CC=CC=C1 SMCLTAARQYTXLW-UHFFFAOYSA-N 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229960004132 diethyl ether Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VRBHURBJIHILRI-UHFFFAOYSA-N 1H-inden-1-ylidene Chemical group C1=CC=C2[C]C=CC2=C1 VRBHURBJIHILRI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101100353526 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pca-2 gene Proteins 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000860 allenylidene group Chemical group [*]=C=C=C([H])[H] 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000538 analytical sample Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PNPBGYBHLCEVMK-UHFFFAOYSA-L benzylidene(dichloro)ruthenium;tricyclohexylphosphane Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-L 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940032007 methylethyl ketone Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- RWUZSCCQJHYWDK-UHFFFAOYSA-N ruthenium(2+);tricyclohexylphosphane Chemical compound [Ru+2].C1CCCCC1P(C1CCCCC1)C1CCCCC1 RWUZSCCQJHYWDK-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 230000007306 turnover Effects 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/54—Metathesis reactions, e.g. olefin metathesis
-
- 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
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/54—Metathesis reactions, e.g. olefin metathesis
- B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
Definitions
- the present invention relates to a ruthenium-carbene catalysts for olefin metathesis reactions, in particular to the preparation of a ruthenium indenylidene carbene catalyst of the formula (PCy 3 )2CI 2 Ru(3- phenyl indenylidene) with the chemical name dichloro(3-phenyl-lH-inden-l- ylidene)bis(tricyclohexylphosphine)ruthenium(II). Furthermore, the inven- tion is directed to a new crystalline form of said catalyst.
- the catalyst product is commercially available as catalyst Umicore M l and hereinafter designated with the abbreviations "Umicore M l” or “M l " for short. It is useful in a variety of olefin metathesis reactions and as precursor for the synthesis of other ruthenium carbene catalysts.
- the present inven- tion provides a one-step method with simple product isolation. A highly crystalline material is obtained, which displays high purity and good thermal stability as well as very good stability towards atmospheric oxygen .
- Olefin metathesis is a fundamental catalytic reaction and one of the most versatile ways to design new molecules by formation and rearrange- ment of carbon-carbon multiple bonds.
- the metathesis reactions not only provide significantly shortening synthetic pathways towards defined target molecules, but also give access to new applications not being feasible with the traditional means of organic chemistry.
- Various classes of metathesis reactions are known, such as, for example, ring-closing metathesis (RCM), ring-opening metathesis polymerization (ROMP) or cross metathesis (CM).
- metathesis has become a widely used method for the formation of carbon-carbon bonds in organic synthesis and polymer chemistry.
- the development of well-defined ruthenium-based carbene catalysts by Grubbs has led to a fast growth in the field of metathesis. More and more, metathesis reactions are applied and integrated in the synthesis design of organic compounds, leading to an increased usage of metathesis catalysts in industrial laboratories. This trend is about to continue in the forthcoming years.
- This catalyst is characterized by a penta- coordinated Ru(II) metal center bearing two phosphine ligands, two chloride ligands and a non-cyclic benzylidene group and has found broad acceptance in the organic synthesis community.
- Ru-carbene catalysts contain the Ru atom in the formal oxidation state +11; they are predominantly penta- coordinated and comprise an indenylidene ring, wherein the carbene C- atom in the indenylidene moiety is part of a bicyclic, condensed ring system.
- the present invention is directed to a preparation method for the Grubbs-l st generation type Ru-phenyl indenylidene catalyst exhibiting the structure of Formula 1 :
- the method of the present invention essentially is a one-step method, starting from the PPh 3 -substituted Ru-complex, which is prepared in a separate reaction.
- the PPh 3 -substituted Ru-indenylidene carbene com ⁇ plex is shown in Formula la:
- this complex (PPh 3 ) 2 CI 2 Ru(3- phenylindenylidene) is itself not active in olefin metathesis reactions and the two triphenylphosphine ligands must be exchanged for tricyclohexyl- phosphine in order to achieve catalytic activity.
- the starting ( PPh3) 2 CI 2 Ru(3-phenyl- indenylidene) complex is prepared separately and isolated as a solid material that is used as educt for the preparation method of the present invention (ref to Example 1).
- the product (PCy 3 ) 2 CI 2 Ru(3-phenylindenylidene) is isolated as brick-red solid in 88% yield after evaporation of the solvent to dryness and trituration of the residue with methanol, followed by washing with methanol and hexane.
- the complex is isolated as brick-red solid in 92% yields by evaporating the solvents and suspending the residues in diethylether. Thereafter the product is filtered and washed frequently with low boiling solvents such as diethylether and pentane to remove impurities. As this procedure is a one- pot, 2-step method, it generally yields a product in lower purity. As the intermediate (PPh 3 ) 2 CI 2 Ru(3-phenylindenylidene) is not isolated but directly reacted with tricyclohexylphosphine, the amount of side products is quite high.
- WO2010/037550A1 describes a one-pot, two-step synthesis of
- the complex is isolated in 95% yields by removing the solvent and suspending the residue in acetone at - 40°C for 10 hours, followed by filtration and washing with methanol, acetone and hexane.
- this synthesis is a one-pot, two-step method, generally yielding a product in lower purity and lower crystallinity.
- the impurities e.g. diphenylallenylidene species, dimeric compounds, mixed PPh 3 /PCy 3 complexes, phosphine oxides etc
- TON turn-over numbers
- the phosphine ligand exchange reac- tion is conducted in chlorinated solvents (typically dichloromethane) at room temperature (i.e. 20 to 25°C). After completion of the reaction, the solvent is evaporated to dryness and the product is washed with big amounts of low boiling solvents in order to wash out the phosphine impurities. In most cases, a high excess of tricyciohexylphosphine (in the range of 2.5 to 3.2 equivalents) is employed. This may lead to phosphine and phosphine oxide residues in the final product. Furthermore, as the currently known procedures do not comprise a specific purification step (other than washing the residual material with solvent) the impurities are not efficiently removed from the final product.
- chlorinated solvents typically dichloromethane
- the present invention is directed to a one-step method for preparation of the ruthenium indenylidene catalyst of Formula 1,
- the resulting ruthenium- indenylidene catalyst of Formula 1 may precipitate in a crystalline cyclic ether solvate.
- it may precipitate as a crystalline cyclic ether solvate comprising > 1 cyclic ether molecules per molecule of catalyst
- the cyclic ether solvent generally is selected from the group consisting of tetrahydrofurane (THF), methyl-tetrahydrofuran, dimethyltetra- hydrofuran and mixtures or combinations thereof.
- the cyclic ether solvent is tetrahydrofurane (THF).
- the resulting ruthenium catalyst of Formula 1 is precipitated from the reaction mixture in crystalline form as a tetrahydrofurane (THF) solvate comprising between 1 and 2 molecules of THF per molecule of catalyst.
- THF tetrahydrofurane
- the molecular formula of this Ml catalyst product may then be given as x n(C 4 H 8 0) wherein 1 ⁇ n ⁇ 2.
- the tricyclohexylphosphine (PCy 3 ) ligand is added to the reaction mixture in quantities in the range of 2 to 3 equivalents, preferably 2.1 to 2.5 equivalents based on the (PPh 3 ) 2 CI 2 Ru(3-phenylindenylidene) starting complex.
- reaction temperature conditions are typically under solvent reflux, thus the boiling point of the cyclic ether solvent is decisive here.
- the reaction temperature should be in the range of 30 to 100°C.
- the reaction temperature should be in the range of 50 to 80°C (i.e. within the boiling range of THF).
- the method may further comprise a cooling-down step.
- the reaction mixture may be cooled down to room temperature and below, i.e. to a temperature in the range of -30 to 25°C, preferably to a temperature in the range of 0 to 25°C.
- Suitable reaction times are depending on the reaction scale and should be in the range of 0.1 to 3 hours, preferably in the range of 0.5 to 2 hours.
- the cyclic ether solvent may be partially distilled off during the reaction, either under vacuum or under a flow of inert gas.
- the method comprises steps and measures of separating the catalyst product from the reaction mixture. Such isolation may be performed by filtration, centrifugation, decantation or other similar operations known to the skilled person.
- the method may comprise additional washing and/or drying steps.
- ketone solvents such as methyl- ethyl ketone or acetone are preferably employed for washing. Drying of the catalyst may be performed in box ovens under inert atmosphere or under vacuum conditions at elevated temperatures.
- the present invention is directed to a new crystal- line form of the Umicore M l catalyst.
- Figure 1 shows the ORTEP plot of the single-crystal structure of Ml catalyst (THF-solvate) as determined by X-ray analysis.
- the crystallized complex comprises two co-crystallized THF molecules.
- the ellipsoids prob- ability is shown at 50%, H-atoms are omitted.
- Space group is orthorhombic (Pca2( l)).
- the product crystallizes in dark red crystals.
- a beneficial effect of the product crystallinity of the present invention is the ease with which the crystalline M l material can be handled, filtered and washed. Product washing is necessary to remove PPh 3 and other impurities generated in the reaction.
- the crystalline Ml product may loose some THF during washing, drying and further handling.
- the crystalline product obtainable by the method of the present invention comprises > 1 molecule of cyclic ether per molecule of catalyst (as determined by X-ray analysis and 'H-NMR spectroscopy).
- the crystalline M l product comprises between 1 and 2 molecules of THF per molecule of catalyst (as determined by X-ray analysis and ⁇ -NMR spectroscopy).
- the orange catalyst product which is state of the art (ref to the earlier cited preparation methods) comprises very fine needles.
- the orange form of the catalyst material produced according to standard methods is very bulky. In this form, the material is very difficult to filtrate, wash and to handle. The filtration time of the orange version is substantially prolonged, which in turn results in a product of low purity. It is likely that upon precipitation, the impurities are trapped in the orange version due to its flocculent form.
- the orange catalyst material is also more sensitive to the air oxygen since it has a larger specific surface area. As a consequence, it is much easier oxidized and it likely contains more phosphine oxides impurities unless it is rigorously stored under inert conditions.
- the desired bis-PCy 3 complex may be obtained in acceptable purity only by using a large excess of PCy 3 (typically in the range of 3 equivalents) which is not feasible from an industrial point of view due to the high cost of PCy 3 .
- the mixture of complexes is isolated and subjected to further treatment with PCy 3 . This is again not feasible at industrial scale because additional purifi- cation steps are needed.
- the catalyst produced according to the method of the invention is a crystalline material which shows high purity.
- the high purity is a direct consequence of the crystalline shape of the product.
- the amount of impurity X in the M l product made according to the invention is ⁇ 3%, preferably ⁇ 1% and most preferred ⁇ 0.5% (based on the total weight of the catalyst product) .
- the presence of mixed complex X in M l will deteriorate its catalytic activity since it is known that the Ru- indenylidene complex bearing PPh 3 groups is not metathesis active.
- This impurity X can be easily identified by 31 P-N MR as it displays two small peaks close to the product peak (when measured in CD 2 CI 2 ) or only one small peak (when measured in CDCI 3 ) .
- the peak integration method is employed.
- the purity of the Ru- indenylidene catalyst prepared according to the invention is >97%, preferably > 99% and particularly preferred >99.5% (as determined by 31 P-N M R spectroscopy) .
- Figures 2a-c. show the XRD diffractograms of three batches of catalyst Umicore M l made according to the method of the present invention, which, according to ⁇ -N MR analysis, contain different amounts of THF per mol Ru complex respectively :
- Figure 2a shows a XRD plot of M l (red crystalline material, method of this invention, containing 1.54 mol TH F per mol of complex)
- Figure 2b shows a XRD plot of M l (red crystalline material, method of this invention, containing 1.4 mol THF per mol of complex)
- Figure 2c shows a XRD spectrum of M l (red crystalline material, method of this invention, containing 1.1 mol THF per mol of complex).
- Figure 3a shows for comparative reasons a XRD diffractogram of the
- M l catalyst made according to Umicore Standard Method (acc to WO2010/037550A1), which does not contain any THF (as confirmed by H NMR). This product exhibited a bulk density of 0.3 g/ml .
- Figure 3b shows for comparative reasons a XRD diffractogram of the M l catalyst made according to EP 2280033, Example 9, which contains less than 0.1 mol THF/mol product (as confirmed by 1 NMR). This product exhibited a bulk density of 0.25 g/ml .
- the intensities of the peaks and the position of the peaks at various diffraction angles (20°) may slightly vary depending on the sample preparation, on the measurement conditions as well as on the THF content.
- the uncertainty in the peak position is +/- 0.05° 20.
- Figure 4a shows M l (red crystalline material, THF solvate, method of this invention).
- Figure 4b shows M l (orange material, Umicore Standard method) .
- M l range material, Umicore Standard method
- the resulting Ru-indenylidene catalyst M l reveals high product purity, in particular high crystal I in ity.
- this preparation method is applicable to industrial production scale.
- the Umicore M l catalyst of the present invention is useful in a variety of olefin metathesis reactions such as ring-closing metathesis ( RCM ), ring- opening metathesis polymerization (ROM P) and cross metathesis (CM ) . Furthermore, it is a valuable precursor for the synthesis of other, further modified ruthenium carbene catalysts.
- RCM ring-closing metathesis
- ROM P ring- opening metathesis polymerization
- CM cross metathesis
- the present invention is directed to a method for the preparation of ruthenium catalyst (PCy 3 )2CI 2 Ru(phenylindenylidene) (Umicore catalyst "M l") .
- the method comprises a one-step reaction reacting the precursor compound ( PPh 3 ) 2 CI 2 Ru(3-phenylindenylidene) with PCy 3 in a cyclic ether solvent (preferably TH F) in concentrations in the range of 0.2 to 0.6 mol catalyst/1 while simultaneously precipitating the product from the reaction mixture.
- a cyclic ether solvent preferably TH F
- the present invention is further directed to a crystalline modification of ruthenium catalyst Umicore M l ( PCy 3 ) 2 CI 2 Ru( phenyl indenylidene) comprising between 1 and 2 molecules of THF per molecule of catalyst and having the molecular formula C51H7 6 CI2P2 U x n(C 4 H 8 0) wherein 1 ⁇ n ⁇ 2.
- Umicore M l ( PCy 3 ) 2 CI 2 Ru( phenyl indenylidene) comprising between 1 and 2 molecules of THF per molecule of catalyst and having the molecular formula C51H7 6 CI2P2 U x n(C 4 H 8 0) wherein 1 ⁇ n ⁇ 2.
- EXAM PLES Generally, in the Examples glass reactors or flasks with condenser and stirrer are used for the method of the present invention. The reactors are flushed with dry inert gas (argon, nitrogen) prior to use.
- dry inert gas argon, nitrogen
- the NMR spectra are recorded on a BRUKER DRX 500 NMR spec- trometer at about 25°C.
- the chemical shifts are determined relative to external phosphoric acid ( 31 P-NMR) or to residual solvent signal ('H-NMR).
- the XRD diffractograms were recorded in the range 5° ⁇ 20 ⁇ 100° on a PANalytical X'Pert Pro with X-Celerator detector using Cu radiation.
- the sample material was prepared into a 27 mm PAN analytical sample holder (single preparation).
- the XRD data were recorded under the following conditions:
- the uncertainty in the peak position is +/- 0.05° 20.
- a one liter glass reactor with condenser and stirrer is filled with argon and thereafter with 500 ml of THF.
- the solvent is warmed up to 40°C.
- 221.7 g (250 mmol, 1 eq. ) of (PPh 3 ) 2 CI 2 Ru(3-phenylindenylidene) (Umicore AG & Co. KG, Hanau) and 155 g (98.1% purity, 540 mmol, 2.16 eq. ) of tricyclohexylphosphine (PCy 3 , Aldrich) are added successively with stirring.
- the reaction mixture is stirred under reflux (65°C) for 1 h during which time the product precipitates in form of dark red crystals.
- the reaction mixture is cooled down to 5 °C.
- the crystalline precipitate is filtered off, washed with 400 ml of acetone and then dried under vacuum at 80°C. Yield : 236 g, 88% (based on Ru-content 9.41 wt.-%).
- a one liter glass reactor with condenser and stirrer is filled with argon and thereafter with 600 ml of THF. Then 106.4 g ( 120 mmol, 1 eq.) of ( PPh 3 ) 2 C Ru(3-phenylindenylidene) (Umicore AG & Co. KG, Hanau) and 74 g (98.1% purity, 258 mmol, 2.15 eq. ) of tricyclohexylphosphine, PCy 3 are added successively with stirring. The reaction mixture is stirred under reflux (65°C) for 0.5 hour.
- the mixture was stored for 10 hours at - 20°C.
- the residue was filtered by suction filtration (nutsche filter, porosity D4).
- the solid was washed with methanol, acetone and hexane.
- the product was dried in vacuum at room temperature.
- the product was obtained as brick-red powder, 4.63g (5.02mmol, 87% yield on metal base).
- 31 P and 1 H-NMR data shows the presence of several side products: di- phenylallenylidene complex (6 -41 ppm in 31 P NMR) and phosphine oxides.
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Abstract
The present invention is directed to a method for the preparation of ruthenium catalyst ( PCy3)2CI2Ru(phenylindenylidene) (Umicore catalyst "M1"). The method comprises a one-step reaction reacting the precursor compound (PPh3)2CI2Ru(3-phenylindenylidene) with PCy3 in a cyclic ether solvent (preferably THF) in concentrations in the range of 0.2 to 0.6 mol catalyst/I while simultaneously precipitating the product from the reaction mixture. A cyclic ether solvate product with high crystal linity and high purity is obtained.
Description
Method for preparation of a ruthenium
indenylidene complex
Description The present invention relates to a ruthenium-carbene catalysts for olefin metathesis reactions, in particular to the preparation of a ruthenium indenylidene carbene catalyst of the formula (PCy3)2CI2Ru(3- phenyl indenylidene) with the chemical name dichloro(3-phenyl-lH-inden-l- ylidene)bis(tricyclohexylphosphine)ruthenium(II). Furthermore, the inven- tion is directed to a new crystalline form of said catalyst.
The catalyst product is commercially available as catalyst Umicore M l and hereinafter designated with the abbreviations "Umicore M l" or "M l " for short. It is useful in a variety of olefin metathesis reactions and as precursor for the synthesis of other ruthenium carbene catalysts. The present inven- tion provides a one-step method with simple product isolation. A highly crystalline material is obtained, which displays high purity and good thermal stability as well as very good stability towards atmospheric oxygen .
Olefin metathesis is a fundamental catalytic reaction and one of the most versatile ways to design new molecules by formation and rearrange- ment of carbon-carbon multiple bonds. The metathesis reactions not only provide significantly shortening synthetic pathways towards defined target molecules, but also give access to new applications not being feasible with the traditional means of organic chemistry. Various classes of metathesis reactions are known, such as, for example, ring-closing metathesis (RCM), ring-opening metathesis polymerization (ROMP) or cross metathesis (CM).
In the past years, metathesis has become a widely used method for the formation of carbon-carbon bonds in organic synthesis and polymer chemistry. The development of well-defined ruthenium-based carbene catalysts by Grubbs has led to a fast growth in the field of metathesis. More and more, metathesis reactions are applied and integrated in the synthesis design of organic compounds, leading to an increased usage of metathesis
catalysts in industrial laboratories. This trend is about to continue in the forthcoming years.
One of the first catalyst showing high activity, low sensitivity against functional groups as well as sufficient stability, was Grubbs "first genera- tion" catalyst (PCy3)2CI2Ru =CHPh, dichloro(benzylidene)bis(tricyclo- hexylphosphine)ruthenium(II). This catalyst is characterized by a penta- coordinated Ru(II) metal center bearing two phosphine ligands, two chloride ligands and a non-cyclic benzylidene group and has found broad acceptance in the organic synthesis community.
In the meantime, a complete range of different metathesis catalysts, each offering specific features and properties are available on the market from different vendors. Over the past years, a different class of metathesis catalysts, so-called Ruthenium indenylidene carbene catalysts have gained increased importance. These types of Ru-carbene catalysts contain the Ru atom in the formal oxidation state +11; they are predominantly penta- coordinated and comprise an indenylidene ring, wherein the carbene C- atom in the indenylidene moiety is part of a bicyclic, condensed ring system.
The present invention is directed to a preparation method for the Grubbs-lst generation type Ru-phenyl indenylidene catalyst exhibiting the structure of Formula 1 :
This catalyst, dichloro(3-phenyl-lH-inden-l-ylidene)bis-
(tricyclohexylphosphine)-ruthenium(II) (CAS Nr. : 250220-36-1), was first published in 1999 by A.F. Hill et al . in J. Chem. Soc, Dalton Trans. 1999. 285-291. It was obtained by a ligand substitution reaction of dichloro(3-
phenyl- lH-inden-l-ylidene)bis-(triphenylphosphine)ruthenium(II), (PPh3)2 CI2Ru(3-phenylindenylidene) (CAS Nr.: 254972-46-8) with tricyclohexyl- phosphine (PCy3). The molecular formula of Umicore Ml is C5iH76CI2P2Ru.
The method of the present invention essentially is a one-step method, starting from the PPh3-substituted Ru-complex, which is prepared in a separate reaction. The PPh3-substituted Ru-indenylidene carbene com¬ plex is shown in Formula la:
Formula la
The synthesis routes for the starting complex of Formula la are well known in the literature and will be outlined in the following.
Preparation of the starting complex fla) As described by Hill (ref to A.F. Hill et al., cited above) the starting material (PPh3)2CI2Ru(3-phenylindenylidene) is obtained by reacting di- chlorotris(triphenylphosphine)ruthenium(II), [(PPh3)3CI2Ru] with 1,1- diphenyl-2-propyn-l-ol in THF at reflux for 2.5 hours. It was first believed that the reaction would provide the corresponding diphenylallenylidene complex (PPh3)2CI2Ru=C=C=CPh2. However, it was found later by Fuerstner et al. that the structure of this complex was not an allenylidene, instead it was re-arranged to an phenylindenylidene (ref to Fuerstner et al, J. Org. Chem. 1999. 7, No. 64, 8275-8280). This complex (PPh3)2CI2Ru(3- phenylindenylidene) is itself not active in olefin metathesis reactions and the two triphenylphosphine ligands must be exchanged for tricyclohexyl- phosphine in order to achieve catalytic activity.
Recently, the synthesis of the starting complex (PPh3)2CI2Ru(3- phenylindenylidene) was investigated in greater detail by H.-J. Schanz et al.
in J. Organometal. Chemistry 692, 5221-5233 (2007) . The reaction of ( PPh3)3 4CI2Ru with l,l-diphenyl-2-propyn-l-ol is conducted in ref!uxing THF for 1.5 hours to yield the starting complex; improved yields and high purity products are reported under acidic conditions. Schanz also reported that several undesired side products are generated if the reaction conditions are not carefully controlled. This preparation route is shown in equation 1.
Equation 1 :
According to this reaction, the starting ( PPh3)2CI2Ru(3-phenyl- indenylidene) complex is prepared separately and isolated as a solid material that is used as educt for the preparation method of the present invention (ref to Example 1). Preparation of the Umicore M l catalyst
Generally, two different synthetic routes to the metathesis catalyst (PCy3)2CI2Ru(3-phenylindenylidene (Umicore M l catalyst) are reported in the literature: These routes are summarized in equation 2. Equation 2 :
B
The route B (ref to S. Nolan et al, Organometallics, 1999. 18, 5187- 5190) affords a product of poor quality in very low yields. In fact, a mixture of diphenylallenylidene and phenylindenylidene species is obtained. The diphenylallenylidene complex (PCy3)2CI2Ru =C=C=CPh2 displays lower cata- lytic activity compared to the phenylindenylidene complex. This route was evaluated by the present inventors without success and will be not considered here. The "ligand exchange route" A is broadly described in the literature and some variants thereof are known. These variants will be reported hereinafter.
According to Hill (cited above) the product is obtained by a one-step ligand substitution reaction of (PPh3)2Cl2Ru(3-phenylindenylidene) with 2.7 equivalents of tricyclohexylphosphine in dichloromethane at room temperature for 0.5 hours with a concentration of c=0.015 mol/l of the starting Ru- complex. The product (PCy3)2CI2Ru(3-phenylindenylidene) is isolated as brick-red solid in 88% yield after evaporation of the solvent to dryness and trituration of the residue with methanol, followed by washing with methanol and hexane.
Fuerstner described an optimized preparation method, based on the one-step reaction of (PPh3)2Cl2Ru(3-phenylindenylidene) with 3.1 equiva- lents tricyclohexylphosphine (PCy3) in dichloromethane at room temperature for 2 hours in a concentration of c=0.043 mol/l (ref to Fuerstner et al, Chem. Eur. J. 2001. 7, No. 22, 4811-4820). The product is obtained as an orange powder in 80% yield (after evaporation to dryness and trituration and washing with hexane). Since the solvent is stripped off completely be- fore isolation, this method is not suitable for industrial scale manufacturing.
Nolan et al . (Adv. Synth. Catai. 2004. 346, 917-920) described a one-pot, two-step synthesis of (PCy3)2Cl2Ru(3-phenylindenylidene) by reaction of (PPh3)3RuCI2 with l, l-diphenyl-2-propyn-l-ol in refluxing THF, followed by a ligand exchange reaction of the resulting (PPh3)2CI2Ru(3- phenylindenylidene) complex with 2.7 equivalents PCy3 in the same solvent by stirring overnight at room temperature with a concentration of c=0.031 mol/l . The complex is isolated as brick-red solid in 92% yields by evaporating the solvents and suspending the residues in diethylether. Thereafter the
product is filtered and washed frequently with low boiling solvents such as diethylether and pentane to remove impurities. As this procedure is a one- pot, 2-step method, it generally yields a product in lower purity. As the intermediate (PPh3)2CI2Ru(3-phenylindenylidene) is not isolated but directly reacted with tricyclohexylphosphine, the amount of side products is quite high.
Dake et al . (J. Org. Chem., 2008. 73 ( 11), 4131-4138) reported a one-step synthesis of (PCy3)2CI2Ru(3-phenylindenylidene) by reaction of ( PPh3)2CI2Ru(3-phenylindenylidene) with 2.99 equivalents tricyclohexyl- phosphine in dichloromethane at room temperature for 2 hours in a concentration of c=0.022 mol/l . The product is obtained as an orange powder in 66% yield after evaporation to dryness and trituration for 12 hours with hexane. Since the solvent is stripped off completely before isolation, this method is not suitable for industrial scale manufacturing.
WO2010/037550A1 describes a one-pot, two-step synthesis of
(PCy3)2CI2Ru(3-phenylindenylidene) by reaction of (PPh3)3RuCI2 with 1 ,1- diphenyl-2-propyn-l-ol in dioxane at 90°C in presence of an acid. The ligand exchange reaction between the resulting ( PPh3)2CI2Ru(3- phenylindenylidene) complex and 2.33 equivalents PCy3 is carried out with a concentration of c=0.12 mol/l at 90°C for 10 min. The complex is isolated in 90% yield as orange solid by distilling off 60% of the solvent and then by filtration and washing with methanol. This synthesis is a one-pot, 2-step method, which yields a product in lower purity and/or lower crystaliinity. This method is hereinafter cited as "Umicore Standard Method" and will be used for Comparative Experiments.
Afanasiev et al. (EP2280033A1 ) describes a one-pot, two-step synthesis of (PCy3)2CI2Ru(3-phenylindenylidene) by reaction of (PPh3)3RuCI2 with l, l-diphenyl-2-propyn-l-ol in refluxing THF. After removal of 50% of the THF by distillation, the ligand exchange reaction between the resulting ( PPh3)2CI2Ru(3-phenylindenylidene) complex and 3.2 equivalents PCy3 is carried out. Hereby, the mixture is stirred for 8 hours at room temperature with a concentration of c=0.039 mol/l . The complex is isolated in 95% yields by removing the solvent and suspending the residue in acetone at -
40°C for 10 hours, followed by filtration and washing with methanol, acetone and hexane. As with the method of Nolan before, this synthesis is a one-pot, two-step method, generally yielding a product in lower purity and lower crystallinity. The impurities (e.g. diphenylallenylidene species, dimeric compounds, mixed PPh3/PCy3 complexes, phosphine oxides etc) may lead to performance losses of the final catalyst product, such as lower activity, higher catalyst consumption and lower turn-over numbers (TON).
When referring to the one- step methods of preparation (i.e. the methods of Hill, Fuerstner and Dake), the phosphine ligand exchange reac- tion is conducted in chlorinated solvents (typically dichloromethane) at room temperature (i.e. 20 to 25°C). After completion of the reaction, the solvent is evaporated to dryness and the product is washed with big amounts of low boiling solvents in order to wash out the phosphine impurities. In most cases, a high excess of tricyciohexylphosphine (in the range of 2.5 to 3.2 equivalents) is employed. This may lead to phosphine and phosphine oxide residues in the final product. Furthermore, as the currently known procedures do not comprise a specific purification step (other than washing the residual material with solvent) the impurities are not efficiently removed from the final product.
In summary, the currently known preparation methods (either one- step or two-step methods) for the (PCy3)2CI2Ru(3-phenylindenylidene) complex are lengthy, comprise long reaction times, yield a low purity product and are, due to the fact that the solvents are in most cases evaporated to dryness, not applicable to industrial production scale.
It was therefore an objective of the present invention to provide an improved method for preparation of the (PCy3)2CI2Ru(3-phenylindenylidene) complex (Umicore "M l" catalyst). The method should be straightforward and easily scalable; it should yield the M l catalyst in high purity, high crystallinity and good yield, in particular a good space yield (i.e. amount of product per reactor volume). Furthermore, the method should be essentially based on a one-step method and should be applicable to industrial production scale.
This objective is reached by the method of the present invention.
The present invention is directed to a one-step method for preparation of the ruthenium indenylidene catalyst of Formula 1,
Formula 1
said method comprising
reacting (PPh3)2CI2Ru(3-phenylindenylidene) with tricyclohexyl- phosphine (PCy3) in a reaction mixture having a concentration in the range of 0.2 to 0.6 mol catalyst/ 1 in a cyclic ether solvent and precipitating the resulting catalyst of Formula 1 from said reaction mixture during the reaction.
In a specific embodiment of the method, the resulting ruthenium- indenylidene catalyst of Formula 1 may precipitate in a crystalline cyclic ether solvate.
Preferably, it may precipitate as a crystalline cyclic ether solvate comprising > 1 cyclic ether molecules per molecule of catalyst
According to the method of the present invention, the starting complex ( PPh3)2CI2Ru(3-phenylindenylidene) is present in a mixture or solution with a cyclic ether solvent having a concentration in the range of c= 0.2 to 0.6 mol catalyst/I, preferably in the range of c= 0.2 to 0.5 mol Ru- catalyst/l.
The cyclic ether solvent generally is selected from the group consisting of tetrahydrofurane (THF), methyl-tetrahydrofuran, dimethyltetra- hydrofuran and mixtures or combinations thereof.
In a preferred embodiment, the cyclic ether solvent is tetrahydrofurane (THF). In this preferred embodiment, the resulting ruthenium catalyst of Formula 1 is precipitated from the reaction mixture in crystalline form as a tetrahydrofurane (THF) solvate comprising between 1 and 2 molecules of THF per molecule of catalyst. The molecular formula of this Ml catalyst product may then be given as
x n(C4H80) wherein 1 < n <2.
Typically, the tricyclohexylphosphine (PCy3) ligand is added to the reaction mixture in quantities in the range of 2 to 3 equivalents, preferably 2.1 to 2.5 equivalents based on the (PPh3)2CI2Ru(3-phenylindenylidene) starting complex.
The reaction temperature conditions are typically under solvent reflux, thus the boiling point of the cyclic ether solvent is decisive here. Generally the reaction temperature should be in the range of 30 to 100°C. When using THF, the reaction temperature should be in the range of 50 to 80°C (i.e. within the boiling range of THF).
Optionally, the method may further comprise a cooling-down step. To facilitate product precipitation, the reaction mixture may be cooled down to room temperature and below, i.e. to a temperature in the range of -30 to 25°C, preferably to a temperature in the range of 0 to 25°C.
Suitable reaction times are depending on the reaction scale and should be in the range of 0.1 to 3 hours, preferably in the range of 0.5 to 2 hours.
In order to increase the product yield, the cyclic ether solvent may be partially distilled off during the reaction, either under vacuum or under a flow of inert gas.
In a further embodiment, the method comprises steps and measures of separating the catalyst product from the reaction mixture. Such isolation may be performed by filtration, centrifugation, decantation or other similar operations known to the skilled person.
In still further embodiments, the method may comprise additional washing and/or drying steps. Preferably, ketone solvents, such as methyl-
ethyl ketone or acetone are preferably employed for washing. Drying of the catalyst may be performed in box ovens under inert atmosphere or under vacuum conditions at elevated temperatures.
In a further aspect, the present invention is directed to a new crystal- line form of the Umicore M l catalyst.
It has surprisingly been found that by working under the specific concentrated conditions, the M l product precipitates from the reaction mixture as a crystalline material (i.e. in dark red crystals) during the reaction. Experimental data prove that the M l catalyst product obtained according to the method of the present invention crystallizes with THF solvent molecules in the crystal lattice.
Figure 1 shows the ORTEP plot of the single-crystal structure of Ml catalyst (THF-solvate) as determined by X-ray analysis. The crystallized complex comprises two co-crystallized THF molecules. The ellipsoids prob- ability is shown at 50%, H-atoms are omitted. Space group is orthorhombic (Pca2( l)). Cell dimensions and angles: a= 20.520(4), b= 14.543(3), c= 18.761(5); a=90.00°, 6=90.00°, y=90.00°. The product crystallizes in dark red crystals.
A beneficial effect of the product crystallinity of the present invention is the ease with which the crystalline M l material can be handled, filtered and washed. Product washing is necessary to remove PPh3 and other impurities generated in the reaction.
It has been found that the crystalline Ml product may loose some THF during washing, drying and further handling. However, the crystalline product obtainable by the method of the present invention comprises > 1 molecule of cyclic ether per molecule of catalyst (as determined by X-ray analysis and 'H-NMR spectroscopy). Preferably, the crystalline M l product comprises between 1 and 2 molecules of THF per molecule of catalyst (as determined by X-ray analysis and Ή-NMR spectroscopy).
The orange catalyst product which is state of the art (ref to the earlier cited preparation methods) comprises very fine needles. The orange form of the catalyst material produced according to standard methods is
very bulky. In this form, the material is very difficult to filtrate, wash and to handle. The filtration time of the orange version is substantially prolonged, which in turn results in a product of low purity. It is likely that upon precipitation, the impurities are trapped in the orange version due to its flocculent form. The orange catalyst material is also more sensitive to the air oxygen since it has a larger specific surface area. As a consequence, it is much easier oxidized and it likely contains more phosphine oxides impurities unless it is rigorously stored under inert conditions.
According to the known procedures in the art, the desired bis-PCy3 complex may be obtained in acceptable purity only by using a large excess of PCy3 (typically in the range of 3 equivalents) which is not feasible from an industrial point of view due to the high cost of PCy3. Alternatively, the mixture of complexes is isolated and subjected to further treatment with PCy3. This is again not feasible at industrial scale because additional purifi- cation steps are needed.
The inventors have further observed that the known synthesis route A, which is the basis of the method of the present invention, basically yields a product which may contain variable amounts of the side product X ( = Ru complex with mixed substituents comprising a PCy3 and a PPh3 ligand) ac- cording to the following equation 3 :
Equation 3 :
Umicore M1 X
Since the ligand exchange reaction is an equilibrium reaction, the skilled person would expect that a much less cleaner product would be obtained by working under high concentrations: as the reaction proceeds, the
amount of PCy3 diminishes while the amount of liberated PPh3 grows; this leads to a mixture of starting material, product M l and mixed complex X.
To the contrary, the inventors surprisingly found that when working with high concentrations in the range of c = 0.2 to 0.6 mol catalyst/1, the product precipitates simultaneously from the reaction mixture so that it is removed from the reaction equilibrium, which is then shifted to the right side, thus affording the desired catalyst product M l in very good yields and exceptional quality.
The catalyst produced according to the method of the invention is a crystalline material which shows high purity. The high purity is a direct consequence of the crystalline shape of the product.
Typically, the amount of impurity X in the M l product made according to the invention is <3%, preferably < 1% and most preferred <0.5% (based on the total weight of the catalyst product) . The presence of mixed complex X in M l will deteriorate its catalytic activity since it is known that the Ru- indenylidene complex bearing PPh3 groups is not metathesis active. This impurity X can be easily identified by 31P-N MR as it displays two small peaks close to the product peak (when measured in CD2CI2) or only one small peak (when measured in CDCI3) . For quantitative determination of purity, the peak integration method is employed. Based on the impurity data given above, the purity of the Ru- indenylidene catalyst prepared according to the invention is >97%, preferably > 99% and particularly preferred >99.5% (as determined by 31P-N M R spectroscopy) . Figures 2a-c. show the XRD diffractograms of three batches of catalyst Umicore M l made according to the method of the present invention, which, according to Ή-N MR analysis, contain different amounts of THF per mol Ru complex respectively :
Figure 2a shows a XRD plot of M l (red crystalline material, method of this invention, containing 1.54 mol TH F per mol of complex),
Figure 2b shows a XRD plot of M l (red crystalline material, method of this invention, containing 1.4 mol THF per mol of complex),
Figure 2c shows a XRD spectrum of M l (red crystalline material, method of this invention, containing 1.1 mol THF per mol of complex).
Figure 3a shows for comparative reasons a XRD diffractogram of the
M l catalyst made according to Umicore Standard Method (acc to WO2010/037550A1), which does not contain any THF (as confirmed by H NMR). This product exhibited a bulk density of 0.3 g/ml .
Figure 3b shows for comparative reasons a XRD diffractogram of the M l catalyst made according to EP 2280033, Example 9, which contains less than 0.1 mol THF/mol product (as confirmed by 1 NMR). This product exhibited a bulk density of 0.25 g/ml .
The detailed conditions for XRD measurements are given in the Examples section .
In general, the intensities of the peaks and the position of the peaks at various diffraction angles (20°) may slightly vary depending on the sample preparation, on the measurement conditions as well as on the THF content. The uncertainty in the peak position is +/- 0.05° 20.
As a summary, from the analysis of the XRD diffractograms shown in Figures 2a-d vis-a-vis 3a and 3b. it is clearly evident that the M l product made according to the method of the present invention displays a higher crystallinity and furthermore has a different constitution compared to the material available according to the prior art. The Umicore M l obtained by the method of the present invention reveals characteristic peaks at various diffraction angles (20° values) as listed in Table 1. In this table, relative peak intensities are also listed. Moreover, it can be seen from the amorphous halo of the diffractograms in Fig. 3a and 3b that the cristallinity of these compounds according to the prior art is lower than the cristallinity of the compounds obtained according to the subject patent application. Fur- thermore, the reflexes in 3a and 3b and their pattern are different from Fig- 2a-d.
In addition, a powder diffractogram was simulated (software X'Pert HighScore Plus of PANalytical ) based on the crystal data of the single crystal analysis of the THF-solvate. It has been found that the simulated diffractogram is directly comparable to that one obtained experimentally with the material produced according to the present invention . The simulation confirms that Umicore M l made according to the method of the present invention contains TH F molecules in the crystal .
Peak analysis of XRD diffractogram of Umicore M l catalyst (made according to the method of the invention)
Peak No. diffraction angle (20°) rel . intensity*'' a about 7.3 s
b about 8.7 s
c about 9.8 m
d about 11.8 s
e about 14.2 m
f about 14.6 m
g about 17.3 m
h about 17.9 w
i about 18.8 m
j about 20.3 m
* ) relative peak intensities : s = strong ; m = medium ; w = weak
In Figure 4, SEM pictures of two different batches of catalyst Umi- core M l are shown .
Figure 4a shows M l (red crystalline material, THF solvate, method of this invention).
Figure 4b shows M l (orange material, Umicore Standard method) .
By these figure, the highly crystalline nature of the catalyst M l made according to the method of the present invention is clearly demonstrated .
In summary, due to the preparation method of the present invention, the resulting Ru-indenylidene catalyst M l reveals high product purity, in particular high crystal I in ity. As easily scaleable precipitation processes are employed, this preparation method is applicable to industrial production scale.
The Umicore M l catalyst of the present invention is useful in a variety of olefin metathesis reactions such as ring-closing metathesis ( RCM ), ring- opening metathesis polymerization (ROM P) and cross metathesis (CM ) . Furthermore, it is a valuable precursor for the synthesis of other, further modified ruthenium carbene catalysts.
The present invention is directed to a method for the preparation of ruthenium catalyst (PCy3)2CI2Ru(phenylindenylidene) (Umicore catalyst "M l") . The method comprises a one-step reaction reacting the precursor compound ( PPh3)2CI2Ru(3-phenylindenylidene) with PCy3 in a cyclic ether solvent (preferably TH F) in concentrations in the range of 0.2 to 0.6 mol catalyst/1 while simultaneously precipitating the product from the reaction mixture. A cyclic ether solvate product with high crystallinity and high purity is obtained.
The present invention is further directed to a crystalline modification of ruthenium catalyst Umicore M l ( PCy3)2CI2Ru( phenyl indenylidene) comprising between 1 and 2 molecules of THF per molecule of catalyst and having the molecular formula C51H76CI2P2 U x n(C4H80) wherein 1 < n <2. The invention is further described in the following examples without restricting its scope of protection .
EXAM PLES
Generally, in the Examples glass reactors or flasks with condenser and stirrer are used for the method of the present invention. The reactors are flushed with dry inert gas (argon, nitrogen) prior to use.
The NMR spectra are recorded on a BRUKER DRX 500 NMR spec- trometer at about 25°C. The chemical shifts are determined relative to external phosphoric acid (31P-NMR) or to residual solvent signal ('H-NMR).
The XRD diffractograms were recorded in the range 5°< 20 < 100° on a PANalytical X'Pert Pro with X-Celerator detector using Cu radiation. The sample material was prepared into a 27 mm PAN analytical sample holder (single preparation).
The XRD data were recorded under the following conditions:
The uncertainty in the peak position is +/- 0.05° 20.
EXAMPLE 1 Preparation of starting complex iPPh ½a?Rui3-phenvlindenvlidene) according to prior art ( ref to H .-J . Schanz et al.. cited above)
A one liter glass reactor with condenser and stirrer is filled with argon and thereafter with 800 ml of THF. The solvent is warmed up to 50°C. Then 19.7 g (98.6% purity, 93.2 mmol, 1.15 eq. ) of l, l-diphenyl-2-propyn-l-ol, 2.91 ml (40.5 mmol, 0,5 eq. ; GFS Chemicals Inc., Powell, OH, USA) of ace- tylchloride and 99.6 g (81 mmol, 1 eq.) of Ru(PPh3)3 4CI2 (Ru-content 8.22 wt. %; Umicore AG & Co. KG, Hanau) are added successively during stirring. The reaction mixture is stirred under reflux (65°C) for 90 min . Then it is cooled down to 50°C and 700 ml of THF solvent are distilled off under vacuum. The red -brown suspension is cooled down to room temperature and isopropanol (600 ml) is added under stirring. The resulting precipitate is filtered off, washed with isopropanol and petroleum ether and then dried under vacuum at 40°C.
Yield : 85 % (based on Ru-content).
31P- MR (C6D6) : δ = 27.8 ppm (s)
EXAMPLE 2
Preparation of dichloro(3-Dhenyl-lH-inden-l-ylidene^bis-ftricvclohexyl- phosphine)rutheniumfII) (according to the invention : c = 0.5 mol/H
Equation IV:
A one liter glass reactor with condenser and stirrer is filled with argon and thereafter with 500 ml of THF. The solvent is warmed up to 40°C. Then 221.7 g (250 mmol, 1 eq. ) of (PPh3)2CI2Ru(3-phenylindenylidene) (Umicore AG & Co. KG, Hanau) and 155 g (98.1% purity, 540 mmol, 2.16 eq. ) of tricyclohexylphosphine (PCy3, Aldrich) are added successively with stirring. The reaction mixture is stirred under reflux (65°C) for 1 h during which time the product precipitates in form of dark red crystals. The reaction mixture is
cooled down to 5 °C. The crystalline precipitate is filtered off, washed with 400 ml of acetone and then dried under vacuum at 80°C. Yield : 236 g, 88% (based on Ru-content 9.41 wt.-%).
31P- MR (CD2CI2) : 6 (ppm)= 32.0 (s, product), 31.28 and 31.18 (side prod- uct). Purity based on 31P-NMR: >99%.
1H-NMR (CD2CI2) : 6 (ppm)= 8.66 (d, product, 1 H), 7.96 (d, side product, <0.01H), 7.75 (m, product, 2H), 7.7 (m, side product, <0.02H), 7.52 (m, product, 1 H), 7.40 (ms, product, 3H), 7.28 (m, product, 2H), 7.05 (td, side product, <0.01H), 7.016 (s, side product, <0.01H), 3.68 (m, THF, 6.4H), 2.60 (m, product, 6H), 1.9-1 (ms, product, 27H), 1.82 (m, THF, 6.4H). Other signals of the side product are covered by the signals of the product. THF-content based on 1H-NMR= 1.6 mol THF/mol product (~11 wt.-%). Side-product content based on 1H-NMR = <0.01 mol (< 1 wt.-%).
Bulk density: 0,45 g/ml
Space yield : 236 g/l
EXAMPLE 3
Preparation of dichloro(3-phenvl-lH-inden-l-vlideneVbis-(tricvclohexvl- phosphinelrutheniumiin (according to the invention : c = 0.2 mol/h
A one liter glass reactor with condenser and stirrer is filled with argon and thereafter with 600 ml of THF. Then 106.4 g ( 120 mmol, 1 eq.) of ( PPh3)2C Ru(3-phenylindenylidene) (Umicore AG & Co. KG, Hanau) and 74 g (98.1% purity, 258 mmol, 2.15 eq. ) of tricyclohexylphosphine, PCy3 are added successively with stirring. The reaction mixture is stirred under reflux (65°C) for 0.5 hour. Then it is cooled down to 40° C and 250 ml of THF solvent are distilled off causing the precipitation of the product in form of dark red crystals. Alternatively the solvent may be removed by a stream of inert gas during the reaction. The resulting red suspension is cooled down to 5°C and acetone (500 ml) is added under stirring. The crystalline precipitate is filtered off, washed with acetone and then dried under vacuum at 80°C. Yield : 108 g, 85% (based on Ru-content, 9.54 wt.-%).
Purity (31P-NMR) : >99%. The analytical data of the product are comparable to those of Example 2.
Space yield : 108g/l COMPARATIVE EXAMPLE 4
Preparation of dichloro(3-phenvl-l H-inden-l-vlideneVbis-(tricvclohexvl- phosphine)ruthenium(Ii) (according to EP 2280033, Example 9)
A 500ml Schlenk flask was purged with argon for 15 minutes. 5.21 mmol (5.0g) RuCI2( PPh3)3 and 8.49mmol (1.79g) l,l-diphenyl-2-propin-l-ol were placed into the flask. 267ml absolute tetrahydrofurane were added and the reaction mixture was stirred at reflux for 3 hours. The mixture was evaporated by 50% in vacuum and 16.67mmol (4.76g) tricyclohexylphosphine were added. The suspension was stirred for 8 hours at room temperature under argon. Then the solvent was removed in vacuum. The oily residue was added with 135ml of acetone. The mixture was stored for 10 hours at - 20°C. The residue was filtered by suction filtration (nutsche filter, porosity D4). The solid was washed with methanol, acetone and hexane. The product was dried in vacuum at room temperature. The product was obtained as brick-red powder, 4.63g (5.02mmol, 87% yield on metal base).
Analysis
Bulk density : 0.25 g/ml
Space yield : about 14 g/L
Purity (31P NMR) : about 80%.
THF-content (based on Ή NMR. CDZCI2. 20°O : < 0.1 mol THF/mol product ( <0.5 wt.-%).
31 P and 1H-NMR data shows the presence of several side products: di- phenylallenylidene complex (6 -41 ppm in 31 P NMR) and phosphine oxides.
Claims
1. A method for preparation of the ruthenium-indenylidene carbene
catalyst of Formula 1,
Formula 1 said method comprising
reacting (PPh3)2CI2 u(3-phenylindenylidene) with tricyclohexyl- phosphine (PCy3) in a reaction mixture having a concentration in the range of 0.2 to 0.6 mol Ru-catalyst/l in a cyclic ether solvent and
precipitating the resulting catalyst of Formula 1 during the reaction.
2. The method according to claim 1, wherein the catalyst of Formula 1 precipitates in the form of a crystalline cyclic ether solvate.
3. The method according to claim 2, wherein the cyclic ether solvate comprises > 1 molecule of cyclic ether per molecule of catalyst.
4. The method according to any one of claims 1 to 3, wherein the cyclic ether solvent is selected from THF, methyl-THF, dimethyl-THF or mixtures thereof.
5. The method according to any one of claims 1 to 4, wherein the cyclic ether solvent is THF.
6. The method according to any one of claims 1 to 5, wherein the reaction temperature is in the range of 30 to 100°C, preferably in the range of 50 to 80°C.
7. The method according to any of claims 1 to 6, wherein the PCy3 is present in the range of 2 to 3 equivalents, preferably in the range of 2.1 to 2.5 equivalents.
8. The method according to any of claims 1 to 7, wherein the cyclic
ether solvent may be partially distilled off during the reaction.
9. The method according to any one of claims 1 to 8, further comprising a cooling step, wherein the reaction mixture is cooled down to a temperature in the range of -30 to 25°C, preferably in the range of
0 to 25°C.
10. The method according to any one of claims 1 to 9, wherein the
reaction time is in the range of 0.1 to 3 hours, preferably in the range of 0.5 to 2 hours.
11. The method according to any one of claims 1 to 10, further
comprising steps of separating the resulting ruthenium-indenylidene catalyst from the reaction mixture.
12. The method according to any one of claims 1 to 10, further
comprising steps for washing and drying the resulting ruthenium- indenylidene catalyst.
13. Ruthenium-indenylidene carbene catalyst obtainable by the method according to any one of claims 1 to 12, having a purity of >97%, preferably >99 % and particularly preferred >99.5 % (as determined by 31P- MR spectroscopy).
14. Ruthenium-indenylidene carbene catalyst obtainable by the method according to any one of claims 1 to 12, being present in a crystalline cyclic ether solvate form, comprising > 1 molecule of cyclic ether per molecule of catalyst (as determined by ^- MR and X-ray analysis).
15. Ruthenium-indenylidene carbene catalyst obtainable by the method according to claim 5, being present in a crystalline THF solvate form, comprising between 1 and 2 molecules of THF per molecule of catalyst (as determined by JH-NMR and X-ray analysis).
16. Ruthenium-indenylidene carbene catalyst of Formula 1,
Formula 1 being present in a crystalline THF solvate form and showing peaks at diffraction angles (20°) in XRD powder diffractometry (Cu-X-ray tube, tube excitation 40kV, 40mA) as listed in the following table:
Peak No. diffraction angle (20°) a about 7.3
b about 8.7
c about 9.8
d about 11.8
e about 14.2
f about 14.6
g about 17.3
h about 17.9
i about 18.8
j about 20.3
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EP13731747.5A EP2864341B1 (en) | 2012-06-26 | 2013-06-25 | Method for preparation of a ruthenium indenylidene complex |
PL13731747T PL2864341T3 (en) | 2012-06-26 | 2013-06-25 | Method for preparation of a ruthenium indenylidene complex |
CN201380033705.7A CN104411711B (en) | 2012-06-26 | 2013-06-25 | Method for preparing ruthenium sub-indenyl complex compound |
JP2015519040A JP6475161B2 (en) | 2012-06-26 | 2013-06-25 | Process for preparing ruthenium indenylidene complexes |
US14/410,160 US9339804B2 (en) | 2012-06-26 | 2013-06-25 | Method for preparation of a ruthenium indenylidene complex |
US15/131,308 US9604205B2 (en) | 2012-06-26 | 2016-04-18 | Method for preparation of a ruthenium indenylidene complex |
US15/335,493 US20170043332A1 (en) | 2012-06-26 | 2016-10-27 | Method for Preparation of a Ruthenium Indenylidene Complex |
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WO2017087710A2 (en) | 2015-11-18 | 2017-05-26 | Provivi, Inc. | Production of fatty olefin derivatives via olefin metathesis |
WO2017087846A1 (en) | 2015-11-18 | 2017-05-26 | Provivi, Inc. | Microorganisms for the production of insect pheromones and related compounds |
WO2018213554A1 (en) | 2017-05-17 | 2018-11-22 | Provivi, Inc. | Microorganisms for the production of insect pheromones and related compounds |
US11214818B2 (en) | 2016-06-06 | 2022-01-04 | Provivi, Inc. | Semi-biosynthetic production of fatty alcohols and fatty aldehydes |
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EP2280033A1 (en) | 2008-05-22 | 2011-02-02 | Limited Liability Company "United Research and Development Centre" | Dicyclopentadiene metathesis polymerisation catalyst |
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DE60134196D1 (en) * | 2000-02-10 | 2008-07-10 | Mitsui Chemicals Inc | METHOD FOR THE SELECTIVE PREPARATION OF A 1-PHOSPHORYLATED SUGAR DERIVATIVE ANOMER AND METHOD FOR THE PRODUCTION OF NUCLEOSIDES |
JP2002338587A (en) * | 2001-05-21 | 2002-11-27 | Hokko Chem Ind Co Ltd | Method for producing phosphonium salt containing carboxy group |
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WO2017087846A1 (en) | 2015-11-18 | 2017-05-26 | Provivi, Inc. | Microorganisms for the production of insect pheromones and related compounds |
US10308962B1 (en) | 2015-11-18 | 2019-06-04 | Provivi, Inc. | Microorganisms for the production of insect pheromones and related compounds |
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US11109596B2 (en) | 2015-11-18 | 2021-09-07 | Provivi, Inc. | Microorganisms for the production of insect pheromones and related compounds |
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WO2018213554A1 (en) | 2017-05-17 | 2018-11-22 | Provivi, Inc. | Microorganisms for the production of insect pheromones and related compounds |
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US11866760B2 (en) | 2017-05-17 | 2024-01-09 | Provivi, Inc. | Microorganisms for the production of insect pheromones and related compounds |
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US20150190795A1 (en) | 2015-07-09 |
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