WO2012168183A1 - New complexes of ruthenium, method for their preparation, and their application in olefin metathesis reactions - Google Patents

New complexes of ruthenium, method for their preparation, and their application in olefin metathesis reactions Download PDF

Info

Publication number
WO2012168183A1
WO2012168183A1 PCT/EP2012/060498 EP2012060498W WO2012168183A1 WO 2012168183 A1 WO2012168183 A1 WO 2012168183A1 EP 2012060498 W EP2012060498 W EP 2012060498W WO 2012168183 A1 WO2012168183 A1 WO 2012168183A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
denotes
aryl
independently
atom
Prior art date
Application number
PCT/EP2012/060498
Other languages
French (fr)
Inventor
Karol Grela
Michal Barbasiewicz
Michal MICHALAK
Original Assignee
Umicore Ag & Co. Kg
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Umicore Ag & Co. Kg filed Critical Umicore Ag & Co. Kg
Priority to BR112013031131A priority Critical patent/BR112013031131A2/en
Priority to CN201280027153.4A priority patent/CN103648644B/en
Priority to EP12725437.3A priority patent/EP2718016B1/en
Priority to JP2014514017A priority patent/JP6198723B2/en
Priority to US14/116,378 priority patent/US9074028B2/en
Priority to PL12725437T priority patent/PL2718016T3/en
Publication of WO2012168183A1 publication Critical patent/WO2012168183A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F132/08—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
    • 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)
    • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
    • C07C329/02—Monothiocarbonic acids; Derivatives thereof
    • C07C329/04—Esters of monothiocarbonic acids
    • C07C329/06—Esters of monothiocarbonic acids having sulfur atoms of thiocarbonic groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/70—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/28—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/20—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hydrogen atoms and substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D309/22—Radicals substituted by oxygen atoms
    • 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
    • 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 invention concerns new ruthenium complexes which act as (pre) catalysts, a method for their preparation, and their application in olefin metathesis reactions.
  • This invention is used in organic synthesis in a broad sense.
  • Catalysts 2, 3, and 4 contain an isopropoxyl group which chelates an atom of the metal.
  • the higher activity of arrangements 3 and 4 is explained by the spatial hindrance introduced by the adjacency of the phenyl group or (substituted) naphthyl group in the ortho position in relation to the isopropoxyl group (see Angew. Chemie Int. Ed. 2002, 114, 832-834; Angew. Chemie Int. Ed. 2002, 114, 2509-2511) .
  • Formula 1 which contain a chelate ring created by a halogen atom are thermally stable and display good catalytic activity.
  • these compounds display significant changes in activity as a function of temperature, which may be applied to control catalytic processes by changing the temperature of a reaction mixture.
  • Known catalytic arrangements have not shown significant changes in catalytic activity as a function of temperature.
  • L 1 denotes an inert ligand
  • Z 1 and Z 2 denote, independently, an anion ligand
  • X denotes a halogen atom
  • R 1 denotes an atom of hydrogen, a halogen atom, C 1 -C 1 2 alkyl, C3-C 1 2 cycloalkyl, C2-C 1 2 alkenyl, C3-C 1 2 cycloalkenyl C2-C 1 2 alkynyl, C3-C 1 2 cycloalkynyl , C 1 -C 1 2 alkoxyl, C5-C20 aryl, C5-C20 heteroaryl, or 3-12-membered heterocycle ;
  • A denotes a bivalent radical selected from a group comprising C 1 -C 1 2 alkylene, C2-C 1 2 alkenylene, C2-C 1 2 alkynylene, C5-C20 arylene, or C5-C20 heteroarylene, in which the C 1 -C 1 2 alkylene, the C2-C 1 2 alkenylene, the C2- C12 alkynylene, the C5-C20 arylene, and the C5-C20 heteroarylene may be optionally substituted with at least one functional group R 2 ;
  • R 2 groups with adjacent atoms may bond together, creating C5-C2 0 aryl or 3-12-membered heterocycle;
  • R 2 groups with adjacent atoms may bond with the R 1 group, creating C5-C2 0 aryl, indenylene, heteroindenylene, 3-12-membered heterocycle, and polycyclic or heteropolycyclic arrangements, whilst the C5-C2 0 aryl, indenylene, heteroindenylene, 3-12-membered heterocycle, and polycyclic or heteropolycyclic arrangements may be substituted with at least one functional group selected from the group comprising a halogen atom, C 1 -C 1 2 alkyl, C2-C 1 2 alkenyl, C2-C 1 2 alkynyl, -OR 3 , -SR 3 , -S(0) m R 3 , -S0 2 NR 3 R 4 , -S(0) 2 OR 3 , -N0 2 , -NO, - SCN, -NR 3 R 4 , -CN, -C(0)R 3 , -0C(0)R 3 , - -
  • each functional group R 3 , R 4 , R 5 , and R 6 denotes, independently, an atom of hydrogen, a halogen atom, Ci- C 1 2 alkyl, C 2 -Ci 2 alkenyl, C 2 -Ci 2 alkynyl, C3-C 1 2 cycloalkyl, C5-C2 0 aryl, 5-12-membered heterocycle; each m denotes, independently, 0, 1, or 2 ;
  • each n denotes, independently, 0, 1, 2, 3, or 4 ;
  • each p denotes, independently, 1 or 2.
  • R in formula 1 denotes an atom of hydrogen
  • the inert ligand L 1 is selected from a group comprising -P(R 7 )3, -P(OR 7 )3, or an N-heterocyclic carbene ligand with formula 7a, 7b, 7c, 7d, 7e, 7f, 7g, 7h, 7i, 7j , 7k, 71, 7m, 7n, 7o, or 7p:
  • each R 7 denotes, independently, C 1 -C 1 2 alkyl, C3-C 1 2 cycloalkyl, C5-C2 0 aryl, or 5-12-membered heteroaryl; each R 8 , R 9 , R 10 , R 11 , and R 12 denote, independently, an atom of hydrogen, C 1 -C 1 2 alkyl, C3-C 1 2 cycloalkyl, C2-C 1 2 alkenyl, or C5-C2 0 aryl, which may be optionally substituted with at least one C 1 -C 1 2 alkyl, C 1 -C 1 2 perhalogenalkyl, C 1 -C 1 2 alkoxyl, or a halogen atom;
  • R 8 , R 9 , R 10 , R 11 , and R 12 may optionally bond with each other and
  • X 1 and X 2 denote, independently, a halogen atom.
  • the carbene ligands may be coordinated classically, as in structures 7a-7h, or non-classically ('abnormal carbenes ' , see Chem. Rev. 2009, 109, 3445), as in structures 7i-7p.
  • anion ligands Z 1 and Z 2 in formula 1 denote an atom of chlorine
  • X denotes an atom of bromine or iodine
  • A denotes 1 , 2-phenylene, 1 , 2-naphthylene, 2,3- naphthylene or 1 , 8-naphthylene, which may be substituted with at least one functional group selected from a group comprising -NO2, - Me2," and
  • the inert ligand L 1 denotes a ligand with formula 7a or 7b;
  • Formula 7a Formula 7b in which the functional groups R , R , R , and R may have the meaning described above.
  • the anion ligands Z 1 and Z 2 in formula 1 denote an atom of chlorine; and X denotes an atom of bromine or iodine; and A denotes 1 , 2-phenylene, 1 , 2-naphthylene, 2,3- naphthylene or 1 , 8-naphthylene, which may be substituted with at least one functional group selected from a group comprising -OMe, Me and the inert ligand L 1 denotes a ligand with formula 7a or 7b as listed above.
  • An object of the invention is also to provide a method of preparing ruthenium complexes with formula 1, which comprises the reaction of the compound of formula 9
  • R and R denote, independently, an atom of hydrogen or the alkyl group C 1 -C 1 2;
  • R 1 denotes hydrogen, a halogen atom, C 1 -C 1 2 alkyl, C3-C 1 2 cycloalkyl, C2-C 1 2 alkenyl, C3-C 1 2 cycloalkenyl , C2-C 1 2 alkynyl, C3-C 1 2 cycloalkynyl , C 1 -C 1 2 alkoxyl, C5-C20 aryl, C5-C2 0 heteroaryl, or 3-12-membered heterocycle;
  • X denotes a halogen atom
  • A denotes a bivalent radical selected from a group comprising C 1 -C 1 2 alkylene, C2-C 1 2 alkenylene, C2-C 1 2 alkynylene, C5-C20 arylene, or C5-C20 heteroarylene, in which the C 1 -C 1 2 alkylene, the C2-C 1 2 alkenylene, the C2- C12 alkynylene, the C5-C20 arylene, and the C5-C20 heteroarylene may be optionally substituted with at least one functional group R 2 ;
  • R 2 groups with adjacent atoms may bond together, creating C5-C2 0 aryl or 3-12-membered heterocycle;
  • R 2 groups with adjacent atoms may bond with the R 1 group, creating C5-C2 0 aryl, indenylene, heteroindenylene, 3-12-membered heterocycle, and polycyclic or heteropolycyclic arrangements, whilst the C5-C2 0 aryl, indenylene, heteroindenylene, 3-12-membered heterocycle, and polycyclic or heteropolycyclic arrangements may be substituted with at least one functional group selected from the group comprising a halogen atom, C 1 -C 1 2 alkyl, C2-C 1 2 alkenyl, C2-C 1 2 alkynyl, -OR 3 , -SR 3 , -S(0) m R 3 , -S0 2 NR 3 R 4 , -S(0) 2 OR 3 , -N0 2 , -NO, - SCN, -NR 3 R 4 , -CN, -C(0)R 3 , -0C(0)R 3 , - -
  • each functional group R 3 , R 4 , R 5 , and R 6 denotes, independently, an atom of hydrogen, a halogen atom, Ci- Ci2 alkyl, C 2 ⁇ C 12 alkenyl, C 2 ⁇ C 12 alkynyl, C 3 cycloalkyl, C5-C2 0 aryl, 5-12-membered heterocycle;
  • each m denotes, independently, 0, 1, or 2 ;
  • each n denotes, independently, 0, 1, 2, 3, or 4 ;
  • each p denotes, independently, 1 or 2 ; with a ruthenium carbene complex of formula 11a, 11c, or lid:
  • L 1 , L 2 , and L 3 denote, independently, an inert ligand
  • Z 1 and Z 2 denote, independently, an anion ligand
  • R 16 has the same meaning as R 1 in formula 9;
  • R 17 denotes an atom of hydrogen, C5-C20 aryl, C5-C20 heteroaryl, vinyl, or allenyl.
  • the reaction between the compound of formula 9 and the ruthenium complex of formula 11a, lib, 11c, or lid is carried out in the presence of anhydrous halogen salts of copper (I) such as CuCl or CuBr, or in the presence of Br0nsted acids such as H 2 SO 4 , HC1, HNO 3 , H 3 PO 4 , sulphonated polymers (Nafion-H) , or other acids bonded with a fixed substrate, in a solvent .
  • anhydrous halogen salts of copper (I) such as CuCl or CuBr
  • Br0nsted acids such as H 2 SO 4 , HC1, HNO 3 , H 3 PO 4
  • sulphonated polymers Nafion-H
  • the reaction is carried out at a temperature in the range of 0-120°C.
  • reaction is carried out in a chlorinated solvent or in aromatic hydrocarbons or in protic or aprotic solvents such as alcohol or ketone or in mixtures thereof.
  • the reaction is carried out in a solvent such as methylene chloride and/or toluene.
  • a solvent such as methylene chloride and/or toluene.
  • the invention also concerns the application and use of the ruthenium complexes defined in formula 1 as (pre) catalysts in metathesis reactions.
  • ruthenium complexes with formula 1 are used as (pre) catalysts in ring-opening metathesis reactions, homometathesis , cross-metathesis, alkene- alkyne (ene-yne) type metathesis, ring-closing metathesis and ROMP-type polymerisation reactions.
  • halogen atom denotes an element selected from F, CI, Br, and I.
  • carbene denotes a molecule containing an inert atom of carbon with a valence number of two and two unpaired valence electrons.
  • carbene also denotes carbene analogues in which the carbon atom is replaced with another chemical element such as boron, silicon, germanium, tin, lead, nitrogen, phosphorus, sulphur, selenium, and tellurium.
  • alkyl relates to a saturated, linear, or branched functional hydrocarbon group with an indicated number of atoms of carbon.
  • alkyl functional group examples include -methyl, -ethyl, -n-propyl, -n- butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n- nonyl, and -n-decyl .
  • Representative branched - (Ci-Cio) alkyls include -iso-propyl, -sec-butyl, -iso-butyl, tert-butyl, -iso-pentyl, -neopentyl, -1-methylbutyl,
  • alkoxyl refers to an alkyl functional group as defined above connected using an oxygen atom.
  • perfluoroalkyl denotes an alkyl group as defined above in which all atoms of hydrogen are replaced with the same or different halogen atoms.
  • cycloalkyl refers to a saturated monocyclic or polycyclic functional hydrocarbon group with an indicated number of carbon atoms.
  • a cycloalkyl functional group are -cyclopropyl , cyclobutyl, -cyclopentyl , -cyclohexyl, -cycloheptyl , cyclooctyl, -cyclononyl, -cyclodecyl, and similar.
  • alkenyl refers to a saturated, linear, or branched non-cyclic functional hydrocarbon group with an indicated number of atoms of carbon and containing at least one double carbon-carbon bond.
  • alkenyl functional group are -vinyl, -allyl, 1-butenyl -2-butenyl, -iso-butylenyl , -1-pentenyl, -2-pentenyl, - 3-methyl-l-butenyl, -2-methyl-2-butenyl, -2 , 3-dimethyl- 2-butenyl, -1-hexenyl, -2-hexenyl, -3-hexenyl, -1- heptenyl, -2-heptenyl, -3-heptenyl, -1-octenyl, -2- octenyl, -3-octenyl, -1-nonenyl, -2-nonenyl, -3- non- non
  • cycloalkenyl refers to a saturated monocyclic or polycyclic functional hydrocarbon group with an indicated number of atoms of carbon and containing at least one double carbon-carbon bond.
  • Examples of the cycloalkenyl functional group are cyclopentenyl , -cyclopentadienyl , -cyclohexenyl , cyclohexadienyl , -cycloheptenyl , -cycloheptadienyl , cycloheptatrienyl , -cyclooctenyl , -cyclooctadienyl , cyclooctatrienyl , -cyclooctatetraenyl, -cyclononenyl , - cyclononadienyl , -cyclodecenyl , -cyclodecadienyl , and similar .
  • alkynyl refers to a saturated, linear, or branched non-cyclic functional hydrocarbon group with an indicated number of atoms of carbon and containing at least one triple carbon-carbon bond.
  • alkynyl functional group examples include -acetylenyl, -propynyl, 1-butynyl, -2-butynyl, -1-pentynyl, -2-pentynyl, -3- methyl- 1-butynyl, -4- pentynyl, -1-hexynyl, -2-hexynyl, -5-hexynyl, and similar.
  • cycloalkynyl refers to a saturated monocyclic or polycyclic functional hydrocarbon group with an indicated number of atoms of carbon and containing at least one triple carbon-carbon bond.
  • Examples of a cycloalkynyl functional group are cyclohexynyl , -cycloheptynyl , -cyclooctynyl , and similar .
  • aryl refers to an aromatic monocyclic or polycyclic functional hydrocarbon group with an indicated number of atoms of carbons.
  • Examples of an aryl functional group are -phenyl, -tolyl, -xylyl, naphthyl, and similar.
  • heteroaryl refers to an aromatic monocyclic or polycyclic functional hydrocarbon group with an indicated number of atoms of carbon with at least one atom of carbon replaced with a heteroatom selected from 0, N, and S.
  • a heteroaryl functional group are -furyl, -thienyl, -imidazolyl, oxazolyl, -thiazolyl, -isoxazolyl, -triazolyl, oxadiazolyl, -thiadiazolyl , -tetrazolyl, -pirydyl, pyrimidyl, -triazynyl, -indolyl, -benzo [b] furyl, benzo [b] thienyl, -indazolyl, -benzoimidazolyl , azaindolyl, -chinolyl, -isochinolyl , -carbazolyl, and similar .
  • heterocycle refers to a saturated or partly saturated monocyclic or polycyclic functional hydrocarbon group, with an indicated number of atoms with at least one atom of carbon replaced with a heteroatom selected from 0, N, and S.
  • a heterocyclic functional group are -furyl, -thiophenyl, -pyrrolyl, -oxazolyl, -imidazolyl, -thiazolyl, isoxazolyl, -pyrazolyl, -isothiazolyl , -triazynyl, pyrrolidinolyl , -pyrrolidinyl , -hydrantoinyl , oxyranil, -oxetanyl, -tetrahydrofuranyl , tetrahydrothiophenyl, -quinolinyl, -isoquinolinyl , chromonyl, -coumarinyl, -indolyl, -indolizin
  • inert ligand refers to a functional group without a charge capable of coordinating with the metallic centre (the ruthenium atom) .
  • examples of such ligands are: amines, phosphines and oxides thereof, aryl and alkyl phosphoranes and phosphorines , arsines and oxides thereof, ethers, aryl and alkyl sulphides, coordinated hydrocarbons, and aryl and alkyl halides.
  • indenylene refers to an unsaturated functional hydrocarbon with an indene skeleton (benzocyclopentadiene) .
  • heteroindenylene refers to an indenylene functional group, defined above, in which at least one atom of carbon has been replaced with a heteroatom from a group comprising: nitrogen, oxygen, and sulphur.
  • anion ligand refers to a functional group capable of coordination with the metallic centre (the ruthenium atom) with a charge capable of partial or full compensation of the metallic centre charge.
  • ligands may be: fluoride, chloride, bromide, iodide, cyanide, cyanate, and thiocyanate, carboxylic acid anions, alcohol anions, phenol anions, thiol and thiophenol anions, hydrocarbon anions with a delocalised charge (e.g. cyclopentadiene) ,
  • An anion ligand may have a group L 1 , L 2 , or L 3 linked like a catechol anion, an acetylacetone anion, or a salicylic aldehyde anion.
  • Anion ligands (Z 1 and Z 2 ) and inert ligands (L 1 , L 2 , and L 3 ) may be linked with each other, creating polydentate ligands, e.g.: the bidentate ligand (Z 1 , Z 2 ) , the tridentate ligand (Z 1 , Z 2 , L 1 ) , the tetradentate ligand (Z 1 , Z , L , I ), the bidentate ligand (Z 1 , L ) , the tridentate ligand (Z 1 , L 1 , L 2 ) , the tetradentate ligand (Z 1 , L 1 , L 2 , L 3 ) , the bidentate ligand (L 1 , L 2 ) , and the tridentate ligand (L 1 , L 2 , L 3 ) .
  • Examples of such ligands are: catechol anion, acetylacetone
  • the olefination reaction of substituted aromatic and heteroaromatic halogen aldehyde derivatives with formula 8, where R 1 has the meaning given above, is advantageously carried out in accordance with Tebbe ' s method with Tebbe ' s titanium reagent or in accordance with Wittig's method with Wittig's reagent, or in accordance with Peterson's method.
  • the reaction is carried out in solvents such as alcohol and glycol ethers or cyclic ethers, advantageously THF, aromatic and aliphatic hydrocarbons, and mixtures of all of the above.
  • Compounds with the general formula 9 are also beneficially obtained from the protected aldehyde 10 without generation and purification of the halogen aldehyde with the general formula 8 (Diagram I, experimental data Examples I-III).
  • the complex with formula 1 is obtained as presented in Diagram II (for experimental data, see Examples IV-XI) in a reaction between the substituted compound with formula 9 and the ruthenium complex 11a, lib, 11c, or lid, where the functional group has the meaning given above, possibly in the presence of an anhydrous halogen salt of copper (I), such as CuCl or CuBr.
  • the reaction is carried out advantageously in chlorinated solvents, e.g. methylene chloride, or in aromatic hydrocarbons, or in mixtures thereof, over 1-24 hours at a temperature of 0-120°C.
  • protic and aprotic solvents may be used, such as alcohols or ketones.
  • the reaction may be carried out also in the presence of Br0nsted acids such as H 2 S0 4 , HC1, HN0 3 , H 3 P0 4 , sulphonated polymers (Nafion-H) , or other acids bonded with a fixed substrate, in the solvent described above.
  • Br0nsted acids such as H 2 S0 4 , HC1, HN0 3 , H 3 P0 4 , sulphonated polymers (Nafion-H) , or other acids bonded with a fixed substrate, in the solvent described above.
  • reaction mixture is diluted with cyclohexane (30 ml) , the sediment is filtered off, and the solvent is evaporated at reduced pressure.
  • Formula 24 Formula 25 l-Iodo-2- (prop-l-enyl) naphthalene .
  • ketal with formula 24 (4.63 g, 14.3 mmol) in a mixture of 1,4-dioxane (40 ml) and water (5 ml)
  • p- toluenesulfonic acid (1.36 g, 7.15 mmol) is added and mixed for 16 hours at room temperature. Then, the reaction mixture is diluted with water (100 ml) and a saturated hydrous solution K 2 CO 3 (10 ml), and EtOAc (3 x 20 ml) is extracted.
  • the combined organic extracts are rinsed with a saturated solution of NaCl (2 x 30 ml) and dried using MgSC ⁇ , and the solvent is evaporated at reduced pressure, obtaining aldehyde in the form of a yellow solid (3.99 g, 99%) .
  • the aldehyde obtained is used for the subsequent reaction without further purification .
  • Procedure B using a protective atmosphere of argon, in a Schlenk flask are placed bromonaphthalene derivative with formula 21 (0.741 g, 3.0 mmol, 1.10 equivalent), dry, deoxygenated toluene (67 ml), and solid carbene ruthenium complex with formula 6b:
  • reaction mixture is cooled to room temperature, diluted with n-pentane (50 ml) , filtered off using a Buchner funnel, rinsed with n-pentane (2 x 4 ml), and dried for 16 hours, obtaining [a catalyst] with formula 14 as a dark green solid (0.823 g, 70%, solvate with toluene 1:1, in accordance with X H NMR) .
  • Procedure A using a protective atmosphere of argon, in a Schlenk flask are placed iodonaphthalene derivative with formula 25 (0.706 g, 2.4 mmol, 1.10 equivalent), dry, deoxygenated toluene (50 ml) , and solid carbene ruthenium complex with formula 6b ('M31 catalyst', Umicore AG & Co KG, 1.52 g, 2.0 mmol), in the sequence indicated. The suspension obtained is mixed at a temperature of 80 °C for 45 minutes. From this moment, all operations are carried out in air, without the use of a protective atmosphere of argon.
  • the reaction mixture is cooled to room temperature, diluted with n- pentane (50 ml) , filtered off using a Buchner funnel, rinsed with n-pentane (2 x 20 ml), and dried for 16 hours, obtaining a catalyst with formula 15 as a dark green solid (1.385 g, 93%).
  • Procedure B using a protective atmosphere of argon, in a Schlenk flask are placed anhydrous CuCl (0.0156 mg, 0.158 mmol , 1.05 equivalent) , iodonaphthalene derivative with formula 25 (0.0485 g, 0.165 mmol, 1.10 equivalent), dry, deoxygenated CH 2 CI 2 (7.5 ml), and solid carbene ruthenium complex with formula 5a:
  • reaction mixture is cooled to room temperature, diluted with n-pentane (20 ml) , filtered using a Schott filter, rinsed with n-pentane (3 x 10 ml) , and dried under pressure, obtaining a compound with formula 17 as a light green solid (0.659 g, 79%, solvate with toluene 1:1 in accordance with X H NMR) .
  • Formula 29 dry, deoxygenated toluene (20 ml) and solid carbene ruthenium complex with formula 6b ('catalyst M31 ' , Umicore AG & Co KG, 0.787 g, 1.04 mmol) .
  • the suspension obtained is mixed at a temperature of 80°C for 1 hour. From this moment, all operations are carried out in air, without the use of a protective atmosphere of argon.
  • the reaction mixture is cooled to room temperature, diluted with n-pentane (20 ml) , filtered using a Schott filter, rinsed with n-pentane (3 x 15 ml) , and dried under pressure, obtaining a catalyst with formula 18 as a bronze-coloured solid (0.745 g, 86%, solvate with toluene 1:1, in accordance with X H NMR) .
  • Formula 26 dry, deoxygenated toluene (20 ml) , and solid carbene ruthenium complex with formula 6b ('catalyst M31 ' , Umicore AG & Co KG, 0.780 g, 1.03 mmol) , in the sequence indicated.
  • the suspension obtained is mixed at a temperature of 80 °C for 30 minutes. From that moment, all operations are carried out in air, without the use of a protective atmosphere of argon.
  • the reaction mixture is cooled to room temperature, diluted with n- pentane (20 ml) , filtered using a Schott filter, rinsed with n-pentane (2 x 10 ml) , and dried under pressure, obtaining a catalyst with formula 13 as a dark green solid (0.408 g, 57%) .
  • Formula 27 dry, deoxygenated toluene (6 ml), and a solid carbene ruthenium complex with formula 6b ('catalyst M31 ' , Umicore AG & Co KG, 0.239 g, 0.316 mmol), in the sequence indicated.
  • the suspension obtained is mixed at a temperature of 80°C for 1 hour. From this moment, all operations are carried out in air, without the use of a protective atmosphere of argon.
  • the reaction mixture is cooled to room temperature, diluted with n-pentane (1 ml) , filtered using a Schott filter, rinsed with n- pentane (2 x 10 ml) , and dried under pressure, obtaining a catalyst with formula 16 as a dark green solid (0.183 g, 78%) .
  • Formula 30 dry, deoxygenated toluene (6 ml), and solid carbene ruthenium complex with formula 6b ('catalyst M31 ' , Umicore AG & Co KG, 0.237 mg, 0.313 mmol), in the sequence referred to.
  • the suspension obtained is mixed at a temperature of 80 °C for 1 hour. From that moment, all subsequent operations are carried out in air, without the use of a protective atmosphere of argon.
  • the reaction mixture is cooled to room temperature, diluted with n-pentane (6 ml), filtered using a Schott filter, rinsed with n-pentane (2 x 10 ml) , and dried under pressure, obtaining a catalyst with formula 19, as a dark green solid (0.113 mg, 48%) .
  • diethyl diallylmalonate (0.2882 g, 0.12 mmol)
  • CD 2 C1 2 is added up to the nominal value.
  • Diagram V Table 2 Results of reactions on a model substrate in accordance with Diagram V
  • Diagram VII Table 4 : Results of reactions on a model substrate in accordance with Diagram VII
  • Diagram IX Table 6 Results of reactions on a model substrate in accordance with Diagram IX
  • dicyclopentadiene (0.132 g, 1.0 mmol) in CH 2 CI 2 (5 ml) , and mixing takes place at room temperature. Then, solution is added of the catalyst with formula 14 (0.0000025 g, 0.0003 mol%) , and the contents of the flask are mixed at the same temperature for 1 minute. The contents of the flask are poured into another vessel containing 15 ml of methyl alcohol, and a solid precipitates, which is separated by filtration and dried at reduced pressure with the use of a pressure pump. Polydicyclopentadiene is obtained as an elastic white solid.

Landscapes

  • 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)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hydrogenated Pyridines (AREA)
  • Pyrane Compounds (AREA)

Abstract

The present invention provides new ruthenium complexes of Formula (1), which contain a chelate ring created by a halogen atom X. The invention concerns also a method for the preparation of the new ruthenium complexes and their application in metathesis reactions.

Description

NEW COMPLEXES OF RUTHENIUM, METHOD FOR THEIR
PREPARATION, AND THEIR APPLICATION IN OLEFIN METATHESIS REACTIONS
The invention concerns new ruthenium complexes which act as (pre) catalysts, a method for their preparation, and their application in olefin metathesis reactions. This invention is used in organic synthesis in a broad sense.
In applications of olefin metathesis in organic synthesis, significant progress has been made in recent years. In the state of the art, a number of carbene complexes of ruthenium are known which act as (pre) catalysts and which display both high activity in various types of metathesis reaction and broad tolerance of functional groups. The above combination of properties makes this type of (pre) catalyst suitable in organic synthesis.
From the point of view of practical application, particularly on an industrial scale, it is highly desirable for such ruthenium complexes to be stable over a long period at an elevated temperature and to be stored and/or purified and/or used without a protective gas atmosphere.
Complexes of ruthenium with such properties are already known (see: J. Am. Chem. Soc. 2000, 122, 8168- 8179; Tetrahedron Lett. 2000, 41, 9973-9976), although it has turned out that better stability is linked with reduced catalytic activity. This type of limitation was found in the case of the (pre) catalyst with formula 2, in which Mes denotes 2 , 4 , 6-trimethylphenyl (for a comparison of catalytic activity, see Angew. Chem. Int. Ed. 2002, 114, 832-834) .
Figure imgf000003_0001
Formula 2
Then, (pre) catalysts are described with formulae and 4, which show higher catalytic activity comparison with the (pre) catalyst of formula 2.
Figure imgf000003_0002
Catalysts 2, 3, and 4 contain an isopropoxyl group which chelates an atom of the metal. The higher activity of arrangements 3 and 4 is explained by the spatial hindrance introduced by the adjacency of the phenyl group or (substituted) naphthyl group in the ortho position in relation to the isopropoxyl group (see Angew. Chemie Int. Ed. 2002, 114, 832-834; Angew. Chemie Int. Ed. 2002, 114, 2509-2511) .
Then, other catalysts are also described with formulae 5a, 5b, 6a, and 6b, in which Cy denotes cyclohexyl.
Figure imgf000003_0003
Formula 5a Formula 5b
Figure imgf000004_0001
Unexpectedly, it was found that new complexes of ruthenium in accordance with the invention presented in formula 1:
Figure imgf000004_0002
Formula 1 which contain a chelate ring created by a halogen atom are thermally stable and display good catalytic activity. In addition, these compounds display significant changes in activity as a function of temperature, which may be applied to control catalytic processes by changing the temperature of a reaction mixture. Known catalytic arrangements have not shown significant changes in catalytic activity as a function of temperature.
Complexes with formula 1, in accordance with the invention, are applied broadly. With a good result, numerous reactions can be carried out consisting not only in ring-closing metathesis but also in homometathesis , cross metathesis and metathesis of the alkene-alkyne (ene-yne) type, and ring-opening metathesis polymerisation (ROMP) .
Thus, the synthesis of compounds that contain the double C=C bond and other functional groups, when the new catalysts in accordance with the invention are applied, proceeds with a very good result. When such new complexes are applied in accordance with the invention as (pre) catalysts, the temperature of the reaction can be increased and/or, at the same time, the duration of the reaction can be increased in comparison with those conditions necessary when other known catalysts are used. In this way, there is an improvement both in yield and in the technical opportunity for carrying out the reaction. One of the objects of the present invention is to provide new complexes of ruthenium with formula 1:
Figure imgf000005_0001
Formula 1 in which:
L1 denotes an inert ligand;
Z1 and Z2 denote, independently, an anion ligand;
X denotes a halogen atom;
R1 denotes an atom of hydrogen, a halogen atom, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C3-C12 cycloalkenyl C2-C12 alkynyl, C3-C12 cycloalkynyl , C1-C12 alkoxyl, C5-C20 aryl, C5-C20 heteroaryl, or 3-12-membered heterocycle ;
A denotes a bivalent radical selected from a group comprising C1-C12 alkylene, C2-C12 alkenylene, C2-C12 alkynylene, C5-C20 arylene, or C5-C20 heteroarylene, in which the C1-C12 alkylene, the C2-C12 alkenylene, the C2- C12 alkynylene, the C5-C20 arylene, and the C5-C20 heteroarylene may be optionally substituted with at least one functional group R2;
each R2 functional group denotes, independently, a halogen atom, C1-C12 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, -OR3, -SR3, -S(0)mR3, -S02NR3R4, -S(0)2OR3, -N02, -NO, - SCN, -NR3R4, -CN, -C(0)R3, -OC(0)R3, -0 (CR3R4) nR5, NR3C(0)R4, - (CR3R4) nC (0) OR5, - (CR3R4) nOR5, -C (=NR3) NR4R5, - NR3C (0) NR4R5, -NR3S(0)pR4, -NC (=0) R3C (=0) R4, -NR3P (=0) R4R5, -NR3As (=0) R4R5, -PR3R4, -POR3R4, -POR3OR4, -P(=0)R3R4, - P(=0)OR3R4, -P (=0) OR3OR4, -AsR3R4, -AsOR3R4, -AsOR3OR4, - As(=0)R3R4, -As (=0) OR3R4, -As (=0) OR3OR4, -NR3-C (=NR4) NR5R6, -C(=0)R3, -C(=0)OR3, -C(=S)OR3, -C(=0)SR3, -C(=S)SR3, - C(=S)NR3R4, -SiR3R4R5, -SiOR3R4R5, -SiOR3OR4R5, SiOR3OR4OR5, - (CR3R4) n (3-12-membered heterocycle), (CR3R4)n(C3-C12 cycloalkyl), - (CR3R4) n (C5-C20 aryl) , (CR3R4) n (5-12-membered heteroaryl) , - (CR3R4) nC (0) NR5R6, or - (CR3R4) nC (0) R5;
and/or R2 groups with adjacent atoms may bond together, creating C5-C20 aryl or 3-12-membered heterocycle;
and/or R2 groups with adjacent atoms may bond with the R1 group, creating C5-C20 aryl, indenylene, heteroindenylene, 3-12-membered heterocycle, and polycyclic or heteropolycyclic arrangements, whilst the C5-C20 aryl, indenylene, heteroindenylene, 3-12-membered heterocycle, and polycyclic or heteropolycyclic arrangements may be substituted with at least one functional group selected from the group comprising a halogen atom, C1-C12 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, -OR3, -SR3, -S(0)mR3, -S02NR3R4, -S(0)2OR3, -N02, -NO, - SCN, -NR3R4, -CN, -C(0)R3, -0C(0)R3, -0 (CR3R4) nR5, NR3C(0)R4, - (CR3R4) nC (0) OR5, - (CR3R4) n0R5, -C (=NR3) NR4R5, - NR3C (0) NR4R5, -NR3S(0)pR4, -NC (=0) R3C (=0) R4, -NR3P (=0) R4R5, -NR3As (=0) R4R5, -PR3R4, -POR3R4, -POR3OR4, -P(=0)R3R4, - P(=0)OR3R4, -P (=0) OR3OR4, -AsR3R4, -AsOR3R4, -AsOR3OR4, - As(=0)R3R4, -As (=0) OR3R4, -As (=0) OR3OR4, -NR3-C (=NR4) NR5R6, -C(=0)R3, -C(=0)0R3, -C(=S)0R3, -C(=0)SR3, -C(=S)SR3, - C(=S)NR3R4, -SiR3R4R5, -SiOR3R4R5, -SiOR3OR4R5, SiOR3OR4OR5, - (CR3R4) n (3-12-membered heterocycle), (CR3R4)n(C3-C12 cycloalkyl), - (CR3R4) n (C5-C20 aryl), (CR3R4) n (5-12-membered heteroaryl) , - (CR3R4) nC (0) NR5R6, or - (CR3R4) nC (0) R5;
each functional group R3, R4, R5, and R6 denotes, independently, an atom of hydrogen, a halogen atom, Ci- C12 alkyl, C2-Ci2 alkenyl, C2-Ci2 alkynyl, C3-C12 cycloalkyl, C5-C20 aryl, 5-12-membered heterocycle; each m denotes, independently, 0, 1, or 2 ;
each n denotes, independently, 0, 1, 2, 3, or 4 ;
each p denotes, independently, 1 or 2.
In one embodiment of the invention, R in formula 1 denotes an atom of hydrogen, whilst
anion ligands Z1 and Z2 denote, independently, a halogen atom, the group -CN, -SCN, -OR13, -SR13, -0(C=0)R13, - 0(S02)R13, -OSiR3 13, where R13 denotes C1 - C12 alkyl, C3- C12 cycloalkyl, C2 - C12 alkenyl, or C5- C20 aryl, which may be optionally substituted with at least one C1 - C12 alkyl, C1 - C12 perhalogenalkyl, C1 - C12 alkoxyl, or a halogen atom; and
the inert ligand L1 is selected from a group comprising -P(R7)3, -P(OR7)3, or an N-heterocyclic carbene ligand with formula 7a, 7b, 7c, 7d, 7e, 7f, 7g, 7h, 7i, 7j , 7k, 71, 7m, 7n, 7o, or 7p:
Figure imgf000007_0001
Formula 7a Formula 7b Formula 7c Formula 7d
Figure imgf000007_0002
Formula 7e Formula 7f Formula 7g Formula 7h
Figure imgf000007_0003
Formula 7i Formula 7j Formula 7k Formula 71
Figure imgf000008_0001
Formula 7m Formula 7n Formula 7o Formula 7p where :
each R7 denotes, independently, C1-C12 alkyl, C3-C12 cycloalkyl, C5-C20 aryl, or 5-12-membered heteroaryl; each R8, R9, R10, R11, and R12 denote, independently, an atom of hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, or C5-C20 aryl, which may be optionally substituted with at least one C1-C12 alkyl, C1-C12 perhalogenalkyl, C1-C12 alkoxyl, or a halogen atom;
the groups R8, R9, R10, R11, and R12 may optionally bond with each other and
X1 and X2 denote, independently, a halogen atom.
The carbene ligands may be coordinated classically, as in structures 7a-7h, or non-classically ('abnormal carbenes ' , see Chem. Rev. 2009, 109, 3445), as in structures 7i-7p.
In a further embodiment of the invention, the anion ligands Z1 and Z2 in formula 1 denote an atom of chlorine; and
X denotes an atom of bromine or iodine; and
A denotes 1 , 2-phenylene, 1 , 2-naphthylene, 2,3- naphthylene or 1 , 8-naphthylene, which may be substituted with at least one functional group selected from a group comprising -NO2, - Me2," and
the inert ligand L1 denotes a ligand with formula 7a or 7b;
Figure imgf000008_0002
Formula 7a Formula 7b in which the functional groups R , R , R , and R may have the meaning described above.
In a still further embodiment of the invention, the anion ligands Z1 and Z2 in formula 1 denote an atom of chlorine; and X denotes an atom of bromine or iodine; and A denotes 1 , 2-phenylene, 1 , 2-naphthylene, 2,3- naphthylene or 1 , 8-naphthylene, which may be substituted with at least one functional group selected from a group comprising -OMe, Me and the inert ligand L1 denotes a ligand with formula 7a or 7b as listed above.
An object of the invention is also to provide a method of preparing ruthenium complexes with formula 1, which comprises the reaction of the compound of formula 9
Figure imgf000009_0001
Formula 9 in which R and R denote, independently, an atom of hydrogen or the alkyl group C1-C12;
R1 denotes hydrogen, a halogen atom, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C3-C12 cycloalkenyl , C2-C12 alkynyl, C3-C12 cycloalkynyl , C1-C12 alkoxyl, C5-C20 aryl, C5-C20 heteroaryl, or 3-12-membered heterocycle;
X denotes a halogen atom;
A denotes a bivalent radical selected from a group comprising C1-C12 alkylene, C2-C12 alkenylene, C2-C12 alkynylene, C5-C20 arylene, or C5-C20 heteroarylene, in which the C1-C12 alkylene, the C2-C12 alkenylene, the C2- C12 alkynylene, the C5-C20 arylene, and the C5-C20 heteroarylene may be optionally substituted with at least one functional group R2;
each R2 functional group denotes, independently, a halogen atom, C1-C12 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, -OR3, -SR3, -S(0)mR3, -S02NR3R4, -S(0)2OR3, -N02, -NO, - SCN, -NR3R4, -CN, -C(0)R3, -OC(0)R3, -0 (CR3R4) nR5, NR3C(0)R4, - (CR3R4) nC (0) OR5, - (CR3R4) n0R5, -C (=NR3) NR4R5, - NR3C (0) NR4R5, -NR3S(0)pR4, -NC (=0) R3C (=0) R4, -NR3P (=0) R4R5, -NR3As (=0) R4R5, -PR3R4, -POR3R4, -POR3OR4, -P(=0)R3R4, - P(=0)OR3R4, -P (=0) OR3OR4, -AsR3R4, -AsOR3R4, -AsOR3OR4, - As(=0)R3R4, -As (=0) OR3R4, -As (=0) OR3OR4, -NR3-C (=NR4) NR5R6, -C(=0)R3, -C(=0)OR3, -C(=S)OR3, -C(=0)SR3, -C(=S)SR3, - C(=S)NR3R4, -SiR3R4R5, -SiOR3R4R5, -SiOR3OR4R5, SiOR3OR4OR5, - (CR3R4) n (3-12-membered heterocycle), (CR3R4)n(C3-C12 cycloalkyl), - (CR3R4) n (C5-C20 aryl) ,
(CR3R4) n (5-12-membered heteroaryl) , - (CR3R4) nC (0) NR5R6, or
- (CR3R4) nC (0) R5;
and/or R2 groups with adjacent atoms may bond together, creating C5-C20 aryl or 3-12-membered heterocycle;
and/or R2 groups with adjacent atoms may bond with the R1 group, creating C5-C20 aryl, indenylene, heteroindenylene, 3-12-membered heterocycle, and polycyclic or heteropolycyclic arrangements, whilst the C5-C20 aryl, indenylene, heteroindenylene, 3-12-membered heterocycle, and polycyclic or heteropolycyclic arrangements may be substituted with at least one functional group selected from the group comprising a halogen atom, C1-C12 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, -OR3, -SR3, -S(0)mR3, -S02NR3R4, -S(0)2OR3, -N02, -NO, - SCN, -NR3R4, -CN, -C(0)R3, -0C(0)R3, -0 (CR3R4) nR5,
NR3C(0)R4, - (CR3R4) nC (0) OR5, - (CR3R4) n0R5, -C (=NR3) NR4R5, - NR3C (0) NR4R5, -NR3S(0)pR4, -NC (=0) R3C (=0) R4, -NR3P (=0) R4R5, -NR3As (=0) R4R5, -PR3R4, -POR3R4, -POR3OR4, -P(=0)R3R4, - P(=0)OR3R4, -P (=0) OR3OR4, -AsR3R4, -AsOR3R4, -AsOR3OR4, - As(=0)R3R4, -As (=0) OR3R4, -As (=0) OR3OR4, -NR3-C (=NR4) NR5R6, -C(=0)R3, -C(=0)0R3, -C(=S)0R3, -C(=0)SR3, -C(=S)SR3, - C(=S)NR3R4, -SiR3R4R5, -SiOR3R4R5, -SiOR3OR4R5, SiOR3OR4OR5, - (CR3R4) n (3-12-membered heterocycle), (CR3R4)n(C3-C12 cycloalkyl), - (CR3R4) n (C5-C20 aryl), (CR3R4) n (5-12-membered heteroaryl) , - (CR3R4) nC (0) NR5R6, or
- (CR3R4) nC (0) R5;
each functional group R3, R4, R5, and R6 denotes, independently, an atom of hydrogen, a halogen atom, Ci- Ci2 alkyl, C2 ~C12 alkenyl, C2 ~C12 alkynyl, C3 cycloalkyl, C5-C20 aryl, 5-12-membered heterocycle;
each m denotes, independently, 0, 1, or 2 ;
each n denotes, independently, 0, 1, 2, 3, or 4 ;
each p denotes, independently, 1 or 2 ; with a ruthenium carbene complex of formula 11a, 11c, or lid:
Figure imgf000011_0001
Formula 11a Formula lib Formula 11c Formula lid in which
L1, L2, and L3 denote, independently, an inert ligand; Z1 and Z2 denote, independently, an anion ligand;
R16 has the same meaning as R1 in formula 9;
R17 denotes an atom of hydrogen, C5-C20 aryl, C5-C20 heteroaryl, vinyl, or allenyl. Advantageously, the reaction between the compound of formula 9 and the ruthenium complex of formula 11a, lib, 11c, or lid is carried out in the presence of anhydrous halogen salts of copper (I) such as CuCl or CuBr, or in the presence of Br0nsted acids such as H2SO4, HC1, HNO3, H3PO4, sulphonated polymers (Nafion-H) , or other acids bonded with a fixed substrate, in a solvent .
Advantageously, the reaction is carried out at a temperature in the range of 0-120°C.
Advantageously, the reaction is carried out in a chlorinated solvent or in aromatic hydrocarbons or in protic or aprotic solvents such as alcohol or ketone or in mixtures thereof.
Advantageously, the reaction is carried out in a solvent such as methylene chloride and/or toluene. The invention also concerns the application and use of the ruthenium complexes defined in formula 1 as (pre) catalysts in metathesis reactions.
Advantageously, ruthenium complexes with formula 1 are used as (pre) catalysts in ring-opening metathesis reactions, homometathesis , cross-metathesis, alkene- alkyne (ene-yne) type metathesis, ring-closing metathesis and ROMP-type polymerisation reactions.
The term halogen atom denotes an element selected from F, CI, Br, and I.
The term carbene denotes a molecule containing an inert atom of carbon with a valence number of two and two unpaired valence electrons. The term carbene also denotes carbene analogues in which the carbon atom is replaced with another chemical element such as boron, silicon, germanium, tin, lead, nitrogen, phosphorus, sulphur, selenium, and tellurium.
The term alkyl relates to a saturated, linear, or branched functional hydrocarbon group with an indicated number of atoms of carbon. Examples of an alkyl functional group are -methyl, -ethyl, -n-propyl, -n- butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n- nonyl, and -n-decyl . Representative branched - (Ci-Cio) alkyls include -iso-propyl, -sec-butyl, -iso-butyl, tert-butyl, -iso-pentyl, -neopentyl, -1-methylbutyl,
2-methylbutyl, -3-methylbutyl , -1, 1-dimethylpropyl,
1, 2-dimethylpropyl, -1-methylpentyl, -2-methylpentyl, -
3-methylpentyl , -4-methylpentyl, -1-ethylbutyl, -2- ethylbutyl, -3-ethylbutyl, -1, 1-dimethylbutyl, -1,2- dimethylbutyl , -1, 3-dimethylbutyl, -2, 2-dimethylbutyl, -2 , 3-dimethylbutyl , -3 , 3-dimethylbutyl , -1-methylhexyl, -2-methylhexyl, -3-methylhexyl , -4-methylhexyl, -5- methylhexyl, -1, 2-dimethylpentyl, -1, 3-dimethylpentyl, -1, 2-dimethylhexyl, -1, 3-dimethylhexyl, -3,3- dimethylhexyl , -1, 2-dimethylheptyl, -1,3- dimethylheptyl , and -3 , 3-dimethylheptyl , and similar.
The term alkoxyl refers to an alkyl functional group as defined above connected using an oxygen atom. The term perfluoroalkyl denotes an alkyl group as defined above in which all atoms of hydrogen are replaced with the same or different halogen atoms.
The term cycloalkyl refers to a saturated monocyclic or polycyclic functional hydrocarbon group with an indicated number of carbon atoms. Examples of a cycloalkyl functional group are -cyclopropyl , cyclobutyl, -cyclopentyl , -cyclohexyl, -cycloheptyl , cyclooctyl, -cyclononyl, -cyclodecyl, and similar.
The term alkenyl refers to a saturated, linear, or branched non-cyclic functional hydrocarbon group with an indicated number of atoms of carbon and containing at least one double carbon-carbon bond. Examples of an alkenyl functional group are -vinyl, -allyl, 1-butenyl -2-butenyl, -iso-butylenyl , -1-pentenyl, -2-pentenyl, - 3-methyl-l-butenyl, -2-methyl-2-butenyl, -2 , 3-dimethyl- 2-butenyl, -1-hexenyl, -2-hexenyl, -3-hexenyl, -1- heptenyl, -2-heptenyl, -3-heptenyl, -1-octenyl, -2- octenyl, -3-octenyl, -1-nonenyl, -2-nonenyl, -3- nonenyl, -1-decenyl, -2-decenyl, -3-decenyl, and similar .
The term cycloalkenyl refers to a saturated monocyclic or polycyclic functional hydrocarbon group with an indicated number of atoms of carbon and containing at least one double carbon-carbon bond. Examples of the cycloalkenyl functional group are cyclopentenyl , -cyclopentadienyl , -cyclohexenyl , cyclohexadienyl , -cycloheptenyl , -cycloheptadienyl , cycloheptatrienyl , -cyclooctenyl , -cyclooctadienyl , cyclooctatrienyl , -cyclooctatetraenyl, -cyclononenyl , - cyclononadienyl , -cyclodecenyl , -cyclodecadienyl , and similar .
The term alkynyl refers to a saturated, linear, or branched non-cyclic functional hydrocarbon group with an indicated number of atoms of carbon and containing at least one triple carbon-carbon bond. Examples of an alkynyl functional group are -acetylenyl, -propynyl, 1-butynyl, -2-butynyl, -1-pentynyl, -2-pentynyl, -3- methyl- 1-butynyl, -4- pentynyl, -1-hexynyl, -2-hexynyl, -5-hexynyl, and similar.
The term cycloalkynyl refers to a saturated monocyclic or polycyclic functional hydrocarbon group with an indicated number of atoms of carbon and containing at least one triple carbon-carbon bond. Examples of a cycloalkynyl functional group are cyclohexynyl , -cycloheptynyl , -cyclooctynyl , and similar .
The term aryl refers to an aromatic monocyclic or polycyclic functional hydrocarbon group with an indicated number of atoms of carbons. Examples of an aryl functional group are -phenyl, -tolyl, -xylyl, naphthyl, and similar.
The term heteroaryl refers to an aromatic monocyclic or polycyclic functional hydrocarbon group with an indicated number of atoms of carbon with at least one atom of carbon replaced with a heteroatom selected from 0, N, and S. Examples of a heteroaryl functional group are -furyl, -thienyl, -imidazolyl, oxazolyl, -thiazolyl, -isoxazolyl, -triazolyl, oxadiazolyl, -thiadiazolyl , -tetrazolyl, -pirydyl, pyrimidyl, -triazynyl, -indolyl, -benzo [b] furyl, benzo [b] thienyl, -indazolyl, -benzoimidazolyl , azaindolyl, -chinolyl, -isochinolyl , -carbazolyl, and similar .
The term heterocycle refers to a saturated or partly saturated monocyclic or polycyclic functional hydrocarbon group, with an indicated number of atoms with at least one atom of carbon replaced with a heteroatom selected from 0, N, and S. Examples of a heterocyclic functional group are -furyl, -thiophenyl, -pyrrolyl, -oxazolyl, -imidazolyl, -thiazolyl, isoxazolyl, -pyrazolyl, -isothiazolyl , -triazynyl, pyrrolidinolyl , -pyrrolidinyl , -hydrantoinyl , oxyranil, -oxetanyl, -tetrahydrofuranyl , tetrahydrothiophenyl, -quinolinyl, -isoquinolinyl , chromonyl, -coumarinyl, -indolyl, -indolizinyl, benzo [b] furanyl, -benzo [b] thiophenyl -indazolyl, purinyl, -4H-quinolizinyl, -isoquinolyl , -quinolyl, phthalazinyl , -naphthyridinyl , -carbazolyl, -β- carbolinyl, and similar.
The term inert ligand refers to a functional group without a charge capable of coordinating with the metallic centre (the ruthenium atom) . Examples of such ligands are: amines, phosphines and oxides thereof, aryl and alkyl phosphoranes and phosphorines , arsines and oxides thereof, ethers, aryl and alkyl sulphides, coordinated hydrocarbons, and aryl and alkyl halides.
The term indenylene refers to an unsaturated functional hydrocarbon with an indene skeleton (benzocyclopentadiene) .
The term heteroindenylene refers to an indenylene functional group, defined above, in which at least one atom of carbon has been replaced with a heteroatom from a group comprising: nitrogen, oxygen, and sulphur.
The term anion ligand refers to a functional group capable of coordination with the metallic centre (the ruthenium atom) with a charge capable of partial or full compensation of the metallic centre charge. Examples of such ligands may be: fluoride, chloride, bromide, iodide, cyanide, cyanate, and thiocyanate, carboxylic acid anions, alcohol anions, phenol anions, thiol and thiophenol anions, hydrocarbon anions with a delocalised charge (e.g. cyclopentadiene) ,
(organo) sulphuric and (organo) phosphoric acid anions and their esters (e.g. alkyl sulphonic and aryl sulphonic acid anions, alkyl phosphoric and aryl phosphoric acid anions, sulphuric acid alkyl and aryl ester anions, phosphoric acid alkyl and aryl ester anions, alkyl phosphoric and aryl phosphoric acid alkyl and aryl ester anions) . An anion ligand may have a group L1, L2, or L3 linked like a catechol anion, an acetylacetone anion, or a salicylic aldehyde anion. Anion ligands (Z1 and Z2) and inert ligands (L1, L2, and L3) may be linked with each other, creating polydentate ligands, e.g.: the bidentate ligand (Z1, Z2) , the tridentate ligand (Z1, Z2, L1) , the tetradentate ligand (Z1, Z , L , I ), the bidentate ligand (Z1, L ) , the tridentate ligand (Z1, L1, L2) , the tetradentate ligand (Z1, L1, L2, L3) , the bidentate ligand (L1, L2) , and the tridentate ligand (L1, L2, L3) . Examples of such ligands are: catechol anion, acetylacetone anion, and salicylic aldehyde anion.
The stages of synthesis which are generally used in producing ligands with formula 9 are presented in general in Diagram I, in accordance with which the synthesis of the compounds with formulae 21, 23, and 25 is carried out (Examples I-III) .
Figure imgf000016_0001
Formula 8 Formula 9 Formula 10
n = 1, 2
Diagram 1
The olefination reaction of substituted aromatic and heteroaromatic halogen aldehyde derivatives with formula 8, where R1 has the meaning given above, is advantageously carried out in accordance with Tebbe ' s method with Tebbe ' s titanium reagent or in accordance with Wittig's method with Wittig's reagent, or in accordance with Peterson's method. The reaction is carried out in solvents such as alcohol and glycol ethers or cyclic ethers, advantageously THF, aromatic and aliphatic hydrocarbons, and mixtures of all of the above. Compounds with the general formula 9 are also beneficially obtained from the protected aldehyde 10 without generation and purification of the halogen aldehyde with the general formula 8 (Diagram I, experimental data Examples I-III).
In the method in accordance with the invention, the complex with formula 1 is obtained as presented in Diagram II (for experimental data, see Examples IV-XI) in a reaction between the substituted compound with formula 9 and the ruthenium complex 11a, lib, 11c, or lid, where the functional group has the meaning given above, possibly in the presence of an anhydrous halogen salt of copper (I), such as CuCl or CuBr. The reaction is carried out advantageously in chlorinated solvents, e.g. methylene chloride, or in aromatic hydrocarbons, or in mixtures thereof, over 1-24 hours at a temperature of 0-120°C. Furthermore, protic and aprotic solvents may be used, such as alcohols or ketones. The reaction may be carried out also in the presence of Br0nsted acids such as H2S04, HC1, HN03, H3P04, sulphonated polymers (Nafion-H) , or other acids bonded with a fixed substrate, in the solvent described above.
Figure imgf000017_0001
Formula 11a Formula lib
Figure imgf000017_0002
Formula 9 Formula 1
Diagram II
The examples above explain the production and use of the new complexes. The comparative examples with the use of known complexes confirm that the complexes in accordance with the invention of formula 1 are thermally more stable than complexes known from the state of the art and furthermore display higher catalytic activity.
Example I :
Synthesis of a ligand with formula 23 (in accordance with Diagram I) .
Figure imgf000018_0001
Formula 22 Formula 23 l-iodo-2- (prop-l-enyl) benzene . To the suspension of ethyl triphenyl phosphonium bromide (6.72 g, 18.3 mmol) in THF (30 ml) , a solution is added by drops of tert- amylate (8.5 ml, 14.5 mmol, 1.7 M solution in toluene) at room temperature. After 1 hour, the reaction mixture is cooled to a temperature of 0°C, an aldehyde solution with formula 22 is added (2.80 g, 12.1 mmol) in THF (10 ml) , the cooling bath is removed, and the mixing is continued for 3 hours at room temperature. This is followed by the addition of water (0.5 ml), dilution with n-hexane (30 ml) , drying using MgSC^, and the solvent is evaporated at reduced pressure. The residue is chromatographed on silica gel (cyclohexane) , obtaining a styrene derivative with formula 23 in the form of a colourless oil as a mixture of isomers E:Z = 1.83:1 (2.69 g, 91%) .
XH NMR (200 MHz): 7.80-7.70 (m, 1H) , 7.45-7.18 (m, 1H) , 6.96-6.78 (m, 1H) , 6.62-6.26 (m, 1H) , 1.90 (dd, J = 6.6 Hz, 1.6 Hz, 0.35 x 3H) , 1.73 (dd, J = 7.0 Hz, 1.6 Hz, 0.65 x 1H) . 13C NMR (50 MHz): 140.8, 139.3, 139.0, 134.7, 133.7, 129.8, 129.0, 128.3, 128.2, 128.2, 127.7, 127.6, 126.3, 100.2, 99.2, 18.6, 14.1.
The compound described in Synlett 2007, 929-933, and J. Am. Chem. Soc. 2003, 125, 4804-4807 without spectral data . Example II:
Synthesis of a ligand with formula 21 (in accordance with Diagram I) .
Figure imgf000019_0001
l-bromo-2- (prop-l-enyl) naphthalene . To the suspension of ethyl triphenyl phosphonium bromide (3.72 g, 10.0 mmol) in anhydrous THF (8 ml), a solution is added by drops of potassium tert-amylate (5.5 ml, 9.3 mmol, 1.7 M solution in toluene) using a syringe at room temperature. After 1 hour, the reaction mixture is cooled to a temperature of 0°C, a solution is added of aldehyde with formula 20 (1.68 g, 7.16 mmol), the cooling bath is removed, and mixing is carried out for 3 hours at room temperature. Then, the reaction mixture is diluted with cyclohexane (30 ml) , the sediment is filtered off, and the solvent is evaporated at reduced pressure. The residue is chromatographed on silica gel (cyclohexane) , obtaining a naphthalene derivative with formula 21 in the form of an oil as a mixture of isomers E:Z = 1.82:1 (1.66 g, 94%).
XH NMR (200 MHz): 8.44-8.32 (m, 1H) , 7.88-7.40 (m, 5H) , 7.18-7.02 (m, 0.65 x 1H) , 6.76 (dd, J = 11.4, 1.6 Hz, 0.35 x 1H) , 6.35 (dq, J = 15.8, 6.6 Hz, 0.65 x 1H) , 6.00 (dq, J = 11.4, 7.0 Hz, 0.35 x 1H) , 2.03 (dd, J = 6.6, 1.6 Hz, 0.65 x 3H) , 1.88-1.82 (m, 0.35 x 3H) .
13C NMR (50 MHz): 135.7, 135.1, 133.5, 133.3, 132.6, 131.0, 130.6, 129.7, 128.1, 128.0, 127.9, 127.6, 127.5,
127.4, 127.3, 127.2, 126.8, 126.2, 126.1, 124.2, 123.6,
122.5, 18.9, 14.6.
HR MS was calculated for C13HnBr: 246.0044. Found: 246.0054. Spectroscopy data in accordance with the literature: Daiichi Sankyo Company, Ltd. Patent application: EP 1 914 229 Al, 2008.
Example III:
Synthesis of a ligand with formula 25 (in accordance with Diagram I) .
Figure imgf000020_0001
Formula 24 Formula 25 l-Iodo-2- (prop-l-enyl) naphthalene . To the solution of ketal with formula 24 (4.63 g, 14.3 mmol) in a mixture of 1,4-dioxane (40 ml) and water (5 ml), p- toluenesulfonic acid (1.36 g, 7.15 mmol) is added and mixed for 16 hours at room temperature. Then, the reaction mixture is diluted with water (100 ml) and a saturated hydrous solution K2CO3 (10 ml), and EtOAc (3 x 20 ml) is extracted. The combined organic extracts are rinsed with a saturated solution of NaCl (2 x 30 ml) and dried using MgSC^, and the solvent is evaporated at reduced pressure, obtaining aldehyde in the form of a yellow solid (3.99 g, 99%) . The aldehyde obtained is used for the subsequent reaction without further purification .
To the suspension of ethyl triphenyl phosphonium bromide (5.69 g, 15.3 mmol) in anhydrous THF (30 ml), a solution is added by drops of potassium tert-amylate (8.7 ml, 14.7 mmol, 1.7 M solution in toluene) using a syringe at room temperature. After 1 hour, the reaction mixture is cooled to a temperature of 0°C, the solution of crude aldehyde previously obtained is added (3.32 g, 11.79 mmol) in THF (10 ml), and mixing is continued for 16 hours at room temperature. Then, water (1 ml) is added, and dilution takes place with n-hexane (30 ml) . The sediment created is filtered, and the residue is chromatographed on silica gel (cyclohexane) , obtaining naphthalene derivative with formula 25 in the form of a yellow oil (3.12 g, 90%).
Example IV:
Synthesis of a catalyst with formula 12, in which Mes denotes 2 , 4 , 6-trimethylphenyl (in accordance with Diagram II).
Figure imgf000021_0001
Formula 12 Procedure A: using a protective atmosphere of argon, in a Schlenk flask are placed anhydrous CuCl (0.0208 g, 0.21 mmol, 1.05 equivalent), bromonaphthalene equivalent with formula 21 (0.0544 g, 0.22 mmol, 1.10 equivalent), dry, deoxygenated CH2CI2 (10 ml), and solid carbene ruthenium complex with formula 5a (in which Mes denotes 2 , 4 , 6-trimethylphenyl , and Cy denotes cyclohexyl) :
Figure imgf000021_0002
Formula 5a
('Grubbs' II generation catalyst, 0.170 g, 0.20 mmol) in the sequence indicated. The suspension obtained is mixed at boiling point for 2 hours. From this moment, all subsequent operations are carried out without the use of a protective atmosphere of argon. The reaction mixture is concentrated in a rotary evaporator, and the residue obtained is chromatographed on silica gel (20 ml), using as eluent 20% ethyl acetate in CH2CI2. Then, solvents are evaporated at reduced pressure, obtaining a catalyst with Formula 12 as a green solid (0.094 g, 68%) .
Procedure B: using a protective atmosphere of argon, in a Schlenk flask are placed bromonaphthalene derivative with formula 21 (0.741 g, 3.0 mmol, 1.10 equivalent), dry, deoxygenated toluene (67 ml), and solid carbene ruthenium complex with formula 6b:
Figure imgf000022_0001
Formula 6b
('catalyst M31', Umicore AG & Co KG, 1.52 g, 2.0 mmol) in the sequence indicated. The suspension obtained is mixed at a temperature of 80 °C for 2 hours. From that moment, all operations are carried out without the use of a protective atmosphere of argon. The product suspension obtained is filtered off using a Buchner funnel, rinsed with n-pentane (2 x 8 ml) , and dried for 16 hours, obtaining a catalyst with formula 12 as a dark green solid (1.05 g, 75%) .
XH NMR (500 MHz, CD2C12) : 17.97 (s, 1H) , 8.22 (dd, J = 8.5, 1.0 Hz, 1H) , 7.89 (d, J = 8.0 Hz, 1H) , 7.75 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H) , 7.72 (d, J = 8.0 Hz, 1H) , 7.64 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H) , 7.18 (2 s ovl, 2H) , 7.10 (d, J = 8.5 Hz, 1H) , 6.97 (s, 1H) , 5.73 (s, 1H) , 4.26-4.19 (m, 1H) , 4.12-4.04 (m, 2H) , 3.87-3.80 (m, 1H) , 2.64 (s, 3H) , 2.53 (s, 3H) , 2.46 (s, 3H) , 2.43 (s, 3H) , 2.17 (s, 3H) , 1.34 (s, 3H) .
13C NMR (125 MHz, CD2C12) : 278.1, 214.1, 149.4, 141.0, 140.6, 139.1, 138.1, 137.1, 135.7, 135.4, 134.4, 131.9, 131.7, 131.3, 130.4, 130.0, 129.7, 129.5, 129.4, 129.3, 128.3, 127.4, 126.7, 124.8, 52.0, 51.9, 21.6, 21 20.4, 19.5, 18.8, 17.3.
Elemental analysis for C32H34Cl2Br 2Ru : calculated: 55.02, H 4.91, N 4.01. Found: C 56.11, H 5.16, N 3.88
Example V:
Synthesis of a catalyst with formula 14 (in accordance with Diagram II) .
Figure imgf000023_0001
Formula 14
Using a protective atmosphere of argon, in a Schlenk flask are placed iodostyrene with formula 23 (0.549 g, 2.25 mmol, 1.10 equivalent), dry, deoxygenated toluene (50 ml) and solid carbene ruthenium complex with formula 6b ('catalyst M31', Umicore AG & Co KG, 1.14 g, 1.50 mmol), in the sequence indicated. The suspension obtained is mixed at a temperature of 80°C for 2 hours. From this moment, all subsequent operations are carried out in air, without the use of a protective atmosphere of argon. The reaction mixture is cooled to room temperature, diluted with n-pentane (50 ml) , filtered off using a Buchner funnel, rinsed with n-pentane (2 x 4 ml), and dried for 16 hours, obtaining [a catalyst] with formula 14 as a dark green solid (0.823 g, 70%, solvate with toluene 1:1, in accordance with XH NMR) . XH NMR (500 MHz, CD2C12) : 18.06 (d, J = 1.0 Hz, 1H) , 7.61-7.57 (m, 1H) , 7.35 (ddd, J = 9.0, 7.5, 1.5 Hz, 1H) , 7.29 (ddd, J = 8.5, 7.0, 1.0 Hz, 1H) , 7.17 (s, 1H) , 7.04 (s, 1H) , 6.94 (s, 1H) , 6.91 (dd, J = 7.2, 3.7 Hz, 1H) , 6.01 (s, 1H) , 4.25-4.17 (m, 1H) , 4.10-3.96 (m, 2H) , 3.91-3.84 (m, 1H) , 2.71 (s, 3H) , 2.50 (s, 3H) , 2.41 (s, 3H) , 2.38 (s, 3H) , 2.16 (s, 3H) , 1.62 (s, 3H) .
Signals of toluene omitted.
13C NMR (125 MHz, CD2C12) : 281.7, 214.7, 157.7, 141.0, 140.5, 139.0, 138.2, 136.5, 136.0, 135.7, 134.3, 132.0, 131.4, 130.8, 130.3, 130.0, 129.5, 129.3, 128.1, 100.7, 52.1, 51.8, 21.5, 21.2, 20.6, 20.3, 19.0, 18.2. Signals of toluene omitted.
Elemental analysis for C35H4oCl2ln2Ru : calculated: C 53.38, H 5.12, N 3.56. Found: C 53.32, H 5.10, N 3.90.
Example VI :
Synthesis of a catalyst with formula 15 (in accordance with Diagram II) .
Figure imgf000024_0001
Formula 15
Procedure A: using a protective atmosphere of argon, in a Schlenk flask are placed iodonaphthalene derivative with formula 25 (0.706 g, 2.4 mmol, 1.10 equivalent), dry, deoxygenated toluene (50 ml) , and solid carbene ruthenium complex with formula 6b ('M31 catalyst', Umicore AG & Co KG, 1.52 g, 2.0 mmol), in the sequence indicated. The suspension obtained is mixed at a temperature of 80 °C for 45 minutes. From this moment, all operations are carried out in air, without the use of a protective atmosphere of argon. The reaction mixture is cooled to room temperature, diluted with n- pentane (50 ml) , filtered off using a Buchner funnel, rinsed with n-pentane (2 x 20 ml), and dried for 16 hours, obtaining a catalyst with formula 15 as a dark green solid (1.385 g, 93%). Procedure B: using a protective atmosphere of argon, in a Schlenk flask are placed anhydrous CuCl (0.0156 mg, 0.158 mmol , 1.05 equivalent) , iodonaphthalene derivative with formula 25 (0.0485 g, 0.165 mmol, 1.10 equivalent), dry, deoxygenated CH2CI2 (7.5 ml), and solid carbene ruthenium complex with formula 5a:
Figure imgf000025_0001
Formula 5a
('Grubbs II generation catalyst', 0.127 g, 0.150 mmol), in the sequence indicated. The suspension obtained is mixed at boiling point for 10 minutes. From this moment, all operations are carried out in air, without the use of a protective atmosphere of argon. The reaction mixture is concentrated in a rotary evaporator, and the residue obtained is chromatographed on silica gel (20 ml) , using, as eluent, 10% ethyl acetate in CH2CI2. Then, the solvents are evaporated at reduced pressure, obtaining a catalyst with formula 15 as an olive green solid (0.0923 g, 83%) .
LR NMR (500 MHz, CD2C12) : 18.26 (s, =CH, 1H) , 7.97 (d, J = 8.0 Hz, 1H) , 7.82 (d, J = 8.0 Hz, 1H) , 7.76-7.71 (m, 2H) , 7.63-7.58 (m, 1H) , 7.19 (s, 1H) , 7.09 (s, 1H) , 6.97 (s, 1H) , 6.96 (d, J = 8.0 Hz, 1H) , 5.76 (s, 1H) , 4.26-4.17 (m, 1H) , 4.10-3.95 (m, 2H) , 3.88-3.80 (m, 1H) , 2.74 (s, 3H) , 2.54 (s, 3H) , 2.48 (s, 3H) , 2.41 (s, 3H) , 2.16 (s, 3H) , 1.39 (s, 3H) .
13C NMR (125 MHz, CD2C12) : 281.2, 214.3, 156.3, 141.0, 140.5, 139.0, 138.2, 136.5, 135.8, 135.5, 134.6, 133.9, 132.1, 131.4, 130.9, 130.4, 130.1, 129.8, 129.5, 129.4, 128.4, 126.4, 105.8, 52.2, 51.8, 21.5, 21.2, 20.6, 19.1, 18.1.
Elemental analysis for C32H34C I 2 I 2RU : calculated: C 51.55, H 4.60, N 3.76. Found: C 52.26, H 4.61, N 3.59. Example VII:
Synthesis of a catalyst with formula 17 (in accordance with Diagram II) .
Figure imgf000026_0001
Formula 17
Procedure: using a protective atmosphere of argon, in a Schlenk flask are placed iodostyrene derivative with formula 28 (0.433 g, 1.5 mmol) :
Figure imgf000026_0002
Formula 28 and dry, deoxygenated toluene (20 ml) , and solid, carbene complex of ruthenium with formula 6b ('M31 catalyst', Umicore AG & Co KG, 0.761 g, 1.0 mmol), in the sequence indicated. The suspension obtained is mixed at a temperature of 80 °C for 1 hour. From this moment, all operations are carried out in air, without the use of a protective atmosphere of argon. The reaction mixture is cooled to room temperature, diluted with n-pentane (20 ml) , filtered using a Schott filter, rinsed with n-pentane (3 x 10 ml) , and dried under pressure, obtaining a compound with formula 17 as a light green solid (0.659 g, 79%, solvate with toluene 1:1 in accordance with XH NMR) .
XH NMR (200 MHz, CD2C12) : 18.11 (d, J = 1.0 Hz, =CH, 1H) , 8.19, (dd, J = 8.5, 2.5 Hz, 1H) , 7.79 (dd, J = 8.5, 1.0 Hz, 1H) , 7.72 (d, J = 2.5 Hz, 1H) , 7.27-7.12 (m, 1H + toluene), 7.05 (s, 1H) , 7.02 (s, 1H) , 6.05 (s, 1H) , 4.27-4.20 (m, 1H) , 4.13-3.97 (m, 2H) , 3.93-3.85 (m, 1H) , 2.69 (s, 3H) , 2.50 (s, 3H) , 2.42 (s, 3H) , 2.39 (s, 3H) , 2.34 (s, toluene), 2.08 (s, 3H) , 1.61 (s, 3H) . 13C NMR (125 MHz, CD2C12) : 276.9, 212.9, 157.7, 149.5, 141.2, 140.5, 139.8, 138.4, 136.2, 135.8, 135.6, 134.7, 131.39, 131.37, 130.22, 130.20, 129.4, 129.0, 128.6, 125.6, 123.5, 120.9, 107.6, 52.0, 51.7, 21.5, 21.4, 20.7, 20.4, 20.1, 18.8, 18.1. Signals of toluene were omitted .
Example VIII:
Synthesis of a catalyst with formula 18 (in accordance with Diagram II) .
Figure imgf000027_0001
Formula 18
Procedure: using a protective atmosphere of argon, in a Schlenk flask are placed an iodostyrene derivative with formula 29 (0.453 g, 1.56 mmol) :
Figure imgf000027_0002
Formula 29 dry, deoxygenated toluene (20 ml) and solid carbene ruthenium complex with formula 6b ('catalyst M31 ' , Umicore AG & Co KG, 0.787 g, 1.04 mmol) . The suspension obtained is mixed at a temperature of 80°C for 1 hour. From this moment, all operations are carried out in air, without the use of a protective atmosphere of argon. The reaction mixture is cooled to room temperature, diluted with n-pentane (20 ml) , filtered using a Schott filter, rinsed with n-pentane (3 x 15 ml) , and dried under pressure, obtaining a catalyst with formula 18 as a bronze-coloured solid (0.745 g, 86%, solvate with toluene 1:1, in accordance with XH NMR) .
XH NMR (500 MHz, CD2C12) : 18.12 (s, =CH, 1H) , 8.41 (dd, J = 8.0, 1.5 Hz, 1H) , 7.52 (dd, J = 8.0, 7.5 Hz, 1H) , 7.26-7.12 (m, 2H + toluene), 7.08 (s, 1H) , 6.96 (s, 1H) , 5.97 (s, 1H) , 4.25-4.18 (m, 1H) , 4.11-3.95 (m, 2H) , 3.92-3.84 (m, 1H) , 2.69 (s, 3H) , 2.51 (s, 3H) , 2.47 (s, 3H) , 2.39 (s, 3H) , 2.34 (s, toluene), 2.14 (s, 3H) , 1.62 (s, 3H) .
13C NMR (125 MHz, CD2C12) : 279.0, 212.9, 158.7, 150.7, 141.1, 140.4, 139.1, 138.4, 138.3, 136.1, 135.7, 135.5, 132.2, 131.4, 131.3, 131.1, 130.22, 130.17, 129.4, 129.1, 128.6, 125.6, 125.4, 93.1, 51.9, 51.8, 21.4, 21.1, 20.4, 20.1, 18.8, 18.2. Signals of toluene are omitted .
Example IX :
Synthesis of a catalyst with formula 13 (in accordance with Diagram II) :
Figure imgf000028_0001
formula 13
Procedure: using a protective atmosphere of argon, in a Schlenk flask are placed a bromostyrene derivative with formula 26 (0.371 g, 1.55 mmol) :
Figure imgf000029_0001
Formula 26 dry, deoxygenated toluene (20 ml) , and solid carbene ruthenium complex with formula 6b ('catalyst M31 ' , Umicore AG & Co KG, 0.780 g, 1.03 mmol) , in the sequence indicated. The suspension obtained is mixed at a temperature of 80 °C for 30 minutes. From that moment, all operations are carried out in air, without the use of a protective atmosphere of argon. The reaction mixture is cooled to room temperature, diluted with n- pentane (20 ml) , filtered using a Schott filter, rinsed with n-pentane (2 x 10 ml) , and dried under pressure, obtaining a catalyst with formula 13 as a dark green solid (0.408 g, 57%) .
XH NMR (500 MHz, CD2C12) : 17.75 (s, =CH, 1H) , 7.28 (d, J = 10.2 Hz, 1H) , 7.16 (s, 1H) , 7.11 (s, 1H) 6.94 (s, 1H) , 6.80 (dd, J = 9.0, 3.0 Hz, 1H) , 6.41 (d, J = 3.0 Hz, 1H) , 6.19 (s, 1H) , 4.24-4.16 (m, 1H) , 4.11-4.02 (m, 1H) , 4.02-3.92 (m, 1H) , 3.92-3.81 (m, 1H) , 2.97 (s, 6H, N(CH3)2), 2.63 (s, 3H) , 2.42 (2s ovl, 6H) , 2.40 (s, 3H) , 2.17 (s, 3H) , 1.60 (s, 3H) .
13C NMR (125 MHz, CD2C12) : 280.9, 214.8, 152.5, 151.3, 140.6, 140.2, 138.5, 137.8, 136.9, 136.2, 135.5, 131.8, 131.0, 130.0, 129.7, 129.3, 128.5, 113.7, 114.4, 110.7, 51.9, 51.6, 40.6, 21.3, 20.9, 20.1, 19.1, 18.6, 17.2. Example X:
The synthesis of a catalyst with formula
accordance with Diagram II) .
Figure imgf000030_0001
Formula 16
Procedure: using a protective atmosphere of argon, in a Schlenk flask are placed iodonaphthalene derivative with formula 27 (0.137 g, 0.466 mmol) :
Figure imgf000030_0002
Formula 27 dry, deoxygenated toluene (6 ml), and a solid carbene ruthenium complex with formula 6b ('catalyst M31 ' , Umicore AG & Co KG, 0.239 g, 0.316 mmol), in the sequence indicated. The suspension obtained is mixed at a temperature of 80°C for 1 hour. From this moment, all operations are carried out in air, without the use of a protective atmosphere of argon. The reaction mixture is cooled to room temperature, diluted with n-pentane (1 ml) , filtered using a Schott filter, rinsed with n- pentane (2 x 10 ml) , and dried under pressure, obtaining a catalyst with formula 16 as a dark green solid (0.183 g, 78%) .
XH NMR (500 MHz, CD2C12) : 18.08 (d, J = 1.0 Hz, =CH, 1H) , 8.12 (s, 1H) , 8.00 (d, J = 8.5 Hz, 1H) , 7.77-7.70 (m, 2H) , 7.56 (ddd, J = 7.5, 6.0, 2.0 Hz, 1H) , 7.42 (s, 1H) , 7.17 (s, 1H) , 7.06 (s, 1H) , 6.95 (s, 1H) , 5.59 (s, 1H) , 4.25-4.18 (m, 1H) , 4.11-3.95 (m, 2H) , 3.91-3.84 (m, 1H) , 2.70 (s, 3H) , 2.50 (s, 3H) , 2.44 (s, 3H) , 2.39 (s, 3H) , 1.88 (s, 3H) , 1.63 (s, 3H) .
13C NMR (125 MHz, CD2C12) : 280.6, 215.0, 154.7, 140.8, 140.5, 138.9, 138.2, 136.4, 136.1, 135.7, 134.2, 133.49, 133.47, 131.9, 131.2, 130.11, 130.10, 129.8, 129.0, 128.7, 128.4, 127.7, 126.5, 95.8, 51.9, 51.6, 21.4, 21.0, 20.4, 20.2, 18.9, 18.1.
Example XI :
Synthesis of a catalyst with formula 19 (in accordance with Diagram II) .
Figure imgf000031_0001
Formula 19
Procedure: using a protective atmosphere of argon, in the Schlenk flask are placed iodonaphthalene derivative with formula 30 (0.138 g, 0.469 mmol) .
Figure imgf000031_0002
Formula 30, dry, deoxygenated toluene (6 ml), and solid carbene ruthenium complex with formula 6b ('catalyst M31 ' , Umicore AG & Co KG, 0.237 mg, 0.313 mmol), in the sequence referred to. The suspension obtained is mixed at a temperature of 80 °C for 1 hour. From that moment, all subsequent operations are carried out in air, without the use of a protective atmosphere of argon. The reaction mixture is cooled to room temperature, diluted with n-pentane (6 ml), filtered using a Schott filter, rinsed with n-pentane (2 x 10 ml) , and dried under pressure, obtaining a catalyst with formula 19, as a dark green solid (0.113 mg, 48%) .
XH NMR (500 MHz, CD2C12) : 18.69 (s, =CH, 1H) , 7.99-7.94 (m ovl, 2H) , 7.95 (d, J = 7.5 Hz, 1H) , 7.32-7.22 (m, 2H) , 7.18 (dd, J = 8.0, 8.0 Hz, 1H) , 7.13 (s, 1H) , 7.02 (s, 1H) , 6.83 (s, 1H) , 5.63 (s, 1H) , 4.32-4.22 (m, 1H) ,
4.15-4.04 (m, 2H) , 3.97-3.88 (m, 1H) , 2.75 (s, 3H) ,
2.57 (s, 3H) , 2.47 (s, 3H) , 2.37 (s, 3H) , 2.02 (s, 3H) ,
1.50 (s, 3H) .
13C NMR (125 MHz, CD2C12) : 284.2, 216.3, 144.6, 140.7, 140.0, 138.6, 138.5, 138.1, 136.9, 136.3, 136.1, 135.7, 134.9, 133.0, 132.9, 132.4, 131.3, 131.2, 130.04, 130.00, 128.8, 127.4, 127.2, 87.6, 52.1, 51.5, 21.3, 21.1, 20.4 (ovl), 19.1, 18.0.
Example XII:
Testing the catalytic activity for cyclisation of diethyl diallylmalonate using XH-NMR methods (in accordance with diagram III) .
1 mol% catalyst
Figure imgf000032_0001
Diagram III
Solution A:
To the 5 ml measurement flask is added diethyl diallylmalonate (0.2882 g, 0.12 mmol) , and CD2C12 is added up to the nominal value.
Solution B:
To a 1.5 ml vial is added a catalyst in accordance with the invention (12-19, 0.012 mmol), and 1 ml of CD2C12 is added . Reaction profile measurements:
To an NMR tube is added 0.5 ml of solution A, and a micro-syringe is used to add 0.1 ml of solution B. The tube is closed with a cork, and, simultaneously, the time starts to be calculated and the content is mixed and placed in an NMR thermostatic device (at a temperature of 25°C, unless otherwise indicated), with successive XH NMR spectra being recorded over a total period of 75 minutes. In an identical manner, the activity is studied of the commercially available catalysts 5a and 6a. On the basis of the integration of signals δ 2.6-2.9 ppm, conversions are determined, and the results are presented in Figure 1 , which shows progress during the course of the diethyl diallylmalonate cyclisation reaction in relation to various catalysts (XH NMR) .
On the basis of data obtained from tests of the catalytic activity of the complexes in accordance with the invention, it can be found that, at a temperature of 25°C, they are much more active than the commercially available catalyst of formula 6a.
Example XIII:
Test of the effect of temperature on the catalytic activity of complexes with formulae 15 and 18 in diethyl diallylmalonate cyclisation using 1R NMR methods (in accordance with Diagram III) . The test was carried out in accordance with the procedure described in example XII at temperatures of 25, 40, and 55°C. The reactions carried out at a temperature of 55°C were carried out in an NMR Wilmad pressure tube. The results obtained are presented in Figure 2 and Figure 3, which show progress during the course of the diethyl diallylmalonate cyclisation reaction at various temperatures (by XH NMR) .
The results obtained show that the catalysts in accordance with the invention show thermal stability (and can also act at an elevated temperature) , and, thanks to changes in activity as a function of temperature, the course of catalytic processes can be easily controlled.
Example XIV:
Examples of application
Tests were carried out into catalytic activity with various substrates in accordance with Diagrams IV-X (the results are shown in tables 1-7 respectively) .
o p catalyst, 5 mol
Figure imgf000034_0001
toluene, 80°C
1 mol 2 mol
Diagram IV
Table 1 : Results of reactions on a model substrate in accordance with Diagram IV
Figure imgf000034_0003
Figure imgf000034_0002
toluene,
80°C
1 mol 2 mol
Diagram V Table 2 : Results of reactions on a model substrate in accordance with Diagram V
Figure imgf000035_0003
Figure imgf000035_0001
toluene,
hours, 80
1 mol 2 mol
Diagram VI
Table 3 : Results of reactions on a model substrate accordance with Diagram VI
Figure imgf000035_0004
Figure imgf000035_0002
toluene, 6
hours
boiling
point
1 mol 6 mol
Diagram VII Table 4 : Results of reactions on a model substrate in accordance with Diagram VII
Figure imgf000036_0003
Figure imgf000036_0001
toluene, 7
hours
boiling
point
6 mol mol
Diagram
Table 5 : Results of reactions on a model substrate accordance with Diagram VIII
Figure imgf000036_0004
Figure imgf000036_0002
Diagram IX Table 6 : Results of reactions on a model substrate in accordance with Diagram IX
Figure imgf000037_0002
catalyst, 5 mol%
toluene, 6 hours
room temperature
Figure imgf000037_0001
Diagram X
Table 7 : Results of reactions on a model substrate
accordance with Diagram X
Figure imgf000037_0003
The results presented in tables 3, 4, and 7 show clearly that the complexes in accordance with the invention are much more active than the catalyst 6a, which is known from the state of the art. Example XV:
An example of the application of new ruthenium complexes in accordance with the invention as ROMP-type (ring-opening metathesis polymerisation-type) poly- merisation catalysts.
Obtaining the polydicyclopentadiene:
To the flask is added dicyclopentadiene (0.132 g, 1.0 mmol) in CH2CI2 (5 ml) , and mixing takes place at room temperature. Then, solution is added of the catalyst with formula 14 (0.0000025 g, 0.0003 mol%) , and the contents of the flask are mixed at the same temperature for 1 minute. The contents of the flask are poured into another vessel containing 15 ml of methyl alcohol, and a solid precipitates, which is separated by filtration and dried at reduced pressure with the use of a pressure pump. Polydicyclopentadiene is obtained as an elastic white solid.
This example demonstrates that complexes in accordance with the invention may successfully be applied in a ROMP-type polymerisation reaction.
On the basis of the examples of embodiment presented above, it can be found that ruthenium complexes in accordance with the invention show high catalytic activity in comparison with complexes known from the state of the art. In addition, complexes in accordance with the invention are stable at an elevated temperature and may be stored without a protective gas atmosphere . Example XVI :
Synthesis of a catalyst with formula 31 (in accordance with Diagram II) .
Figure imgf000039_0001
Formula 31
Procedure: using a protective atmosphere of argon, the styrene derivative l-bromo-2- (1-propenyl) -4 -methyl- benzene (254 mg, 1.2 mmol) and the solid carbene ruthenium complex with formula 6b ('catalyst M31 ' , Umicore AG & Co KG; 749 mg, 1 mmol) are combined in a Schlenk flask and 20 ml of dry, deoxygenated toluene is added. The suspension obtained is stirred at a temperature of 80 °C for 15 minutes under argon. In the course of the reaction, the M31 complex dissolves within 3-5 minutes, while in 5-10 minutes a green precipitate is observed. The reaction mixture is cooled to room temperature, filtered on a Schott filter, washed with toluene and dried under vacuum obtaining catalyst with formula 31 as green powder (89 mg, 0.13 mmol, 13%) . XH NMR (500 MHz, CD2C12) : 17.75 (d, J=l .0 Hz, Ru=CH, 1H) , 7.40 (d, J=8.0 Hz, 1H) , 7.32 (dd, J=0.5, 8.0Hz, 1H) , 7.16 (s, 1H) , 7.11 (s, 1H) , 6.98 (s, 1H) , 6.86 (d, J=0.5 Hz, 1H) , 6.11 (s, 1H) , 4.24-4.15 (m, 1H) , 4.11- 4.02 (m, 1H) , 4.01-3.92 (m, 1H) , 3.90-3.82 (m, 1H) , 2.62 (s, 3H) , 2.45 (s, 3H) , 2.44 (s, 3H) , 2.42 (s, 3H) , 2.40 (s, 3H) , 2.22 (s, 3H) , 1.54 (s, 3H) .
13C NMR (125 MHz, CD2C12) : 279.0, 214.5, 151.8, 140.8, 140.3, 139.8, 138.9, 138.0, 136.9, 136.1, 135.5, 131.7, 131.2, 131.0, 130.1, 129.7, 129.2, 128.5, 127.3, 123.0, 51.9, 51.6, 21.4, 21.2, 20.9, 20.2, 19.2, 18.6, 17.2. Trace signals of the solvent (toluene) were not listed.
Example XVII:
Synthesis of a catalyst with formula 32 (in accordance with Diagram II) .
Figure imgf000040_0001
Formula 32
Procedure: using a protective atmosphere of argon, the styrene derivative l-bromo-2- (1-propenyl) -4-methoxy- benzene (545 mg, 2.4 mmol) and the solid carbene ruthenium complex with formula 6b ('catalyst M31 ' , Umicore AG & Co KG; 1497 mg, 2 mmol) are combined in a Schlenk flask and 40 ml of dry, deoxygenated toluene is added. The suspension obtained is stirred at a temperature of 80 °C for 15 minutes under argon. In the course of the reaction, the M31 complex dissolves within 3-5 minutes, while in 5-10 minutes a green precipitate is observed. The reaction mixture is cooled to room temperature, filtered on a Schott filter, washed with toluene and dried under vacuum obtaining a catalyst with formula 32, as a green powder (396 mg, 0.58 mmol, 29%) . lR NMR (500 MHz, CD2C12) : 17.76 (d, J=l .0 Hz, Ru=CH, 1H) , 7.40 (dd, J=1.0, 6.7 Hz, 1H) , 7.16 (s, 1H) , 7.12 (s, 1H) , 7.06 (dd, J=3.0, 8.6Hz, 1H) , 6.96 (s, 1H) , 6.60 (d, J=3.0 Hz, 1H) , 6.15 (s, 1H) , 4.25-4.15 (m, 1H) , 4.11-4.04 (m, 1H) , 4.01-3.94 (m, 1H) , 3.90-3.83 (m, 1H) , 3.81 (s, OCH3, 3H) , 2.61 (s, 3H) , 2.43 (s, 3H) , 2.42 (s, 3H) , 2.40 (s, 3H) , 2.20 (s, 3H) , 1.60 (s, 3H) . iJC NMR (125 MHz, CD2C12) : 278.2, 214.3, 160.9, 152.7, 140.8, 140.3, 138.9, 137.9, 136.8, 136.0, 135.4, 131.6, 131.0, 130.1, 129.7, 129.2, 129.0, 116.2, 116.0, 111.5, 56.2, 51.9, 51.6, 21.3, 20.9, 20.2, 19.1, 18.5, 17.3. Trace signals of the solvent (toluene) were not listed.

Claims

Patent claims
1. New complexes of ruthenium with formula 1,
Figure imgf000042_0001
formula 1 wherein
L1 denotes an inert ligand;
Z1 and Z2 denote, independently, an anion ligand;
X denotes a halogen atom;
R1 denotes an atom of hydrogen, a halogen atom, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C3-C12 cycloalkenyl , C2-C12 alkynyl, C3-C12 cycloalkynyl, C1-C12 alkoxyl, C5-C20 aryl, C5-C20 heteroaryl, or 3-12- membered heterocycle;
A denotes a bivalent radical selected from a group comprising C1-C12 alkylene, C2-C12 alkenylene, C2-C12 alkynylene, C5-C20 arylene, or C5-C20 heteroarylene, in which the C1-C12 alkylene, the C2-C12 alkenylene, the C2-C12 alkynylene, the C5-C20 arylene, and the C5- C20 heteroarylene may be optionally substituted with at least one functional group R2 ;
each R2 functional group denotes, independently, a halogen atom, C1-C12 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, -OR3, -SR3, -S(0)mR3, -S02NR3R4, -S(0)2OR3, - N02, -NO, -SCN, -NR3R4, -CN, -C(0)R3, -OC(0)R3, - 0(CR3R4)nR5, -NR3C(0)R4, - (CR3R4) nC (0) OR5, - (CR3R4) nOR5,
-C (=NR3) NR4R5, -NR3C (0) NR4R5, -NR3S(0)pR4,
NC (=0) R3C (=0) R4, -NR3P (=0) R4R5, -NR3As (=0) R4R5, -PR3R4, -POR3R4, -POR3OR4, -P(=0)R3R4, -P(=0)OR3R4, P(=0)OR3OR4, -AsR3R4, -AsOR3R4, -AsOR3OR4, -As(=0)R3R4, -As (=0) OR3R4, -As (=0) OR3OR4, -NR3-C (=NR4) NR5R6, C(=0)R3, -C(=0)OR3, -C(=S)OR3, -C(=0)SR3, -C(=S)SR3, - C(=S)NR3R4, -SiR3R4R5, -SiOR3R4R5, -SiOR3OR4R5, SiOR3OR4OR5, - (CR3R4) n (3-12-membered heterocycle), (CR3R4)n(C3-C12 cycloalkyl), - (CR3R4) n (C5-C20 aryl) , - (CR3R4) n (5-12-membered heteroaryl), - (CR3R4) nC (0) NR5R6, or - (CR3R4) nC (0) R5;
and/or R2 groups with adjacent atoms may bond together, creating C5-C20 aryl or 3-12-membered heterocycle; and/or R2 groups with adjacent atoms may bond with the R1 group, creating C5-C20 aryl, indenylene, heteroindenylene, 3-12-membered heterocycle, and polycyclic or heteropolycyclic arrangements, whilst the C5-C20 aryl, indenylene, heteroindenylene, 3-12- membered heterocycle, and polycyclic or heteropolycyclic arrangements may be substituted with at least one functional group selected from the group comprising a halogen atom, C1-C12 alkyl, C2-C12 alkenyl, C2-Ci2 alkynyl, -OR3, -SR3, -S(0)mR3, S02NR3R4, -S(0)2OR3, -NO2, -NO, -SCN, -NR3R4, -CN, - C(0)R3, -OC(0)R3, -0 (CR3R4) nR5, -NR3C(0)R4,
(CR3R4) nC (0) OR5, - (CR3R4) nOR5, -C (=NR3) NR454,
NR3C (0) NR4R5, -NR3S(0)pR4, -NC (=0) R3C (=0) R4,
NR3P (=0) R4R5, -NR3As (=0) R4R5, -PR3R4, -POR3R4, -POR3OR4, -P(=0)R3R4, -P(=0)OR3R4, -P (=0) OR3OR4, -AsR3R4, AsOR3R4, -AsOR3OR4, -As(=0)R3R4, -As (=0) OR3R4,
As (=0) OR3OR4, -NR3-C (=NR4) NR5R6, -C(=0)R3, -C(=0)0R3, - C(=S)0R3, -C(=0)SR3, -C(=S)SR3, -C(=S)NR3R4, -SiR3R4R5, -SiOR3R4R5, -SiOR3OR4R5,
-SiOR3OR4OR5, - (CR3R4) n (3-12-membered heterocycle), - (CR3R4)n(C3-C12 cycloalkyl), - (CR3R4) n (C5-C20 aryl), -
(CR3R4) n (5-12-membered heteroaryl), - (CR3R4) nC (0) NR5R6, or - (CR3R4) nC (0) R5;
each functional group R3, R4, R5, and R6 denotes, independently, an atom of hydrogen, a halogen atom, C1-C12 alkyl, C2-Ci2 alkenyl, C2-Ci2 alkynyl, C3-C12 cycloalkyl, C5-C20 aryl, 5-12-membered heterocycle; each m denotes, independently, 0, 1, or 2;
each n denotes, independently, 0, 1, 2, 3, or 4;
each p denotes, independently, 1 or 2.
2. Complexes according to Claim 1,
characterised in that
anion ligands Z1 and Z2 denote, independently, a halogen atom, the group - CN , -SCN, -OR13, -SR13, -0(C=0)R13, - 0(S02)R13, -OSiR3 13, where R13 denotes C1 - C12 alkyl, C3 - C12 cycloalkyl, C2-C12 alkenyl, or C5-C20 aryl, which may be optionally substituted with at least one Ci - C12 alkyl, C1 - C12 perhalogenalkyl, C1 - C12 alkoxyl, or a halogen atom; and
R1 denotes an atom of hydrogen,
the inert ligand L1 is selected from a group comprising -P(R7)3, -P(OR7)3, or a N-heterocyclic carbene ligand with formula 7a, 7b, 7c, 7d, 7e, 7f, 7g, 7h, 7i, 7j, 7k, 71, 7m, 7n, 7o, or 7p:
Figure imgf000044_0001
formula 7a formula 7b formula 7c formula 7d
Figure imgf000044_0002
formula 7e formula 7f formula 7g formula 7h
Figure imgf000044_0003
formula 7i formula 7j formula 7k formula 71
Figure imgf000044_0004
formula 7m formula 7n formula 7o formula 7p wherein
each R7 denotes, independently, C1-C12 alkyl, C3-C12 cycloalkyl, C5-C20 aryl, or 5-12-membered heteroaryl; each R8, R9, R10, R11, and R12 denote, independently, an atom of hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C2- C12 alkenyl, or C5-C20 aryl, which may be optionally substituted with at least one C1-C12 alkyl, C1-C12 perhalogenalkyl , C1-C12 alkoxyl, or a halogen atom, and the groups R8, R9, R10, R11, and R12 may optionally bond with each other,
X1 and X2 denote, independently, a halogen atom.
3. Complexes according to Claim 1 or 2,
characterised in that
Z1 and Z2 each denote an atom of chlorine;
X denotes an atom of bromine or iodine; and
Ri denotes an atom of hydrogen,
A denotes -1 , 2-phenylene, -1 , 2-naphthylene, -2,3- naphthylene or -1 , 8-naphthylene, which may be substituted with at least one functional group selected from a group comprising -NO2, - Me2," and the inert ligand L1 denotes a ligand with formula 7a or
7b;
Figure imgf000045_0001
formula 7a formula 7b in which the functional groups R8, R9, R10, and R11 may have the meaning described above.
4. Method of producing the ruthenium complexes according to Claim 1,
characterised in that the compound with formula 9
Figure imgf000046_0001
formula 9 in which R and R denote, independently, an atom of hydrogen or the alkyl group C1-C12;
R1 denotes hydrogen, a halogen atom, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C3-C12 cycloalkenyl , C2-C12 alkynyl, C3-C12 cycloalkynyl , C1-C12 alkoxyl, C5-C20 aryl, C5-C20 heteroaryl, or 3-12-membered heterocycle;
X denotes a halogen atom;
A denotes a bivalent radical selected from a group comprising C1-C12 alkylene, C2-C12 alkenylene, C2-C12 alkynylene, C5-C20 arylene, or C5-C20 heteroarylene, in which the C1-C12 alkylene, the C2-C12 alkenylene, the C2-C12 alkynylene, the C5-C20 arylene, and the C5- C20 heteroarylene may be optionally substituted with at least one functional group R2;
where each R2 functional group denotes, independently, a halogen atom, C1-C12 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, -OR3, -SR3, -S(0)mR3, -S02NR3R4, -S(0)2OR3, - N02, -NO, -SCN, -NR3R4, -CN, -C(0)R3, -OC(0)R3, - 0(CR3R4)n 5, -NR3C(0)R4, - (CR3R4) nC (0) OR5, - (CR3R4) nOR5, -C (=NR3) NR454, -NR3C (0) NR4R5, -NR3S(0)pR4,
NC (=0) R3C (=0) R4, -NR3P (=0) R4R5, -NR3As (=0) R4R5, -PR3R4,
-POR3R4, -POR3OR4, -P(=0)R3R4, -P(=0)OR3R4, P(=0)OR3OR4, -AsR3R4, -AsOR3R4, -AsOR3OR4, -As(=0)R3R4, -As (=0) OR3R4, -As (=0) OR3OR4, -NR3-C (=NR4) NR5R6, C(=0)R3, -C(=0)0R3, -C(=S)0R3, -C(=0)SR3, -C(=S)SR3, - C(=S)NR3R4, -SiR3R4R5, -SiOR3R4R5, -SiOR3OR4R5,
SiOR3OR4OR5, - (CR3R4) n (3-12-membered heterocycle), (CR3R4)n(C3-C12 cycloalkyl), - (CR3R4) n (C5-C20 aryl), - (CR3R4) n (5-12-membered heteroaryl), - (CR3R4) nC (0) NR5R6, or - (CR3R4) nC (0) R5; and/or R groups with adjacent atoms may bond together, creating C5-C20 aryl or 3-12-membered heterocycle; and/or R2 groups with adjacent atoms may bond with the R1 group, creating C5-C20 aryl, indenylene, heteroindenylene, 3-12-membered heterocycle, and polycyclic or heteropolycyclic arrangements, whilst the C5-C20 aryl, indenylene, heteroindenylene, 3-12- membered heterocycle, and polycyclic or heteropolycyclic arrangements may be substituted with at least one functional group selected from the group comprising a halogen atom, C1-C12 alkyl, C2-C12 alkenyl, C2-Ci2 alkynyl, -OR3, -SR3, -S(0)mR3, S02NR3R4, -S(0)2OR3, -NO2, -NO, -SCN, -NR3R4, -CN, - C(0)R3, -OC(0)R3, -0 (CR3R4) n 5, -NR3C(0)R4, (CR3R4) nC (0) OR5, - (CR3R4) nOR5, -C (=NR3) NR4R5, NR3C (0) NR4R5, -NR3S(0)pR4, -NC (=0) R3C (=0) R4, NR3P (=0) R4R5, -NR3As (=0) R4R5, -PR3R4, -POR3R4, -POR3OR4, -P(=0)R3R4, -P(=0)OR3R4, -P (=0) OR3OR4, -AsR3R4, AsOR3R4, -AsOR3OR4, -As(=0)R3R4, -As (=0) OR3R4, As (=0) OR3OR4, -NR3-C (=NR4) NR5R6, -C(=0)R3, -C(=0)0R3, - C(=S)0R3, -C(=0)SR3, -C(=S)SR3, -C(=S)NR3R4, -SiR3R4R5, -SiOR3R4R5, -SiOR3OR4R5, -SiOR3OR4OR5, - (CR3R4) n (3-12- membered heterocycle), - (CR3R4) n (C3-C12 cycloalkyl) , - (CR3R4) n (C5-C20 aryl), - (CR3R4) n (5-12-membered heteroaryl), - (CR3R4) nC (0) NR5R6, or - (CR3R4) nC (0) R5; each functional group R3, R4, R5, and R6 denotes, independently, an atom of hydrogen, a halogen atom, C1-C12 alkyl, C2-Ci2 alkenyl, C2-Ci2 alkynyl, C3-C12 cycloalkyl, C5-C20 aryl, 5-12-membered heterocycle; each m denotes, independently, 0, 1, or 2;
each n denotes, independently, 0, 1, 2, 3, or 4;
each p denotes, independently, 1 or 2;
undergoes a reaction with a carbene ruthenium complex with formula 11a, lib, 11c, or lid:
Figure imgf000048_0001
formula 11a formula lib formula 11c formula lid in which
L1, L2, and L3 denote, independently, an inert ligand; Z1 and Z2 denote, independently, an anion ligand;
R16 has the same meaning as R1 in formula 9;
R17 denotes an atom of hydrogen, C5-C20 aryl, C5-C20 heteroaryl, vinyl, or allenyl.
5. Method according to Claim 4,
characterised in that
the reaction is carried out in the presence of anhydrous halogen salts of copper (I) such as CuBr or CuCl in the presence of Br0nsted acids such as H2SO4, HC1, HNO3, H3PO4, sulphonated polymers (Nafion-H) , or other acids bonded with a fixed substrate, in a solvent .
6. Method according to Claim 4 or 5,
characterised in that
the reaction is carried out at a temperature in the range of 0-120°C.
7. Method according to Claim 4 or 5 or 6,
characterised in that
the reaction is carried out in a protic or aprotic solvent or a chlorinated solvent or in an aromatic hydrocarbon solvent, or in mixtures thereof.
8. Method according to any one of Claims 4 to 7, characterised in that
the reaction is carried out in a solvent such as methylene chloride and/or toluene.
9. Use of the ruthenium complexes of formula 1 as (pre) catalysts in metathesis processes.
Use according to Claim 9,
characterised in that the ruthenium complexes are used as (pre) catalysts in ring-opening metathesis reactions, homometathesis , cross-metathesis, metathesis of the alkene-alkyne (ene-yne) type, ring-closing metathesis or ROMP-type polymerisation reactions .
11. Complexes according to Claim 1 or 2,
characterised in that
Z1 and Z2 each denote an atom of chlorine;
X denotes an atom of bromine or iodine; and
Ri denotes an atom of hydrogen,
A denotes -1 , 2-phenylene, -1 , 2-naphthylene, -2,3- naphthylene or -1 , 8-naphthylene, which may be substituted with at least one functional group selected from a group comprising -OMe, -Me and the inert ligand L1 denotes a ligand with formula 7a or
7b;
Figure imgf000049_0001
formula 7a formula 7b in which the functional groups R , R , R 10 and R may have the meaning described above.
PCT/EP2012/060498 2011-06-06 2012-06-04 New complexes of ruthenium, method for their preparation, and their application in olefin metathesis reactions WO2012168183A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BR112013031131A BR112013031131A2 (en) 2011-06-06 2012-06-04 ruthenium complexes, method for their preparation and application in olefin metathesis reactions
CN201280027153.4A CN103648644B (en) 2011-06-06 2012-06-04 New ruthenium complex, its preparation method, and the application in olefin metathesis reaction
EP12725437.3A EP2718016B1 (en) 2011-06-06 2012-06-04 New complexes of ruthenium, method for their preparation, and their application in olefin metathesis reactions
JP2014514017A JP6198723B2 (en) 2011-06-06 2012-06-04 Novel complex of ruthenium, process for its preparation and its application in olefin metathesis reactions
US14/116,378 US9074028B2 (en) 2011-06-06 2012-06-04 Complexes of ruthenum, method for their preparation, and their application in olefin metathesis reactions
PL12725437T PL2718016T3 (en) 2011-06-06 2012-06-04 New complexes of ruthenium, method for their preparation, and their application in olefin metathesis reactions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PLP.395131 2011-06-06
PL395131A PL216649B1 (en) 2011-06-06 2011-06-06 New ruthenium complexes, process for the preparation thereof and the use thereof in olefin metathesis reactions

Publications (1)

Publication Number Publication Date
WO2012168183A1 true WO2012168183A1 (en) 2012-12-13

Family

ID=46208061

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2012/060498 WO2012168183A1 (en) 2011-06-06 2012-06-04 New complexes of ruthenium, method for their preparation, and their application in olefin metathesis reactions

Country Status (8)

Country Link
US (1) US9074028B2 (en)
EP (1) EP2718016B1 (en)
JP (1) JP6198723B2 (en)
CN (1) CN103648644B (en)
BR (1) BR112013031131A2 (en)
HU (1) HUE046857T2 (en)
PL (2) PL216649B1 (en)
WO (1) WO2012168183A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
EP3008078B1 (en) 2013-06-12 2018-12-19 Trustees of Boston College Catalysts for efficient z-selective metathesis
WO2020201314A1 (en) * 2019-04-02 2020-10-08 Apeiron Synthesis Spolka Akcyjna New use of metal complexes having organic ligands for activating olefin metathesis ruthenium (pre)catalysts
US11214818B2 (en) 2016-06-06 2022-01-04 Provivi, Inc. Semi-biosynthetic production of fatty alcohols and fatty aldehydes

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL227609B1 (en) 2012-11-15 2018-01-31 Univ Warszawski New ruthenium complexes, their preparation and their use
CN114908370B (en) * 2022-03-31 2023-11-10 西湖大学 Copper-based CO 2 Preparation method and application of reduced molecular catalyst

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070043180A1 (en) * 2005-07-04 2007-02-22 Zheng-Yun James Zhan Recyclable ruthenium catalysts for metathesis reactions
EP1914229A1 (en) 2005-08-09 2008-04-23 Daiichi Sankyo Company, Limited Novel cercosporamide derivative
US20080275247A1 (en) * 2007-05-03 2008-11-06 Renat Kadyrov Sulphur-containing metathesis catalysts

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL199412B1 (en) 2002-10-15 2008-09-30 Boehringer Ingelheim Int Ruthenium new complexes as (pre) catalytic agents of permutation reaction, new derivatives of 2-alkoxy-5-nitrostyrene as intermediate compounds and method of their receiving
GB0601394D0 (en) * 2006-01-24 2006-03-01 Hemocorm Ltd Therapeutic delivery of carbon monoxide
EP2027920B1 (en) * 2007-08-21 2014-10-08 LANXESS Deutschland GmbH Catalysts for metathesis reactions
EP2260047B2 (en) 2008-04-08 2016-07-20 Evonik Degussa GmbH Method for manufacturing ruthenium carbene complexes
CN102083798B (en) 2008-04-09 2016-10-26 马特里亚公司 With the ruthenium olefin metathesis catalyst with the N-heterocyclic carbene ligand replacing skeleton
WO2010151879A1 (en) * 2009-06-26 2010-12-29 The Trustees Of Columbia University In The City Of New York Photolabile compounds
EP2428269A1 (en) * 2010-09-08 2012-03-14 Bergen Teknologioverføring AS Novel olefin metathesis catalysts

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070043180A1 (en) * 2005-07-04 2007-02-22 Zheng-Yun James Zhan Recyclable ruthenium catalysts for metathesis reactions
EP1914229A1 (en) 2005-08-09 2008-04-23 Daiichi Sankyo Company, Limited Novel cercosporamide derivative
US20080275247A1 (en) * 2007-05-03 2008-11-06 Renat Kadyrov Sulphur-containing metathesis catalysts

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
ANGEW. CHEM. INT. ED., vol. 114, 2002, pages 832 - 834
ANGEW. CHEMIE INT. ED., vol. 114, 2002, pages 2509 - 2511
ANGEW. CHEMIE INT. ED., vol. 114, 2002, pages 832 - 834
CHEM. REV., vol. 109, 2009, pages 3445
HEJL AA ET AL: "Latent Olefin Metathesis Catalysts Featuring Chelating Alkylidenes", ORGANOMETALLICS, ACS, WASHINGTON, DC, US, vol. 25, no. 26, 1 January 2006 (2006-01-01), pages 6149 - 6154, XP002496195, ISSN: 0276-7333, [retrieved on 20061114], DOI: 10.1021/OM060620U *
J. AM. CHEM. SOC., vol. 122, 2000, pages 8168 - 8179
J. AM. CHEM. SOC., vol. 125, 2003, pages 4804 - 4807
SYNLETT, 2007, pages 929 - 933
TETRAHEDRON LETT., vol. 41, 2000, pages 9973 - 9976

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3008078B1 (en) 2013-06-12 2018-12-19 Trustees of Boston College Catalysts for efficient z-selective metathesis
EP3868890A1 (en) 2015-11-18 2021-08-25 Provivi, Inc. Microorganisms for the production of insect pheromones and related compounds
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
WO2017087710A2 (en) 2015-11-18 2017-05-26 Provivi, Inc. Production of fatty olefin derivatives via olefin metathesis
US11109596B2 (en) 2015-11-18 2021-09-07 Provivi, Inc. Microorganisms for the production of insect pheromones and related compounds
EP4234522A2 (en) 2015-11-18 2023-08-30 Provivi, Inc. Production of fatty olefin derivatives via olefin metathesis
US11844353B2 (en) 2015-11-18 2023-12-19 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
WO2018213554A1 (en) 2017-05-17 2018-11-22 Provivi, Inc. Microorganisms for the production of insect pheromones and related compounds
US11104921B2 (en) 2017-05-17 2021-08-31 Provivi, Inc. Microorganisms for the production of insect pheromones and related compounds
US11866760B2 (en) 2017-05-17 2024-01-09 Provivi, Inc. Microorganisms for the production of insect pheromones and related compounds
WO2020201314A1 (en) * 2019-04-02 2020-10-08 Apeiron Synthesis Spolka Akcyjna New use of metal complexes having organic ligands for activating olefin metathesis ruthenium (pre)catalysts

Also Published As

Publication number Publication date
US9074028B2 (en) 2015-07-07
BR112013031131A2 (en) 2016-12-06
PL216649B1 (en) 2014-04-30
PL395131A1 (en) 2012-12-17
EP2718016A1 (en) 2014-04-16
CN103648644A (en) 2014-03-19
PL2718016T3 (en) 2020-01-31
EP2718016B1 (en) 2019-08-14
US20140171607A1 (en) 2014-06-19
JP6198723B2 (en) 2017-09-20
JP2014523407A (en) 2014-09-11
HUE046857T2 (en) 2020-03-30
CN103648644B (en) 2016-06-22

Similar Documents

Publication Publication Date Title
EP2718016B1 (en) New complexes of ruthenium, method for their preparation, and their application in olefin metathesis reactions
AU2016330158B2 (en) Process for producing ruthenium complexes and intermediates thereof and their use in olefin metathesis
EP3294747B1 (en) Ruthenium complexes, method of producing them, and their use
EP3548501B1 (en) Novel ruthenium complex, method of its production and its use in reaction of olefine metathesis
PL227609B1 (en) New ruthenium complexes, their preparation and their use
EP2760581B1 (en) Ruthenium complex, method for its preparation and use thereof
PL221841B1 (en) New ruthenium complexes, their preparation and their use in olefin metathesis
WO2023135582A1 (en) New stereoretentive ruthenium complexes, method of their preparation, intermediates used in this method and use of new stereoretentive ruthenium complexes in olefin metathesis reactions
PL245084B1 (en) Method of preparing phosphine (III) from appropriate phosphine oxides (V) and method of preparing phosphine complexes (III) with transition metals
EP4452490A1 (en) New sterically activated chelating ruthenium complexes, method of their preparation and their use in olefin metathesis reactions
EP3947515A1 (en) New use of metal complexes having organic ligands for activating olefin metathesis ruthenium (pre)catalysts
PL216625B1 (en) Ruthenium complexes, their preparation and their use

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12725437

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014514017

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112013031131

Country of ref document: BR

WWE Wipo information: entry into national phase

Ref document number: 14116378

Country of ref document: US

ENP Entry into the national phase

Ref document number: 112013031131

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20131203