EP4081343A2 - Complexe de ruthénium et procédé de mise en ?uvre de réactions de métathèse d'oléfines avec la formation d'une liaison interne à l'aide du complexe de ruthénium utilisé comme catalyseur - Google Patents

Complexe de ruthénium et procédé de mise en ?uvre de réactions de métathèse d'oléfines avec la formation d'une liaison interne à l'aide du complexe de ruthénium utilisé comme catalyseur

Info

Publication number
EP4081343A2
EP4081343A2 EP20845698.8A EP20845698A EP4081343A2 EP 4081343 A2 EP4081343 A2 EP 4081343A2 EP 20845698 A EP20845698 A EP 20845698A EP 4081343 A2 EP4081343 A2 EP 4081343A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
denotes
aryl
perhaloalkyl
cycloalkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20845698.8A
Other languages
German (de)
English (en)
Inventor
Michal CHWALBA
Anna GAWIN
Krzysztof Skowerski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Apeiron Synthesis Sp zoo
Original Assignee
Apeiron Synthesis Sp zoo
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 Apeiron Synthesis Sp zoo filed Critical Apeiron Synthesis Sp zoo
Publication of EP4081343A2 publication Critical patent/EP4081343A2/fr
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • 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)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • 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
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • 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
    • C07C67/343—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 by increase in the number of carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium

Definitions

  • the invention finds application in organic synthesis in its broad sense.
  • the (pre)catalysts most widely described in the literature are complexes of the Grubbs type (Gru), Hoveyda type (Hov), indenylidene, and recently Bertrand type catalysts having carbene cycloalkylamine ligand (CAAC) [ Grubbs etal. Chem. Rev. 2010, 110, 1746-1787; Nolan etal. Chem. Commun. 2014, 50, 10355-10375 ].
  • most of the olefin metathesis catalyst structures are derived from the above-mentioned ruthenium complexes.
  • Gre-II in this process made it possible to significantly reduce the amount of catalyst used, as well as the solvent volume, compared to the process conditions wherein Hov-I catalyst was used.
  • Hov-II-12 catalyst having iodide ligands is known in the art [ Wappel , Urbina-Bianco, C.A., Abbas, M, Albering, J.H., Saf, R, Nolan, S.P., Slugovc, C. Beilstein ./. Org. Chem. 2010, 6, 1091-1098 ].
  • the use of this compound was presented on the example of ring closing metathesis (RCM) and cross-metathesis (CM) reactions.
  • Catalysts bearing iodide ligands have greater steric hindrance, they are latent catalysts, which allowed to effectively use them in polymerization reactions of the ROMP type (they were activated at a temperature of at least 85°C).
  • the present invention relates to a ruthenium complex of general formula (1) wherein
  • R 1 denotes: hydrogen atom; halogen atom; C 1 -C 25 alkyl; C 1 -C 25 perhaloalkyl; C 3 -C 7 cycloalkyl; C 1 -C 25 alkoxy; C 5 -C 24 aryl; C 7 -C 24 aralkyl; C 5 -C 25 heteroaryl; 3-12 membered heterocycle, wherein the alkyl groups may be attached to each other to form a ring; or a group -OR’, -SR’, -NO 2 , -CN, -CONR’R”, -COOR’, -SO 2 R' -SO 2 NR'R", - COR’, in which the groups R’ and R”, each independently, denote C 1 -C 25 alkyl, C 1 -C 25 perhaloalkyl, C 5 -C 24 aryl, C 5 -C 25 heteroaryl or C 5 -C 24 perhaloaryl;
  • R 2 denotes C 1 -C 25 alkyl; C 1 -C 25 perhaloalkyl; C3-C7 cycloalkyl; C 1 -C 25 alkoxy; C 5 -C 24 aryl; a group -R’CONR"OR’, -CONR'R", -COOR’, -SO 2 R' -SO 2 NR’R”, -COR’, in which the groups R’ and R” each independently, denote C 1 -C 25 alkyl, C 1 -C 25 perhaloalkyl, C 5 -C 24 aryl, C 5 -C 25 heteroaryl or C 5 -C 24 perhaloaryl;
  • L denotes a neutral ligand in form of a P(R’) 3 group, wherein each R’ independently denotes C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 5 -C 24 aryl, C 7 -C 24 aralkyl, C 5 -C 24 perhaloaryl, or two R’ are linked together to form a cycloalkyl ring containing a ring phosphorus atom; or L denotes an L -heterocyclic carbene ligand of formula (2a) or (2b): in which: each R 3 and R 4 independently denotes C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 5 -C 20 aryl or C 5 -C 20 heteroaryl, which is optionally substituted with at least one C 1 -C 12 alkyl, C 1 -C 12 perhaloalkyl, C 2 -C 12 alkoxy or a halogen
  • the ruthenium complex according to the invention is selected from the following compounds:
  • the ruthenium complex is used selected from the compounds of the formulae 1-12, 2-12, 3-12, 4-12, 5-12 and 6-12 given above.
  • the reaction is carried out in an organic solvent, preferably selected from toluene, benzene, mesityl ene, di chi orom ethane, ethyl acetate, methyl acetate, tert-butyl methyl ether and cyclopentyl methyl ether.
  • organic solvent preferably selected from toluene, benzene, mesityl ene, di chi orom ethane, ethyl acetate, methyl acetate, tert-butyl methyl ether and cyclopentyl methyl ether.
  • reaction is carried out in the absence of a solvent.
  • the reaction is carried out at a temperature of 0 to 150°C, in particular 20 to 120°C.
  • the reaction time ranges from 1 minute to 24 hours.
  • the compound of formula (1) is added to the reaction mixture in a solid form.
  • the compound of formula (1) is added to the reaction mixture in form of a solution in an organic solvent.
  • the solution of the compound of formula (1) in an organic solvent is added to the reaction mixture by an infusion pump.
  • the method of the invention comprises conducting a metathesis reaction selected from ring closing metathesis (RCM), homometathesis (self-CM) and cross-metathesis (CM).
  • a metathesis reaction selected from ring closing metathesis (RCM), homometathesis (self-CM) and cross-metathesis (CM).
  • Ring-closing metathesis (RCM), homometathesis (self-CM) and cross-metathesis (CM) were particularly highly selective. It was also noted that adding the catalyst according to the invention by an infusion pump allowed to obtain a higher selectivity than adding it portion-wise.
  • carbene as used herein means a particle containing a neutral carbon atom with a valence of two and having two unpaired valence electrons.
  • carrier also includes carbene analogs in which the carbon atom is replaced with another chemical element such as boron, silicon, germanium, tin, lead, nitrogen, phosphorus, sulfur, selenium, tellurium.
  • halogen atom denotes an atom of an element selected from F, Cl, Br, I.
  • alkyl refers to a saturated, linear or branched hydrocarbon substituent with the indicated number of carbon atoms.
  • alkyl substituents are -methyl, -ethyl, -n- propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl, and -n-decyl.
  • Representative branched -(C 1 -C 10 )-alkyls include -isopropyl, -sec-butyl, -isobutyl, -tert-butyl, -isopentyl, - 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-dimethylobutyI, -1,3- dimethylbutyl, -2,2-dimethylbutyl, -2,3-dimethylbutyl, -3, 3 -dimethyl
  • alkoxy refers to an alkyl substituent as defined above attached through an oxygen atom.
  • perhaloalkyl denotes an alkyl group as defined above in which all the hydrogen atoms have been replaced with the same or different halogen atoms.
  • cycloalkyl refers to a saturated mono- or polycyclic hydrocarbon substituent having
  • cycloalkyl substituents are -cyclopropyl, -cyclobutyl, - cyclopentyl, -cyclohexyl, -cycloheptyl, -cyclooctyl, -cyclononyl, -cyclodecyl.
  • alkenyl refers to a saturated, linear or branched non-cyclic hydrocarbon substituent comprising 2-25 carbon atoms and containing at least one carbon-carbon double bond.
  • alkenyl substituents are -vinyl, -allyl, -1-butenyl, -2-butenyl, -isobutylenyl, -1- pentenyl, -2-pentenyl, -3 -methyl- 1-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-
  • aryl refers to an aromatic mono- or polycyclic hydrocarbon substituent having 5-24 carbon atoms.
  • aryl substituents are -phenyl, -tolyl, -xylyl, -naphthyl, -2,4,6- trimethylphenyl, -2 -fluorophenyl, -4-fluorophenyl, -2,4,6-trifluorophenyl, -2,6-difluorophenyl, -4-nitrophenyl.
  • aralkyl refers to an alkyl substituent as defined above substituted with at least one aryl as defined above. Examples of the aralkyl substituent are -benzyl, -diphenylmethyl, - triphenylmethyl and the like.
  • heteroaryl refers to an aromatic, mono- or polycyclic hydrocarbon substituent, having 5-25 carbon atoms, wherein at least one carbon atom has been replaced with a heteroatom selected from O, N and S.
  • heteroaryl substituents are -furyl, - thienyl, -imidazolyl, -oxazolyl, -thiazolyl, -isoxazolyl, -triazolyl, -oxadiazolyl, -thiadiazolyl, - tetrazolyl, -pyridyl, -pyrimidyl, -triazinyl, -indolyl, -benzo [b] furyl, -benzo [b] thienyl, - indazolyl, -benzoimidazolyl, -azaindolyl, -quinolyl, -isoquinolyl, -carbazolyl.
  • heterocycle refers to a saturated or partially unsaturated, mono- or polycyclic hydrocarbon substituent having 3-12 carbon atoms, wherein at least one carbon atom has been replaced by a heteroatom selected from O, N and S.
  • heterocyclic substituents are furyl, thiophenyl, pyrrolyl, oxazolyl, imidazolyl, thiazolyl, isoxazolyl, pyrazolyl, isothiazolyl, triazinyl, pyrrolidinonyl, pyrrolidinyl, hydantoinyl, oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydrothiophenyl, indurinyl, chinolinyl, chrominyl, chinolinyl, chrominyl, furanyl, benzo [b] thiophenyl, indazolyl, purinyl, 4H-quinolys
  • neutral ligand refers to an uncharged substituent capable of coordination with a metallic center (ruthenium atom).
  • ligands are: amines, phosphines and their oxides, orthophosphates (III) and alkyl and aryl phosphates, arsines and their oxides, ethers, alkyl and aryl sulfides, coordinated hydrocarbons, alkyl and aryl halides.
  • anionic ligand refers to a substituent capable of coordination with a metallic center (ruthenium atom) having a charge capable of partially or fully compensating for the charge of the metallic center.
  • ligands are fluoride, chloride, bromide, iodide, cyanide, cyanate and thiocyanate anions, carboxylic acid anions, alcohol anions, phenol anions, thiol and thiophenol anions, delocalized hydrocarbon anions (e.g.
  • organo(sulfuric) acid anions and (organo)phosphorus acid anions as well as esters thereof such as, for example, anions of alkylsulfonic and arylsulfonic acids, anions of alkylphosphoric and arylphosphoric acids, anions of alkyl and aryl esters of sulfuric acid, anions of alkyl and aryl esters of phosphoric acids, anions of alkyl and aryl esters of alkylphosphoric and arylphosphoric acids.
  • the anionic ligand may have neutral groups linked thereto, such as a catechol anion, an acetylacetone anion, and a salicylaldehyde anion.
  • Anionic ligands and neutral ligands may be linked together to form multidentate ligands, for example bidentate ligand, tridentate ligand, tetradentate ligand.
  • multidentate ligands for example bidentate ligand, tridentate ligand, tetradentate ligand.
  • examples of such ligands are: catechol anion, acetylacetone anion and salicylaldehyde anion.
  • heteroatom denotes an atom selected from the group comprising oxygen, sulfur, nitrogen, phosphorus and others.
  • Substrates benzyl(allyl)hex-5-en-2-ynyl carbamate (S1), hexenol acetate (S2b), ethyl undecenoate (S2b) and 9-decenoic acid methyl ester (S3) are commercially available compounds.
  • S1 and S2b were distilled under reduced pressure and stored over activated alumina. All reactions were carried out under argon atmosphere. Toluene was washed with citric acid, water, dried with 4 ⁇ molecular sieves and deoxygenated with argon.
  • composition of the reaction mixtures was determined by gas chromatography using a PerkinElmer Clarus 680 GC apparatus equipped with a GL Sciences InertCap® 5MS / NP capillary column. Individual components of the reaction mixtures were identified by comparing the retention times to commercial standards or those isolated from reaction mixtures for which the structure was confirmed by NMR.
  • Example 1
  • Table 1 Comparison of conversion degree when using iodide and chloride complexes (1 and 2) in the RCM reaction of the S1 substrate.
  • Table 2. Comparison of conversion degree when using iodide and chloride 3-6 complexes in the RCM reaction of the S1 substrate.
  • CM reaction was performed using only iodide complexes, which were added to the mixture by an infusion pump at a dropping rate of 20 ⁇ L/min.
  • the project is co-fmanced by the European Union from the European Regional Development Fund under the Intelligent Development Operational Program 2014-2020, on the basis of the co-financing agreement No. POIR.01.01.01-00-1186 / 15-00.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un complexe de ruthénium de formule générale (I) dans laquelle R1, R2 et L sont tels que définis dans la description. En outre, l'invention concerne un procédé de mise en œuvre d'une réaction de métathèse d'oléfines pour former une liaison C=C interne à l'aide du complexe de ruthénium de formule générale (1) utilisé comme catalyseur.
EP20845698.8A 2019-12-23 2020-12-17 Complexe de ruthénium et procédé de mise en ?uvre de réactions de métathèse d'oléfines avec la formation d'une liaison interne à l'aide du complexe de ruthénium utilisé comme catalyseur Pending EP4081343A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PL432325A PL242934B1 (pl) 2019-12-23 2019-12-23 Kompleks rutenu i zastosowanie kompleksu rutenu jako katalizatora
PCT/IB2020/062079 WO2021130622A2 (fr) 2019-12-23 2020-12-17 Complexe de ruthénium et procédé de mise en œuvre de réactions de métathèse d'oléfines avec la formation d'une liaison interne à l'aide du complexe de ruthénium utilisé comme catalyseur

Publications (1)

Publication Number Publication Date
EP4081343A2 true EP4081343A2 (fr) 2022-11-02

Family

ID=74236238

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20845698.8A Pending EP4081343A2 (fr) 2019-12-23 2020-12-17 Complexe de ruthénium et procédé de mise en ?uvre de réactions de métathèse d'oléfines avec la formation d'une liaison interne à l'aide du complexe de ruthénium utilisé comme catalyseur

Country Status (3)

Country Link
EP (1) EP4081343A2 (fr)
PL (1) PL242934B1 (fr)
WO (1) WO2021130622A2 (fr)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL238806B1 (pl) * 2015-09-30 2021-10-04 Apeiron Synthesis Spolka Akcyjna Kompleks rutenu i sposób jego wytwarzania, związek pośredni stosowany w tym sposobie oraz zastosowanie kompleksu rutenu i związku pośredniego w metatezie olefin
WO2019207096A1 (fr) * 2018-04-27 2019-10-31 Arlanxeo Deutschland Gmbh Utilisation de catalyseurs à base de ruthénium et d'osmium pour la métathèse de caoutchoucs nitrile

Also Published As

Publication number Publication date
WO2021130622A2 (fr) 2021-07-01
PL432325A1 (pl) 2021-06-28
WO2021130622A3 (fr) 2021-08-05
PL242934B1 (pl) 2023-05-22

Similar Documents

Publication Publication Date Title
KR102637889B1 (ko) 루테늄 복합체 및 그의 중간체를 제조하는 방법 및 올레핀 복분해에서 그의 사용방법
IL266559B2 (en) Use of ruthenium complexes in metathesis reactions of olefins
WO2019202509A1 (fr) Nouveaux complexes de ruthénium et leur utilisation dans des réactions de métathèse d'oléfines
EP3820609B1 (fr) Utilisation de complexes de ruthénium n-chélatants dans la réaction de métathèse
EP4081343A2 (fr) Complexe de ruthénium et procédé de mise en ?uvre de réactions de métathèse d'oléfines avec la formation d'une liaison interne à l'aide du complexe de ruthénium utilisé comme catalyseur
JP7466908B2 (ja) オレフィンメタセシス用の触媒前駆体としての有機ルテニウム錯体
EP3548501B1 (fr) Nouveau complexe de ruthénium, son procédé de production et son utilisation dans la réaction de métathèse d'oléfines
WO2023121492A1 (fr) Nouveaux complexes de ruthénium chélatants activés stériquement, leur procédé de préparation et leur utilisation dans des réactions de métathèse d'oléfines
JP5908093B2 (ja) ルテニウムまたはオスミウム錯体、その調製のための方法、およびその使用
WO2023135582A1 (fr) Nouveaux complexes de ruthénium stéréorétentifs, procédé de leur préparation, intermédiaires utilisés dans ce procédé et utilisation de nouveaux complexes de ruthénium stéréorétentifs dans des réactions de métathèse d'oléfines
Sahu et al. Metal–Carbon Multiple Bonded Compounds
WO2023248205A1 (fr) Nouveaux complexes de ruthénium, leur procédé de synthèse, composés intermédiaires utilisés dans ce procédé, leur procédé de synthèse et l'utilisation de nouveaux complexes de ruthénium dans des réactions de métathèse d'oléfines
WO2020201314A1 (fr) Nouvelle utilisation de complexes métalliques ayant des ligands organiques pour activer des (pré)catalyseurs de ruthénium pour la métathèse d'oléfines

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20220719

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230629