WO2026027552A2 - Composés organométallique - Google Patents

Composés organométallique

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Publication number
WO2026027552A2
WO2026027552A2 PCT/EP2025/071813 EP2025071813W WO2026027552A2 WO 2026027552 A2 WO2026027552 A2 WO 2026027552A2 EP 2025071813 W EP2025071813 W EP 2025071813W WO 2026027552 A2 WO2026027552 A2 WO 2026027552A2
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WIPO (PCT)
Prior art keywords
aromatic
compound
zinc
formula
carbon atoms
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Pending
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PCT/EP2025/071813
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English (en)
Inventor
Angelino Doppiu
Sebastian AURIS
Matthias HENROT
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Umicore AG and Co KG
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Umicore AG and Co KG
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Priority claimed from EP24191397.9A external-priority patent/EP4686722A1/fr
Application filed by Umicore AG and Co KG filed Critical Umicore AG and Co KG
Publication of WO2026027552A2 publication Critical patent/WO2026027552A2/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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    • 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
    • B01J31/226—Sulfur, e.g. thiocarbamates
    • 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
    • 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
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc
    • 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
    • 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
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—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

Definitions

  • Ruthenium-based stereo- retentive olefin metathesis catalysts have more become of interest, so novel and more scalable, industrially suitable methods are needed.
  • Aromatic dithiols are valuable compounds in various chemical industries due to their unique properties and applications, but have also become a key starting material in the field of ruthenium-based stereo- retentive olefin metathesis catalysts.
  • EP3008078 shows the use of aromatic 1,2-dithiols as ligands in transition metal complexes for stereoselective metathesis catalysts.
  • Halogenated Aromatics o Processes: Some methods utilize halogenated aromatic compounds as starting materials, which are then reacted with sulfur- containing reagents. o Conditions: These reactions often require high temperatures and prolonged reaction times. o Examples: The conversion of dihalobenzenes to dithiols using sodium sulfide or other sulfur sources.
  • Catalytic Methods o Processes: Catalytic methods involve the use of metal catalysts to facilitate the formation of thiol groups on aromatic rings. o Conditions: These methods can be more efficient but often require expensive and sensitive catalysts. o Examples: Palladium-catalyzed thiolation reactions of aromatic halides.
  • Harsh Reaction Conditions o Issue: Many prior art methods require harsh conditions, such as high temperatures, strong acids or bases, and toxic reagents. o Impact: These conditions can pose safety risks, environmental concerns, and difficulties in scaling up the processes for industrial applications.
  • Cost and Scalability o Issue: The use of expensive catalysts and reagents, as well as the need for specialized equipment, can increase the cost of production. o Impact: High production costs and scalability issues can limit the practical application of these methods in large-scale manufacturing.
  • Polyhedron 2016 (117) 39 265-272 shows several methods for the preparation of thiols and dithiols, focusing on three key approaches.
  • aromatic compounds are directly thiolated using thiolating agents such as thiourea or thiolacetic acid in the presence of catalysts like copper or palladium and are conducted under mild to moderate temperatures, which is straightforward and can be applied to a variety of aromatic substrates.
  • Reduction of disulfides consists of a reduction to thiols using reducing agents such as sodium borohydride (NaBH4) or lithium aluminum hydride (LiAIH4) typically carried out in polar solvents like ethanol or tetra hydrofuran (THF), which provides high yields of thiols and is useful for synthesizing thiols from readily available disulfides.
  • reducing agents such as sodium borohydride (NaBH4) or lithium aluminum hydride (LiAIH4) typically carried out in polar solvents like ethanol or tetra hydrofuran (THF), which provides high yields of thiols and is useful for synthesizing thiols from readily available disulfides.
  • the hydrolysis of thioesters employs hydrolyzation to thiols using bases such as sodium hydroxide (NaOH) or potassium hydroxide (KOH) in aqueous or alcoholic solutions at elevated temperatures, which is efficient and allows for the selective preparation of
  • Catalytic Thiolation relates to thiolation of aromatic halides with catalytic systems involving transition metals such as palladium or nickel and are conducted under mild conditions with the use of ligands to enhance the catalytic activity. This method offers high selectivity and efficiency, making it suitable for complex aromatic compounds.
  • photochemical thiolation thiols are generated through irradiation of aromatic compounds in the presence of sulfur sources and is carried out under UV light or visible light, often in the presence of photosensitizers, resulting in reactions that are environmentally friendly and can be performed under ambient conditions.
  • Enzymatic thiolation makes use of enzymes such as thiolases to catalyze the formation of thiols from precursor molecules.
  • the reactions are conducted in aqueous media at physiological temperatures and pH. They are highly specific and operate under mild conditions, making them suitable for sensitive substrates.
  • SU1421736 shows a method for producing aromatic dithiols by reduction of disulfonyl chlorides to dithiols by reduction with zinc and hydrochloric acid.
  • the thiol groups of the aromatic dithiols are located on different aromatic rings of the compounds.
  • stereo- retentive olefin metathesis catalysts can be prepared by using dithiolates such as (arene-l,2-dithiolato)(eth- ylenediamine)zinc(II) compounds, such as (3,6-dichlorobenzene-l,2-dithio- lato) (ethylenediamine)zinc(II), for example.
  • dithiolates such as (arene-l,2-dithiolato)(eth- ylenediamine)zinc(II) compounds, such as (3,6-dichlorobenzene-l,2-dithio- lato) (ethylenediamine)zinc(II), for example.
  • Such catalysts and their preparation are shown, for example, in WO 2017/100585.
  • Such dithiolate species need to be isolated in a separate step. This isolation is difficult and not possible on a production scale because the required filtration is very slow, difficult and poses hazards as hot chloroform is needed to remove impurities.
  • the product contains ethylenediamine, which is classified as a very toxic substance and has been added to the "Substance of Very High Concern” (SVHC) list of ECHA.
  • SVHC Very High Concern
  • ethylenediamine can have a detrimental effect on the catalyst properties, see for example Fogg et al. : Decomposition of Olefin Metathesis Catalysts by Brpnsted Base: Metallacyclobutane Deprotonation as a Primary Deactivating Event, J. Am. Chem. Soc. 2017, 139, 46, 16446-16449.
  • Zn(ethyl)2 for the in situ generation of a Zn-dithiolate species.
  • Zn(Et) 2 is pyrophoric, sensitive to moisture and thus it is not well suitable for use in production.
  • WO 2014/201300 shows a method for making zinc dithiolate compounds in section [00602] from 3,6-dichlorobenzene-l,2-dithiol with a fourfold molar excess of zinc acetate and ethylenediamine at 22°C for one hour.
  • the reaction product was assigned the following formula:
  • Zinc dithiolates exhibit bad solubility.
  • the zinc dithiolate of WO 2014/201300 is washed with hot chloroform, confirming the bad solubility and thus are bad to characterize and to analyze.
  • section [0084] shows an identical method of making the zinc dithiolate compound under the very same conditions from the very same educts as the zinc dithiolate of WO 2014/201300, but this time the structure shown is compound 10 having the structure given as follows:
  • an aromatic dithiol substituted on adjacent aromatic carbon atoms with thiol groups wherein in a first step an aromatic compound substituted with two leaving groups on adjacent aromatic carbon atoms are reacted with alkali trithiocarbonate to obtain an aromatic benzodithiole-thi- one, which in a subsequent step is reacted / hydrolysed with a base; providing a zinc dithiolate compound by reacting the aromatic dithiol with a zinc carboxylate in an organic solvent;
  • XI and X2 are, independently of each other, are anionic ligands and are the same or different; L and L2 are, independently of each other, neutral electron donor ligands and are the same or different; Ar is an aromatic group which may be substituted and that can be bridged with L, if L is an alkoxy group;
  • ruthenium catalyst of formula 4 or 4a wherein the anionic ligands are a bridging dithiolate forming a ring via its sulfur atoms
  • R1 to R4 are, independently of each other, are selected from hydrogen, halogen, alkyl, aryl, or R.1 with R3, R3 with R4 or R2 with R4 are forming together an aliphatic or aromatic ring.
  • the first reaction is a method for the preparation of 1,2-dithiols, wherein an aromatic compound substituted with leaving groups in the 1,2 position are reacted with an alkali trithiocarbonate to obtain an aromatic benzodithiole- thione, which subsequently is hydrolysed with a base. It is the first step of the method for making a ruthenium catalyst as claimed herein. This method also is a subject of this patent application.
  • the second reaction is the method for the preparation of a zinc dithiolate compound by reacting the aromatic dithiol with a zinc carboxylate in an organic solvent. It is the second step of the method for making a ruthenium catalyst as claimed herein. This method also is a subject of this patent application.
  • This problem is solved by a method for the preparation of aromatic dithiols substituted with thiol groups on adjacent aromatic carbon atoms, wherein in a first step an aromatic compound substituted with two leaving groups on adjacent aromatic carbon atoms are reacted with alkali trithiocarbonate to obtain an aromatic benzodithiole-thione, which in a subsequent step is reacted / hydrolysed with a base to obtain an aromatic dithiol substituted with thiol groups on adjacent aromatic carbon atoms.
  • This method addresses the shortcomings of the prior art by providing a more efficient, straightforward, and environmentally friendly approach to synthesizing aromatic dithiols. It allows for the use of a variety of aromatic and heteroaromatic compounds, offers flexibility in the choice of leaving groups and alkali, and employs milder reaction conditions, making the process safer and more scalable for industrial applications.
  • the method provides a more efficient and straightforward approach to synthesizing aromatic dithiols. It allows for the use of a variety of aromatic and heteroaromatic compounds and offers flexibility in the choice of leaving groups and alkali.
  • the milder reaction conditions and the use of polar solvents make the process safer and more environmentally friendly.
  • the invention provides a method for the preparation of aromatic dithiols substituted on adjacent aromatic carbon atoms with thiol groups.
  • the method comprises the following steps: a) Reaction with Alkali Trithiocarbonate: An aromatic compound substituted with two leaving groups on adjacent aromatic carbon atoms is reacted with alkali trithiocarbonate to obtain an aromatic benzodithiole- thione. b) Hydrolysis with Base: The aromatic benzodithiole-thione obtained in the first step a) is subsequently reacted or hydrolyzed with a base to yield the desired aromatic dithiols.
  • the Invention can exhibit the following embodiments:
  • Method of item 1 wherein the leaving groups are selected from the group consisting of halogens or pseudohalogens, or are selected from the group consisting of Cl, Br, I, -OCN and combinations thereof. 3. Method of any of items 1 or 2, wherein the aromatic dithiols and the aromatic compounds are comprising an aromatic or heteroaromatic ring or ring system exhibiting 5 to 26 carbon atoms, or 6 to 22 carbon atoms, or 6 to 16, or 6 to 8 carbon atoms.
  • the method involves reacting an aromatic compound, substituted with two leaving groups on adjacent aromatic carbon atoms, with alkali trithiocarbonate.
  • the leaving groups can be selected from halogens or pseudohalo- gens, specifically Cl, Br, I, or -OCN.
  • the aromatic dithiols and the aromatic compounds used in this method can comprise an aromatic or heteroaromatic ring or ring system with 5 to 26 carbon atoms, preferably 6 to 22, more preferably 6 to 16, and most preferably 6 to 8 carbon atoms. These compounds can also be further substituted with halogens (F, Cl, Br, I) or alkyl groups having 1 to 5 carbon atoms.
  • the alkali used in the reaction can be selected from lithium, sodium, potassium, or combinations thereof, in particular sodium or potassium, or sodium.
  • the aromatic dithiols obtained can be 1,2-dithiols or, if substituted, 2,3-di- thiols, in particular compounds of formula 2 or formula 2a,
  • R1 to R4 are, independently of each other, are selected from hydrogen, halogen, alkyl, aryl, or R.1 with R3, R3 with R4 or R2 with R4 are forming together an aliphatic or aromatic ring.
  • R.1 to R4 independently of each other, are selected from hydrogen, F, Cl, Br, I, Cl to C8 alkyl, or C5 to C14 aryl, optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C8 alkyl, or C5 to C14 aryl or combinations thereof.
  • R.1 with R3, R3 with R4 or R2 with R4, taken together are forming an aromatic ring or an aromatic ring system exhibiting 5 to 14 carbon atoms; or R1 with R3, R3 with R4 or R2 with R4, taken together, are forming an aromatic ring or an aromatic ring system with 6 to 10 carbon atoms.
  • R3 and R4 taken together, are forming an aromatic ring or ring system which can exhibit 5 to 14 carbon atoms or 6 to 10 carbon atoms, optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C8 alkyl, or Cl to C4 alkyl, or C5 to C14 aryl, or C6 to CIO aryl or combinations thereof.
  • R2 and R4 taken together, are forming an aromatic ring or ring system which can exhibit 5 to 14 carbon atoms or 6 to 10 carbon atoms, optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C8 alkyl, or Cl to C4 alkyl, or C5 to C14 aryl, or C6 to CIO aryl or combinations thereof.
  • R1 and R3, taken together, are forming an aromatic ring or ring system which can exhibit 5 to 14 carbon atoms or 6 to 10 carbon atoms, optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C8 alkyl, or Cl to C4 alkyl, or C5 to C14 aryl, or C6 to CIO aryl or combinations thereof.
  • R1 and R3, taken together, are forming an aromatic ring or ring system which can exhibit 5 to 14 carbon atoms or 6 to 10 carbon atoms, optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C8 alkyl, or Cl to C4 alkyl, or C5 to C14 aryl, or C6 to CIO aryl or combinations thereof; and additionally R2 and R4, taken together, are forming an aromatic ring or ring system which can exhibit 5 to 14 carbon atoms or 6 to 10 carbon atoms, optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C8 alkyl, or Cl to C4 alkyl, or C5 to C14 aryl, or C6 to CIO aryl or combinations thereof.
  • the positions Rl, R2, R3 or R4 not part of an aromatic ring or ring system can be selected from hydrogen, halogen, alkyl, aryl and can in particular be selected from hydrogen, F, Cl, Br, I, Cl to C8 alkyl, or C5 to C14 aryl, optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C8 alkyl, or C5 to C14 aryl or combinations thereof; or the positions Rl, R2, R3 or R4 not part of an aromatic ring or ring system can be selected from hydrogen, halogen, alkyl, aryl and can in particular be selected from hydrogen, F, Cl, Br, I, Cl to C4 alkyl, or C6 to CIO aryl, optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C4 alkyl, or C6 to CIO aryl or combinations thereof.
  • Rl, R2, R3 and R4 are hydrogen, halogen (F, Cl, Br, I), methyl, ethyl n-propy, isopropyl, n-butyl, iso-butyl, tert. -butyl, or phenyl, naphthyl, fluorenyl, phenalenyl, anthracenyl, phenanthrenyl, which each can be unsubstituted or substituted with F, Cl, Br, I, Cl to C8 alkyl, such as, for example, methyl, ethyl n-propyl, isopropyl, n-butyl, iso-butyl, tert. -butyl, or combinations thereof.
  • Rl and R2 are hydrogen, halogen, methyl, ethyl or phenyl
  • R3 and R4 are hydrogen, halogen, methyl, ethyl or phenyl or R3 und R4, taken together, are forming an aromatic ring or ring system with 6 to 10 carbon atoms, which are optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C8 alkyl, or C5 to C14 aryl, C6 to CIO aryl or combinations thereof; or
  • Rl to R4 are selected from hydrogen, F, Cl, Br, I, Cl to C8 alkyl, or C5 to C14 aryl, optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C8 alkyl, or C5 to C14 aryl or combinations thereof.
  • R.1 is hydrogen or halogen, or together with R.3 may form an optionally substituted polycyclic ring;
  • R.3 is hydrogen, or together with R.1 may form an optionally substituted polycyclic ring;
  • R4 is hydrogen or together with R2 may form an optionally substituted polycyclic ring;
  • R2 is optionally substituted Ce-io aryl, halogen, or together with R4 may form an optionally substituted polycyclic ring.
  • R1 is halogen;
  • R3 is hydrogen;
  • R4 is hydrogen or together with R2 forms an optionally substituted naphtyl or phenantryl ring;
  • R2 is halogen or together with R4 forms an optionally substituted naphtyl or phenantryl ring.
  • R1 is hydrogen, methyl or Cl, or together with R3 forms 2-phenyl-naphthyl or phenanthryl; R3 is hydrogen, or together with R1 forms 2-phenyl-naphthyl or phenanthryl;
  • R4 is hydrogen or together with R2 forms 2-phenyl-naphthyl, phenanthryl, or methylphenantryl;
  • R2 is Cl, 3,5-dichloro-phenyl, phenyl, t-Bu or together with R4 forms 2-phenyl-naphthyl, phenanthryl or methylphenantryl.
  • R1 is Cl; R3 is hydrogen; R4 is hydrogen or together with R2 forms naphthyl or phenanthryl; R2 is hydrogen, Cl, or together with R4 forms naphtyl or phenanthryl.
  • R1 is hydrogen or Cl
  • R3 is hydrogen
  • R4 is hydrogen or together with R2 forms naphthyl or phenantryl
  • R2 is Cl, phenyl or together with R4 forms naphthyl or phenantryl.
  • R1 is hydrogen, methyl or Cl, or together with R3 forms 2-phenyl-naphthyl or phenanthryl;
  • R3 is hydrogen, or together with R1 forms 2-phenyl-naphthyl or phenanthryl;
  • R4 is hydrogen or together with R2 forms 2-phenyl-naphthyl, naphtyl, phenanthryl, or methylphenantryl;
  • R2 is Cl, 3,5-dichloro-phenyl, phenyl, t-Bu or together with R4 forms 2-phenyl-naphthyl, naphtyl, phenanthryl or methylphenantryl; or
  • R1 is hydrogen or Cl;
  • R3 is hydrogen;
  • R4 is hydrogen or together with R2 form an optionally substituted naphthyl or an optionally substituted phenanthryl ring;
  • R2 is Cl, phenyl or together with R4 form an optionally substituted naphthy
  • R.1, R2, R3 and R4 are fluorine.
  • Rl, R2, R3 and R4 are so selected that the compound of formula 2 or formula 2a is selected from the group consisting of
  • the aromatic compounds used can be dihalobenzenes, tetrahalobenzenes, pentahalobenzenes, or hexahalobenzenes. They can also be heteroaromatic compounds, such as quinoxalines, specifically 2,3-difluoroquinoxaline, 2,3- dichloroquinoxaline, and 2,3-dibromoquinoxaline.
  • the aromatic compounds can be selected from hexahalobenzene, pentahalo- benzene, and 1,2,3,4-tetrahalobenzene.
  • Specific examples include hexafluorobenzene, hexachlorobenzene, hexabromobenzene, 2,3-dichloro- 1,4,5,6-tetrafluorobenzene, 2,3-dibromo-l,4,5,6-tetrafluorobenzene, pentafluorobenzene, 2,3-dichloro-l,4,5-trifluorobenzene, 2,3-dibromo-l,4,5-tri- fluorobenzene, pentachlorobenzene, pentabromobenzene, 1,2,3,4-tetra- fluorobenzene, 2,3-dichloro-l,4-difluorobenzene, 2,3-dibromo-l,4-difluoro-
  • aromatic compound suitable as educts for the aromatic dithiols described above are compounds of formula 2b and 2c
  • A is selected from the group consisting of Cl, Br, I, -OCN and combinations thereof, in particular if A are Cl and the same.
  • the aromatic compound can have the following structure, with A being as defined above, in particular with A being Cl or Br:
  • the alkali trithiocarbonate has the general formula
  • M is an alkali metal as defined above, in particular sodium or potassium, in particular sodium.
  • the alkali trithiocarbonate is employed in a molar excess over the aromatic compound, specifically in an excess of 1.1 to 2 equivalents, preferably 1.2 to 1.9, and more preferably 1.3 to 1.5 equivalents.
  • the reaction of alkali trithiocarbonate with the aromatic compound is carried out at a temperature of about 80°C to 120°C, in particular at 90°C to 110°C or 95°C to 105°C.
  • the reaction of alkali trithiocarbonate with the aromatic compound is carried out in a polar solvent, such as water, dimethyl formamide, or combinations thereof.
  • the base used for hydrolysis is a solution of an alkali hydroxide, in particular sodium or potassium hydroxide, in an alcohol such as methanol, ethanol, n- propanol or isopropanol, more specifically ethanol.
  • the alcohol also serves as the solvent of the reaction of the aromatic benzodithiole-thione with the base.
  • the base that is, the alkali hydroxide, is employed in an excess of 3 to 8 equivalents, preferably 4 to 6, and more preferably about 5 equivalents versus the aromatic benzodithiole-thione.
  • the reaction of the base with the aromatic benzodithiole-thione is carried out at the boiling temperature of the solvent, which usually is a temperature in the range of about 65°C to 100°C or 70°C to 97°C or 75°C to 85°C.
  • invention provides a method for the preparation of aromatic dithiols of formula 2 or formula 2a, Formula 2,
  • R.1 to R4 are, independently of each other, are selected from hydrogen, halogen, alkyl, aryl, or R.1 with R3, R3 with R4 or R2 with R4 are forming together an aliphatic or aromatic ring comprising the steps of: a) Reaction of an alkali trithiocarbonate, in particular a sodium or potas- sium trithiocarbonate, with an aromatic compound of formula 2b or 2c wherein Rl, R2, R3 and R4 as defined above and wherein substituent A is a leaving group and can be the same or different, and wherein A is selected from the group consisting of Cl, Br, I, -OCN and combinations thereof, in particular if A are Cl and the same so as to obtain a benzodithiole-thione, and b) Hydrolysis of the benzodithiole-thione obtained in step a) with an alkali hydroxide, in particular sodium or potassium hydroxide dissolved in an alcohol, in particular
  • a further problem to be solved was the investigation of an in-situ preparation of a Zn-dithiolate species without addition of ethylenediamine or other bases.
  • reaction with an isolated Zn-dithiolate species containing no amine residue was another option to solve the problem.
  • Yet another problem to be solved was the provision of a zinc dithiolate compound having improved solubility in organic solvents.
  • This method provides a significant simplification of the process since no distillation is necessary anymore and no isolation of intermediate products have to be undertaken.
  • the product is easy to isolate in very high yields and purities.
  • a further remarkable advantage is that dithiol of poor quality and low purity can well be used and the production method of the zinc-dithiolato complex acts as a purification step. This is particularly important as the dithiol is commercially available in poor purity (60-90%).
  • the quality problems are solved by using the method of the Invention as means for purification, no distillation for product isolation is needed because a simple filtration and washing procedure for product isolation is sufficient and in addition, in- creased yield and space utilization is effected.
  • the problem is solved by a method for making a zinc dithiolate compound by reacting a compound of formula 2 or formula 2a,
  • R.1 to R4 are as described above in the section on Preparation of aromatic 1,2-dithiols. More specifically R.1 to R4 independently of each other, are selected from hydrogen, halogen, alkyl, aryl, or R1 with R3, R3 with R4 or R2 with R4 are forming together an aliphatic or aromatic ring, with a zinc carboxylate in an organic solvent.
  • Method for making a zinc dithiolate compound by reacting a compound of formula 2 or 2a, or u a a wherein R.1 to R.4 are, independently of each other, are selected from hydrogen, halogen, alkyl, aryl, or R.1 with R3, R3 with R4 or R2 with R4 are forming together an aliphatic or aromatic ring, with a zinc carboxylate in an organic solvent.
  • R1 to R4 are, independently of each other, are selected from hydrogen, F, Cl, Br, I, Cl to C8 alkyl, or C5 to C14 aryl, optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C8 alkyl, or C5 to C14 Aryl or combinations thereof.
  • XI and X2 are, independently of each other, are anionic ligands and are the same or different; L and L2 are, independently of each other, neutral electron donor ligands and are the same or different; Ar is an aromatic group which may be substituted and that can be bridged with L, if L is an alkoxy group;
  • ruthenium catalyst of formula 4 or 4a wherein the anionic ligands are a bridging dithiolate forming a ring via its sulfur atoms with R.1 to R4 being as defined in one or more of the preceding items.
  • R1 to R4 independently of each other, are selected from hydrogen, F, Cl, Br, I, Cl to C8 alkyl, or C5 to C14 aryl, optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C8 alkyl, or C5 to C14 aryl or combinations thereof.
  • R1 with R3, R3 with R4 or R2 with R4, taken together are forming an aromatic ring or an aromatic ring system exhibiting 5 to 14 carbon atoms; or R1 with R3, R3 with R4 or R2 with R4, taken together, are forming an aromatic ring or an aromatic ring system with 6 to 10 carbon atoms.
  • R3 and R4 taken together, are forming an aromatic ring or ring system which can exhibit 5 to 14 carbon atoms or 6 to 10 carbon atoms, optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C8 alkyl, or Cl to C4 alkyl, or C5 to C14 aryl, or C6 to CIO aryl or combinations thereof.
  • R2 and R4 taken together, are forming an aromatic ring or ring system which can exhibit 5 to 14 carbon atoms or 6 to 10 carbon atoms, optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C8 alkyl, or Cl to C4 alkyl, or C5 to C14 aryl, or C6 to CIO aryl or combinations thereof.
  • Rl and R3, taken together, are forming an aromatic ring or ring system which can exhibit 5 to 14 carbon atoms or 6 to 10 carbon atoms, optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C8 alkyl, or Cl to C4 alkyl, or C5 to C14 aryl, or C6 to CIO aryl or combinations thereof.
  • R.1 and R3, taken together, are forming an aromatic ring or ring system which can exhibit 5 to 14 carbon atoms or 6 to 10 carbon atoms, optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C8 alkyl, or Cl to C4 alkyl, or C5 to C14 aryl, or C6 to CIO aryl or combinations thereof; and additionally R2 and R4, taken together, are forming an aromatic ring or ring system which can exhibit 5 to 14 carbon atoms or 6 to 10 carbon atoms, optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C8 alkyl, or Cl to C4 alkyl, or C5 to C14 aryl, or C6 to CIO aryl or combinations thereof.
  • the positions Rl, R2, R3 or R4 not part of an aromatic ring or ring system can be selected from hydrogen, halogen, alkyl, aryl and can in particular be selected from hydrogen, F, Cl, Br, I, Cl to C8 alkyl, or C5 to C14 aryl, optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C8 alkyl, or C5 to C14 aryl or combinations thereof; or the positions Rl, R2, R3 or R4 not part of an aromatic ring or ring system can be selected from hydrogen, halogen, alkyl, aryl and can in particular be selected from hydrogen, F, Cl, Br, I, Cl to C4 alkyl, or C6 to CIO aryl, optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C4 alkyl, or C6 to CIO aryl or combinations thereof.
  • Rl, R2, R3 and R4 are hydrogen, halogen (F, Cl, Br, I), methyl, ethyl n-propy, isopropyl, n-butyl, iso-butyl, tert. -butyl, or phenyl, naphthyl, fluorenyl, phenalenyl, anthracenyl, phenanthrenyl, which each can be unsubstituted or substituted with F, Cl, Br, I, Cl to C8 alkyl, such as, for example, methyl, ethyl n-propyl, isopropyl, n-butyl, iso-butyl, tert. -butyl, or combinations thereof.
  • Rl and R.2 are hydrogen, halogen, methyl, ethyl or phenyl
  • R3 and R4 are hydrogen, halogen, methyl, ethyl or phenyl or R3 und R4, taken together, are forming an aromatic ring or ring system with 6 to 10 carbon atoms, which are optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C8 alkyl, or C5 to C14 aryl, C6 to CIO aryl or combinations thereof; or
  • Rl to R4 are selected from hydrogen, F, Cl, Br, I, Cl to C8 alkyl, or C5 to C14 aryl, optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C8 alkyl, or C5 to C14 aryl or combinations thereof.
  • Rl is hydrogen or halogen, or together with R3 may form an optionally substituted polycyclic ring;
  • R3 is hydrogen, or together with Rl may form an optionally substituted polycyclic ring;
  • R4 is hydrogen or together with R2 may form an optionally substituted polycyclic ring;
  • R2 is optionally substituted Ce-io aryl, halogen, or together with R4 may form an optionally substituted polycyclic ring.
  • Rl is halogen;
  • R3 is hydrogen;
  • R4 is hydrogen or together with R2 forms an optionally substituted naphtyl or phenantryl ring;
  • R2 is halogen or together with R4 forms an optionally substituted naphtyl or phenantryl ring.
  • Rl is hydrogen, methyl or Cl, or together with R3 forms 2-phenyl-naphthyl or phenanthryl;
  • R3 is hydrogen, or together with Rl forms 2-phenyl-naphthyl or phenanthryl;
  • R4 is hydrogen or together with R2 forms 2-phenyl-naphthyl, phenanthryl, or methylphenantryl;
  • R2 is Cl, 3,5-dichloro-phenyl, phenyl, t-Bu or together with R4 forms 2-phenyl-naphthyl, phenanthryl or methylphenantryl.
  • Rl is Cl; R3 is hydrogen; R4 is hydrogen or together with R2 forms naphthyl or phenanthryl; R2 is hydrogen, Cl, or together with R4 forms naphtyl or phenanthryl.
  • Rl is hydrogen or Cl; R3 is hydrogen; R4 is hydrogen or together with R2 forms naphthyl or phenantryl; R2 is Cl, phenyl or together with R4 forms naphthyl or phenantryl.
  • Rl is hydrogen, methyl or Cl, or together with R3 forms 2-phenyl-naphthyl or phenanthryl;
  • R3 is hydrogen, or together with Rl forms 2-phenyl-naphthyl or phenanthryl;
  • R4 is hydrogen or together with R2 forms 2-phenyl-naphthyl, naphtyl, phenanthryl, or methylphenantryl;
  • R2 is Cl, 3,5-dichloro-phenyl, phenyl, t-Bu or together with R4 forms 2-phenyl-naphthyl, naphtyl, phenanthryl or methylphenantryl; or
  • Rl is hydrogen or Cl;
  • R3 is hydrogen;
  • R4 is hydrogen or together with R2 form an optionally substituted naphthyl or an optionally substituted phenanthryl ring;
  • R2 is Cl, phenyl or together with R4 form an optionally substituted naphthy
  • Rl and R2 are hydrogen or halogen, in particular Cl or Br and R3 and R4 are hydrogen.
  • Rl, R2, R3 and R4 are fluorine.
  • the zinc carboxylate can in principle be any soluble carboxylic acid salt of zinc, more specifically a zinc salt of a carboxylic acid exhibiting 1 to 8, in particular 1 to three carbon atoms, such as zinc formate, zinc acetate, zinc propionate, zinc isopropionate, zinc butyrate, zinc pivalate, zinc valerate, zinc caproate or zinc heptanoate, zinc octanoate, zinc 2-ethylhexanoate or zinc nonanoate, either water free or the hydrate.
  • the use of zinc acetate (Zn(OAc)2) or zinc pivalate, either water free or as hydrate, has shown to be practical.
  • Suitable organic solvents are polar solvents, such as polar aprotic or polar protic solvents.
  • organic solvent are selected from the group consisting of alkohols, ethers, ketones, esters and combinations thereof. More specifically, the organic solvent is selected from the group consisting of methanol, ethanol, isopropanol, tetra hydrofuran, acetone, ethyl acetate and combinations thereof.
  • Acetone has shown to be a practical solvent for the reaction since it dissolves the aromatic dithiol, its impurities and the zinc carboxylate, but the zinc dithiolate shows a poor solubility, so it can be easily precipitated and filtrated as well as washed. For washing, acetone and petrol ether have been found useful.
  • the reaction can be carried out at temperatures of from 10°C to 50°C, in particular from 10°C to 40°C or from 15°C to 35°C or 20°C to 30°C.
  • the reaction is quite robust and can be carried out at usual room temperatures so that normally no heating of the reation mixture is necessary.
  • Reaction times vary from about 2 hours to about 48 hours, in particular 4 to 36 hours or 6 to 24 hours.
  • the Invention also relates to a zinc dithiolate compound with a nitrogen content of less than 1 weight percent, which is obtainable by the method above.
  • the Invention also relates to a method for making a ruthenium catalyst employing such a zinc dithiolate compound.
  • the invention thus also relates to a method for making a ruthenium catalyst comprising the steps of
  • ruthenium catalyst of formula 4 or 4a wherein the anionic ligands are a bridging dithiolate forming a ring via its sulfur at- oms with R.1 to R4 being as defined above.
  • Ar can be an aromatic group bridged with L, wherein L is an alkoxy group being a substituent of Ar.
  • anionic ligands XI and X2 independently of each other, can be halogens selected from F, Cl, Br, I and combinations thereof, in particular Cl or Br.
  • XI and X2 are the same, in particular XI and X2 are the same and are Cl.
  • Ar is aryl, in particular aryl with 5 to 14 carbon atoms, or aryl with 6 to 10 carbon atoms, in particular phenyl or naphthyl, which is optionally substituted, in particular substituted with halogen, nitro, aminocarbonyl, alkyl with 1 to 8 carbon atoms or alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 8 carbon atoms or alkoxy with 1 to 4 carbon atoms, aryl with 5 to 14 car- bon atoms or aryl with 6 to 10 carbon atoms or combinations thereof.
  • aryl Ar can be substituted with one or more substituents selected from the group consisting of nitro, F, Cl, Br, I, Cl to C8 alkyl, Cl to C4 alkoxy, C6 to CIO aryl or combinations thereof.
  • Ar is substituted as described above, then Ar and L are bridged.
  • Ar is aryl with 5 to 14 carbon atoms, or aryl with 6 to 10 carbon atoms, in particular phenyl, which is substituted with halogen, nitro, or aminocarbonyl and if Ar and L are bridged.
  • aryl Ar is optionally substituted with one or more substituents selected from the group consisting of F, Cl, Br, I, Cl to C4 alkyl, Cl to C4 alkoxy, C6 to CIO aryl or combinations thereof.
  • Ar is a structure of formula 5, wherein Formula 5
  • W is hydrogen, halogen selected from F, Cl, Br or I, particularly Cl, Br and I, or W is oxygen;
  • R.19 is alkyl with 1 to 6 carbon atoms or phenyl, which is optionally substituted in the para position with nitro, Cl to C4 alkyl, Cl to C5 alkoxy, halogen selected from F, Cl, Br or I; or R.19 is methyl, ethyl, isopropyl or tert.- butyl, with the proviso that if W is hydrogen or halogen, then R19 is nil;
  • R20, R21 and R23 are hydrogen, alkyl with 1 to 6 carbon atoms, aryl with 6 to 10 carbon atoms, or R20 is hydrogen, alkyl with 1 to 4 carbon atoms, aryl with 6 to 10 carbon atoms, or R19 is hydrogen, methyl, ethyl, isopropyl, phenyl or naphthyl.
  • W is oxygen
  • R.19 is alkyl with 1 to 4 carbon atoms
  • R.20 is hydrogen or aryl with 6 to 10 carbon atoms, in particular phenyl
  • R.21 and R.23 are hydrogen
  • R.22 is nitro, Cl, Br, I or trifluormethyl
  • W is oxygen, R.19 is isopropyl, R20 is hydrogen or phenyl, R21 and R23 are hydrogen, R22 is nitro or trifluormethyl; or
  • W is oxygen, R19 is isopropyl, R20, R21 and R23 are hydrogen, R22 is nitro or trifluormethyl; or
  • W is oxygen, R19 is alkyl with 1 to 4 carbon atoms, R20 is phenyl, R21, R22 and R23 are hydrogen; or
  • W is oxygen
  • R19 is isopropyl
  • R20 is phenyl
  • R21, R22 and R23 are hydrogen.
  • L and L2 are neutral electron donor ligands.
  • L2 can be a phosphine or an NHC ligand.
  • L is a sulfoxide, such as DMSO (dimethyl sulfoxide), a phosphine, or L is a halogen or an alkoxy group -O-R19 with R19 being a Cl to C6 alkyl.
  • DMSO dimethyl sulfoxide
  • phosphine a phosphine
  • L is a halogen or an alkoxy group -O-R19 with R19 being a Cl to C6 alkyl.
  • L can be an alkoxy group -O-alkyl with alkyl having 1 to 6 carbon atoms, namely alkyl being selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert. -butyl or -O-aryl with aryl having 5 to 10 carbon atoms, in particular phenyl, which can be optionally substituted with alkoxy as defined hereinabove, nitro, halogen such as F, Cl, Br, I, amino, alkylamino or dialkylamino with alkyl as defined hereinabove, more specifically with the substituent in the para-position to the oxygen atom.
  • alkyl being selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert. -butyl or -O-aryl with aryl having 5 to 10 carbon atoms, in particular phenyl
  • L can also be a sulfoxide carrying two alkyl substituents as defined above, or wherein the two alkyl are a saturated alkyl bridge so at to form a cyclic sulfoxide; suitable sulfoxides are, for example, dimethyl sulfoxide (DMSO) or the cyclic tetramethylensulfoxide.
  • DMSO dimethyl sulfoxide
  • Other suitable embodiments for L is pyridine.
  • both L and L2 can be defined as phosphines having the structure wherein the groups R31, R32 and R33 are each independently for each occurrence selected from the group consisting of substituted or unsubstituted primary, secondary or tertiary alkyl or cycloalkyl with 1 to 20, in particular 1 to 10 carbon atoms; substituted or unsubstituted aryl or heteroaryl exhibiting 5 to 20, in particular 5 to 10 carbon atoms, or optionally two or more of the groups R31, R32 and R33 are fused to form a ring.
  • R31, R32, R33 may be substituted, for example once, twice, or three times, e.g. once, i.e. formally replacing one or more hydrogen atoms of the alkyl, cycloalkyl, aryl or heteroaryl group.
  • substituents are halogen (e.g. fluoro, chloro, bromo and iodo), SFs, CF3, alkyl, aryl hydroxyl, nitro, amino, alkoxy, alkylthio, carboxy, cyano, thio, formyl, ester, acyl, thioacyl, amido, sulfonamido, carbamate and the like.
  • the substituent is amino it may be amino, hydrocarbylamino or dihy- drocarbylamino, where the hydrocarbyl substituents on the nitrogen may be alkyl, aryl or heteroaryl such as substituted or unsubstituted Cl- C20 alkyl, aryl or heteroaryl or even C1-C10 alkyl, aryl or heteroaryl.
  • the groups R31, R32, R33 are cycloalkyl they may be for example cyclohexyl or cyclopentyl. The cyclohexyl or cyclopentyl groups if present may be substituted as described hereinabove.
  • heteroaryl moieties are a subset of aryl moieties that comprise one or more heteroatoms, typically 0, N or S, in place of one or more carbon atoms and any hydrogen atoms attached thereto.
  • exemplary R31, R32, R33 aryl substituents for example, include phenyl or naphthyl that may be substituted.
  • exemplary R.31, R32, R33 heteroaryl substituents for example, include pyridinyl, furanyl, pyrrolyl and pyrimidinyl.
  • heteroaromatic rings include pyridazinyl (in which 2 nitrogen atoms are adjacent in an aromatic 6-membered ring); pyrazinyl (in which two nitrogen atoms are 1,4-disposed in a 6-membered aromatic ring); pyrimidinyl (in which 2 nitrogen atoms are 1,3-disposed in a 6-membered aromatic ring); or 1,3,5- triazinyl (in which 3 nitrogen atoms are 1,3,5-disposed in a 6- membered aromatic ring).
  • L or L2 as being phosphines are Triphenylphosphine, Tricyclohexyl phosphine, Tri(o-tolyl)phosphine, Tris(4-chlorphenyl)phosphine, Tris(3- chlorphenyl)phosphine, Tris-(4-fluorphenyl)-phosphine, Tris-(pentafluor- phenyl)-phosphine, Tris(4-trifluormethylphenyl)phosphine, Tris(trimethylsi- lyl)phosphine, Diphenyl(p-tolyl)phosphine, Tris-(4-methoxyphenyl)-phos- phine, Tri(p-tolyl)phosphine, Tris(2,4,6-trimethylphenyl)phosphine, Tris(3,5-dimethylphenyl)phosphine, Tri(l-adamantyl)phosphine
  • L is a phosphite of the structure wherein R31, R.32 and R.33 are as defined above for the section relating to phosphines.
  • Examples for phosphite include P(OMe)3, P(0Et)3, P(OPr)3 and P(OPh)3.
  • Examples of group L as a phosphine include in particular PCy3 and PPhs - where Cy is cyclohexyl and Ph is phenyl.
  • group L as a phosphite include P(OMe)3 P(0Et)3, P(OiPr)3 and P(OPh)3.
  • L2 is nucleophilic carbene, in particular N -heterocyclic carbene/phosphite, phosphine/phosphite and phosphine/phosphine.
  • NHC ligands N-heterocyclic carbenes
  • a description thereof can be found, for example, in Frank Glorius, "N-Heterocy-rod Carbenes in Transition Metal Catalysis", Springer Verlag Heidelberg 2007, in particular the general definition on pages 10 and 11, figures 3 to 4.
  • L2 can be represented by the structure of Formula 6
  • Rll, R.12, R.13 and R.14 are independently hydrogen, unsubstituted C1-C12 alkyl, substituted C1-C12 alkyl, unsubstituted C4-C12 cycloalkyl, substituted C4-C12 cycloalkyl, unsubstituted C5-C24 aryl, substituted C5-C24 aryl, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 aralkyl, substituted C6-C24 aralkyl, unsubstituted C6-C24 heteroaralkyl or substituted C 6 -C 2 4 heteroaralkyl;
  • R.15 is methyl, ethyl, n-propyl, or phenyl; or together with R.16 can form a five to ten membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached; and
  • R.16 is methyl, ethyl, n-propyl, or phenyl; or together with R15 can form a five- to ten- membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached;
  • R17 is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2- methyl-6-tert-butylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phe- nyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl or 2-methyl-phenyl.
  • L2 can be represented by the structure of Formula (7) or Formula (8)
  • Rll, R.12, R.13 and R.14 are independently Ci-Ce alkyl or hydrogen;
  • R.15 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-methyl-6- tert-butylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl, 2,6-di- ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 2,6-difluoro- phenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl or 2-methyl-phenyl;
  • R.16 is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2- methyl-6-tert-butylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phe- nyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 2,6- difluorophenyl, 3, 5-di -tert- butyl phenyl, 2,4-dimethylphenyl or 2-methyl- phenyl.
  • the zinc dithiolate in this method for making a ruthenium catalyst can be provided by a method as described above.
  • the step of providing the zinc dithiolate compound may be carried out in situ in the same reactor and is used in the following steps in the method for making the ruthenium catalyst described above, which is carried out as a one pot reaction.
  • the method for making the ruthenium catalyst described above as a one pot reaction is carried out wherein the step of providing the zinc dithiolate compound is carried out in the same reactor used in the following steps and once completed, the missing educts for making the ruthenium catalyst (such as e.g. the ruthenium compound of formula 3) are added lateron once the zinc dithiolate has been made.
  • the method for making the ruthenium catalyst described above as a one-pot reaction is carried out wherein the step of providing the zinc dithiolate compound is carried out in the same reactor used in the following steps and the educts for making the ruthenium catalyst (such as e.g. the ruthenium compound of formula 3) are added before the step of providing the zinc dithiolate compound is completed, so that all these steps are carried out in one reaction mixture.
  • the step of providing the zinc dithiolate compound can be carried out in situ in the reaction mixture with the ruthenium compound of formula 3 and the method is carried out as a one pot reaction.
  • the subject patent application also relates to a compound of the following formula wherein R1 to R4 are defined as above and Y is nil or a neutral electron donor ligand that is not a base, in particular not a nitrogen containing ligand and more specifically that is not an amine, but it may be a solvent, for example DMSO (dimethyl sulfoxide).
  • Y is nil or a neutral electron donor ligand that is not a base, in particular not a nitrogen containing ligand and more specifically that is not an amine, but it may be a solvent, for example DMSO (dimethyl sulfoxide).
  • DMSO dimethyl sulfoxide
  • the Invention also relates to compounds of the structures
  • a reactor was charged with sodium hydroxide (56-2 g, 1.41 mol, 5.0 equivalents) and absolute ethanol (1000 mL) under stirring. The reactor was evacuated and flushed with nitrogen for three times and nitrogen was bubbled through the mixture for 30 minutes. 4,7-dichloro-l,3-benzodithiole-2-thione (95.8%, 71.2 g, 281.2 mmol, 1 equivalent) was added under a stream of nitrogen. The mixture was heated under reflux for 1 hour. The mixture was allowed to cool to 22°C and washed under nitrogen atmosphere with dichloromethane (3 times with 1000 mL). After cooling to 5°C, concentrated hydrochloric acid (125 mL) was added in order to lower the pH to 1.
  • isolation of zinc dithiolate proves to be a reproducible purification method to achieve excellent ligand quality without the need of toxic additives.
  • the isolated material consists of approx. 80 wt% dithiolate, 10 wt% water and 10 wt% acetone. No other signal from impurities are detected by NMR..
  • the composition was determined by elemental analysis, qNMR. and TGA. We therefore propose the existence of a zinc dithiolate-hydrate- acetone complex. R.esidual solvent can be removed by drying at higher temperature in-vacuo.
  • the downside of dried material is a significantly lower solubility in solvents other than DMSO.
  • M3002 is obtained as a dark green, crystalline solid (3.9 g, 84% yield). M3002 can be also prepared in high yield (>90%) and very good purity using isolated Zn dithiolate.

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Abstract

L'invention concerne un procédé de fabrication d'un catalyseur au ruthénium comprenant les étapes consistant à : -fournir un dithiol aromatique substitué sur des atomes de carbone aromatiques adjacents par des groupes thiol, dans une première étape, un composé aromatique substitué par deux groupes partants sur des atomes de carbone aromatiques adjacents étant mis à réagir avec du trithiocarbonate alcalin pour obtenir une benzodithiole-thione aromatique, qui, dans une étape ultérieure, est mise à réagir/hydrolysée avec une base ; -fournir un composé de dithiolate de zinc par réaction du dithiol aromatique avec un carboxylate de zinc dans un solvant organique ; -faire réagir le composé dithiolate de zinc avec un composé de ruthénium dans lequel X1 et X2 sont, indépendamment l'un de l'autre, sont des ligands anioniques et sont identiques ou différents ; L et L2 sont, indépendamment l'un de l'autre, des ligands donneurs d'électrons neutres et sont identiques ou différents ; Ar est un groupe aromatique qui peut être substitué et qui peut être ponté avec L, si L est un groupe alcoxy ; -obtenir un catalyseur au ruthénium de formule 4 ou 4a, dans laquelle R1 à R4 sont, indépendamment l'un de l'autre, choisis parmi hydrogène, halogène, alkyle, aryle, ou R.1 avec R3, R3 avec R4 ou R2 avec R4 forment ensemble un cycle aliphatique ou aromatique.
PCT/EP2025/071813 2024-07-29 2025-07-29 Composés organométallique Pending WO2026027552A2 (fr)

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Publication number Priority date Publication date Assignee Title
SU1421736A1 (ru) 1987-03-24 1988-09-07 Ярославский политехнический институт Способ получени ароматических дитиолов
WO2014201300A1 (fr) 2013-06-12 2014-12-18 Trustees Of Boston College Catalyseurs pour une métathèse z-sélective efficace
WO2017100585A1 (fr) 2015-12-10 2017-06-15 Materia, Inc. Catalyseurs de métathèse d'oléfines
WO2018087230A1 (fr) 2016-11-09 2018-05-17 Ximo Ag Complexes de ruthénium utiles pour catalyser des réactions de métathèse

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Publication number Priority date Publication date Assignee Title
SU1421736A1 (ru) 1987-03-24 1988-09-07 Ярославский политехнический институт Способ получени ароматических дитиолов
WO2014201300A1 (fr) 2013-06-12 2014-12-18 Trustees Of Boston College Catalyseurs pour une métathèse z-sélective efficace
EP3008078A1 (fr) 2013-06-12 2016-04-20 Trustees of Boston College Catalyseurs pour une métathèse z-sélective efficace
WO2017100585A1 (fr) 2015-12-10 2017-06-15 Materia, Inc. Catalyseurs de métathèse d'oléfines
WO2018087230A1 (fr) 2016-11-09 2018-05-17 Ximo Ag Complexes de ruthénium utiles pour catalyser des réactions de métathèse

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