EP4247553A2 - Système catalytique - Google Patents

Système catalytique

Info

Publication number
EP4247553A2
EP4247553A2 EP21702883.6A EP21702883A EP4247553A2 EP 4247553 A2 EP4247553 A2 EP 4247553A2 EP 21702883 A EP21702883 A EP 21702883A EP 4247553 A2 EP4247553 A2 EP 4247553A2
Authority
EP
European Patent Office
Prior art keywords
catalyst system
rearrangement
zinc
aminophenol
mixture
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
EP21702883.6A
Other languages
German (de)
English (en)
Inventor
Angela KÖCKRITZ
Elka KRALEVA
Katja NEUBAUER
Regina BIENERT
Stefan Lambrecht
Johannes Panten
Michael Sebek
Bernhard RUSSBÜLDT
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.)
Symrise AG
Original Assignee
Symrise AG
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 Symrise AG filed Critical Symrise AG
Publication of EP4247553A2 publication Critical patent/EP4247553A2/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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0202—Alcohols or phenols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0237—Amines
    • B01J31/0238—Amines with a primary amino group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
    • 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
    • B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/58—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in three-membered 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
    • 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
    • B01J2231/52—Isomerisation reactions
    • 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
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/76—Dehydrogenation
    • B01J2231/763—Dehydrogenation of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species
    • 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
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0205—Oxygen-containing compounds comprising carbonyl groups or oxygen-containing derivatives, e.g. acetals, ketals, cyclic peroxides
    • B01J31/0208—Ketones or ketals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the invention is in the field of heterogeneous catalysis and relates to catalysts for the rearrangement of epoxides and corresponding processes for the production of allyl alcohols and alpha, beta-unsaturated carbonyl compounds using these catalysts.
  • Allyl alcohols are used in the chemical industry, for example, as aromas and fragrances. In addition, they can serve as intermediate products, for example in the production of alpha, beta-unsaturated carbonyl compounds by Oppenauer oxidation. In general, the rearrangement of epoxides to allyl alcohols and the further oxidation of the alcohols obtained can be expressed as follows:
  • RI, R2 and R3 denote a hydrogen atom, alkyl, aryl or aralkyl groups or together form a cycloalkyl group.
  • heterogeneous catalysts have also been proposed for the conversion of epoxide to allyl alcohols. These include metal oxides, in particular different aluminum acid molecules, silicon dioxide, titanium dioxide, zirconium oxide and mixed oxides (see review article by K. Tanabe, R. Ohnishi, K. Arata, "Rearrangement of epoxides over solid acids) Base catalysts", Chapter 2.5, in: Terpene Chemistry, Ed. J. Varghese. Tata McGraw-Hill Publishing Company, Ltd., 1982, pp. 67-88). The highest selectivity that was achieved in the 1,2-limonene oxide rearrangement to carveol catalyzed by metal oxides was 59% compared to aluminum oxide (K. Arata, K.
  • Lithium phosphate supported on silica (US Pat. No. 5,455,215) and sodium phosphate supported on zirconium oxide (JP 11 049709 A) were also used to bring about the rearrangement of epoxides.
  • EP 1404635 B1 (MILENNIUM SPECIALITY) discloses a catalyst system which is suitable both for the rearrangement of epoxides into allyl alcohols and for Oppenauer oxidation and discloses, for example, the combination of zinc octanoate with aminophenol.
  • the selectivity to Carveol is below 40%.
  • a first object of the present invention was therefore to provide catalysts with the help of which epoxides, in particular 1,2-limonene epoxide, are converted into allyl alcohols with conversions of at least 70% and preferably at least 80% and yields of at least 40%, preferably at least 45%.
  • a first object of the invention relates to a catalyst system, in particular for the rearrangement of epoxides into allyl alcohols and for the production of alpha, beta unsaturated carbonyl compounds, comprising or consisting of
  • XY (I) in which X stands for Zn 2+ and / or Co 2+ and Y represents an anion which is selected from the group formed by laurate, palmitate, stearate, picolinate, glycinate, gluconate, naphthenate , 2-hexyl decanoate, 2-octyl dodecanoate, cyclohexane butyrate and their mixtures, and
  • the catalyst system catalyzes both the rearrangement of epoxides in allyl alcohols and the Oppenauer oxidation of the allyl alcohols to the corresponding alpha, beta-unsaturated carbonyl compounds and this with conversions above 70% and yields of more than 40%.
  • the catalyst system of the invention consists of two components, namely (a) the primary catalyst and (b) an activator or modifier.
  • Component (a) is a defined salt of divalent zinc or cobalt, in particular zinc stearate, cobalt stearate, zinc glycinate, zinc naphthenate and mixtures thereof.
  • the term “salt” is to be understood here to mean that it is an at least predominantly ionic compound which contains Zn 2+ and / or Co 2+ cations and a correspondingly stoichiometric number of the anions mentioned, so that a neutral compound application is present.
  • Component (b) has the task of activating component (a), since in many cases this alone has little or no catalytic properties. At the same time, as a modifier, it has the property of controlling the selectivity.
  • Aminophenols, in particular 2-aminophenol, are suitable activators / modifiers.
  • catalyst systems which are the combination of (a) zinc stearate, cobalt stearate, zinc glycinate, zinc 2-ethylhexanoate, zinc naphthenate and mixtures thereof with (b) 2-aminophenol.
  • the catalyst systems can contain components (a) and (b) in a weight ratio of about 10,000: 1 to about 10: 1, preferably about 5,000: 1 to about 100: 1 and in particular about 1,000: 1 to about 500: 1 contain PROCIEEDINGS
  • a second object of the invention relates to a method for rearrangement of epoxides in allyl alcohols, comprising or consisting of the following steps:
  • a third subject matter of the invention relates to a process for the rearrangement and Oppenauer oxidation of epoxides into alpha, beta-unsaturated carbonyl compounds, comprising or consisting of the following steps:
  • epoxides can be converted to allyl alcohols.
  • terminal, cyclic, disubstituted, trisubstituted epoxides are 1,2-limonene oxide, 8,9-limonene oxide, alpha-pinene oxide, beta-pinene oxide, 2,3-carene oxide, 3,4-carene oxide, 1,2-terpinolene oxide , 4,8-terpinolene oxide, sylvestrene oxide, 1,2-menthenoxide, 2,3-menthenoxide, 3,4-menthenoxide, 7,8-dihydromyrcene oxide, caryophyllene oxide, 1,2-epoxycyclododecane and the like.
  • the rearrangement of epoxides to allyl alcohols according to the present invention can be carried out by bringing epoxide into contact with the catalyst system under suitable reaction conditions, e.g. B. at elevated temperature, usually under reflux.
  • the epoxy rearrangement can be carried out batchwise or continuously.
  • Other appropriate steps can also be included in the relocation process. For example, it may be preferable to remove water contained in the starting materials or formed in the process. In such cases, water can be removed before or during a rearrangement by known methods: If an allyl alcohol is an end product, the rearrangement can be stopped, e.g. B. after all epoxide has been implemented or the ge desired conversion is achieved. In addition, the following can be used after the rearrangement Steps are applied.
  • the catalyst can be removed by any suitable method (filtration, washing, extraction, distillation, etc.) and the product, e.g. B. allyl alcohol, can be isolated and purified using any art recognized technique, such as by distillation or crystall
  • Both processes are carried out at the same or very similar temperatures, in particular in the range from about 200 to about 230.degree. C. and in particular about 210 to about 220.degree.
  • the catalyst component (a) is usually in amounts of about 0.05 to about 5 mol%, preferably about 0.1 to about 1 mol% and the catalyst component (b) in amounts of about 0.01 to about 0.00001 mol%, preferably about 0.001 to about 0.0001 mol% - in each case based on the starting compounds - are used.
  • Another advantage of the invention is that the rearrangement and the Oppenauer oxidation can be carried out simultaneously as a “one-pot reaction” or one after the other.
  • the reaction is carried out as a one-pot reaction in which both reactions take place simultaneously, the sacrificial agent can in principle be used together with the catalyst system, but it is more advantageous to initially let the reaction run for a while so that a sufficient amount of allyl alcohol is present and only then add the sacrificial agent and thus start the oxidation.
  • Aldehydes or ketones, including quinones are particularly suitable as sacrificial agents. Typical examples include benzaldehyde, acetone, cyclohexanone, benzoquinone or isophorone. These are typically used in very small amounts, for example about 1 to about 100 mmol, preferably about 10 to about 50 mmol of sacrificial agent, based on the amount of starting compound.
  • 1,2-limonene epoxide to the corresponding allyl alcohol carveol as well as its further reaction by Oppenauer oxidation to the alpha-beta-unsaturated carbonyl compound car from.
  • Rearrangement with preformed catalysts c / s-limonene-1,2-epoxide can be rearranged more quickly than trans-limonene-1,2-epoxide.
  • the rearrangement of trans-limonene-1,2-epoxide is facilitated if c / s-limonene-1,2-epoxide is present in the reaction mixture. It is therefore advantageous to use either pure as-limonene-1,2-epoxide or a mixture of ice- and trans-limonene-1,2-epoxide with a high c / s content as the substrate.
  • Preformed Zn (aminophenolate) 2 complexes 1-8 are also particularly suitable as catalysts. They enable the rearrangement of the epoxide even at milder reaction temperatures from 155 ° C (see table, example 2, 4, 5). They could be prepared as follows in analogy to a literature regulation (H. R. Hoppe, K. Andrä, Z. Chem. 26 (1986)):

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

Abstract

L'invention concerne un système catalytique, en particulier pour le réarrangement d'époxydes en alcools allyliques, comprenant ou étant constitué de (a) un sel de formule (I) XY, dans laquelle X représente Zn2+ et/ou Co2+ et Y représente un anion choisi dans le groupe constitué par le laurate, le palmitate, le stéarate, le picolinate, le glycinate, le gluconate, le naphténate, le 2-hexyldécanoate, le 2-octyldodécanoate, le cyclohexanebutyrate, ainsi que leurs mélanges, et (b) au moins un aminophénol.
EP21702883.6A 2020-01-27 2021-01-22 Système catalytique Pending EP4247553A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP2020051924 2020-01-27
PCT/EP2021/051455 WO2021151790A2 (fr) 2020-01-27 2021-01-22 Système catalytique

Publications (1)

Publication Number Publication Date
EP4247553A2 true EP4247553A2 (fr) 2023-09-27

Family

ID=74505189

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21702883.6A Pending EP4247553A2 (fr) 2020-01-27 2021-01-22 Système catalytique

Country Status (3)

Country Link
US (1) US20240051907A1 (fr)
EP (1) EP4247553A2 (fr)
WO (1) WO2021151790A2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113979836B (zh) * 2021-10-13 2023-05-30 上海应用技术大学 一种4-异丙烯基-1-甲基-2-环己烯-1-醇的制备方法
EP4633805A1 (fr) 2022-12-15 2025-10-22 Firmenich SA Procédé de préparation d'alcool allylique
CN120303060A (zh) 2022-12-15 2025-07-11 弗门尼舍有限公司 制备α,β-不饱和羰基化合物的方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2426624A (en) 1946-07-02 1947-09-02 Standard Oil Co Extraction of quinonoid hydrocarbons from benzenoid hydrocarbons by means of anhydrous hydrogen fluoride
DE109524C (fr) 1959-04-02
JPS5518697B2 (fr) 1973-09-21 1980-05-21
US4496776A (en) 1983-08-11 1985-01-29 Shell Oil Company Epoxide isomerization process
US5455215A (en) 1994-10-17 1995-10-03 Arco Chemical Technology, L.P. Epoxide isomerization catalysts
JP3989598B2 (ja) 1997-08-05 2007-10-10 株式会社クラレ アリル型アルコールの製造方法
US6835686B2 (en) * 2001-07-05 2004-12-28 Millennium Specialty Chemicals Catalyst system and process for rearrangement of epoxides to allylic alcohols

Also Published As

Publication number Publication date
WO2021151790A2 (fr) 2021-08-05
WO2021151790A3 (fr) 2021-09-23
US20240051907A1 (en) 2024-02-15

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