[go: up one dir, main page]

WO2008145627A1 - Oxydation électrochimique sur des groupes allyle - Google Patents

Oxydation électrochimique sur des groupes allyle Download PDF

Info

Publication number
WO2008145627A1
WO2008145627A1 PCT/EP2008/056406 EP2008056406W WO2008145627A1 WO 2008145627 A1 WO2008145627 A1 WO 2008145627A1 EP 2008056406 W EP2008056406 W EP 2008056406W WO 2008145627 A1 WO2008145627 A1 WO 2008145627A1
Authority
WO
WIPO (PCT)
Prior art keywords
mediator
double bond
oxidation
electrochemical oxidation
ionone
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.)
Ceased
Application number
PCT/EP2008/056406
Other languages
German (de)
English (en)
Inventor
Ulrich Griesbach
Laszlo Szarvas
Jörg Botzem
Hansgeorg Ernst
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of WO2008145627A1 publication Critical patent/WO2008145627A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/23—Oxidation

Definitions

  • the invention relates to a process for the electrochemical oxidation of an organic compound on a carbon atom, which is bonded directly to a non-aromatic double bond (alpha position to the double bond), characterized in that a mediator is used.
  • DE-A 27 04 406 describes the oxidation of such compounds with halogenated oxygen acids or their salts as oxidizing agents.
  • Elisabeth Becher et al., Helvetia Chimica Acta. Vol. 64 (7), pages 2419 to 2434 (1981) use pyridinium chlorochromate as the oxidizing agent in the preparation.
  • simple processes are desired which, if possible, do without halogen-containing oxidants or chromates, have a high yield and selectivity, and require no complicated work-up of the reaction products.
  • Electrochemical oxidations including those using mediators, are known in principle.
  • Mediators are understood as meaning redox pairs which allow indirect electrochemical oxidation.
  • the mediator is electrochemically transferred to the higher oxidation state, then acts as an oxidant and then regenerates again by electrochemical oxidation.
  • Pierre Vaudano et al, Chimia 49, pages 12-16 (1995) describes the electrochemical oxidation of aromatics, e.g. of p-tert-butyl-benzaldehyde from p-tert-butyl-toluene with manganese sulfates as mediators.
  • DE-A 100 45 664 relates to the use of mediators in electrochemical processes using a diamond electrode, Ce (III / IV), Mn (II / III), Mn (II / IV) and V (III / IV) being among others and V (IVA /).
  • the object of the invention was a process for the oxidation of a C atom, which is bonded directly to a non-aromatic double bond (alpha position to the double bond), which works as possible without halogen-containing oxidant and without chromates. With high yield and selectivity, the process should be as simple and effective.
  • an organic compound is oxidized on a carbon atom directly bonded to a non-aromatic double bond.
  • the C atom is also referred to as an alpha-C atom or allylic C atom.
  • This C atom preferably has at least one hydrogen atom as a substituent.
  • the C atom may, for example, still have a hydroxyl group as a substituent; two hydrogen atoms are particularly preferred as substituents on the alpha-C atom to be oxidized.
  • the non-aromatic double bond is part of a non-aromatic ring system, more preferably a cyclohexene ring system.
  • the organic compound is cyclohexene and its derivatives.
  • the cyclohexene ring there are two C atoms adjacent to the double bond.
  • one of these C atoms is protected by appropriate substitution so that oxidation occurs selectively only on the other remaining C atom.
  • the protected C atom preferably has no more hydrogens than substituents. In particular, it has only alkyl groups, e.g. C1-C4 alkyl groups as substituents.
  • Particularly preferred organic compounds are those of the formula I.
  • X represents a hydrogen atom or a hydroxyl group
  • R 1, R 2 and R 3 independently of one another represent a C 1 to C 4 alkyl group
  • Y is an organic radical having at least 2 C atoms.
  • X is an H atom and R 1, R 2 and R 3 are a methyl group.
  • Y is preferably an organic radical having at least 2 C atoms, in particular an organic radical having 2 to 40 C atoms; the organic radical may optionally contain oxygen atoms in the form of carbonyl groups.
  • Y is particularly preferably an aliphatic organic radical having 2 to 40 carbon atoms which contains a carbonyl group.
  • the aliphatic radical contains at least one further double bond.
  • the double bond of the cyclohexene ring is in conjugation with at least one further non-aromatic double bond of the radical Y.
  • two double bonds are in conjugation when they are connected via a single C-C single bond.
  • Preferred organic compounds are e.g.
  • R C1 to C8 alkyl
  • R C1 to C8 alkyl
  • the C atom to be oxidized is preferably oxidized to a carbonyl group.
  • ⁇ -ionone becomes 4-oxo- ⁇ -ionone of the formula
  • a mediator is used in the electrochemical oxidation according to the invention.
  • Mediators are understood as meaning redox pairs which allow indirect electrochemical oxidation.
  • the mediator is converted electrochemically into the higher oxidation state, then acts as an oxidant and then regenerates again by electrochemical oxidation. It is therefore an indirect electrochemical oxidation of the organic compound, since the mediator is the oxidizing agent.
  • the oxidation of the organic compound with the mediator in the oxidized form can thereby be carried out in the electrochemical cell in which the mediator has been converted into the oxidized form, or in one or more separate reactors ("ex-cell process”)
  • the latter method has the advantage that any remaining traces of the organic compound to be oxidized do not interfere with the production or regeneration of the mediator.
  • Suitable mediators are compounds which can be present in two oxidation states, act as oxidants in the higher oxidation state and can be regenerated electrochemically.
  • salts or complexes of the following redox couples can be used as mediators: Ce (III / IV), Cr (II / III), Cr (III / VI), Ti (II / III), V (II / III), V ( III / IV), V (IVA /), Ag (1 / ll), AgOVAgO ", Cu (1 / ll), Sn (II / IV), Co (II / III), Mn (II / III, Mn ( II / IV), Os (IVA / III), Os (III / IV), Br 2 / Br7Br0 3, I- / I2, I3VI2 IO3VIO4 "Fremys salt (dipotassium nitrosodisulfonate) or also organic mediators like ABTS (2,2 '-Azino-bis- (3-ethylbenzothiazoline-6-sulfonic acid), TEMPO, Vio- logene such as violuric acid, NA
  • Preferred mediators are compounds, in particular salts, of cerium, vanadium and manganese. Very particular preference is given to compounds, in particular salts of manganese.
  • the redox couple Mn (II / IV) is used as a mediator.
  • the mediator is preferably in the form of a salt and is sufficiently soluble in the solvent used in the electrochemical oxidation. If the oxidized form of Mediators as in the case of the system Mn (ll / IV) is present as a water-insoluble oxide (M1-1O2), it is used as a suspension.
  • Suitable anions of the salts are the salts of strong mineral or oxo acids, e.g. Sulfates, phosphates or sulfonates.
  • the mediator is used in particular in amounts of from 0.1 to 30% by weight, particularly preferably from 1 to 20% by weight, based on the composition used in the electrochemical oxidation, generally of a solution or suspension.
  • the weight of the mediator refers only to the metal portion of the mediator, e.g. with manganese oxide only to those contained in the composition
  • the amount of mediator is optionally limited by a limited solubility of its metal salts in the electrolyte and possibly too high conductivity.
  • the electrochemical oxidation (generation of the mediator) is preferably carried out in a solvent, in particular in water.
  • the pH of the solution may be acidic or basic, it will be adjusted depending on the conditions required to generate the mediator.
  • the system IVIn (I l / l 11) and Mn (ll / IV) is preferably generated at pH values between 0 and 5.
  • an inert solvent can also be used (co-solvent).
  • Inert solvents are solvents which are not oxidized under the chosen conditions. Suitable examples include tertiary alcohols, ketones, esters, ethers, carbonates, amides, nitriles and halogen-containing hydrocarbons or fluorinated alcohols.
  • tert-butanol ethyl acetate, acetone, methyl ethyl ketone, DMF, THF, dimethoxyethane, dichloromethane, chloroform, 1, 1, 2,2-tetrachloroethane, propylene carbonate, acetonitrile, 1, 1, 1, 3,3,3-hexafluoroisopropanol and hexafluoroacetone.
  • conductive salts can be used. These have the task of depolarizing the electrodes. These are generally alkali metal, tetra (C 1 - to C 6 -alkyl) ammonium, preferably tri (C 1 - to C 6 -alkyl) -methylammonium salts.
  • Suitable counterions are sulfate, bisulfate, alkyl sulfates, aryl sulfates, alkyl sulfonates, arylsulfonates, halides, phosphates, phosphonates, carbonates, alkyl phosphates, alkyl phosphonates, alkyl carbonates, nitrate, alcoholates, tetrafluoroborate, hexafluorophosphate or perchlorate.
  • acids derived from the abovementioned anions are suitable as conductive salts.
  • MTBS methyltributylammonium methylsulfates
  • TABF4 tetrabutylammonium tetrafluoroborate
  • strong mineral acids and sulfonic acids are suitable as conductive salts in the present invention.
  • Examples are H2SO4, H3PO4., Methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid.
  • H2SO4 is usually preferred.
  • Suitable anodes in the process according to the invention are customary electrodes, eg Pb / PbC "2 electrodes, mixed metal oxide electrodes, such as RuO x / TiO x electrodes, DSA (dimensionally stable anodes) or diamond electrodes.
  • cathode materials for example, iron, steel, stainless steel, nickel, lead or noble metals such as platinum and graphite or carbon materials and diamond electrodes are considered.
  • the system is preferably diamond electrode as anode and cathode, diamond electrode as anode and nickel, stainless steel or steel as cathode, as well as lead or lead dioxide on lead as anode and steel, nickel or lead as cathode.
  • the mediator is generated at the anode and protons are reduced to hydrogen at the cathode.
  • a diamond electrode is used in which the diamond layer is applied to a base body as the electrode material.
  • the diamond material used for the diamond layer is preferably doped with N, P and / or B (boron). Particularly preferred is the doping with B.
  • a diamond electrode is used in which the boron content in the diamond layer is between 10 ppm and 10000 ppm. Particularly preferred are boron contents between 10 ppm and 4000 ppm, most preferably between 100 ppm and 3000 ppm.
  • the main body preferably has one or more of the following materials: graphite, silicon, gold, titanium, molybdenum, niobium, or consists of one or more of the stated materials.
  • the thickness of the diamond coating is preferably in a range of 0.1 to 50 ⁇ m, more preferably 1 to 15 ⁇ m.
  • Diamond electrodes which can be used according to the invention are commercially available, for example, from the company Adamant Technologies under the type designation WD or from the company Condias under the designation Diachem® electrode.
  • electrolysis is carried out in the usual, known in the art electrolysis cells. Suitable electrolysis cells are known to the person skilled in the art. Preferably one works continuously or discontinuously with undivided flow cells.
  • bipolar switched capillary gap cells or Plattenstapelzellen in which the electrodes are designed as plates and are arranged plane-parallel (see Ullmann's Encyclopedia of Industrial Chemistry, 1999 electronic release, Sixth Edition, VCH Verlag Weinheim, Volume Electrochemistry, Chapter 3.5 Special cell designs and Chapter 5, Organic Electrochemistry, Subchapter 5.4.3.2 Cell Design).
  • the current densities at which the process is carried out are generally 1 to 1000, preferably 20 to 200 mA / cm 2.
  • the temperatures are usually from -20 to 60 0 C, preferably 0 to 60 0 C. In general common carried out at atmospheric pressure. Higher pressures are preferably used when operating at higher temperatures to avoid boiling of the co-solvents.
  • the organic compound to be oxidized can also be added in any form, for example in liquid form, as a solution or as a solid. Liquids are preferably added in bulk to the oxidized form of the mediator solution. Solids may also be used in bulk as a suspension or dissolved in an inert solvent.
  • reaction of the compound to be oxidized can be carried out either in the electrolysis cell or in a separate reactor.
  • the latter method is called "ex-cell method”.
  • the organic compound to be oxidized can be used either in excess or in excess to achieve the highest possible selectivity to the desired product. To achieve the fullest possible conversion usually an excess of the oxidizing agent is required.
  • the mediator is first activated, which then oxidizes the organic compound.
  • the required amount of charge is applied to achieve the desired oxidation state.
  • the mediator solution obtained in this way is directly reacted further with the organic compound to be oxidized.
  • the process according to the invention results in oxidation to allyl position. Halogenic oxidants or chromates are not needed. High yields and product selectivities are achieved.
  • ⁇ -ionone can be easily oxidized to 4-oxo- ⁇ -ionone or ⁇ -carotene easily to canthaxantin.
  • Anode Circular diamond-coated niobium plate 0 100 mm, thickness 2 mm, about 10 micron film thickness, about 1000 ppm boron doping B (commercially available DIACHEM electrode ® of the company Condias, Itzehoe, Germany)
  • Cathode Circular diamond-coated niobium plate, 0 100 mm, thickness 2 mm, about 10 micron film thickness, about 1000 ppm boron doping B (commercially available DIACHEM electrode ® of the company Condias, Itzehoe, Germany)
  • Electrode distance 3.2 mm active electrode area: 63.8 cm 2
  • Electrolyte 59.2 g (0.35 mol) MnSO 4 -H 2 O, 1 17.6 g (1, 2 mol) of H 2 SO 4 96%, 523.2 g of deionized water, batch size 700 g, according to a Mn concentration of 2.7 g / 100g of electrolyte.
  • the electrolyte was pumped through the cell. After completion of the electrolysis, the cell was emptied and transferred the dark brown reaction mixture for further reaction in a 1-L stirred apparatus with Ultra-Turrax stirrer, temperature probe and Eisbadkühlung. Was added, 15.3 g (0.08 mol) beta-ionone and stirred for 20 min at 13,500 Umin-. 1
  • the internal temperature is kept below 65 ° C.
  • the reaction mixture became clear yellow-orange.
  • the phases were separated and the aqueous phase was extracted twice more with 20 ml of methyl tert-butyl ether each time. The combined phases were dried and freed of the solvent.
  • Electrode distance 10 mm active electrode area: 10.0 cm 2
  • H 2 SO 4 96% pure 44.7 g of deionized water, batch size 60 g, corresponding to a Mn concentration of 2.8 g / 100 g of electrolyte.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention concerne un procédé d'oxydation électrochimique d'un composé organique sur un atome de C directement lié à une double liaison non-aromatique (position alpha par rapport à la liaison double), le procédé étant caractérisé par l'utilisation d'un médiateur.
PCT/EP2008/056406 2007-06-01 2008-05-26 Oxydation électrochimique sur des groupes allyle Ceased WO2008145627A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP07109384.3 2007-06-01
EP07109384 2007-06-01

Publications (1)

Publication Number Publication Date
WO2008145627A1 true WO2008145627A1 (fr) 2008-12-04

Family

ID=39758791

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/056406 Ceased WO2008145627A1 (fr) 2007-06-01 2008-05-26 Oxydation électrochimique sur des groupes allyle

Country Status (1)

Country Link
WO (1) WO2008145627A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130116473A1 (en) * 2011-11-09 2013-05-09 Basf Se Process for the preparation of oxovinylionol and its o-protected derivatives
WO2013068465A3 (fr) * 2011-11-09 2013-07-18 Basf Se Procédé de production d'oxovinylionol et de ses dérivés à protection o
CN111423349A (zh) * 2020-04-02 2020-07-17 万华化学集团股份有限公司 一种角黄素的合成方法
CN113416968A (zh) * 2021-06-08 2021-09-21 万华化学集团股份有限公司 一种无氧化剂电化学催化制备角黄素的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3448022A (en) * 1966-12-28 1969-06-03 Mobil Oil Corp Electrochemical acyloxylation of olefins
US3650918A (en) * 1969-08-27 1972-03-21 Continental Oil Co Electrochemical oxidation of olefinic compounds
DE2704406A1 (de) * 1977-02-03 1978-08-10 Basf Ag Verfahren zur einfuehrung einer carbonylgruppe in einen cyclohexenring
US4193850A (en) * 1979-04-12 1980-03-18 Hoffmann-La Roche Inc. Alkanoyloxylation of beta-ionone

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3448022A (en) * 1966-12-28 1969-06-03 Mobil Oil Corp Electrochemical acyloxylation of olefins
US3650918A (en) * 1969-08-27 1972-03-21 Continental Oil Co Electrochemical oxidation of olefinic compounds
DE2704406A1 (de) * 1977-02-03 1978-08-10 Basf Ag Verfahren zur einfuehrung einer carbonylgruppe in einen cyclohexenring
US4193850A (en) * 1979-04-12 1980-03-18 Hoffmann-La Roche Inc. Alkanoyloxylation of beta-ionone

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130116473A1 (en) * 2011-11-09 2013-05-09 Basf Se Process for the preparation of oxovinylionol and its o-protected derivatives
WO2013068465A3 (fr) * 2011-11-09 2013-07-18 Basf Se Procédé de production d'oxovinylionol et de ses dérivés à protection o
US9061982B2 (en) 2011-11-09 2015-06-23 Basf Se Process for the preparation of oxovinylionol and its O-protected derivatives
TWI576333B (zh) * 2011-11-09 2017-04-01 巴地斯顏料化工廠 製備側氧基乙烯基紫羅蘭醇及其氧－保護衍生物之方法
EP2776447B1 (fr) 2011-11-09 2018-05-30 Basf Se Procédé de production d'oxovinylionol et de ses dérivés o-protégés
CN111423349A (zh) * 2020-04-02 2020-07-17 万华化学集团股份有限公司 一种角黄素的合成方法
CN111423349B (zh) * 2020-04-02 2022-02-15 万华化学集团股份有限公司 一种角黄素的合成方法
CN113416968A (zh) * 2021-06-08 2021-09-21 万华化学集团股份有限公司 一种无氧化剂电化学催化制备角黄素的方法
CN113416968B (zh) * 2021-06-08 2022-11-08 万华化学集团股份有限公司 一种无氧化剂电化学催化制备角黄素的方法

Similar Documents

Publication Publication Date Title
EP2748353B1 (fr) Procédé de préparation électrochimique d'esters d'acide gamma-hydroxycarboxylique et de gamma-lactones
EP1348043B1 (fr) Procede de production de liaisons carbonyle alcoxylees par oxydation anodique et reaction de couplage cathodique pour realiser une synthese organique
DE69319342T2 (de) Elektrokatalytische asymmetrische dihydroxylierung von olefinen
WO2008145627A1 (fr) Oxydation électrochimique sur des groupes allyle
EP2411564B1 (fr) Procédé électrochimique de production de 3-tert-butylbenzaldehyde-dimetylacetals
EP0902846B1 (fr) Procede pour preparer des phtalides
EP1619273B1 (fr) Procédé de production de 2-alcyne-1-acetals
EP1863781A1 (fr) Procede pour produire des derives alkoxyles de 2,5-dihydrofurane- ou de tetra-1,1,4,4-but-2-ene
EP2534281B1 (fr) Procédé de préparation de 4-isopropylcyclohexylméthanol
EP0237762B1 (fr) Procédé pour la préparation de pyrazoles
EP1430165B1 (fr) Procede pour produire des orthotrialkylesters d'acide carboxylique
EP0326855B1 (fr) Procédé de préparation de l'acide fluoromalonique et de ses dérivés
EP1769103B1 (fr) Procédé electrochimique pour la préparation de cyclopropylbenzylamines
DE3152459C2 (fr)
DE68906589T2 (de) Elektrochemische Synthese von 2-Aryl-Hydrochinonen.
EP0237769B1 (fr) Acétals dialkyliques de benzaldéhyde
EP0384315B1 (fr) Procédé de production de lactones
EP1913178A1 (fr) Procede pour produire des derives de 1,1,4,4-tetraalcoxy-but-2-ene
EP0221022A2 (fr) Procédé de préparation de 5-nitro-1,4-naphtoquinone
WO2023186658A1 (fr) Oxydation électrochimique de cycloalcènes pour former des acides alpha, oméga-dicarboxyliques et des acides cétocarboxyliques
EP1637628A2 (fr) Procédé de préparation d'alkyl ester-dialkylacetal d'acide glyoxylique
DE10143161A1 (de) Verfahren zur Herstellung von Oxo-cyclohexyl-oder Oxo-cyclohexylenderivaten
DE1961364A1 (de) Verfahren zur Herstellung von substituierten Hydrazinen
DE10142220A1 (de) Verfahren zur Herstellung von Oxo-cyclohexyl- oder Oxo-cyclohexylenderivaten
DE2923531A1 (de) Verfahren zur herstellung von gegebenenfalls substituierten benzaldehyd- dialkylacetalen

Legal Events

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

Ref document number: 08760005

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08760005

Country of ref document: EP

Kind code of ref document: A1