EP2964813A1 - Couplage électrochimique de deux phénols ayant des potentiels d'oxydation différents - Google Patents

Couplage électrochimique de deux phénols ayant des potentiels d'oxydation différents

Info

Publication number
EP2964813A1
EP2964813A1 EP13811833.6A EP13811833A EP2964813A1 EP 2964813 A1 EP2964813 A1 EP 2964813A1 EP 13811833 A EP13811833 A EP 13811833A EP 2964813 A1 EP2964813 A1 EP 2964813A1
Authority
EP
European Patent Office
Prior art keywords
phenol
alkyl
solvent
mmol
phenols
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.)
Withdrawn
Application number
EP13811833.6A
Other languages
German (de)
English (en)
Inventor
Katrin Marie DYBALLA
Robert Franke
Dirk Fridag
Siegfried R. Waldvogel
Bernd Elsler
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.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
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 Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Publication of EP2964813A1 publication Critical patent/EP2964813A1/fr
Withdrawn legal-status Critical Current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
    • C25B3/29—Coupling reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms

Definitions

  • the following invention relates to an electrochemical process for the coupling of two phenols, which differ in their oxidation potential. Furthermore, the invention relates to novel biphenols which can be prepared, for example, by the electrochemical coupling.
  • a direct coupling of two different phenols is so far described only by non-electrochemical means: Sartori et al. J. Org. Chem. 1993, 58, 7271-7273.
  • the coupling takes place here using an oxidizing agent such as FeCl 3 , VOCl 3 , p-benzoquinone, CuBr 2 or 2, 3-dichloro-5,6-dicyano-1, 4-benzoquinone (DDQ) and with the addition of AICI 3 .
  • the object of the present invention was to provide an electrochemical process in which phenols with different oxidation potentials can be coupled together, and the yield of biphenol from two different phenols is above that which can be achieved with the electrochemical methods known from the literature Thus, more selective to produce over the biphenol of two different phenols.
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 10 , R 11 , R 12 , R 13 , R 14 , R 16 , R 18 , R 19 , R 20 , R 21 , R 24 are selected from: -H, -alkyl, -O-alkyl, -O-aryl, -S-alkyl, -S-aryl;
  • R 8 , R 15 , R 17 are alkyl
  • R 1 , R 9 , R 22 , R 23 is selected from: -H, -alkyl
  • R 3 is -Me
  • R 1 and R 2 do not simultaneously stand for -H.
  • Alkyl represents a non-branched or branched aliphatic carbon chain having 1 to 10 carbon atoms.
  • the carbon chain has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.
  • Aryl for aromatic (hydrocarbon) radicals preferably having up to 14 carbon atoms, for.
  • phenyl C 6 H 5 -
  • naphthyl Ci 0 H 7 -
  • anthryl C 14 H 9 -
  • phenyl preferably phenyl.
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 10 , R 11 , R 12 , R 13 , RR 16 , R 18 , R 19 , R 20 , R 21 , R 24 are selected from: -H, -alkyl, -O-alkyl, -O-aryl.
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 10 , R 11 , R 12 , R 13 , RR 16 , R 18 , R 19 , R 20 , R 21 , R 24 is selected from: -H, -alkyl.
  • R 4 and R 5 are -H.
  • R 3 and R 6 are alkyl.
  • R 11 is -O-alkyl
  • R 13 is -alkyl
  • a partial aspect of the invention is that the yield of the reaction can be controlled by the difference between the oxidation potentials ( ⁇ AE ⁇ ) of the two phenols.
  • Another aspect of the invention is that the difference between the two oxidation potentials ( ⁇ AE ⁇ ) can be influenced by the solvents or solvent mixtures used.
  • compound A which has the lower oxidation potential, releases an electron to the anode.
  • Compound A becomes a very strong acid due to the positive charge and spontaneously cleaves a proton.
  • the resulting radical then reacts with the compound B, which in relation to the compound A in excess in the solution is present.
  • the biphenol AB radical formed by the coupling releases an electron to the anode and a proton to the solvent.
  • the counterions of the conducting salts are selected from the group consisting of sulfate, hydrogensulfate, alkylsulfates, arylsulfates, alkylsulfonates, arylsulfonates, halides, phosphates, carbonates, alkylphosphates, alkylcarbonates, nitrate, tetrafluoroborate, hexafluorophosphate, hexafluorosilicate, fluoride and perchlorate.
  • the ratio of first phenol to second phenol is in the range of 1: 2 to 1: 4.
  • the solvent or solvent mixture is chosen so that ⁇ AE ⁇ is in the range of 20 mV to 400 mV, preferably in the range of 30 mV to 350 mV.
  • the reaction solution is free of fluorinated compounds. In a variant of the method, the reaction solution is free of transition metals.
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 10 , R 11 , R 12 , R 13 , R 14 , R 16 , R 18 , R 19 , R 20 , R 21 , R 24 are selected from: -H, -alkyl, -O-alkyl;
  • R 8 , R 15 , R 17 are alkyl; R 1 , R 9 , R 22 , R 23 is selected from: -H, -alkyl,
  • FIG. 1 shows a reaction apparatus in which the one described above
  • FIG. 5 shows the dependence of the oxidation potential ⁇ 0 ⁇ of the 2,4-disubstituted phenols on the amount of methanol added.
  • FIG. 6 shows the dependence of the oxidation potential ⁇ 0 ⁇ of the 3,4-disubstituted phenols on the amount of methanol added.
  • TLC thin-layer chromatography
  • PSC precast plates Kieselgel 60 F254 from Merck KGaA, Darmstadt were used. The Rf values are given as a function of the solvent mixture used.
  • a cerium-molybdophosphoric acid solution was used as the dipping reagent.
  • Cerium Molybdatophosphoric Acid Reagent 5.6 g molybdophosphoric acid, 2.2 g cerium (IV) sulfate tetrahydrate and 13.3 g concentrated sulfuric acid to 200 mL water.
  • Melting points were measured using the melting point determination device SG 2000 from HW5, Mainz and are uncorrected.
  • the elemental analyzes were prepared in the analytical department of the Institute of Organic Chemistry of the Johannes Gutenberg University Mainz on a Vario EL Cube of the company Foss-Heraeus, Haunau.
  • the electrolysis takes place galvanostatically.
  • Solvent: HFIP. ⁇ 0 ⁇ E (Ox.Pot.Kuppiungsp a rtner- Ox.Pot Ta beiieneintrag.) - NP: by-product; GC: Gas chromatographic integration of product ratios.
  • FIG. 3 shows the dependence of the oxidation potential ⁇ 0 ⁇ of the para substituents on the amount of methanol added. As the methanol concentration in HFIP increases, a reduction in the oxidation potentials (E ox ) of almost all para-substituted phenols can be seen. Only the isopropyl derivative experiences a slight increase of about 50 mV beyond 15%.
  • Table 4 shows that the greatest possible ⁇ 0 ⁇ are advantageous here.
  • Entry 1 shows a 10 mV larger ⁇ 0 ⁇ in the HFIP / MeOH system than in pure HFIP, whereby an excellent selectivity for the formation of the cross-coupling product is given.
  • Side reactions can also drastically reduce the yield, as entry 3 shows.
  • a ⁇ 0 ⁇ in HFIP / MeOH of only -0.05 V causes a collapse of the amount of cross-coupling product formed.
  • FIG. 4 shows the dependence of the oxidation potential ⁇ 0 ⁇ of the meia substituent on the amount of methanol added.
  • the corresponding meia-substituted derivatives are similar for 3-methyl and 3-methoxyphenol.
  • the course of E ox is more complex. In these cases, there is a successive increase in E ox from about 13% v / v MeOH.
  • Table 5 shows in entry 1 that the optimal AE 0x window may not have been hit either in pure HFIP or with 18% MeOH content. In both cases by-products occur and the GC product integrals suggest only minor amounts of the cross-coupling product. Entry 2 shows a decrease of the yield with a rising ⁇ 0 ⁇ (here
  • 0.25 V). The optimum seems to lie at 0.13 V ⁇
  • 0.13 V is underpinned in entry 3. Here no cross-coupling product formation occurs, whereas at slightly larger ⁇ 0 ⁇ in pure HFIP here traces of the desired biphenol can be isolated.
  • Solvent: HFIP. ⁇ 0 ⁇ Ox.Pot. K uppiungspartner- Ox.Pot.iabeiieneintrag- NP: by-product; Gas chromatographic integration of product ratios.
  • Table 6 shows the dependence on the respective substrate classes of AE 0x window sizes. The importance of the size of ⁇ 0 ⁇ on the selectivity of the reaction is supported by this.
  • FIG. 5 shows the dependence of the oxidation potential ⁇ 0 ⁇ of the 2,4-disubstituted phenols on the amount of methanol added. Within the scope of the error, 2,4-disubstituted phenols show a marked decrease in the oxidation potential with increasing methanol concentration.
  • Solvent: HFIP. ⁇ 0 ⁇ Ox.Pot.-coupling partner - Ox.Pot.iabeiieneintrag- NP: by-product; Gas chromatographic integration of product ratios.
  • Table 7 shows the complexity of ⁇ 0 ⁇ window sizes .
  • Entry 1 shows a high proportion of homocoupling products in pure HFIP when coupled with 2,3-dimethylphenol. This can be explained by the almost identical oxidation potential of both reactants. Only when adding MeOH does a ⁇ 0 ⁇ of -30 mV develop . As a result, the formation of the unbalanced product is only possible.
  • FIG. 6 shows the dependence of the oxidation potential ⁇ 0 ⁇ of the 3,4-disubstituted phenols on the amount of methanol added. Apart from 3,4-dimethylphenol, a uniform reduction of E ox of all phenols can also be seen here. Electron-poorer derivatives experience from about 18% v / v methanol an almost constant lowered potential. Coupling partner HFIP pure 18% MeOH
  • Solvent: HFIP. ⁇ 0 ⁇ Ox.Pot. C oupling partners - Ox.Pot.iabeiientrag- NP: By-product; Gas chromatographic integration of product ratios

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Automation & Control Theory (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé électrochimique pour le couplage de deux phénols ayant des potentiels d'oxydation différents, ainsi que de nouveaux diphénols pouvant être préparés par ce couplage électrochimique.
EP13811833.6A 2013-03-07 2013-12-10 Couplage électrochimique de deux phénols ayant des potentiels d'oxydation différents Withdrawn EP2964813A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013203865.8A DE102013203865A1 (de) 2013-03-07 2013-03-07 Elektrochemische Kupplung zweier Phenole, welche sich in ihrem Oxidationspotential unterscheiden
PCT/EP2013/076078 WO2014135236A1 (fr) 2013-03-07 2013-12-10 Couplage électrochimique de deux phénols ayant des potentiels d'oxydation différents

Publications (1)

Publication Number Publication Date
EP2964813A1 true EP2964813A1 (fr) 2016-01-13

Family

ID=49880701

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13811833.6A Withdrawn EP2964813A1 (fr) 2013-03-07 2013-12-10 Couplage électrochimique de deux phénols ayant des potentiels d'oxydation différents

Country Status (11)

Country Link
US (1) US9879353B2 (fr)
EP (1) EP2964813A1 (fr)
JP (2) JP6104412B2 (fr)
KR (1) KR101779684B1 (fr)
CN (1) CN105164318A (fr)
AR (1) AR095046A1 (fr)
DE (1) DE102013203865A1 (fr)
MY (1) MY197129A (fr)
SG (1) SG11201507160SA (fr)
TW (1) TWI586843B (fr)
WO (1) WO2014135236A1 (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013203866A1 (de) 2013-03-07 2014-09-11 Evonik Industries Ag Elektrochemische Kupplung eines Phenols mit einem Naphthol
DE102014201756A1 (de) 2014-01-31 2015-08-06 Evonik Degussa Gmbh Reinigung chlorverschmutzter Organophosphorverbindungen
ES2644297T3 (es) 2014-12-04 2017-11-28 Evonik Degussa Gmbh Monofosfitos que presentan un mentol
EP3029054B1 (fr) 2014-12-04 2016-11-23 Evonik Degussa GmbH Phosphoramidite présentant une unité de phényle-phényle ou une unité de phényle-naphtyle
EP3029052B1 (fr) 2014-12-04 2018-02-28 Evonik Degussa GmbH Esters monophosphites de 9-Anthrol comme ligands de catalysateurs d'hydroformylation
ES2615894T3 (es) 2014-12-04 2017-06-08 Evonik Degussa Gmbh Monofosfitos que presentan un naftol
EP3031816B1 (fr) 2014-12-04 2019-02-27 Evonik Degussa GmbH Terphenyl-2-oxy-phosphites en tant que ligand dans catalysateurs de la hydroformylation
EP3029013B1 (fr) 2014-12-04 2018-06-13 Evonik Degussa GmbH Monophosphites à unités de structure 4,4,5,5-Tétraphényl-1,3,2-dioxaphospholane en tant que ligands de catalyseurs d'hydroformylation
DE102015216001A1 (de) * 2015-08-21 2017-02-23 Evonik Degussa Gmbh Verfahren zur Herstellung von unsymmetrischen OCO-Pincerliganden aus der Gruppe der m-Terphenylverbindungen
EP3178828A1 (fr) 2015-12-07 2017-06-14 Evonik Degussa GmbH Heterocycliques de phosphite de seleniat et leur procedes de fabrication
EP3178827A1 (fr) 2015-12-07 2017-06-14 Evonik Degussa GmbH Heterocycliques de biphosphite et de selenium et leur procede de fabrication
WO2020104956A1 (fr) * 2018-11-21 2020-05-28 Piramal Enterprises Limited Installation et procédés de réaction organique électrochimique
CN111270259B (zh) * 2020-02-18 2021-07-16 广西师范大学 一种电化学合成六氟异丙氧基苯胺化合物的方法
EP3922758A1 (fr) 2020-06-10 2021-12-15 Evonik Operations GmbH Procédé de fabrication électrochimique d'acides alcanicarboxyliques par oxydation avec ouverture de cycle au moyen d'une électrode en mousse ni(o)oh dopée

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0532579A (ja) 1991-08-01 1993-02-09 Banyu Pharmaceut Co Ltd エストロゲン物質ｂｅ−２５３２７及びその製造法
US5783733A (en) * 1996-06-13 1998-07-21 General Electric Company Process for manufacture of bisphenol
JP5705216B2 (ja) 2009-06-05 2015-04-22 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ アレーンの陽極クロス脱水素二量化法
EP2438215A1 (fr) * 2009-06-05 2012-04-11 Basf Se Procédé de préparation de biaryle-alcools dissymétriques
DE102013203867A1 (de) 2013-03-07 2014-09-11 Evonik Industries Ag Elektrochemische Kupplung von Anilinen
DE102014202274B4 (de) 2013-03-07 2016-11-10 Evonik Degussa Gmbh Elektrochemisches Verfahren zur Kupplung von Phenol mit Anilin
DE102013203866A1 (de) 2013-03-07 2014-09-11 Evonik Industries Ag Elektrochemische Kupplung eines Phenols mit einem Naphthol

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2014135236A1 *

Also Published As

Publication number Publication date
DE102013203865A1 (de) 2014-09-11
KR20150124996A (ko) 2015-11-06
JP6104412B2 (ja) 2017-03-29
JP2016517397A (ja) 2016-06-16
JP6336145B2 (ja) 2018-06-06
MY197129A (en) 2023-05-26
AR095046A1 (es) 2015-09-16
JP2017110013A (ja) 2017-06-22
TW201500591A (zh) 2015-01-01
US20160010225A1 (en) 2016-01-14
US9879353B2 (en) 2018-01-30
CN105164318A (zh) 2015-12-16
KR101779684B1 (ko) 2017-10-10
TWI586843B (zh) 2017-06-11
SG11201507160SA (en) 2015-10-29
WO2014135236A1 (fr) 2014-09-12

Similar Documents

Publication Publication Date Title
WO2014135236A1 (fr) Couplage électrochimique de deux phénols ayant des potentiels d'oxydation différents
EP2964811B1 (fr) Couplage électrochimique d'anilines
DE102014202274B4 (de) Elektrochemisches Verfahren zur Kupplung von Phenol mit Anilin
EP2964812B1 (fr) Couplage électrochimique d'un phénol à un naphthol
EP3189030B1 (fr) 2,2-diaminobiaryles comprenant deux amines secondaires et préparation desdits 2,2-diaminobiaryles par couplage électrochimique
WO2017064133A1 (fr) Procédé de production de composés aromatiques aminofonctionnels
EP3189032A1 (fr) Nouveaux 2,2-diaminobiaryles comprenant deux amines secondaires et préparation desdits 2,2-diaminobiaryles par couplage électrochimique
DE102014217539A1 (de) 2,2‘-Diaminobiaryle mit Phthaloyl-Gruppe oder Succinoyl-Gruppe
EP3133189A1 (fr) Procede de fabrication de ligands pinces oco asymetriques a partir du groupe des composes de terphenyle m
DE102014217538A1 (de) 2,2‘-Diaminobiaryle mit einem primären und einem sekundären Amin
EP3029050B1 (fr) Bisphosphites présentant une unité de naphtyle-phényle en tant que composant périphérique
EP3143185B1 (fr) Procédé d'amination électrochimique sur des anodes de diamant dopées au bore
DE68912920T2 (de) Verfahren zur elektrochemischen Jodierung von aromatischen Verbindungen.
EP4253603A1 (fr) Oxydation électrochimique des cycloalcanes en composés de cycloalkanone
EP3489390A1 (fr) Procédé électrochimique de couplage o-c des phénols non protégés avec les arylamines optiquement pures
EP3133054B1 (fr) Procede de fabrication de ligands pinces symetriques provenant du groupe des composes de terphenyle m
EP0026846B1 (fr) Dérivés de fulvalènophane substitués, leur préparation et leur utilisation
DE102015215998A1 (de) Verfahren zur Herstellung von OCN-Pincerliganden aus der Gruppe der m-Terphenylverbindungen
EP3029051A1 (fr) Bisphosphites présentant une unité de naphtyle-phényle en tant que composant périphérique et une unité de 2,3'-bisphénol en tant que composant central
DE2522854A1 (de) Verfahren zur herstellung von chlorierten hydrochinondimethylaethern
WO2014056900A1 (fr) Procédé de production d'azulène et de dérivés d'azulène
CH605512A5 (en) Chlorinated hydroquinone dimethylethers prepn.

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20150907

AK Designated contracting states

Kind code of ref document: A1

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

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20170410

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

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20170717