WO2014135236A1 - Elektrochemische kupplung zweier phenole, welche sich in ihrem oxidationspotential unterscheiden - Google Patents
Elektrochemische kupplung zweier phenole, welche sich in ihrem oxidationspotential unterscheiden Download PDFInfo
- Publication number
- WO2014135236A1 WO2014135236A1 PCT/EP2013/076078 EP2013076078W WO2014135236A1 WO 2014135236 A1 WO2014135236 A1 WO 2014135236A1 EP 2013076078 W EP2013076078 W EP 2013076078W WO 2014135236 A1 WO2014135236 A1 WO 2014135236A1
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- WIPO (PCT)
- Prior art keywords
- phenol
- alkyl
- solvent
- mmol
- phenols
- Prior art date
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- 0 Cc1cc(OC)c(*)cc1-c1cc(OS)ccc1O Chemical compound Cc1cc(OC)c(*)cc1-c1cc(OS)ccc1O 0.000 description 8
- GPBFCQRAFWJWQW-UHFFFAOYSA-N Cc(cc1)cc(O)c1-c(cc(C)cc1OC)c1O Chemical compound Cc(cc1)cc(O)c1-c(cc(C)cc1OC)c1O GPBFCQRAFWJWQW-UHFFFAOYSA-N 0.000 description 1
- PETRWTHZSKVLRE-UHFFFAOYSA-N Cc(cc1)cc(OC)c1O Chemical compound Cc(cc1)cc(OC)c1O PETRWTHZSKVLRE-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/29—Coupling reactions
-
- 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.
- phenols is used in this application as a generic term and thus also includes substituted phenols. Two phenols which have a different oxidation potential must therefore also be substituted differently.
- 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 .
- a problem that arises in the electrochemical coupling of different molecules is that the reactants usually have different oxidation potentials E 0x .
- the molecule with the lower oxidation potential has a higher tendency to donate an electron (e " ) to the anode and an H + ion to, for example, the solvent than the molecule with the higher oxidation potential E 0x via the Nernst equation:
- 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
- R 19 is alkyl.
- a process is claimed with which, for example, the abovementioned compounds can be prepared.
- Electrochemical process for the preparation of biphenols comprising the process steps:
- 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.
- the main product is biphenol, which is formed by the coupling of two molecules of the first phenol.
- 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.
- the difference between the two oxidation potentials ⁇ ⁇ ⁇ ) can be shifted by suitable choice of the solvent / solvent mixture in the desired range.
- 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 conductive salt is selected from the group of alkali, alkaline earth, tetra (C 1 -C 6 -alkyl) -ammonium, 1, 3-di (C 1 -C 6 -alkyl) imidazolium or tetra (C 1 -C 6 -alkyl ) phosphonium salts.
- 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 conductive salt is selected from tetra (C 1 -C 6 -alkyl) ammonium salts and the counterion is selected from sulfate, alkyl sulfate, aryl sulfate.
- the second phenol is used at least twice the amount of the first phenol.
- the ratio of first phenol to second phenol is in the range of 1: 2 to 1: 4.
- either the first phenol or the second phenol has an -O-alkyl group.
- 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.
- the reaction solution is free of substrates having leaving functionalities other than hydrogen atoms.
- the reaction solution is free of organic oxidizing agents.
- the first phenol and the second phenol are selected from: la, Ib. IIa, IIb, purple, IIIb:
- 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,
- 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 C 1 0H 7 -
- anthryl C 14 H 9
- phenyl preferably phenyl.
- FIG. 1 shows a reaction apparatus in which the one described above
- Coupling reaction can be carried out.
- the apparatus comprises a nickel cathode (1) and an anode of boron-doped diamond (BDD) on silicon (5).
- BDD boron-doped diamond
- the apparatus can be cooled by means of the cooling jacket (3).
- the arrows indicate the flow direction of the cooling water.
- the reaction space is closed with a Teflon stopper (2).
- the reaction mixture is mixed through a magnetic stir bar (7).
- the apparatus On the anodic side, the apparatus is closed by screw clamps (4) and seals (6).
- FIG. 2 shows a reaction apparatus in which the coupling reaction described above can be carried out on a larger scale.
- the apparatus comprises two glass flanges (5 '), on which are pressed by screw clamps (2') and seals electrodes (3 ') of boron-doped diamond (BDD) coated carrier materials or other, known in the art, electrode materials.
- the reaction space can be provided with a reflux condenser via a glass sleeve (1 ').
- the reaction mixture is mixed with the aid of a magnetic stirring bar (4 ').
- FIG. 3 shows the dependence of the oxidation potential ⁇ 0 ⁇ of the ara substituents on the amount of methanol added.
- FIG. 4 shows the dependence of the oxidation potential ⁇ 0 ⁇ of the meia substituent on the amount of methanol added.
- 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 NMR spectroscopic investigations were carried out on multicore resonance spectrometers of the type AC 300 or AV II 400 from Bruker, Analytical Messtechnik, Düsseldorf.
- the solvent used was CDCl 3 .
- the 1 H and 13 C spectra were calibrated according to the residual content of non-deuterated solvent according to the NMR Solvent Data Chart from Cambridge Isotopes Laboratories, USA.
- the assignment of the 1 H and 13 C signals was carried out in part by means of H, H-COZY, ⁇ , ⁇ -NOESY, H, C-HSQC and H, C-HMBC spectra.
- the chemical shifts are given as ⁇ values in ppm.
- the coupling reaction was carried out in an apparatus as shown in FIG.
- 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
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- 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
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP13811833.6A EP2964813A1 (de) | 2013-03-07 | 2013-12-10 | Elektrochemische kupplung zweier phenole, welche sich in ihrem oxidationspotential unterscheiden |
JP2015560568A JP6104412B2 (ja) | 2013-03-07 | 2013-12-10 | 酸化電位の異なる2つのフェノールの電気化学的カップリング |
US14/772,874 US9879353B2 (en) | 2013-03-07 | 2013-12-10 | Electrochemical coupling of two phenols which differ in their oxidation potential |
MYPI2015002208A MY197129A (en) | 2013-03-07 | 2013-12-10 | Electrochemical coupling of two phenols which differ in their oxidation potential |
SG11201507160SA SG11201507160SA (en) | 2013-03-07 | 2013-12-10 | Electrochemical coupling of two phenols which differ in their oxidation potential |
CN201380076323.2A CN105164318A (zh) | 2013-03-07 | 2013-12-10 | 氧化电位不同的两种酚的电化学偶联 |
KR1020157027237A KR101779684B1 (ko) | 2013-03-07 | 2013-12-10 | 그의 산화 전위가 상이한 2개의 페놀의 전기화학적 커플링 |
Applications Claiming Priority (2)
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DE102013203865.8A DE102013203865A1 (de) | 2013-03-07 | 2013-03-07 | Elektrochemische Kupplung zweier Phenole, welche sich in ihrem Oxidationspotential unterscheiden |
DE102013203865.8 | 2013-03-07 |
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WO2014135236A1 true WO2014135236A1 (de) | 2014-09-12 |
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PCT/EP2013/076078 WO2014135236A1 (de) | 2013-03-07 | 2013-12-10 | Elektrochemische kupplung zweier phenole, welche sich in ihrem oxidationspotential unterscheiden |
Country Status (11)
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US (1) | US9879353B2 (de) |
EP (1) | EP2964813A1 (de) |
JP (2) | JP6104412B2 (de) |
KR (1) | KR101779684B1 (de) |
CN (1) | CN105164318A (de) |
AR (1) | AR095046A1 (de) |
DE (1) | DE102013203865A1 (de) |
MY (1) | MY197129A (de) |
SG (1) | SG11201507160SA (de) |
TW (1) | TWI586843B (de) |
WO (1) | WO2014135236A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9670585B2 (en) | 2013-03-07 | 2017-06-06 | Evonik Degussa Gmbh | Electrochemical coupling of a phenol to a naphthol |
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DE102014201756A1 (de) | 2014-01-31 | 2015-08-06 | Evonik Degussa Gmbh | Reinigung chlorverschmutzter Organophosphorverbindungen |
ES2670512T3 (es) | 2014-12-04 | 2018-05-30 | Evonik Degussa Gmbh | Ésteres monofosfitos de 9-antrol como ligandos para catalizadores de hidroformilación |
EP3031817B1 (de) | 2014-12-04 | 2019-05-01 | Evonik Degussa GmbH | Terphenyl-2-oxy-phosphite als liganden in hydroformylierungskatalysatoren |
EP3031813B1 (de) | 2014-12-04 | 2016-11-23 | Evonik Degussa GmbH | Monophosphite die ein menthol aufweisen |
EP3037427B1 (de) | 2014-12-04 | 2016-11-23 | Evonik Degussa GmbH | Monophosphite die ein naphthol aufweisen |
EP3029013B1 (de) | 2014-12-04 | 2018-06-13 | Evonik Degussa GmbH | Monophosphite mit Struktureinheit 4,4,5,5-Tetraphenyl-1,3,2-dioxaphospholan als Liganden für Hydroformylierungskatalysatoren |
EP3029054B1 (de) | 2014-12-04 | 2016-11-23 | Evonik Degussa GmbH | Phosphoramidite welche eine Phenyl-Phenyl-Einheit oder eine Phenyl-Naphthyl-Einheit aufweisen |
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 (de) | 2015-12-07 | 2017-06-14 | Evonik Degussa GmbH | Heterozyklische selena-phosphite sowie verfahren zu deren herstellung |
EP3178827A1 (de) | 2015-12-07 | 2017-06-14 | Evonik Degussa GmbH | Heterozyklische selena-biphosphite sowie verfahren zu deren herstellung |
US20210371992A1 (en) * | 2018-11-21 | 2021-12-02 | Piramal Pharma Limited | Electrochemical organic reaction setup and methods |
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 (de) | 2020-06-10 | 2021-12-15 | Evonik Operations GmbH | Verfahren zur elektrochemischen herstellung von alkandicarbonsäuren durch ringöffnende oxidation mittels einer dotierten ni(o)oh schaumelektrode |
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WO2010139685A1 (de) * | 2009-06-05 | 2010-12-09 | Basf Se | Verfahren zur anodischen kreuz-dehydrodimerisierung von arenen |
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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 |
CN102459707A (zh) * | 2009-06-05 | 2012-05-16 | 巴斯夫欧洲公司 | 制备不对称联芳基醇的方法 |
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 |
DE102013203867A1 (de) | 2013-03-07 | 2014-09-11 | Evonik Industries Ag | Elektrochemische Kupplung von Anilinen |
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- 2013-12-10 WO PCT/EP2013/076078 patent/WO2014135236A1/de active Application Filing
- 2013-12-10 CN CN201380076323.2A patent/CN105164318A/zh active Pending
- 2013-12-10 EP EP13811833.6A patent/EP2964813A1/de not_active Withdrawn
- 2013-12-10 US US14/772,874 patent/US9879353B2/en active Active
- 2013-12-10 JP JP2015560568A patent/JP6104412B2/ja active Active
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9670585B2 (en) | 2013-03-07 | 2017-06-06 | Evonik Degussa Gmbh | Electrochemical coupling of a phenol to a naphthol |
Also Published As
Publication number | Publication date |
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AR095046A1 (es) | 2015-09-16 |
EP2964813A1 (de) | 2016-01-13 |
DE102013203865A1 (de) | 2014-09-11 |
JP2016517397A (ja) | 2016-06-16 |
KR101779684B1 (ko) | 2017-10-10 |
JP2017110013A (ja) | 2017-06-22 |
TW201500591A (zh) | 2015-01-01 |
JP6336145B2 (ja) | 2018-06-06 |
MY197129A (en) | 2023-05-26 |
JP6104412B2 (ja) | 2017-03-29 |
US9879353B2 (en) | 2018-01-30 |
KR20150124996A (ko) | 2015-11-06 |
US20160010225A1 (en) | 2016-01-14 |
CN105164318A (zh) | 2015-12-16 |
TWI586843B (zh) | 2017-06-11 |
SG11201507160SA (en) | 2015-10-29 |
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