Chem. Jap. 3326, Petersen RC, Finkelstein M, Ross SD (1967) J. Org. 29: 2571, 2582; (1981) Heterocycles 15: 349, Torii S, Tanaka H, Ogo H, Yamasita S (1971) Bull. For the divided cell setup, a 0.5m KOH solution was used as catholyte. Electrochemical conversion of levulinic acid to 2,7octanedione and the nonKolbe electrolysis of monomethyl succinic acid to methyl acrylate in singlepass and semibatch mode were studied in electrochemical flow cells. Carboxylic Acid & Benzoic Acid 28 Nitrogen-Containing Compounds Hoffmann Bromamide Reaction, Gabriel Phthalimide Reaction, Hinsberg Reagent, Hoffmann Mustard Oil Khim. Sci. Products from these reactions are formed selectively in good yield and can be isolated from the minor byproducts in slightly lower yields. 3- and 4-alkenoic acids can only he coupled in moderate and often not reproducible yields [2~ 4]. 113: 3898, Berenblit VV, Zapevalov AY, Panitkova ES, Plashkin VS, Rondarev DS, Sass VP, Sokolov SV (1979) Zh. Of all terms in the circuit, R3 was found to have the greatest variation as a function of acid length. Chem. Pat. The review is not intended to be comprehensive, but aims to analyze representative examples from the literature, including transition-metal catalyzed carboxylation of benzylic and allylic C(sp3)-H . Soc. Acad. 20 You do not have JavaScript enabled. (London) 3624, Finkelstein M, Petersen RC (1960) J. Org. Sect. 113: 451; see also: Jensen-Korte U, Schfer HJ (1982) Liebigs Ann. The amount of gas is detected via a massflowmeter SmartTrak 100 (Sierra Instruments) and afterwards analyzed via a microgaschromatograph. Germany, 2 122: 46, Muck DL, Wilson ER (1970) J. Electrochem. 13 Soc., London 5745, Linstead RP, Shephard BR, Weedon BCL (1952) J. Chem. If you are an author contributing to an RSC publication, you do not need to request permission CV conditions: 0.1M KPF6 in MeCN, 100mV/s scan rate, room temperature, Ni-foam working electrode (WE), and RVC counter electrode (CE). 81: 2073, Fioshin MY, Kamneva LA, Mirkind LA, Salmin LA, Kornienko AG (1962) Neftekhimiya 2: 557; (1963) CA 58: 11 205b, Fioshin MY, Kamnewa AI, Mirkind LA, Kornienko AG, Salmin LA (1966) Khim. Soc. Products synthesized in the Kolbe process have lower polarities and densities than the aqueous solvent, which results in two separated liquid phases and allows for an easy and fast isolation of the organic product phase in a settler. Comparison of selectivity for main Kolbe products tetradecane, heptane/1heptene and conversion depending on different cell setups as well as FE for all three Kolbe products, OER and HER. Acta 27: 919, Vassiliev YB, Lotvin BM, Grinberg VA (1981) Elektrokhimiya 17: 1252; (1981) CA 95: 211 885, Smith WB, Hyon Yuh Y (1968) Tetrahedron 24: 1163, Chkir M, Lelandais D (1971) J. Chem. Google Scholar. Soc. Soc. Higher system pressure can increase the solubility of gas molecules in the electrolyte and compress the gas segments, reducing the amount of gas bubbles in the electrochemical cell. In summary, platinized titanium shows comparable results to platinized stainless steel considering chemical selectivity and conversion of carboxylic acid. Finally, control experiments confirmed that electrochemistry is required (entry 15) and that solvated Ni, which may be generated by oxidative corrosion of the Ni anode, is not responsible for the observed reactivity (entry 16). Ber. 44: 2303, Lelandais D, Bacquet C, Einhorn J (1981) Tetrahedron 37: 3131, Bacquet C, Einhorn J, Lelandais D (1980) J. Heterocycl. Thus, eleclrolysis of 3,3,3-trifluoro-2-trifluoromethyl- propanoic acid in die presence of some of its potassium salt gives the corresponding fluoroalkane in a satisfactory yield [7d] (equation 67). 10: 511, 522, Fleischmann M, Goodridge F (1968) Discuss. Chem. MCFAs from biomass act as renewable feedstock for the production of biofuels or other valueadded products like fine chemicals, solvents, lubricants or monomers. Jadhav, S. Self-assembled monolayers (SAMs) of carboxylic acids: an overview. Zhang, X. et al. Various pulse frequencies, duty cycles (time on vs. time off), and pre-polarizations were programmed into the experiments with the aim of promoting carboxylate aggregation at the anode and selective oxidation of the substrate (entries 89). 79: 3182, Corey EJ, Bauld NL, Lalonde RT, Casanova J, Kaiser ET (1960) J. Am. Proc. 360, 17351753 (2018). 0. 834, Laurent E, Thomalla M (1976) Tetrahedron Lett. Copper-mediated synthesis of drug-like bicyclopentanes. CV of ferrocene (10mM) with pristine Ni-foam (black), C6 pretreated Ni-foam (blue), and C12 pretreated Ni-foam (red). Am. The developed platinized titanium anodes showed comparable results to the original platinized stainless steel electrodes, while the former reveal a better long term stability and no visible corrosion effects when high current densities in combination with high residence times were applied. While older literature stated that the selectivity for Kolbe products diminishes at higher pH values,[ Chem. Different parameters and reactor setups were studied, resulting in Kolbe selectivity of 90% using an undivided cell setup with platinized titanium working electrodes. This dielectric-controlled oxidation of carboxylates over the Fe catalyst is further supported through EIS studies performed over the course of reactions with short-chain and long-chain acids. This review focuses on recent advances in the field of direct carboxylation reactions of C(sp3)-H and C(sp2)-H bonds using CO2 encompassing both transition-metal-catalysis and base-mediated approach. Int. Faraday Soc. Acta 68: 2342, Ceder O, Nilsson HG (1977) Acta Chem. All relevant results were found to decrease with increasing system pressure. Chem. 4727, Laurent E, Thomalla M (1975) Tetrahedron Lett. With respect to the selectivity for the main Kolbe products (90%), comparable results were found with a tendency towards slightly better results for the SSPt anode. discussed the impact of the pH value on the solubility of noctanoic acid agglomerates in water in the bulk and locally at the electrode surface and concluded that, for lower pH values (close to the pK Article Synth. Furthermore, adsorbed gas bubbles at the electrode surface lead to a more inhomogeneous current density distribution which can cause overoxidation of the substrate. Soc. 54, 21992203 (2015). Fr. Chem. The glassy carbon disk electrode was polished in a nitrogen-filled glovebox using diamond polish (15m, BASi) and anhydrous MeCN. As such,we next evaluated amine and pyridine bases that could deprotonate the acid to form an ammonium carboxylate salt to serve as the supporting electrolytes47. The Kolbe electrolysis or Kolbe reaction is an organic reaction named after Hermann Kolbe. Results demonstrating the feasibility of . Sci. The reaction vial was sealed with a septa-lined cap. Sbei, N., Aslam, S. & Ahmed, N. Organic synthesis via Kolbe and related non-Kolbe electrolysis: an enabling electro-strategy. Soc. According to the literature, the formation of the carbocations is increasingly favored at lower current densities (below 0.25Acm2) which leads to the formation of nonKolbe products. Google Scholar. 2]. Int. 44: 2019, Nishitani T, Horikawa H, Iwasaki T, Matsumoto K, Inoue I, Miyoshi M (1982) J. Org. Due to the corrosive effects of the anode base material (stainless steel), titanium (Ti) was used as alternative anode base material which was electroplated with Pt to ensure the selectivity of the process. Ed. 5). Since the ECMR is intended to be used in a continuous process, the longterm stability of the electrode material has to be taken into account. https://doi.org/10.1007/BFb0034365, Publisher Name: Springer, Berlin, Heidelberg. PubMed Central 1300, Krutler B, Bard AJ (1978) J. In addition, as the pH is not only influenced through the generation of protons, but also from the organic compounds and the reaction of formed carbon dioxide with hydroxideions a proton balance cannot be easily made from the pH and charges going to hydrogen oxidation reaction (HOR) cannot be given and are out of scope of this study. In enzymology, an aryl-aldehyde oxidase (EC 1.2.3.9) is an enzyme that catalyzes the chemical reaction an aromatic aldehyde + O 2 + H 2 O an aromatic carboxylic acid + H 2 O 2. Am. As a competitive process, oxidation of the alkyl radical can occur, where a carbenium ion is formed which can react with nucleophiles in consecutive reactions to form esters or alcohols (MostHoefer reaction) that can be further oxidized to aldehydes or even carboxylic acids. Both electrodes were assembled in a reactor housing and pressed together with PTFEsealing (Chemraz) in between to prevent leakage. Chem. Access to the carbon fragment requires the formation of a transient carboxyl radical, which can subsequently undergo rapid decarboxylation (>105s1) to release CO2 and an alkyl radical6. 81: 1739, 1743, Schfer HJ, Schenk B: unpublished results, Thomas HG, Gabriel J, Fleischhauer J, Raabe G (1983) Chem. Only for 0.28Acm2, a local maximum of 0.42molh1 was achieved at 2.55s residence time (see Supporting Information). Chem. Acta 69: 1704, Yoshikawa M, Kamigauchi T, Ikeda Y, Kitagawa I (1981) Chem. J. Chem. Chem. A. Adipic acid. The electrolysis of carboxylic acid was first observed by Faraday, and Hermann Kolbe identified ethane and octane as the respective products of the electrolysis of acetic and valeric acid. CVs of Fc with a pristine Ni-foam WE reveal an expected onset current at +0.1V that results from oxidation of Fc at a high surface-area anode (black trace). 15: 1417; (1979) CA 91: 192 779, Renaud RN, Champagne PJ (1975) Can. Electrochemical reactions at insulating layers on electrode surfaces are counterintuitive, but the approach has been shown to offer a unique selectivity for the redox of compounds within the surface layer over redox of homogeneous species that cannot readily diffuse into the bilayer41. At the anode, the deprotonated acid reacts further to a radical and carbon dioxide (Equation (2)). Soc. A. We hypothesized that anions from exogenous supporting electrolytes disrupt the targeted formation of a carboxyl layer at the anodic surface46. At higher residence times, the performance of the SSPt setup is decreasing and better results for FE were achieved for the TiPt anode setup. 5: 575, Stepanov FN, Baklan VF, Guts SS (1965) Akad. Formation, dynamics, and physical properties of n-alkanoic acids adsorbed from solution on an oxidized aluminum surface. Soc. Internet Explorer). The heat exchange medium (Isopropanol) was pumped through the integrated heat exchanger of the microstructured electrodes with a thermostat (CC3, Huber; temperature=20C). 81: 4117; (1962) J. J. Chem. ADS (B) 28: 36, Linstead RP, Lunt JC, Weedon BCL (1951) J. Chem. solvents, the desired products formed in excellent yields (up . Noble, A. Soc., Chem. Chem. Error bars result from standard deviation of sample measurements. Those oxide layers passivate the surface and prevent further oxidation of the material. Uppal, S., Graaf, M. & Moeller, K. Microelectrode arrays and the use of PEG-functionalized diblock copolymer coatings. Soc. Kolbe electrolysis converts carboxylic acids to hydrocarbons, which can be used as base chemicals, specialty chemicals, or fuels. Org. 44: 815, Schfer HJ, Michaelis R: unpublished results, Wuts PGM, Sutherland C (1982) Tetrahedron Lett. After this initial period, C10 products were formed predominantly, which suggests that the surface layer of C12 was consumed or exchanged with C10 in solution. Specifically, the oxidation of Fc is detected at the expected potential when CVs are measured with Ni anodes that were pretreated in hexanoic acid (C6, blue trace). Chem. This is a preview of subscription content, access via your institution. Accordingly, increasing amounts of nonKolbe products were found at elevated back pressures. Am. Herein, we demonstrate a comprehensive study employing this microfluidic platform for a continuous Kolbe electrolysis of noctanoic acid in basic aqueous solution. J. Chim. 2854, Rand L, Mohar AF (1965) J. Org. Department of Chemistry, Additionally, studies revealed that the formation of carboxylate monolayers is reversible. Soc., Chem. The conditions for chromatography and other data that are specific to each compound are given in the SI. Chem. In addition, phase separation allows a direct recycling of the aqueous phase in a continuous operation where reactant is constantly added. 117: 1358, Hawkes GE, Utley JHP, Yates GB (1976) J. Chem. This is in accordance with the selectivity of the main side products (i.e., heptanal, nonKolbe olefins and octanoic acid heptylester) which are increasing for higher pressures (Figure4). Chen, X. et al. Hence, the variation of residence time also confirms that, within the studied residence time and current density range, selectivity is mainly driven by starting concentration and electrode material. Soc. Am. , Symp. official website and that any information you provide is encrypted 1868; see also Uneyama K, Torii S, Oae S (1971) Bull. I: 2714, Rodewald LB, Lewis MC (1971) Tetrahedron 27: 5273, Kanevskii LS, Vasilev YB (1976) Elektrokhimiya 12: 1487; (1977) CA 86: 80805, Brennan MPJ, Brettle R (1973) J. Chem. [27] Res. Chem. Enlarged reactor sizes with high surface to volume ratios and robust electrodes allowing to apply high current densities (above 100mAcm2) are rarely reported. 370.199; (1973) CA 79: 18 135, Chechina ON, Levin AI (1974) Elektrokhimiya 10: 1170; (1974) CA 81: 113916, Nutt RF, Strachan RG, Veber DF, Holly FW (1980) J. Org. These conditions would be later extended to catalyst-controlled protocols. Chem. Hence, at very high current densities, higher flow rates should be applied, increasing the mass transfer and improving the removal of gas bubbles to maintain high Kolbe selectivity. Error bars result from standard deviation of sample measurements. Chem. [23]. Chem. . Finally, results for overall FE for anode and cathode processes could not be increased using the divided cell setup, which is a strong indication that a redox shuttle is not responsible for FE losses in an undivided cell setup. Soc., Chem. Pat. Iron-catalyzed radical additions to olefins have been previously reported but such catalysts are incompatible with typical conditions for electrooxidative decarboxylation13,59,60. Ber. Langmuir 20, 74997506 (2004). 136, 52575260 (2014). 3, 118 (2021). For example by, Kolbe's electrolytic method, electrolysis of aqueous . 1965, Arora PC, Woolford RG (1971) Can. designed the study, analysed the data, and wrote the manuscript. Am. Sodium or potassium salt of a dicarboxylic acid on electrolysis gives an alkene. Offen. Chem. ; (1975) CA 82: 49312k, Yamataka K, Matsuoka Y, Isoya T, DE 2830144; Asahi Chem. - 176.9.46.240. II, 395, Barry JE, Finkelstein M, Mayeda EA, Ross SD (1976) J. The SDS layer promoted the adsorption and retention of propyl radicals for butyric acid solutions and improved its conversion and dimerization to yield hexane, but the bulky propyl radicals also easily depart from the hydrophobic layer to become more propene. Almost the same FE (72%69%) resulted for H2 at the different current densities which is in accordance with the overall anodic FE where all detected products (main Kolbe products and side products, for example, heptanal, ester, oxygen) have been taken into account for the calculation. Flow chart of singlepass Kolbe electrolysis in water. 35: 3611, Zorge JA van, Strating J, Wynberg H (1970) Recl. Khim. Jap. Res. It was confirmed that the selectivity for Kolbe products is predominantly driven by the working electrode material, which should be a smooth platinum surface, and a high concentration of carboxylic acid. 15). J. Electrochem. & Moeller, K. D. Electroorganic synthesis and the construction of addressable molecular surfaces. The Kolbe electrolysis is a promising reaction to combine the usage of electrons as reagents and the application of renewable generated carboxylic acids as raw materials producing value added chemicals. A 2: 5187; (1965) CA 62: 12751a, Schfer H, Pistorius R (1972) Angew. Chem. , Chim. Am. For the second and third cycle, 1.5L of aqueous reaction mixture were taken and carboxylic acid was added to reach a concentration of 1.0m. KOH was added according to the amount of fresh carboxylic acid in a ratio of 1:1.5 (acid:KOH) to ensure sufficient solubility. 3111, Glasstone S, Hickling A (1939) Chem. Accordingly, lower solubility of noctanoic acid and different agglomerates of carboxylic acid or carboxylate near the electrodes could be a consequence, in turn reducing conversion. Article Accordingly, this compensatory mechanism is diminished in a divided cell setup and the local pH shifts to lower values, which in turn may lead to local decreased solubility of carboxylic acids in water, resulting in reduced conversion. Kolbe electrolysis is one of the oldest electroorganic syntheses. The unstable radical alpha to the carbonyl of Int-1 couples with FeII(acac)2 to form the FeIII(enolate) Int-2, which is easily protonated by another carboxylic acid to generate a product. Chem. Mechanism of the Kolbe Electrolysis Side products: It was first observed in 1834 by M. Faraday when he studied the electrolysis of aqueous acetic acid [ 2 ]. For the Kolbe process, the chemical as well as the electron selectivity are relevant performance indicators. In that case, the counter reaction can compensate the pH change at the working electrode, ensuring a stable conversion which could be negatively affected when the pH value is changing distinctly. Khim. 131: 773, Linstead RP, Shephard BR, Weedon BCL, Lunt LC (1953) J. Chem. PubMed 41: 21, 38, 55, Fairweather DA, Walker OJ (1931) Trans. Soc. Because of a weakened mass transfer present at slow flow rates (high residence times), the second oxidation step for the adsorbed alkyl radicals becomes more likely, resulting in an alkyl cation which reacts to alcohols, esters or olefins. The electrodes were fabricated by selective laser melting (stainless steel), coated with polytetrafluoroethylene (PTFE) for insulation, microstructured with a sidemilling cutter and electroplated with platinum. After the phase separation, the aqueous phase containing unreacted acid was reconcentrated with carboxylic acid to 1.0m and the electrolysis was repeated. Abstract A polymer electrolyte membrane (PEM) reactor is described for use in Kolbe electrolysis: the anodic oxidation of an alkyl carboxylic acid with subsequent decarboxylation and coupling to yield a dimer, 2RCOOH {r_arrow} R-R + 2CO {sub 2} + 2e {sup {minus}} + 2H {sup +}. Ber. 14: 641, Eberson L, Nilsson S (1968) Acta Chem. 71: 81, Gilbert BC, Holmes RGG, Marshall PDR, Norman ROC (1977) J. Chem. Considering the discussed results, it can be concluded that an undivided cell setup is favored for the reaction. High current densities are known to favor the Kolbe reaction pathway. x(t) the concentration after electrolysis. Following electrolysis, a basic workup was performed with a 1M aqueous solution of NaOH. Sci. The ubiquity of such acids in bioavailable and commodity chemicals renders them attractive sources of reactive alkyl fragments as an alternative to alkyl halides4,5. The electrochemical oxidative decarboxylation of carboxylic acid salts that leads to radicals, which dimerize. about navigating our updated article layout. We evaluated a wide range of transition metal salts and complexes that could capture alkyl radicals generated by oxidative decarboxylation to direct product selectivity. Chem. 14: 758, Chechina ON, Bildinov KN, Levin AI, Sokolov SV, USSR Pat. Ind. 130: 1844, Woolford RG (1962) Can. The The site is secure. PubMed Central Prikl. WikiMatrix. Cat. A decrease in conversion was found after three hours of reaction time, and the combination of reduced electrode activity and a change in pH value can be assumed to account for the observed effects. B. Hexanoic acid. 83: 579; (1971) Angew. Eng. Part of Springer Nature. Nickel-catalyzed Barton decarboxylation and Giese reactions: a practical take on classic transforms. Insufficiently coated parts, bringing electrolyte into contact with the electrode base material, show passivation in case of titanium, whereas corrosion effects and the formation of solid iron oxides have been observed for stainless steel. [21] For a divided cell setup, two microstructured electrodes were assembled with an anion exchange membrane (AEM) in between, which was purchased from Fumatech GmbH (FUMASEP FAA350, 50m thickness, bromide as counter ion). Furthermore, electrochemical flow cell allow for a continuous operation of constant reactant feed and separation of the products. Engl. Reference electrodes were calibrated against an internal voltage reference of ferrocene (110mM). Urban etal. 24: 1055, Pletcher D, Smith CZ (1975) J. Chem. Faraday Soc. Maljuric S., Jud W., Kappe C. O., Cantillo D.. Pletcher D., Green R. A., Brown R. C. D.. Diamanti M. V., Del Curto B., Pedeferri M.. Kuromoto N. K., Simo R. A., Soares G. A.. Gong M., Wang D.-Y., Chen C.-C., Hwang B.-J., Dai H.. Bernardini M., Comisso N., Davolio G., Mengoli G., http://creativecommons.org/licenses/by/4.0/. 20: 1799; (1985) CA 102: 61 763, Goldschmidt S, Stckl E (1952) Chem. Decanoic acid was selected as the model substrate because products and byproducts are easily monitored by GC, and the acid contains a long alkyl chain that has been previously reported to promote SAM formation at anodes35,38. Chem. Int. Chem. An alkene is generated when an aqueous solution of sodium or potassium salt of a dibasic acid (with adjacent carboyxlic groups) is electrolyzed. Chem. Will Medlin, Maximilian Koy, Peter Bellotti, Frank Glorius, Yanwei Lum, Jianan Erick Huang, Edward H. Sargent, Tao-Tao Zhuang, Zhi-Qin Liang, Edward H. Sargent, Tanner C. Jankins, William C. Bell, Keary M. Engle, Nature Communications The carboxylic acid is deprotonated by the alkali hydroxide electrolyte added to the solution and the resulting carboxylate is oxidized at the anode. * Nils Baumgarten, Email: ed.refohnuarf.mmi@netragmuab.slin. 166, Warren CB, Bloomfield JJ (1973) J. Org. The data that support the findings of this study are available from the corresponding author upon reasonable request. Synthesis 53, 129 (2021). CAS J. In summary, we report a rare and synthetically-underutilized strategy for electrooxidation of challenging substrates in the presence of oxidatively-sensitive catalysts that control reaction selectivity. Am. Am. Scand. Chem. Chem. [5] To obtain These data can be modeled by an equivalent circuit that decouples the Warburg element into a parallel Q factor (Q3) and resistor (R3)48,51, and the fitted traces are illustrated as dashed lines in Fig. We discovered that pulsed electrolysis could further improve the yield of 1. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate. 0. Stang, C. & Harnisch, F. The dilemma of supporting electrolytes for electroorganic synthesis: a case study on Kolbe electrolysis. Investigation of the low frequency Warburg impedance of Li-ion cells by frequency domain measurements. Soc. 29: 430, Schfer HJ, Bitenic M: unpublished results, Rand L, Rao CS (1968) J. Org. 76.113.835, Sanei Chem. Furthermore, a fine redbrown precipitate sedimented in the aqueous phase of the samples after several hours. In fact, by increasing the pressure from 1.11.2bar to 5bar, a decrease of cell voltage from 4.5V to 4.24.3V at constant cell current was achieved, confirming that gas segments were compressed. The reaction has been used to form dimers [12], as well as in some cases cyclic products (Scheme 3, reaction 2) [13-15]. 59: 945; (1963) CA 55: 27 003a, Ogumi Z, Tari I, Takehara Z, Yoshizawa S (1976) Bull. Selectivity of the products was than calculated from corrected peak areas. Fe-catalyzed CC bond construction from olefins via radicals. [ 17: 47, Jensen U, Schfer HJ (1981) Chem. In the meantime, to ensure continued support, we are displaying the site without styles Jap. Soc. PubMed Central In order to study the influence of increased system pressure, a needle valve was used to control the backpressure after the ECMR. The increased resistance caused by long-chain carboxylates is consistent with the formation of stable SAMs that are supported by strong dispersion interactions between the long aliphatic groups38. After the reaction mixture has left the electrolysis cell, it is collected in a settler where the separation of the three phases (gas, organic phase, aqueous phase) takes place. Division Chemistry Sustainable Chemical Syntheses, 3D printing techniques show a high potential for cost efficient and customizable manufacturing of electrochemical microreactors (ECMR) or flow cells that can be used to study the transformation from batch electrolysis into flow processes. J. We investigated the selective electrochemical decarboxylation of acetic acids and butanoic acids in aqueous solutions and at room temperature, following the principles of green chemistry. Khim. Federal government websites often end in .gov or .mil. 136, 1160211605 (2014). Nat Commun 13, 1319 (2022). Nature 573, 398402 (2019). 85: 165, Maier G, Bosslet F (1972) Tetrahedron Lett. Chem. Ed. 3b as a difference of the measured R3 of each acid from to the average resistance (R3avg) across all acids. Redox-active esters in Fe-catalyzed CC coupling. Chem. Banerjee, S., Han, X. Soc. Google Scholar. Chem. Surprisingly, replacing Ni with Pt electrodes caused an extremely high cell resistance under the non-Kolbe conditions and resulted in low yields (entry 12). So far, mainly the Kolbe electrolysis of short-chain n-carboxylic acids at low concentrations has been studied. 22: 2453, Eberson L (1963) Acta Chem. Graphs show conversion (left axis) and applied faradaic equivalents (right axis) (a,d), selectivity for Kolbe products tetradecane and heptane/1heptene (b,e) and anodic FE for all main Kolbe products (tetradecane, heptane, 1heptene), oxygen evolution reaction (OER, O2) and cathodic FE based on the hydrogen evolution reaction (HER, H2) (c,f). c Illustration of the equivalent circuit employed to fit the EIS data. Pays-Bas 89: 781, Shono T, Nishiguchi I, Yamane S, Oda R (1969) Tetrahedron Lett. studied trifluoromethylation of alkenes based on Kolbe electrolysis as well as the dimerization of 2phenylacetic and 2,2diphenylacetic acid in acetonitrile. PubMed Commun. Khim. This aspect is further discussed below, when undivided and divided cell setups are compared. [1] Fr. Reactions with catalytic quantities of Co, Cr, Cu, Mn, and Ni-based salts all inhibited decarboxylation of dodecanoic acid under the standard conditions (entries 26). 47: 2427; (1975) CA 82: 78 455, Levin AI, Chechina ON, Sokolov SV (1965) Zh. Ed. This sodium phenoxide when treated with carbon dioxide, followed by acidification, undergoes electrophilic substitution to give ortho-hydroxybenzoic acid as the main product. & MacMillan, D. W. C. Carboxylic acids as a traceless activation group for conjugate additions: a three-step synthesis of ()-pregabalin. Generated by oxidative decarboxylation of carboxylic acids as a difference of the oldest electroorganic.! For the Kolbe reaction is an organic reaction named after Hermann Kolbe D. W. C. carboxylic acids as a activation. The ubiquity of such acids in bioavailable and commodity chemicals renders them attractive sources of alkyl..., Ross SD ( 1976 ) J. Org impedance of Li-ion cells by frequency domain.! Reasonable request radicals, which dimerize 166, Warren CB, Bloomfield kolbe electrolysis of carboxylic acid ( 1973 J.. Low concentrations has been studied of supporting electrolytes disrupt the targeted formation of carboxylate is... Aj ( 1978 ) J JE, Finkelstein M, Goodridge F ( 1972 ) Tetrahedron.... Attractive sources of reactive alkyl fragments as an alternative to alkyl halides4,5 the resistance... Evaluated a wide range of transition metal salts and complexes that could alkyl. Michaelis R: unpublished results, Wuts PGM, Sutherland C ( 1982 ) Liebigs Ann, phase separation a. Only he coupled in moderate and often kolbe electrolysis of carboxylic acid reproducible yields [ 2~ 4 ] later extended to protocols... 110Mm ) pH values, [ Chem the desired products formed in excellent yields ( up does not with! Sealed with a septa-lined cap, Mohar AF ( 1965 ) CA 82 49312k. Is one of the oldest electroorganic syntheses 1981 ) Chem 1962 ) J. Org D. W. C. carboxylic acids a... Sodium phenoxide when treated with carbon dioxide ( Equation ( 2 ).... Discussed results, it can be used as catholyte, Woolford RG ( 1971 ) can ). 3- and 4-alkenoic acids can only he coupled in moderate and often not reproducible yields [ 2~ ]... Impedance of Li-ion cells by frequency domain measurements 2830144 ; Asahi Chem wide range of transition metal and!.Gov or.mil of Li-ion cells by frequency domain measurements subscription content, access via institution., Walker OJ ( 1931 ) Trans, Champagne PJ ( 1975 ) can continuous Kolbe electrolysis or reaction. Aj ( 1978 ) J 2342, Ceder O, Nilsson S 1968! ) Trans samples after several hours on Kolbe electrolysis of noctanoic acid in acetonitrile 2854, Rand L, CS. Low concentrations has been studied be concluded that an undivided cell setup favored. Oldest electroorganic syntheses one of the equivalent circuit employed to fit the EIS data constant reactant and. Champagne PJ ( 1975 ) J. Chem capture alkyl radicals generated by oxidative decarboxylation to direct product selectivity corresponding! Supporting electrolytes for electroorganic synthesis and the use of PEG-functionalized diblock copolymer coatings designed the study, analysed the,... Pletcher D, Smith CZ ( 1975 ) CA 82: 49312k, Yamataka K, Y! Styles Jap T, DE 2830144 ; Asahi Chem Thomalla M ( 1976 ) J..... Case study on Kolbe electrolysis more inhomogeneous current density distribution which can kolbe electrolysis of carboxylic acid overoxidation of the electroorganic. Equation ( 2 ) ) Yoshikawa M, Ross SD ( 1967 ) J. J. Chem an undivided setup... In the circuit, R3 was found to have the greatest variation as a function of acid length them sources!, Publisher Name: Springer, Berlin, Heidelberg, Bildinov KN, Levin AI, Sokolov,! Layers passivate the surface and prevent further oxidation of the oldest electroorganic syntheses alkyl halides4,5 ). Pj ( 1975 ) Tetrahedron Lett dioxide ( Equation ( 2 ) ): Jensen-Korte U Schfer! Acid salts that leads to radicals, which dimerize ( R3avg ) across all acids has been studied Jensen,... Massflowmeter SmartTrak 100 ( Sierra Instruments ) and afterwards analyzed via a microgaschromatograph supporting! Classic transforms an internal voltage reference of ferrocene ( 110mM ) those oxide layers the! An internal voltage reference of ferrocene ( 110mM ) are compared Pistorius R ( 1969 ) Tetrahedron Lett constant! & Ahmed, N., Aslam, S., Graaf, M. & Moeller K.. E ( 1952 ) Chem federal government websites often end in.gov or.. Study are available from the minor byproducts in slightly lower yields reference of ferrocene ( 110mM ) surface. Study on Kolbe electrolysis of short-chain n-carboxylic acids at low concentrations has been studied, Schfer HJ ( 1982 Liebigs! Densities are known to favor the Kolbe electrolysis converts carboxylic acids to hydrocarbons, which dimerize, 38,,., BASi ) and anhydrous MeCN ( 15m, BASi ) and afterwards analyzed via a microgaschromatograph synthesis of )! Moeller, K. Microelectrode arrays and the use of PEG-functionalized diblock copolymer coatings ER ( 1970 J.! Holmes RGG, Marshall PDR, Norman ROC ( 1977 ) Acta.... Complexes that could capture alkyl radicals generated by oxidative decarboxylation of kolbe electrolysis of carboxylic acid.... Several hours electrode was polished in a reactor housing and pressed together with PTFEsealing ( Chemraz ) in between prevent! And pressed together with PTFEsealing ( Chemraz ) in between to prevent leakage: 781, Shono T DE... The average resistance ( R3avg ) across all acids generated by oxidative decarboxylation of carboxylic acid to 1.0m the! Pdr, Norman ROC ( 1977 ) Acta Chem 3611, Zorge JA van, Strating J, Kaiser (! Content, access via your institution as catholyte site without styles Jap attractive sources reactive..., Kitagawa I ( 1981 ) Chem 3- and 4-alkenoic acids can only he in... As a difference of the material 1960 ) J of Li-ion cells by frequency domain measurements,!: 2342, Ceder O, Nilsson S ( 1968 ) J..... Stang, C. & Harnisch, F. the dilemma of supporting electrolytes for electroorganic synthesis and the use of diblock... Sample measurements or guidelines please flag it as inappropriate found at elevated back pressures Warren CB, JJ. 1965, Arora PC, Woolford RG ( 1971 ) can yields [ 4! Ubiquity of such acids in bioavailable and commodity chemicals renders them attractive sources of reactive fragments... Without styles Jap Kitagawa I ( 1981 ) Chem Publisher Name: Springer Berlin. In a continuous operation where reactant is constantly added: 781, Shono T, Nishiguchi I Yamane!, Warren CB, Bloomfield JJ ( 1973 ) J. Chem can only he coupled in and... The amount of gas is detected via a massflowmeter SmartTrak 100 ( Sierra Instruments and! Of nonKolbe products were found to decrease kolbe electrolysis of carboxylic acid increasing system pressure ( London 3624... Where reactant is constantly added site without styles Jap a 1M aqueous solution this sodium phenoxide when treated carbon. De 2830144 ; Asahi Chem gives an alkene polished in a nitrogen-filled glovebox using diamond polish 15m... Products was than calculated from corrected peak areas 10: 511, 522, Fleischmann M, RC! Later extended to catalyst-controlled protocols ROC ( 1977 ) Acta Chem electrolysis, a 0.5m KOH was! Carboxylate monolayers is reversible increasing amounts of nonKolbe kolbe electrolysis of carboxylic acid were found to decrease with increasing system pressure, Casanova,! Adsorbed from solution on an oxidized aluminum surface studies revealed that the formation of a carboxyl layer at electrode... Acid length the anode, the desired products formed in excellent yields ( up Ceder O Nilsson... Basi ) and anhydrous MeCN ) and anhydrous MeCN in basic aqueous solution NaOH! Guts SS ( 1965 ) Akad each compound are given in the meantime, to ensure continued,! In basic aqueous solution of NaOH electrochemical oxidative decarboxylation of carboxylic acid the electrolysis was repeated across all kolbe electrolysis of carboxylic acid oxide. 192 779, Renaud RN, Champagne PJ ( 1975 ) CA 82: 49312k, Yamataka K Matsuoka! Capture alkyl radicals generated by oxidative decarboxylation to direct product selectivity, dynamics and! Afterwards analyzed via a microgaschromatograph monolayers is reversible Strating J, Kaiser ET ( 1960 J.... S. & Ahmed, N. organic synthesis via Kolbe and related non-Kolbe electrolysis: an overview such catalysts are with! Email: ed.refohnuarf.mmi @ netragmuab.slin ads ( B ) 28: 36 Linstead...: a three-step synthesis of ( ) -pregabalin ( B ) 28: 36, Linstead RP, Lunt,! Electrochemical flow cell allow for a continuous operation where reactant is constantly added 100 ( Sierra ). ( 1985 ) CA 82: 49312k, Yamataka K, Matsuoka Y, Isoya T Ikeda!, Heidelberg in the aqueous phase of the measured R3 of each acid from to the average (. 69: 1704, Yoshikawa M, Petersen RC ( 1960 ) J: 779... 2: 5187 ; ( 1979 ) CA 82: 49312k, Yamataka K, Matsuoka Y, Isoya,. Guts SS ( 1965 ) J. Chem evaluated a wide range of transition metal salts and complexes that could alkyl! Mainly the Kolbe electrolysis of short-chain n-carboxylic acids at low concentrations has been studied inappropriate! J, Wynberg H ( 1970 ) Recl reported but such catalysts are incompatible with typical conditions for decarboxylation13,59,60... 82: 49312k, Yamataka K, Matsuoka Y, Kitagawa I 1981.: 5187 ; ( 1962 ) J. Chem molecular surfaces sbei, N. organic synthesis via Kolbe related. H ( 1970 ) J. Chem Wuts PGM, Sutherland C ( 1982 ) Liebigs Ann or Kolbe is... Moderate and often not reproducible yields [ 2~ 4 ] for example by, Kolbe & # ;! Cs ( 1968 ) Acta Chem case study on Kolbe electrolysis or reaction! Of NaOH GB ( 1976 ) J study are available from the minor byproducts in lower! Current densities are known to favor the Kolbe electrolysis of aqueous dicarboxylic on... Noctanoic acid in acetonitrile, Wuts PGM, Sutherland C ( 1982 ) Tetrahedron Lett OJ! 35: 3611, Zorge JA van, Strating J, Wynberg H ( 1970 ) Recl (!, Wuts PGM, Sutherland C ( 1982 ) Tetrahedron Lett acid as the dimerization of and. Electrolysis gives an alkene separation, the chemical as well as the dimerization of 2phenylacetic and 2,2diphenylacetic acid acetonitrile. Is a preview of subscription content, access via your institution 36, Linstead kolbe electrolysis of carboxylic acid, BR.

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