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WO2018185084A1 - Procédé de production de vinylglycine - Google Patents

Procédé de production de vinylglycine Download PDF

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Publication number
WO2018185084A1
WO2018185084A1 PCT/EP2018/058459 EP2018058459W WO2018185084A1 WO 2018185084 A1 WO2018185084 A1 WO 2018185084A1 EP 2018058459 W EP2018058459 W EP 2018058459W WO 2018185084 A1 WO2018185084 A1 WO 2018185084A1
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WO
WIPO (PCT)
Prior art keywords
vinylglycine
derivatives
glutamic acid
methyl mercaptan
free radical
Prior art date
Application number
PCT/EP2018/058459
Other languages
English (en)
Inventor
Thomas Haas
Christian Richter
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
Priority to EP18726329.8A priority Critical patent/EP3607112A1/fr
Publication of WO2018185084A1 publication Critical patent/WO2018185084A1/fr

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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 present invention relates to a method of producing vinylglycine and/or derivatives thereof.
  • the method relates to a one step method of producing vinylglycine and/or derivatives thereof from glutamic acid and/or derivatives thereof.
  • Vinylglycine (2- aminobut-3-enoic acid).
  • Vinylglycine is a natural, non-protein oamino acid and is usually isolated from fungi and is known to irreversibly inhibit many enzymes that use pyridoxal phosphate (PLP) as a cofactor.
  • PDP pyridoxal phosphate
  • Vinylglycines may also be produced by contacting butadiene with an epoxidase to produce butadiene epoxide which is then hydrolysed, where the epoxide group is converted to the diol. The diol is then oxidised to the hydroxy acid and aminated to form vinylglycine.
  • the present invention attempts to solve the problems above by providing a means of producing vinylglycine and/or derivatives thereof from abundantly available glutamic acid and/or derivatives thereof.
  • the glutamic acid and/or derivative thereof may undergo electooxidation (also known as a non-Kolbe electrolysis) to produce vinylglycine and/or derivatives thereof.
  • the electrooxidation may be an anodic electrooxidation.
  • the electrolytic cell comprises at least two electrodes and an electric current between the electrodes, and wherein the electric current density is about ⁇ 30mA cm2 of electrode.
  • the glutamic acid and/or derivatives according to any aspect of the present invention may be unprotected.
  • the use of unprotected glutamic acid and/or derivatives thereof simplifies the method according to any aspect of the present invention as no extra step is required to protect the glutamic acid and/or derivatives thereof. This saves time and resources.
  • large amounts of toxic oxidant lead(IV) acetate may be used.
  • the use of unprotected glutamic acid and/or derivatives may thereof have less health risks. Usually when an unprotected amino acid is used as a substrate in electrooxidation, many undesired products resulting from dimerization, over- elimination, reduction, and oxidation etc. of the amino acid may be produced.
  • the method according to any aspect of the present invention offers a new substrate, unprotected glutamic acid and/or derivatives thereof, for the production of vinylglycine and/or derivatives thereof.
  • the glutamic acid and/or derivative thereof used as substrate according to any aspect of the present invention may be protected. Protection groups might be Boc, Fmoc, Cbz or ester moieties or a combination of them.
  • the protected glutamic acid and/or derivative thereof however may be selected from N-Boc protected glutamic acid and N- Acetyl protected glutamic acid.
  • Glutamic acid and glutamate is the amino acid with one of the highest production volumes in living things.
  • the glutamate used according to any aspect of the present invention may be an L and/or a D isomer.
  • derivatives of glutamate may be used as substrate according to any aspect of the present invention.
  • Derivatives of glutamic acid include esters and/or amides of glutamic acid.
  • derivatives of glutamic acid may include alkoxy esters, N-Boc protected derivatives, N-Acetyl protected derivatives, salts of glutamic acid, such as sodium glutamate etc., and homo or hetero peptides of glutamic acid.
  • a mixture of glutamic acid and at least one derivative of glutamic acid may be used as a substrate according to any aspect of the present invention for producing vinylglycine and/or the respective derivative.
  • the glutamic acid and/or derivatives thereof may be brought into contact with an electrolysis medium prior to the glutamic acid and/or derivative thereof is subjected to electrooxidation.
  • the electrolysis medium may comprise at least one solvent.
  • the solvent may be selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, water, and a mixture thereof.
  • the solvent may be water, methanol or a mixture of both. More in particular, the solvent may be water.
  • the mixture of both water and methanol may mean the electrolysis medium comprises between about 0.5 percent to about 50 percent water by volume. The resulting mixture of the electrolysis medium and glutamic acid and/or derivative thereof may then be subject to electrooxidation.
  • the electrooxidation may be anodic electrooxidation.
  • the conditions of anodic electrooxidation are known in the art and may be carried out in an electrolytic/ electrochemical cell comprising electrodes (anode and cathode).
  • the material of the electrode may be selected from the group consisting of platinum, iridium, palladium, ruthenium, rhodium, osmium, carbon, lead and a mixture thereof. More in particular, the electrode may be platinum electrodes. In one
  • the electrodes may be coated with platinum.
  • anodic and cathodic compartments may be separated by a
  • the anode and the cathode may be separated by a semi-permeable membrane.
  • the electrooxidation is an example of an organic redox reaction that takes place in an electrochemical cell.
  • This method has several advantages which include for example the possibility to control the potential of the electrode. It may also be considered a simple reaction because no reducing or oxidizing agents are required. In electrooxidation, the oxidation does not take place chemically but electrolytically.
  • the glutamic acid and/or derivative thereof may be oxidised electrolytically to produce vinylglycine and/or the respective derivative thereof.
  • the vinylglycine and/or derivative thereof formed may then be easily separated by decantation, distillation, filtration, liquid-liquid extraction, crystallization or other means known in the art.
  • the electrolytic/ electrochemical cell may comprise at least two electrodes and an electric current between the electrodes, and the electric current may have an density of at least 30mA cm 2 of electrode.
  • An electric current density equal to or greater than 30mA cm 2 of electrode has been shown to result in better yield of vinylglycine and/or derivatives thereof from the substrate of glutamic acid and/or derivatives thereof compared to when the substrate the subjected to a lower electric current density.
  • the electric current density may be about 30 mA cm 2 . More in particular, the electric current density may be selected from the range of 30 to 2000 mA/cm 2 . In one example, the electric current density may be selected from the range of 35-2000, 40-2000, 50-2000, 60-2000, 70-2000, 80-2000, 90-2000, 100-2000, 150-2000, 200-2000, 250-2000, 300-2000, 350-2000, 400-2000, 450- 2000, 500-2000, 550-2000, 600-2000, 650-2000, 700-2000, 750-2000, 800-2000, 850-2000, 900- 2000, 950-2000, 1000-2000, 1 100-2000, 1 150-2000, 1200-2000, 1250-2000, 1300-2000, 1350- 2000, 1400-2000, 1450-2000, 1500-2000 mA/cm 2 and the like.
  • the electric current density present according to any aspect of the present invention may be about 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1 100, 1 150, 1200, 1250, 1300, 1350, 1400, 1450, 1500, 1550, 1600, 1650, 1700, 1750, 1800, 1850, 1900, 1950 mA/cm 2 and the like. More in particular, the current density may be 250- 500 mA/cm 2 , 250-400 mA/cm 2 , 250-350 mA/cm 2 , or 250-300 mA/cm 2 of electrode.
  • the electrooxidation step may comprise the presence of a salt, usually the alkali salt of the glutamic acid, water and two metal electrodes.
  • the salt may be an electrolyte and the electrolyte may be present in the electrolysis medium to improve the movement of the substrate, glutamic acid and/or derivative thereof, between the electrodes.
  • the electrolyte may be an organic or inorganic salt.
  • the electrolyte may be selected from the group consisting of a halide salt, an oxide salt, a perchlorate salt, a borate salt, a carbonate salt, a phosphate salt and mixtures thereof. More in particular, the electrolyte may be selected from the group consisting of perchlorate salt, a p-toluenesulfonate salt, a tetrafluoroborate salt, and mixtures thereof.
  • the electrooxidation may be performed in methanol instead of water as solvent.
  • Platinum electrodes may be used in this example as well.
  • the use of methanol may be considered advantageous as it may yield excellent conversion rates and continuous electrolysis. Selectivity of the electrolysis may be improved with the use of methanol.
  • methanol or mixtures of methanol and water may be used in combination with protected glutamic acid as substrate for solubility reasons.
  • the pH of the electrolysis medium may be adjusted to a value between 5 and 10.
  • the pH may be between 5 and 8. more in particular the pH may be selected from 5 to 7.
  • the pH of the electrolysis medium according to any aspect of the present invention may be maintained by using an acid or alkali where necessary.
  • KOH may be used to adjust the pH.
  • hydroxides, metal oxides, carbonates, phosphates, amines, carboxylic acids, mineral acids and mixtures thereof may be used to adjust and maintain the pH.
  • a skilled person would be capable of maintaining the pH by methods known in the art.
  • the skilled person would regularly measure the pH of the electrolysis medium and adjust the pH by adding an acid or base to the electrolysis.
  • a base such as KOH may be added to the electrolysis medium automatically as the pH is measured automatically.
  • this addition may be manual.
  • the anodic electrooxidation may be conducted at a temperature in a range of 15 °C to 100 °C.
  • the mixture comprising the electrolysis medium with the adjusted pH and glutamic acid and/or derivatives thereof may be introduced into the tank of an electrolysis cell comprising electrodes, particularly platinum, and the temperature may be close to ambient temperature.
  • a potential difference sufficient to cause the substrate, glutamic acid and/or derivative thereof, to be traversed by an electric current is required between the electrodes.
  • an electrolyte may be present in the electrolysis medium to aid in the movement of the substrate.
  • the voltage may be between 5-10V, 6-9 V, 7-9V or 7-10V. In particular, the voltage may be about 7V and the current about 300A to give an optimum yield.
  • the terms "about” and “approximately”, as applied to the conditions for electrooxidation refer to a range of values that are similar to the stated reference value for that condition.
  • the term “about” refers to a range of values that fall within 25, 20, 19, 18, 17, 16, 15, 14, 13, 12, 1 1 , 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 percent or less of the stated reference value for that condition.
  • a temperature employed during the method according to any aspect of the present invention when modified by “about” includes the variation and degree of care typically employed in measuring in an experimental condition in production plant or lab.
  • the temperature when modified by “about” includes the variation between batches in multiple experiments in the plant or lab and the variation inherent in the analytical method.
  • the amounts include equivalents to those amounts. Any value stated herein and modified by “about” can also be employed in the present invention as the amount not modified by “about.”
  • the desired product according to any aspect of the present invention may be vinylglycine and/or derivatives thereof.
  • Vinylglycine has a general chemical formula of C4H7NO2 and a structural formula of:
  • the derivatives of vinylglycine may be selected from the group consisting of amides of vinylglycine, esters of vinylglycine, rhizobitoxin, aminoethoxyvinylglycine, amine esters of vinylglycine, amide esters of vinylglycine, HCI-Salts of vinylglycine, a protected amino acid of vinylglycine and the like. Protection groups might be Boc, Fmoc, Cbz or ester moieties or a combination of them.
  • the derivatives of vinylglycine may be selected from the group consisting of rhizobitoxin, aminoethoxyvinylglycine, amine esters of vinylglycine, amide esters of vinylglycine, amides of vinylglycine, esters of vinylglycine and vinylglycine peptides. More in particular, the derivative of vinylglycine that may be formed according to any aspect of the present invention may depend on the starting material- the derivative of glutamic acid used.
  • only vinylglycine may be produced according to any aspect of the present invention as the starting material used was glutamic acid.
  • a mixture of vinylglycine and at least one derivative may be formed as the starting material used in the method according to any aspect of the present invention may have been glutamic acid and at least one derivative thereof.
  • the starting material according to any aspect of the present invention may have been a mixture of glutamic acid derivatives and the resultant product may be the respective mixture of derivatives of vinylglycine.
  • An intermediate step between steps (a) and (b) according to this aspect of the present invention involves a step of separating the vinylglycine and/or derivative thereof before bringing the vinylglycine and/or derivative thereof in contact with the free radical methyl mercaptan
  • contacting means bringing about direct contact between the vinylglycine and/or derivatives thereof, used as a substrate, and the free radical methyl mercaptan.
  • the vinylglycine may be introduced into an aqueous medium comprising methyl mercaptan.
  • Methyl mercaptan also known as methanethiol has a chemical formula of ChUS and structure of Formula II:
  • the free-radical addition of a methyl mercaptan to vinylglycine may result in the radicalized methyl mercaptan to acting on the terminal carbon-carbon double bond of vinylglycine to produce 2-amino 4- (methylthio) butanoic acid.
  • This step has an advantage of producing L- and/or D-methionine economically through having high conversion rates and short reaction time.
  • the use of vinylglycine has other advantages. For example, using acetylhomoserine as the substrate for methyl mercaptan activity results in the production of a side product, acetic acid.
  • This production may be considered to be a loss in carbon, where not all the carbon from the substrate (i.e. acetylhomoserine) is converted to the target product, methionine. Also, with acetic acid release, the methionine partly absorbs the scent of acetate. The methionine produced using this method thus has a trace of acetate.
  • vinylglycine as a substrate for the activity of radicalized methyl mercaptan does not have the same disadvantages as those mentioned when acetylhomoserine is used. Firstly, there is no loss of carbon as all the carbon in vinylglycine is converted to be part of methionine. There is also no production of acetic acid. Further, the substrate vinylglycine can be synthesized easily from readily available glutamate, the amino acid with one of the highest production volumes in living things. The glutamate may be the L and/or the D isomer.
  • the radicalized methyl mercaptan step also known as Thiol- ene coupling reaction, may also be considered to be relatively selective as no side product may be released when vinylglycine is used as the substrate.
  • the free radicalization of methyl mercaptan by any means known in the art may result in the breaking of the sulfur- hydrogen bond in methyl mercaptan to produce a methyl mercaptan free radical.
  • the methyl mercaptan free radical may then act across the terminal carbon-carbon double bond in the vinylglycine. This action may result in the double bond being reduced to a single bond and a methylthio group added according to the Anti- arkovnikov rule at the terminal carbon atom.
  • the unpaired electron on the adjacent, non-terminal carbon atom in the substrate binds with a hydrogen atom supplied by the methyl mercaptan, thereby creating another methyl mercaptan free radical and this continues the addition cycle.
  • the ratio of methyl mercaptan to vinylglycine or derivatives thereof may be 1 :1 , particularly in the reaction medium.
  • a skilled person would be capable of varying this ratio depending on the initiator used to form the radical.
  • the ratio of methyl mercaptan to vinylglycine or derivatives thereof may be selected from the range of 1 :1 to 1 :10. In particular, the ratio may be 1.2: 1.
  • the ratio of methyl mercaptan to vinylglycine or derivatives thereof may be selected from 3:1-6: 1. This may be advantageous according to any aspect of the present invention as in Thiol-ene coupling reactions, an excess of Thiol may be necessary.
  • the free radicalization of methyl mercaptan may be carried out by contacting the methyl mercaptan with at least one free radical initiator.
  • the free radical initiator may be selected from the group consisting of azobisisobutyronitrile (AIBN), N-bromosuccinimide (NBS), dibenzoyl peroxide (DBPO), Vazo®-44 (2,2'-azobis[2-(2-imidazolin-2-yl)propane]dichloride) and the like.
  • the methyl mercaptan When in contact with any of these free radical initiators, the methyl mercaptan may be radicalized to produce a free radical that may then react with the vinylglycine to produce methionine.
  • AIBN is the free radical initiator. AIBN is thermally stable at room temperature.
  • the Vazo®-44 may be the free radical initiator.
  • the VAZO® series of free radical initiators are available from DuPont Chemicals of Wilmington, Delaware, U.S.A.
  • the free radical initiator may be selected from the group consisting of azobisisobutyronitrile (AIBN) and 2,2- azobis (2-(2-imidazolin-2-yl)propane) dihydrochloride.
  • AIBN azobisisobutyronitrile
  • 2,2- azobis (2-(2-imidazolin-2-yl)propane) dihydrochloride instead of using a chemical agent like a free radical initiator to radicalize methyl mercaptan, an ultraviolet light source may be used.
  • the UV light may be at wavelengths of 300nm or 365nm.
  • the UV light may have a wavelength of 300nm.
  • free radicalization of the methyl mercaptan may be carried out by a combination of UV light and a photo initiator such as 2,2-Dimethoxy-2-phenylacetophenone (DPAP).
  • DPAP 2,2-Dimethoxy-2-phenylacetophenone
  • the UV light may have a wavelength of 365nm.
  • free radicalization of the methyl mercaptan may be carried out without an additional initiator.
  • no chemical initiator and/or UV rays are needed.
  • Radicalization of methyl mercaptan may take place autocatalytically upon heating or may assisted by ultrasonic sound or impurities (e.q. oxygen).
  • a skilled person would be capable of carrying out the radicalization using a variety of means. Reactions without additional chemical initiator may however suffer from low reaction rates and yields.
  • the step of free radicalization of methyl mercaptan may be carried out at the same time as the conversion of vinylglycine to methionine. Therefore, both steps of free radicalization and conversion of vinylglycine to methionine may be carried out in the same pot.
  • a temperature activated free radical initiator such as AIBN
  • the temperature and pressure conditions of the reaction are firstly maintained such that the reactants (i.e. methyl mercaptan, vinylglycine and AIBN) are present as liquids and the temperature is below the activation temperature of the free radical initiator.
  • the reactants i.e. methyl mercaptan, vinylglycine and AIBN
  • the order of introduction of the reactants and free radical initiator into the pot is unimportant as the
  • reaction kick starts and radicalized AIBN results in the formation of the free radical of methyl mercaptan which then attacks the C double bond in vinylglycine to form methionine.
  • the ratio of free radical initiator to methyl mercaptan may be within the range of 1 : 10000 to 1 :5. More in particular, the ratio of the free radical initiator to methyl mercaptan may be within the range of 1 : 10000 to 1 :10. Even more in particular, the ratio of the free radical initiator to methyl mercaptan may be about 1 : 1000, 1 :500, 1 : 100, 1 :50, 1 :20, 1 :30, 1 : 10, 1 :3 and the like.
  • the pot may have a translucent portion (e.g., a reactor window) where UV light may be shone into the pot.
  • the ultraviolet light source may be disposed within a translucent envelope extending into the pot.
  • the UV light in the reaction pot may then radicalize the methyl mercaptan in the pot.
  • the process may take at least about 5 hours or more.
  • the reaction mixture may then be cooled to room temperature and excess methyl mercaptan may be allowed to volatilize and is removed from the reaction pot. The excess methyl mercaptan may then be recovered for reuse. Methionine may then be left behind in the pot.
  • the pot with a translucent portion may comprise vinylglycine, a photo initiator like DPAP and methyl mercaptan. Without UV light, no reaction takes place in the pot.
  • the photo initiator may be activated to radicalize methyl mercaptan. The free radical of methyl mercaptan may then act on vinylglycine to produce methionine. The excess vinylglycine may then be removed as described above and recycled. The resultant product in the pot may then be only methionine.
  • the acid was added dropwise to the thiomethoxide solution over a period of 20 minutes to liberate gaseous methylmercaptan, which was passed into the flask with the Vinylglycine.
  • the flask with the vinylglycine solution was kept at 60 °C for 12 h.
  • This flask was connected to gas washing bottles, which contained a sodium hydrogen peroxide solution (dist. water (100 mL), H202 (35%, 40 mL), NaOH (5.21 g)) in order to destroy escaping methylmercaptan.
  • a nitrogen stream was passed through the reaction mixture for 16 h to push all remaining methylmercaptan into the hydrogen peroxide trap.
  • the residual reaction mixture was evaporated and the off-white residue was analyzed by 1 H-NMR.
  • the NMR measurement revealed that 1 % of the vinylglycine was converted to methionine.
  • the cooling bath of the glass tube was replaced by a water bath to enable condensation of the methylmercaptan inside the autoclave. After complete evaporation of the methylmercaptan inside the glass tube, the autoclave was sealed and the reaction mixture was heated at 60 °C for 18 h (final pressure at 3.5 bar).
  • the autoclave was cooled down below -30 °C (no excess pressure) and the apparatus was pressurized with nitrogen (ca. 1.2 bar).
  • the valves of the autoclave were carefully opened and a nitrogen stream was passed through the reaction mixture for 22 h to push all remaining methylmercaptan into the hydrogen peroxide trap.
  • the autoclave was opened and the yellowish residue was suspended in methanol/water (1/1 , 40 mL).
  • the precipitated methionine was filtered off, washed with methanol (2 x 20 mL) and dried in vacuum.
  • the methionine (0.50 g, 34%, purity ⁇ NMR): 98%) was obtained as an off-white solid.

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

Abstract

La présente invention concerne un procédé de production de vinylglycine et/ou de ses dérivés, le procédé comprenant : - la mise en contact d'acide glutamique et/ou de ses dérivés avec un milieu d'électrolyse ; et - la soumission de l'acide glutamique et/ou de ses dérivés à une électro-oxydation anodique dans une cellule électrolytique pour produire de la vinylglycine et/ou ses dérivés, la cellule électrolytique comprenant au moins deux électrodes et un courant électrique entre les électrodes, et la densité de courant électrique étant ≥ 30 mA/cm2 d'électrode.
PCT/EP2018/058459 2017-04-03 2018-04-03 Procédé de production de vinylglycine WO2018185084A1 (fr)

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EP18726329.8A EP3607112A1 (fr) 2017-04-03 2018-04-03 Procédé de production de vinylglycine

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EP17164537 2017-04-03
EP17164537.7 2017-04-03

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WO2018185084A1 true WO2018185084A1 (fr) 2018-10-11

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110016684A (zh) * 2019-04-08 2019-07-16 天津大学 一种由氨基酸电解制备烯胺的方法

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Publication number Priority date Publication date Assignee Title
US5643438A (en) * 1994-07-08 1997-07-01 Hafslund Nycomed Pharma Aktiengesellschaft Process for the preparation of substituted diamino-dicarboxylic acid derivatives
US5973200A (en) * 1997-01-23 1999-10-26 Novus International, Inc. Process for the preparation of 2-hydroxy-4-(methylthio) butanoic acid or methionine by mercaptan addition
US20110035995A1 (en) * 2007-09-12 2011-02-17 Rainer Busch Biofuel composition and manufacturing process
WO2017191196A1 (fr) * 2016-05-04 2017-11-09 Evonik Degussa Gmbh Production de méthionine

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
US5643438A (en) * 1994-07-08 1997-07-01 Hafslund Nycomed Pharma Aktiengesellschaft Process for the preparation of substituted diamino-dicarboxylic acid derivatives
US5973200A (en) * 1997-01-23 1999-10-26 Novus International, Inc. Process for the preparation of 2-hydroxy-4-(methylthio) butanoic acid or methionine by mercaptan addition
US20110035995A1 (en) * 2007-09-12 2011-02-17 Rainer Busch Biofuel composition and manufacturing process
WO2017191196A1 (fr) * 2016-05-04 2017-11-09 Evonik Degussa Gmbh Production de méthionine

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HANESSIAN; SOHO, TETRAHEDRON LETTERS, vol. 25, 1984, pages 1425 - 1428
HANS-JÜRGEN SCHÄFER: "Recent Contributions of Kolbe Electrolysis to Organic Synthesis", TOPICS IN CURRENT CHEMIS, SPRINGER, BERLIN, DE, vol. 152, 1 January 1990 (1990-01-01), pages 91 - 144, XP009112133, ISSN: 0340-1022 *
KYRIACOU DEMETRIOS K: "Modern Electroorganic Chemistry, CARBOXYLIC ACIDS", 1 January 1994, MODERN ELECTROORGANIC CHEMISTRY, SPRINGER, BERLIN HEIDELBERG, PAGE(S) 47 - 52, ISBN: 978-3-540-57504-7, XP002514688 *
TETRAHEDRON LETTERS, vol. 25, 1984, pages 1425 - 1428

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110016684A (zh) * 2019-04-08 2019-07-16 天津大学 一种由氨基酸电解制备烯胺的方法
CN110016684B (zh) * 2019-04-08 2021-03-16 天津大学 一种由氨基酸电解制备烯胺的方法

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