EP0201365A1 - Verfahren zur Elektrosynthese von Alkoholen und Epoxidverbindungen - Google Patents

Verfahren zur Elektrosynthese von Alkoholen und Epoxidverbindungen Download PDF

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Publication number
EP0201365A1
EP0201365A1 EP86400596A EP86400596A EP0201365A1 EP 0201365 A1 EP0201365 A1 EP 0201365A1 EP 86400596 A EP86400596 A EP 86400596A EP 86400596 A EP86400596 A EP 86400596A EP 0201365 A1 EP0201365 A1 EP 0201365A1
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EP
European Patent Office
Prior art keywords
electrosynthesis
group
alcohols
organic
alcohol
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.)
Granted
Application number
EP86400596A
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English (en)
French (fr)
Other versions
EP0201365B1 (de
Inventor
Jacques Perichon
Amélie Rabemanantsoa
Soline Sibille
Esther D'incan
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.)
Societe Nationale des Poudres et Explosifs
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Societe Nationale des Poudres et Explosifs
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Priority to AT86400596T priority Critical patent/ATE43653T1/de
Publication of EP0201365A1 publication Critical patent/EP0201365A1/de
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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
    • 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
    • C25B3/25—Reduction

Definitions

  • the invention relates to a process for the electrosynthesis of alcohols and epoxy compounds by electrochemical reduction of organic halides in the presence of carbonyl derivatives, process carried out in an electrolysis cell in an organic solvent medium containing an indifferent electrolyte.
  • Alcohols are compounds commonly used in the chemical industry, in particular as synthesis intermediates; they are also used in pharmacy, perfumery, etc.
  • SATOH, SUGINOME, TOKUDA in Bull. Chem., Soc. Jpn., 56, 1791-1794 (1983) describe the electrosynthesis of tertiary alcohols by electrochemical reduction of allylic or benzylic halides in the presence of acetone in an un-compartmentalized electrolysis cell; the electrodes are made of platinum, the cathode can also be made of mercury or carbon.
  • HMPT hexamethylphosphorotriamide -
  • HMPT is a particularly toxic and in particular carcinogenic solvent, which excludes its use in an industrial process.
  • Applicant of a simple process, transposable on an industrial scale, of electrosynthesis of alcohols or of epoxy compounds by electrochemical reduction of organic halides in the presence of carbonyl derivatives in an electrolysis cell in organic solvent medium containing an indifferent electrolyte, having a high yield and of sufficiently general scope, that is to say applicable, as regards carbonyl derivatives, both to aldehydes and to ketones, the reactivity of which is known to be lower than that of aldehydes, and applicable to other halogenated derivatives which are more difficult to reduce than the few polyhalides which are particularly easy to reduce, mentioned above in the prior art.
  • the object of the present invention is such a method.
  • the process according to the invention for electrosynthesis of alcohols and epoxy compounds by electrochemical reduction of organic halides in the presence of carbonyl derivatives in an electrolysis cell provided with electrodes, in an organic solvent medium containing an indifferent electrolyte is characterized in using an anode consumable in a metal chosen from the group of reducing metals and in that the organic halides have at least one atom or a functional group stabilizing carbanions.
  • the electrolysis cell is a conventional cell, well known to those skilled in the art, comprising only one compartment. This possibility of using a single compartment cell is a major advantage as already mentioned.
  • the organic halides have at least one atom or one functional group stabilizing carbanions.
  • this atom or group is attached to the carbon carrying the halogen, that is to say located in position a relative to the halogen.
  • atoms and functional groups which stabilize carbanions are well known to those skilled in the art. Mention may be made, for example, of halogens, ester, ketone, allyl, benzyl, alkoxy or nitrile groups.
  • the alcohols obtained according to the process which is the subject of the present invention correspond to the general formula wherein R, R, and R 2 have the above meaning.
  • Epoxy compounds are obtained when an organic halide compound is used as the organic halides. An elimination of a halogenated acid molecule then occurs.
  • the process which is the subject of the present invention is characterized in that an anode consumable in a metal chosen from the group consisting of reducing metals is used.
  • the metal is chosen from the group comprising magnesium, aluminum, zinc, iron and their alloys.
  • the term "their alloys” means any alloy containing at least one of the above-mentioned metals, namely magnesium, aluminum, zinc and iron.
  • This anode can have any shape and in particular all the classic forms of metal electrodes well known to those skilled in the art (twisted wire, flat bar, cylindrical bar, renewable bed, balls, fabric, grid, etc.).
  • a cylindrical bar of diameter adapted to the dimensions of the cell is used.
  • the diameter of the bar is of the order of 1 cm.
  • the cathode is any metal such as stainless steel, nickel, platinum, gold, silver, or carbon. It is preferably formed by a grid or a cylindrical plate arranged concentrically around the anode.
  • the electrodes are supplied with direct current via a stabilized power supply.
  • organic solvents used in the context of the present invention are all the low-protic solvents usually used in organic electrochemistry. Examples include DMF, acetonitrile, tetramethylurea (TMU), tetrahydrofuran (THF) and THF-HMPT mixtures. Preferably, DMF is used.
  • Acetone can also be used. In this case it plays both the role of solvent and of carbonyl derivative.
  • the indifferent electrolytes used can be those usually used in organic electrochemistry. Mention may be made, for example, of the salts whose anion is a halide, a carboxylate, an alcoholate, a perchlorate or a fluoroborate and the cation a quaternary ammonium, lithium, sodium, potassium, magnesium, zinc or aluminum.
  • tetraalkyl ammonium tetrafluoroborates - tetrabutylammonium tetrafluoroborate, for example
  • tetrabutylammonium perchlorate tetraalkyl ammonium halides (tetrabutylammonium chloride or tetrabutylammonium iodide, for example tetrabutylammonium iodide) lithium.
  • the concentration of indifferent electrolyte in the organic solvent is between 0.01 M and 0.5 M.
  • the concentration of organic halides in the organic solvent is between 0.2 M and 2 M.
  • the ratio of concentrations in the organic solvent between the carbonyl derivative and the organic halide can be arbitrary. It is preferable to use an excess of carbonyl derivative and in particular a concentration ratio of between 0.5 and 10.
  • the electrosynthesis reaction of the invention can be catalyzed by an organometallic complex of the transition metals such as for example the bipyridyl complexes of metal halides and more particularly the nickel bromide complex 2,2'bipyridine.
  • an organometallic complex of the transition metals such as for example the bipyridyl complexes of metal halides and more particularly the nickel bromide complex 2,2'bipyridine.
  • the rest of the solution is then hydrolyzed (for example with water, ammonium chloride or hydrochloric acid).
  • the alcoholate formed is then transformed into alcohol which is then extracted according to conventional methods, with ether for example.
  • the isolated raw alcohol is then purified either by distillation or by separation on a silica column.
  • the pure alcohol thus isolated (purity verified by CPG) is identified by its IR and NMR spectra.
  • the upper glass part is equipped with 5 tubes allowing the arrival and the exit of the inert gas, the possible samples of solution during electrolysis, the electrical passages.
  • the lower part consists of a stopper fitted with a seal, screwed onto the upper glass part.
  • the total volume of the cell is 45 cm3.
  • the anode is formed by a cylindrical bar 1 cm in diameter. It is introduced into the cell through the central tube and is thus located approximately in axial position relative to the cell. It dips into the solution over a length of about 2.5 cm.
  • the cathode consists of a cylindrical fabric arranged concentrically around the anode.
  • the "working" surface of the cathode is of the order of 20 cm 2.
  • the cell is immersed in a thermostatic bath set to the chosen temperature.
  • the particular operating conditions (nature of the electrodes, of the indifferent electrolyte, of the solvent used, the temperature of the bath, etc.) are also specified for each example.
  • the anode is a cylindrical bar of magnesium, diameter 1 cm.
  • the cathode is a cylindrical fabric of nickel foam, arranged concentrically around the anode. Its apparent surface is 20 cm2.
  • Nitrogen is bubbled through the solution for about 15 min and then the nitrogen is kept at atmospheric pressure above the solution.
  • the solution is stirred using a magnetic bar and then the cell is immersed in a thermostatic bath maintained at -20 ° C.
  • the electrodes are supplied with direct current via a stabilized power supply and a constant current density is imposed, equal to 2 A / dm2 on the cathode.
  • the excess acetone is first evaporated and then hydrolyzed with an aqueous ammonium chloride solution, then extracted 3 times with ether.
  • dimethylbenzylcarbinol After evaporation of the ether and of the light products, the dimethylbenzylcarbinol is isolated, which is identified by its NMR and IR spectra. This crude dimethylbenzylcarbinol has a purity of 70%, determined by CPG. Among the impurities, mention may be made of bibenzyl, toluene and DMF and diacetone alcohol.
  • the isolated crude dimethylbenzylcarbinol is then purified by distillation. Pure dimethylbenzylcarbinol is obtained (purity greater than 95% according to analysis by GPC), identified by its IR and NMR spectra. The yield dimethylbenzylcarbinol p ur so obtained is 56%
  • Example 1 The same tests were carried out as that described in Example 1, but modifying certain operating conditions. especially the nature of the anode.
  • the operating conditions, compared with those of Example 1, as well as the results obtained are specified in Table 1.
  • a gem.dihalogenated compound for example benzy chloride lidene
  • the expected alcohol is obtained but also on the other hand and in majority the epoxy compound by elimination of a molecule of HX acid from the alcohol formed.
  • Table 3 lists the indications relating to the starting materials and the conditions specific to each test as well as the results obtained.
  • This catalyst is a nickel-2,2 'bipyridyl bromide complex (NiBrzBipy).
  • This complex is prepared by adding 2 x 10- Z mole of NiBr 2 .2H 2 O and 2 x 10 -2 mole of 2-2'bipyridine (Bipy), in 120 ml of absolute ethanol.
  • This mixture is stirred for 24 hours at a temperature of 20 ° C.
  • the mixture is filtered to recover the NiBr 2 .2-2'Bipy complex which has precipitated.
  • Table 4 brings together the operating conditions and the nature of the starting products and of the products obtained in examples 66 to 71.
  • the yields of alcohol produced and isolated are expressed relative to the carbonylated starting product.
  • the electrolysis is carried out with a carbon cathode and a current density of 1 A / dm 2 .
  • the electrosynthesis process of the invention makes it possible to synthesize compounds which are particularly useful in the field of perfumery such as dimethylbenzylcarbinol, methylethylbenzylcarbinol, for example, or that of pharmacy such as parachlorobenzyl-dimethylcarbinol which is used to manufacture chlortermine.

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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)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Saccharide Compounds (AREA)
EP86400596A 1985-03-29 1986-03-21 Verfahren zur Elektrosynthese von Alkoholen und Epoxidverbindungen Expired EP0201365B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86400596T ATE43653T1 (de) 1985-03-29 1986-03-21 Verfahren zur elektrosynthese von alkoholen und epoxidverbindungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8504743A FR2579627B1 (fr) 1985-03-29 1985-03-29 Procede d'electrosynthese d'alcools
FR8504743 1985-03-29

Publications (2)

Publication Number Publication Date
EP0201365A1 true EP0201365A1 (de) 1986-11-12
EP0201365B1 EP0201365B1 (de) 1989-05-31

Family

ID=9317726

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86400596A Expired EP0201365B1 (de) 1985-03-29 1986-03-21 Verfahren zur Elektrosynthese von Alkoholen und Epoxidverbindungen

Country Status (6)

Country Link
US (1) US4637863A (de)
EP (1) EP0201365B1 (de)
JP (1) JPS61264186A (de)
AT (1) ATE43653T1 (de)
DE (1) DE3663693D1 (de)
FR (1) FR2579627B1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113005472A (zh) * 2021-02-20 2021-06-22 万华化学集团股份有限公司 一种制备香茅醛环氧化物的方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2632978B1 (fr) * 1988-06-17 1990-09-28 Poudres & Explosifs Ste Nale Procede d'electrosynthese de carbinols benzyliques
FR2639364B1 (fr) * 1988-11-23 1990-12-28 Poudres & Explosifs Ste Nale Procede d'electrosynthese d'aldehydes
US10709182B1 (en) * 2017-06-28 2020-07-14 Thomas Henry Healy Garment with draping and access for medical treatment, diagnosis and care

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2530266B1 (fr) * 1982-07-13 1985-07-12 Comp Generale Electricite Procede de preparation des acides arylacetiques et arylpropioniques
US4468297A (en) * 1983-02-25 1984-08-28 Regents Of The University Of California Degradation and detoxification of halogenated olefinic hydrocarbons
US4588484A (en) * 1985-02-28 1986-05-13 Eli Lilly And Company Electrochemical reduction of 3-chlorobenzo[b]thiophenes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
THE CHEMICAL SOCIETY OF JAPAN, vol. 56, juin 1983, pages 1791-1794, Chemical Society of Japan; S. SATOH et al.: "Electrochemical additions of the allyl and the benzyl groups of allyl and benzyl halides to acetone" *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113005472A (zh) * 2021-02-20 2021-06-22 万华化学集团股份有限公司 一种制备香茅醛环氧化物的方法
CN113005472B (zh) * 2021-02-20 2022-04-22 万华化学集团股份有限公司 一种制备香茅醛环氧化物的方法

Also Published As

Publication number Publication date
JPS61264186A (ja) 1986-11-22
FR2579627A1 (fr) 1986-10-03
FR2579627B1 (fr) 1987-05-15
DE3663693D1 (en) 1989-07-06
US4637863A (en) 1987-01-20
EP0201365B1 (de) 1989-05-31
ATE43653T1 (de) 1989-06-15

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