Classifications

• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B3/00—Electrolytic production of organic compounds
  • C25B3/20—Processes
  • C25B3/29—Coupling reactions
• • C—CHEMISTRY; METALLURGY
  • 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
  • C25B3/01—Products
  • C25B3/03—Acyclic or carbocyclic hydrocarbons
• • 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
  • C25B3/01—Products
  • C25B3/07—Oxygen containing 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
  • C25B3/01—Products
  • C25B3/11—Halogen containing compounds

Definitions

• R stands for an aromatic radical and R for an aliphatic radical, in the presence of lower aliphatic alcohols and an electrolyte salt, graphite electrodes being used for effecting the electrolysis.
• This invention relates to a process for the manufacture of butadiene derivatives by the electrolysis of olefinically unsaturated compounds.
• Chem. Rev., 68 (1968), p. 471 discloses that the electrolysis of a-methylstyrene in the presence of methanol and sodium methylate between platinum electrodes produces 1 phenyl 1 methylethylene glycol dimethyl ether, a-methoxyisopropyl benzene, acetophenone and B- methoxyisopropyl benzene.
• the process according to the invention is surprising in that the production of butadiene derivatives thereby was not to be expected, since butadience derivaties could not be observed as reaction products when platinum electrodes were used.
• Preferred starting materials of Formula II are those in which R stands for a phenyl radical which may contain one or two substituents such as alkyl radicals of from 1 to 4 carbon atoms, chlorine or bromine atoms or alkoxy groups of from 1 to 4 carbon atoms, and R stands for an alkyl radical of from 1 to 4 carbon atoms.
• R stands for a phenyl radical and R stands for an alkyl radical of from 1 to 2 carbon atoms are preferred.
• Suitable compounds are, for example, a-methylstyrene, lot-methyl vinyl naphthalene, wethylstyrene, p-chloro-u-methylstyrene and p-methyl-a-methylstyrene.
• the electrolysis is carried out in the presence of lower aliphatic alcohol. It is preferred to use alkanols of from 1 to 3 carbon atoms, in particular methanol. Preferably, from 1 to 5 moles of alcohol is used per mole of olefinically unsaturated compound. Particularly good re sults are obtained when from 1.5 to 3 moles of alcohol is used per mole of olefinically unsaturated compound.
• electrolyte salts are alkali metal iodides, alkali metal perchlorates, alkali metal methylates or mixtures thereof.
• sodium iodide, sodium perchlorate and sodium methylate we have found sodium iodide, sodium perchlorate and sodium methylate to be particularly suitable.
• from 1 to 10% by weight of electrolyte salt is used, based on the solution to be electrolyzed.
• Particularly suitable amounts of electrolyte salt are from 2 to 5% by weight.
• the electrolysis is carried out at temperatures ranging from 40 to C. Particularly good results are obtained by using temperatures in the range 20 to +20 C.
• anode voltages of from +0.5 to 1.8 volts and more preferably from 0.5 to 1.6 volts (against a silver/ silver chloride electrode) and current densities of from 25 to 75 ma./cm. are used.
• An essential feature of the invention is the use of graphite electrodes.
• use is made of commercial graphite electrodes suitable for electrolysis purposes. We have found graphite electrodes to be particularly effective.
• the process of the invention is carried out, for example, by placing an olefinically unsaturated compound of Formula II, a lower aliphatic alcohol and an electrolyte salt of the kind described above in the stated quantities in a suitable electrolysis vessel equipped with graphite electrode spaced, for example, 10 mm. apart and effecting electrolysis under the preferred conditions.
• the electrolysis may be carried out with or without diaphragms preferably without. We have also found it advantageous to circulate the reaction mixture during electrolysis to achieve better mixing.
• the electrolysis is generally carried out until from 0.1 to 0.5 Faraday has been consumed.
• the electrolysis may be carried out continuously in a simple manner.
• the resulting electrolyzed mixture is worked up in the usual manner, for example by fractional distillation, after extraction of the electrolyte salt with water.
• the butadiene derivatives obtained by the process of the invention are suitable as monomers for the manufacture of polymers.
• a process for the manufacture of a butadiene derivative of the formula ice which process comprises carrying out with graphite electrodes an electrolysis of an olefinically unsaturated compound of the formula:
• R and R have the meanings given above, in the presence of a solvent medium consisting essentially of a lower aliphatic alcohol and an electrolyte salt.
• a process as claimed in claim 1 wherein the mixture to be electrolyzed contains from 1 to by weight of electrolyte salt.
• electrolyte salt is sodium iodide, sodium perchlorate or sodium methylate.

Landscapes

• 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)

Applications Claiming Priority (1)

Publications (1)

Family

ID=5744275

Family Applications (1)

Country Status (5)

Families Citing this family (1)

• 1969
  • 1969-09-01 DE DE19691944278 patent/DE1944278A1/de active Pending
• 1970
  • 1970-08-11 FR FR7029529A patent/FR2056839A5/fr not_active Expired
  • 1970-08-13 CH CH1214370A patent/CH528454A/de not_active IP Right Cessation
  • 1970-08-24 US US66573A patent/US3677914A/en not_active Expired - Lifetime
  • 1970-08-28 GB GB4150270A patent/GB1324647A/en not_active Expired

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