US3496216A - Reductive dimerization of alpha,beta-unsaturated nitriles by means of amalgam - Google Patents

Reductive dimerization of alpha,beta-unsaturated nitriles by means of amalgam Download PDF

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Publication number
US3496216A
US3496216A US511210A US51121065A US3496216A US 3496216 A US3496216 A US 3496216A US 511210 A US511210 A US 511210A US 51121065 A US51121065 A US 51121065A US 3496216 A US3496216 A US 3496216A
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mercury
layer
amalgam
reaction
vessel
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Expired - Lifetime
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US511210A
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English (en)
Inventor
Frank Stanley Holland
John Henry Edgar Marsden
Denis Pemberton
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • 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
    • C25B3/295—Coupling reactions hydrodimerisation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions

Definitions

  • This invention relates to the reductive dimerisation of cue-unsaturated nitriles.
  • An object of the present invention is to provide a process for the reductive dimerisation of a,,B-unsaturated nitriles with an amalgam of an alkaline earth metal in an aqueous medium.
  • the pH of the aqueous medium is usually maintained between about 5.0 and a higher pH at which undesirable side reactions begin to occur during the reductive dimerisation process.
  • the process may normally be carried out, however, at pHs within the range 2.0 to 13.0. pH values of from 6.0 to 11.0 are preferred.
  • the pH of the aqueous medium may be controlled by the use of salts of polybasic acids such as alkali metal phosphates, borates or carbonates.
  • the reductive dimerisation may be carried out in an apparatus in the form of an electrolytic cell in which the cathode has as essential parts a layer of mercury supported by a membrane permeable to electrolyte solutions the cathode being interposed between (a) an aqueous solution of an alkali or alkaline earth metal hydroxide or salt containing the anode, and (b) the reaction medium in which reduction is performed.
  • the cell employs as the cathode a mercury layer which may be no thicker than is required to form a continuous barrier between the anode compartment and the medium in which reduction is performed, provided that the layer is bounded on the one side by the reaction medium and on the other by the aqueous medium contained in the anode compartment which forms the source of metal ions responsible for liberating nascenthydrogen in the reaction medium.
  • a mercury layer which may be no thicker than is required to form a continuous barrier between the anode compartment and the medium in which reduction is performed, provided that the layer is bounded on the one side by the reaction medium and on the other by the aqueous medium contained in the anode compartment which forms the source of metal ions responsible for liberating nascenthydrogen in the reaction medium.
  • mercury layer permeable to electrolyte solutions and interposed between the mercury layer and the anode compartment and/or the reaction medium quite thin continuous mercury layers may be used which provide cathodes of relatively large surface area in contact with the reaction medium and with the aqueous medium in the anode compartment, so that the alkali or alkaline earth metal ions reach the cathode in a substantially uniform manner over the whole area of the cathode.
  • the aqueous medium in the anode compartment is separated from the reaction medium by the thickness of the mercury layer and its supports.
  • the mercury layer is preferably disposed horizontally that is to say with its main plane lying in the horizontal position, the anode medium and the reaction 3,496,216 Patented Feb.
  • the mercury layer rests on the membrane support and the layer may be held in position at the edge by a further support which need not be permeable to which the permeable membrane may be attached. It is preferable to arrange that the lower surface of the mercury on its support is slightly convex.
  • the mercury layer may be subjected to gentle agitation if desired, for example by vibration or by stirring, in order to maintain the reaction conditions as uniform as possible.
  • agitation of the layer is not essen tial. Agitation of the reaction medium may also be used if desired to assist in maintaining steady reduction conditions.
  • the reaction vessel is represented by A the bottom of which is formed and closed by a permeable glass cloth membrane B sealed at the periphery of the bottom of the reaction vessel and firmly attached thereto by the sealing ring C.
  • the reaction vessel is fitted with a stirrer D the shaft of which enters through the seal E, a condenser F, a thermometer (not shown) and a platinum electrode G immersed in the mercury to form the cathode lead.
  • Means for introducing the reaction mixture and withdrawing the products of reaction are also provided (not shown).
  • the reaction vessel is supported at the base preferably by a non-metallic gauze to avoid electrolysis at the gauze when high potentials are used, gauze H resting on suitable supports 1, and is placed inside the second vessel I conveniently provided with an outlet tap K.
  • the vessel I is also provided with an anode L formed from a strip of nickel sheet which encircles the vessel A but is spaced from it.
  • the vessel I is provided with cooling coils (not shown).
  • a layer of mercury M is placed inside A so as to cover completely the inner surface of the glass cloth membrane and seal the reaction mixture within A from direct contact with the electrolyte contained in the outer vessel J.
  • the mercury layer M (with its supports) forms the cathode.
  • the amalgam is formed electrolytically during the reduction in a layer of mercury acting as the cathode of an electrolytic cell which cell is separated from the aqueous medium by a layer of mercury.
  • Suitable organic cationic agents for use in the process of the invention are in general those capable of forming organic cations in the aqueous medium under the particular reaction conditions employed. Especially suitable are quaternary ammonium and phosphonium salts and ternary sulphonium salts.
  • the organic cationic agent may be added as the free base, for example a hydroxide such as tetraethyl ammonium hydroxide. It is preferred to employ tetraalkyl ammonium salts in which the alkyl groups contain up to 24 carbon atoms. It is also preferable that the cationic agents should be at least partially soluble in the reaction mixture, and should not decompose during the reductive dimerisation process.
  • agents which have been particularly effective are tetraethyl-ammonium-p-toluene sulphonate, tetraethylammonium iodide, tetraethylammonium phosphate and cetyl-trimethylammonium bromide.
  • a cylindrical glass reaction vessel 5.6 cm. in diameter and 14 cm. deep was closed at its lower end by a glass cloth membrane sealed around the lower periphery of the vessel.
  • the inner surface of the membrane was completely covered by a layer of mercury; the volume of mercury used was 30 ml.
  • the top of the vessel was provided with an inlet for a glass sheathed platinum wire, the Wire emerging from the glass sheath under the surface of the mercury, to form a cathode.
  • the reaction vessel was also provided with a gas inlet tube, an internal cooling coil and a stirrer, all located above the mercury layer.
  • the reaction vessel was immersed to a depth of about 3 cm. in an aqueous solution of sodium hydroxide (30% by weight) contained in an outer cylindrical glass vessel, this outer vessel being filled to a depth of about cm. with the said sodium hydroxide solution.
  • vA reaction mixture consisting of acrylonitrile (22.0 g.), tetraethylammonium p-toluene sulphonate (17.4 g.) and water (10.0 g.) was placed in the reaction vessel. The mixture was vigorously stirred and carbon dioxide gas was bubbled slowly through it, while a current of 10 amp. was passed between the anode and the cathode. The temperature of the reaction mixture was maintained at 25 C. to 35 C.
  • the aqueous residue from the steam distillation was extracted with chloroform (two portions of 50 ml., four portions of 25 ml.).
  • the chloroform extracts were combined, the chloroform was distilled under reduced pressure to give 10.1 g. of crude adiponitrile, shown by analysis to contain 8.8 g. of adiponitrile. This represents a yield of 65% adiponitrile on acrylonitrile consumed and a current efliciency to adiponitrile of 87%.
  • the electrolyte placed in the outer vessel was an aqueous solution of potassium hydroxide (40% by weight), and the reaction mixture, which was placed in the inner vessel, consisted of acrylonitrile (20.3 g.), and aqueous solution of tetraethylammonium hydroxide (30.6 g. of 25% by weight), potassium dihydrogen phosphate (27.1 g.), potassium hydroxide (3.0 g.) and water (36.9 g.).
  • the pH of this mixture was 7. 0.
  • the reaction mixture was vigorously stirred whil a current of 4 amp. was passed between the anode and cathode.
  • the temperature of the reaction mixture was maintained at 50 C. to 64 C.

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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)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Hydrogenated Pyridines (AREA)
US511210A 1964-12-07 1965-12-02 Reductive dimerization of alpha,beta-unsaturated nitriles by means of amalgam Expired - Lifetime US3496216A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB49714/64A GB1111413A (en) 1964-12-07 1964-12-07 Making adiponitrile and like compounds by reductive dimerisation

Publications (1)

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US3496216A true US3496216A (en) 1970-02-17

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US511210A Expired - Lifetime US3496216A (en) 1964-12-07 1965-12-02 Reductive dimerization of alpha,beta-unsaturated nitriles by means of amalgam

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US (1) US3496216A (en:Method)
BE (1) BE673404A (en:Method)
CH (1) CH456564A (en:Method)
FR (1) FR1456402A (en:Method)
GB (1) GB1111413A (en:Method)
NL (1) NL6515603A (en:Method)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3193574A (en) * 1960-05-08 1965-07-06 Katchalsky Aharon Process for the preparation of adiponitrile by dimerization of acrylonitrile
US3356708A (en) * 1964-06-02 1967-12-05 Ici Ltd Process for the reductive dimerization of acrylonitrile

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3193574A (en) * 1960-05-08 1965-07-06 Katchalsky Aharon Process for the preparation of adiponitrile by dimerization of acrylonitrile
US3356708A (en) * 1964-06-02 1967-12-05 Ici Ltd Process for the reductive dimerization of acrylonitrile

Also Published As

Publication number Publication date
GB1111413A (en) 1968-04-24
CH456564A (de) 1968-07-31
BE673404A (en:Method) 1966-06-07
FR1456402A (fr) 1966-10-21
NL6515603A (en:Method) 1966-06-08

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