US3871975A - Electrolytic process for production of perfluorocyclohexane derivatives - Google Patents

Electrolytic process for production of perfluorocyclohexane derivatives Download PDF

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Publication number
US3871975A
US3871975A US340602A US34060273A US3871975A US 3871975 A US3871975 A US 3871975A US 340602 A US340602 A US 340602A US 34060273 A US34060273 A US 34060273A US 3871975 A US3871975 A US 3871975A
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derivatives
perfluorocyclohexane
trifluoromethyl
electrolytic
benzene
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Shunji Nagase
Hajime Baba
Kazuo Kodaira
Takashi Abe
Michimasa Yonekura
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    • 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
    • C25B3/27—Halogenation
    • C25B3/28—Fluorination

Definitions

  • ABSTRACT Aromatic hydrocarbons which have undergone nuclear substitution with a trifluoromethyl group are electrolytically fluorinated in anhydrous hydrogen fluoride.
  • the mixed gas which is consequently formed is sent through the aqueous solution of sodium sulfite containing therein potassium iodide, thereafter cooled and collected, and subjected to refining treatment such as by trap-to-trap distillation, distillation, or gas chromatography to obtain perfluorocyclohexane derivatives.
  • Perfluorocycloalkanes obtained in consequence of complete substitution of hydrogen atoms with fluorine atoms are non-flammable and show unusually high chemical stability. Because of these properties, they are extensively used as coolants, solvents, diluents, etc.
  • One of the methods heretofore disclosed as being useful for the production of perfluorocycloalkanes is such that corresponding aliphatic hydrocarbons or aromatic hydrocarbons are fluorinated with fluorine gas or with a metal fluoride (such as, for example, cobalt trifluoride or silver difluoride).
  • a metal fluoride such as, for example, cobalt trifluoride or silver difluoride.
  • electrolytic fluorination a method whereby partially fluorinated alicyclic hydrocarbons are fluorinated has been known to the art (German Pat. No. 1,119,262). It is universally known that, when aromatic hydrocarbons are directly subjected to electrolytic fluorination, the desired results are not obtained because the electrolysis produces tarry substances which adhere to the surface of electrodes in use and consequently interfere with further passage of electrons.
  • the process according to the present invention effects the production of perfluorocyclohexane derivatives by directly subjecting to electrolytic fluorination, in anhydrous hydrogen fluoride, aromatic hydrocarbons which have undergone nuclear substitution with a trifluoromethyl group.
  • the resultant product of fluorination contains fluorinated hydrocarbons and traces of oxygen difluoride, etc. besides the corresponding perfluorocyclohexane derivatives.
  • the perfluorocyclohexane derivatives aimed at by this invention can be obtained from this mixture by scrubbing the mixture with the aqueous solution of sodium sulfite containing a small proportion of potassium iodide to remove therefrom oxygen difluoride and stripping the residual mixture of fluorinated hydrocarbons by means of trap-to-trap distillation, gas chromatography or some other device.
  • the inventors continued a devoted study with a view to developing a process for producing perfluorocycloalkanes at a high efficiency by direct electrolytic fluorination of aromatic hydrocarbons.
  • they have made the unexpected discovery that, when the electrolytic fluorination is performed on aromatic hydrocarbons which have in advance been subjected to nuclear substitution with a trifluoromethyl group, the reaction proceeds smoothly without entailing the evolution of tarry substances. They have accomplished the present invention on the basis of this discovery.
  • trifluoromethyl-Snbstituted perfluorocyclohexane derivatives can easily be obtained by subjecting to electrolytic fluorination, in anhydrous hydrogen fluoride, benzene derivatives which have undergone nuclear substitution with at least one trihalogenomethyl group.
  • Examples of the benzene derivatives which have undergone nuclear substitution with at least one trihalogenomethyl group and which are usable as raw materials for the present invention include benzotrichloride and other similar benzene derivatives which have such trihalogenomethyl groups as are convertible into trifluoromethyl groups in anhydrous hydrogen fluoride as well as benzene derivatives such as benzotrifluoride and bis-(trifluoromethyl)-benzenes which have undergone nuclear substitution with a trifluoromethyl group.
  • These benzene derivatives may possess additional halogen atoms as nuclear substitution groups. In cases where the nuclear substitution group is halogen atoms excluding fluorine atom, a part of them are sometimes replaced with fluorine atoms in consequence of the electrolytic fluorination.
  • the electrolytic fluorination of the present invention is effected by dissolving the compound selected as the raw material in anhydrous hydrogen fluoride, immersing in the resultant solution paired nickel electrodes and energizing the electrolytic system.
  • the electrolytic bath is maintained at temperatures between l0 and +20C.
  • a bath temperature exceeding the upper limit of +20C is not desirable because at such temperature, anhydrous hydrogen fluoride boils and undergoes vaporization.
  • the voltage is selected in the range between 4 and 9 V and the anode current density in the range between 0.5 and 4.0 A/dm
  • the electrolytic bath may incorporate therein the fluoride of alkali-metal or alkaline earth metal as an agent for enhancing electroconductivity.
  • the suitable amount of this agent is on the order of 10 g per liter of anhydrous hydrogen fluoride.
  • an inert gas such as helium or nitrogen may be blown into the bath in the form of finely divided bubbles for the purpose of heightening the stirring effect of the hydrogen fluoride solution promoting the elimination of the heat of reaction and facilitating the liberation of the vaporized fluorination product from the bath.
  • This electrolytic treatment gives birth to a mixture consisting of perfluorocyclohexane derivatives, other fluorinated hydrocarbons, traces of oxygen difluoride and other components. Of these components, oxygen difluoride is removed by scrubbing the mixture with the aqueous solution of sodium sulfite containing a small proportion of potasium iodide.
  • the perfluorocyclohexane derivatives, other fluorinated hydrocarbons and the like are collected in a trap kept cool with ice and liquefied nitrogen and thereafter separated by means of trap-to-trap distillation, gas chromatography or some other device.
  • the resultant product of electrolytic treatment has a very high boiling point and remains unvaporized, then it settles to the bottom of the electrolytic bath.
  • the product which has gathered on the bottom may be withdrawn through a drain cock provided at the bottom of the cell, stripped of hydrogen fluoride by the treatment using the aqueous solution of an alkali, further freed of moisture content with anhydrous sodium sulfate added thereto, and thereafter refined as by distillation to obtain the desired derivatives.
  • the raw materials to be used for the process of this invention i.e., anhydrous hydrogen fluoride and halogenomethyl benzene derivatives are invariably easy of handling and obtainable at low prices.
  • the process itself can be carried out with a very simple device.
  • the amount of electricity and that of fluorine are both small. Consequently, the process of this invention can be practiced easily on a commercial scale.
  • Example 1 A cylindrical electrolytic cell having a volume of 1.28 liters and made of Monel Metal was used as the reaction vessel.
  • the said electrodes had an equal effective area of 20 dm
  • the top of this electrolytic cell was extended and connected to a tube packed with sodium fluoride via a copper-made reflux condenser cooked with brine at C.
  • the gas which evolved from the electrolytic bath was led through the tube packed with sodium fluoride to the traps cooked with ice and liquefied nitrogen. l-lydro'gen was allowed to escape into the atmosphere.
  • the total amount of electricity used ,in the electrolysis was 129 A. hours.
  • the blowing of helium into the bath was continued for 1.5 hours to forward the portion of product still remaining in the bath and in the sodium fluoride tube to the cooled traps.
  • Example 2 Electrolytic fluorination was conducted on 28.9 g (0.197 mol) of benzotifluoride by faithfully repeating the procedure of Example 1, except that 10 g of sodium fluoride was incorporated as an additive to the electrolytic bath.
  • Example 3 By following substantially the same procedure as that of Example 1, p-chlorobenzotrifluoride was subjected to electrolytic fluorination.
  • the conditions for the electrolysis were anode current density of 1.1 1.5 A/dm bath voltage of 5.5 5.9 V and bath temperature of 7 8C.
  • the total amount of p-chlorobenzotrifluoride was 36.7 g (0.203 mol) and the amount of electricity consumed was A. hours.
  • a process for the production of perfluorocyclohexane derivatives which comprises, dissolving nuclear substituted benzene consisting of benzene substituted by one to six trihalogenomethyl groups in anhydrous hydrogen fluoride, immersing a pair of electrodes in the resultant solution, electrolizing the said resultant solution at a temperature in the range between -10C and +20C, a voltage in the range between 4V and 9V, and an anode current density in the range between 0.5 A/dm and 4.0 A/dm and recovering trifluoromethylsubstituted perfluorocyclohexane derivatives.
  • the electrolized solution contains a member selected from the group consisting of benzotrifluoride, bis(trifluoromethyl) benzene, and p-chlorobenzotrifluoride.

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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)
US340602A 1972-06-01 1973-03-12 Electrolytic process for production of perfluorocyclohexane derivatives Expired - Lifetime US3871975A (en)

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JP47054698A JPS5034552B2 (enrdf_load_stackoverflow) 1972-06-01 1972-06-01

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4654128A (en) * 1985-05-21 1987-03-31 Atochem Process for the preparation of certain organic trihalomethyl derivatives
US6020299A (en) * 1994-10-27 2000-02-01 Occidental Chemical Corporation Single phase cleaning fluid
CN106637283A (zh) * 2016-11-22 2017-05-10 浙江巨圣氟化学有限公司 一种全氟甲基环己烷的制备方法
CN107118074A (zh) * 2017-04-11 2017-09-01 黎明化工研究设计院有限责任公司 一种提纯全氟甲基环己烷的方法
CN107119285A (zh) * 2017-03-10 2017-09-01 黎明化工研究设计院有限责任公司 一种制备全氟甲基环己烷的方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1085087B (it) * 1976-06-28 1985-05-28 Grace W R & Co Metodo per la protezione contro la corrosione di rinforzi metallici per calcestruzzo,e prodotto ottenuto
JP2005265878A (ja) 2004-03-16 2005-09-29 Canon Inc 像回転機能を有する光学系

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3547790A (en) * 1969-08-01 1970-12-15 Hooker Chemical Corp Aromatic condensation products

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3547790A (en) * 1969-08-01 1970-12-15 Hooker Chemical Corp Aromatic condensation products

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4654128A (en) * 1985-05-21 1987-03-31 Atochem Process for the preparation of certain organic trihalomethyl derivatives
AU594678B2 (en) * 1985-05-21 1990-03-15 Atochem Electorchemical process for the preparation of organic trifluoro(or chlorodifluoro or dichlorofluoro) methyl derivatives
US6020299A (en) * 1994-10-27 2000-02-01 Occidental Chemical Corporation Single phase cleaning fluid
CN106637283A (zh) * 2016-11-22 2017-05-10 浙江巨圣氟化学有限公司 一种全氟甲基环己烷的制备方法
CN106637283B (zh) * 2016-11-22 2018-08-07 浙江巨圣氟化学有限公司 一种全氟甲基环己烷的制备方法
CN107119285A (zh) * 2017-03-10 2017-09-01 黎明化工研究设计院有限责任公司 一种制备全氟甲基环己烷的方法
CN107119285B (zh) * 2017-03-10 2019-06-04 黎明化工研究设计院有限责任公司 一种制备全氟甲基环己烷的方法
CN107118074A (zh) * 2017-04-11 2017-09-01 黎明化工研究设计院有限责任公司 一种提纯全氟甲基环己烷的方法
CN107118074B (zh) * 2017-04-11 2019-10-25 黎明化工研究设计院有限责任公司 一种提纯全氟甲基环己烷的方法

Also Published As

Publication number Publication date
DE2313863B2 (de) 1976-04-22
JPS5034552B2 (enrdf_load_stackoverflow) 1975-11-10
JPS4913144A (enrdf_load_stackoverflow) 1974-02-05
DE2313863A1 (de) 1973-12-13

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