EP0376858B1 - Verfahren zur elektrochemischen Jodierung von aromatischen Verbindungen - Google Patents

Verfahren zur elektrochemischen Jodierung von aromatischen Verbindungen Download PDF

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Publication number
EP0376858B1
EP0376858B1 EP89420454A EP89420454A EP0376858B1 EP 0376858 B1 EP0376858 B1 EP 0376858B1 EP 89420454 A EP89420454 A EP 89420454A EP 89420454 A EP89420454 A EP 89420454A EP 0376858 B1 EP0376858 B1 EP 0376858B1
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Prior art keywords
para
diiodobenzene
iodobenzene
cathode
electrolyte
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EP0376858A3 (en
EP0376858A2 (de
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Michael Roy C/O Eastman Kodak Company Cushman
Carl Michael C/O Eastman Kodak Company Lentz
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Eastman Chemical Co
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Eastman Chemical Co
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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

Definitions

  • the present invention relates to the electrochemical iodination of aromatic compounds to selectively and efficiently form a para-substituted iodobenzene derivative.
  • Iodoaromatics are desirable materials because of the wide variety of transformations they can undergo. For example, they can be catalytically carbonylated to form aromatic carboxylic acids and esters. Iodoaromatics are therefore possible starting materials for polycarbonates, polyamides, polysulfides, and polyesters.
  • the halogenation with molecular halogen is one of the classic reactions of aromatic substitution and has been thoroughly investigated owing to its theoretical as well as synthetic value (H. P. Braendlin and E. T. McBee in Friedel-Crafts and Related Reactions ed. G. A. Olan, Wiley, New York, 1964, Volume 3, Ch.
  • the present process is an electrolytic process that provides selective and efficient formation of a para-substituted iodobenzene derivative.
  • This process makes use of a graphitic carbon anode.
  • the present invention is directed to an electrolytic process for the formation of a para-substituted iodobenzene derivative comprising contacting: an anolyte solution of a divided electrolytic cell, wherein said divided electrolytic cell comprises: an anode compartment comprising a graphitic carbon anode and said anolyte solution which comprises solvent and an electrolyte; and a cathode compartment comprising a cathode and a catholyte solution which comprises solvent and an electrolyte; wherein said anode compartment and cathode compartment are separated by a separator, with an iodine source, and a mono-substituted compound of the formula: wherein R is alkyl, halo, unsubstituted aryl, or aryl
  • benzene is used as a starting material to form iodobenzene followed by the further iodination of the iodobenzene, e.g. an electrolytic process for preparing iodobenzene comprising contacting: an anolyte solution of a divided electrolytic cell, wherein said divided electrolytic cell comprises: an anode compartment comprising a graphitic carbon anode and said anolyte solution which comprises a solvent and an electrolyte; and a cathode compartment comprising a cathode and a catholyte solution which comprises a solvent and an electrolyte; wherein said anode compartment and cathode compartment are separated by a separator, with an iodine source, and benzene, and applying to the anode and the cathode an electric potential; the proportion of materials, electric potential, and other conditions being effective to form iodobenzene.
  • Such a process for preparing iodobenzene is known from SU-A-535271 where the anolyte solution contains acetic acid and the electrolysis is carried out at 35-45°C with an anode current density of 0.15-0.2 A/cm2.
  • the yield of product is as high as 91.7 % with respect to benzene.
  • Process II This process for preparing iodobenzene shall be referred to herein as "Process II.”
  • a diiodobenzene could conveniently be deiodinated cathodically, in the presence of a palladium on carbon catalyst, to iodobenzene, which facilitates a continuously run operation, e.g.
  • an electrolytic process for preparing iodobenzene comprising contacting a catholyte solution of a divided electrolytic cell wherein said divided electrolytic cell comprises an anode compartment comprising an anode and an anolyte solution which comprises a solvent and an electrolyte; and a cathode compartment comprising a cathode and a catholyte solution which comprises a solvent and an electrolyte; wherein said anode compartment and cathode compartment are separated by a separator, with a diiodobenzene compound of the formula in the presence of a catalytic amount of palladium on carbon, and applying to the anode and cathode an electric potential; the proportion of materials, electric potential, and other conditions being sufficient to form iodobenzene.
  • Process III This cathodic deiodination process shall be referred to herein as "Process III.”
  • halo refers to chloro, bromo, fluoro or iodo
  • alkyl refers to C1 to C16 straight, branched or cyclic alkyls
  • aryl refers to aryls containing six to 14 carbon atoms.
  • Process I Any of Process I, Process II, or Process III can be carried out batchwise; however, for most industrial applications, it is preferred to perform these processes continuously. Therefore, it is preferred to couple Process I with Process II and/or Process III.
  • a preferred process of the present invention is a continuous process in which Process I is performed simultaneously with Process III. This preferred process can be described as a continuous electrolytic process for the formation of para-diiodobenzene comprising:
  • Process I When Process I is coupled with Process II, it is preferred that such process be performed consecutively in the same electrolytic cell. As a result, the iodobenzene formed from Process II is used as a starting material for Process I.
  • the electric potential applied to the anode and cathode is about 1.5 to about 2.5 volts, more preferred is about 2 volts.
  • the processes of the present invention are performed at a temperature of about 25° to about 100°C, more preferred is about 25° to about 50°C; and at a pressure of about 1 atmosphere (atm) to about 10 atm, more preferred is about 1-2 atms.
  • one or more processes of the present invention is run as a batch process, typically the electric potential is applied for a period of time of about 1 to about 25 hours, preferred is about 2 to about 8 hours.
  • additives such as CF3CO2H, (Et)4NBF4, or trisbromophenyl amine can be added to the reaction medium in the processes of the present invention; however, the presence of such additives are not necessary. If one or more additives are used, they are typically present in a concentration of up to about 10 percent, based on solvent weight.
  • the cathode compartment and anode compartment are separated by a separator such as a membrane, fritted glass, and the like.
  • a separator such as a membrane, fritted glass, and the like.
  • this separator is a membrane.
  • a preferred membrane is a NafionTM membrane.
  • the nature of the anode is important. It has been found that the anode must be comprised of graphitic carbon in order for the iodination process to be sufficiently effective.
  • the graphitic anode can be comprised of spectral grade graphite or can be any other suitable graphite electrode.
  • the nature of the, cathode for any of the processes of the invention, is not particularly critical.
  • the cathode can be comprised of platinum, carbon, copper, lead, tin, palladium, stainless steel, or combinations thereof.
  • Process III since Process III must proceed in the presence of palladium or carbon, it is convenient for the cathode in Process III to be comprised of palladium on carbon.
  • the solvents and electrolyte in the cathode and anode compartments for any of the processes of the present invention can be the same or different; however, it is usually more convenient for the electrolyte and solvents to be the same in each compartment.
  • Preferred solvents are polar organic aprotic or protic solvents. Examples include methanol, ethanol, acetonitrile, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, dimethyl ether, diethyl ether, acetic acid (HOAc), or a mixture thereof. The most preferred solvent is acetonitrile.
  • the electrolyte is present in a concentration sufficient to give the total reaction medium sufficient conductivity at reaction conditions in order for the desired process to proceed satisfactorily.
  • a preferred electrolyte is a tetrafluoroborate. Examples include substituted tetrafluoroborates such as, HBF4, NaBF4, (Me)4NBF4, (Et)4NBF4, (Pr)4NBF4, or (Bu)4NBF4 wherein Me is methyl, Et is ethyl, Pr is propyl and Bu is butyl. The most preferred electrolyte is HBF4, (Me)4NBF4 or (Bu)4NBF4.
  • Process I in addition to the formation of said para-substituted iodobenzene derivative, typically minor amounts of the other isomers are also formed, especially an ortho-substituted iodobenzene derivative. It is an advantage of the present invention that the yield of the para-substituted compound is greater than the yield of the ortho-substituted compound. Preferably the mole ratio of para-substituted iodobenzene derivative to ortho-substituted iodobenzene derivative after reaction is greater than about 1:1 to about 100:1.
  • the weight ratio of the iodine source to the mono-substituted compound to the anolyte solution is about 2.5:3.0:100 to about 1.0:15.0:100, and the weight ratio of electrolyte to solent of the anolyte solution is about 1:1 to about 1:100; said electron-donating group is alkyl, hydroxyl, thiol, -OR′, or -SR′;
  • the iodine source is iodine (I2) or an iodine salt such as HI, NaI, KI, or an alkyl ammonium iodide.
  • R is I and the iodine source is most preferably I2.
  • the purity of the para-substituted iodobenzene derivative is typically greater than about 98 weight percent, preferably greater than about 99 weight percent, after isolation by standard techniques.
  • this compound can be isolated simply by cooling the electrolysis mixture until the desired compound becomes a solid, typically less than about 15°C, followed by filtering. By this simple isolation procedure, typically greater than about 80 weight percent of the available para-isomer can be obtained.
  • the yield of para plus ortho derivatives is greater than about 60 percent preferably greater than about 90 percent, based on the weight of consumed iodine source. Typical by-products formed include iodonium salts.
  • the weight ratio of the iodine source to benzene to the anolyte solution is about 1.25:2.0:100 to about 2.5:1.0:100, the weight ratio of electrolyte to solvent in the anolyte and catholyte solutions is about 1:10 to about 1:100, and that the iodine source is iodine.
  • the weight ratio of the diiodobenzene compound:catholyte solution is about 1:10 to about 1:100; the weight ratio of electrolyte: solvent in the anolyte and catholyte solutions is about 1:10 to about 1:100; and that the diiodobenzene starting material is ortho-diiodobenzene.
  • Process III must be performed in a catalytic amount of palladium on carbon catalyst.
  • a catalytic amount is typically at least about 0.001%, based on the weight of diiodobenzene starting material, preferably about 0.01%.
  • Electrolysis was performed in an H-type cell where the anode and cathode were separated by a Nafion membrane.
  • the cathode was a spectroscopic (UltraCarbon, U50) carbon rod. All reactions were run at the indicated constant potential by way of an ESC Model 410 potentiostatic controller.
  • the electrochemical apparatus was fitted with an ESC Model 630 digital coulometer and, in each case, the theoretical number of coulombs was collected.
  • the cell temperature was not controlled and usually rose to about 28°C in the course of an experiment.
  • the potential is set at 2.00 volts versus SCE (saturated calomel electrode), and current is passed through the electrolysis solution. The electrolysis is stopped after 1930 coulombs are passed.
  • the product is isolated by pouring the anode solution into 500 mL of water and extracting three times with 50 mL of methylene chloride each time. The extracts are combined and washed with 100 mL of water. The organic layer is dried over magnesium sulfate and the solvent is removed in vacuo to afford 4.3 g of a light color oil.
  • the product is analyzed by capillary gas chromatograph versus authentic samples to establish the yield and ortho-para ratio.
  • the electrolysis apparatus employed is as previously described.
  • the catholyte and anolyte solutions are prepared as described for the electrolysis of toluene.
  • To the anode compartment is added 1.26 g of iodine (5 mmols) and 2.04 g of iodobenzene (10 mmols).
  • the system is electrolyzed at a constant potential of 1.7 volts versus SCE. After passing 965 coulombs, the electrolysis is stopped.
  • the anode mixture is cooled to 15°C and the resulting solid isolated by filtration. After water wash and air drying, the solid weighs 2.1 g (64% isolated yield) and is shown by capillary gas chromatography to be 100% p -diiodobenzene.
  • the electrolysis apparatus is as previously described.
  • the catholyte and anolyte solutions are prepared as described for the electrolysis of toluene.
  • To the anode compartment is added 2.54 g (0.01 mole) iodine and 2.42 g (0.031 mole) benzene.
  • the system is electrolyzed at a constant potential of 2.0 volts vs SCE.
  • the electrolysis is stopped after 1950 coulombs are passed.
  • the product is isolated by pouring the anode solution into 500 mL water and extracting three times with 50 mL of methylene chloride. The extracts are combined and washed with 100 mL water.
  • the organic layer is dried over magnesium sulfate and the solvent removed in vacuo to afford 4.1 g of a light yellow oil.
  • the product is analyzed by capillary gas chromatography to afford iodobenzene chemical yield of 95% based on iodine.
  • Example 2 The procedure of Example 1 is substantially repeated except that the working potential is varied.
  • the para selectivity versus working potential is shown in Table 3.
  • TABLE 3 Para Selectivity of Toluene Iodination Versus Working Potential1 Working Potential2 % Para Iodotoluene 1.7 v 62% 1.8 v 61% 1.9 v 66% 2.0 v 65% 2.1 v 62% 1At carbon anode in a divided cell. 2Potential versus SCE.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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Claims (22)

  1. Elektrolytisches Verfahren zur Herstellung eines para-substituierten Iodobenzolderivates, bei dem man in Kontakt bringt:
    eine Anolyt-Lösung einer unterteilten elektrolytischen Zelle, wobei die unterteilte elektrolytische Zelle umfaßt:
    ein Anodenabteil mit einer Graphit-Kohlenstoff-Anode und der Anolyt-Lösung, die ein Lösungsmittel und einen Elektrolyten umfaßt; und ein Kathodenabteil mit einer Kathode und einer Katholyt-Lösung, die ein Lösungsmittel und einen Elektrolyten umfaßt; wobei das Anodenabteil und das Kathodenabteil voneinander durch einen Separator getrennt sind,
    mit
    einem Iodlieferanten und einer mono-substituierten Verbindung der Formel:
    Figure imgb0008
     worin R für steht für Alkyl, Halo, unsubstituiertes Aryl, oder Aryl, substituiert mit bis zu 5 Elecktronen spendenden Gruppen, und
    Anlegen einer elektrischen Spannung an die Anode und die Kathode; wobei die Verhältnisse der Materialien, die elektrische Spannung und andere Bedingungen derart gewählt werden, daß in dem Anodenabteil ein Para-substituiertes Iodobenzolderivat erzeugt wird.
  2. Verfahren nach Anspruch 1, bei dem die angelegte elektrische Spannung etwa 1,5 bis etwa 2,5 Volt beträgt.
  3. Verfahren nach Anspruch 1, bei dem die elektrische Spannung etwa 1 bis etwa 25 Stunden lang angelegt wird, bei einer Temperatur von etwa 25° bis etwa 100°C und bei einem Druck von etwa 1 atm bis etwa 10 atm.
  4. Verfahren nach Anspruch 1, bei dem das Gewichtsverhältnis des Iodlieferanten zu der mono-substituierten Verbindung zur Anolyt-Lösung bei etwa 2,5 : 3,0 : 100 bis etwa 1,0 : 15,0 : 100 liegt und das Gewichtsverhältnis des Elektrolyten zum Lösungsmittel der Anolyt-Lösung bei etwa 1 : 1 bis etwa 1 : 100 liegt.
  5. Verfahren nach Anspruch 1, bei dem die Anolyt-Lösung und die Katholyt-Lösung gleich sind.
  6. Verfahren nach Anspruch 5, bei dem das Lösungsmittel ein polares organisches aprotisches oder protisches Lösungsmittel ist und der Elektrolyt in einer Konzentration vorliegt, die ausreicht, dem Gesamt-Reaktionsmedium eine ausreichende Leitfähigkeit unter Reaktionsbedingungen zu verleihen.
  7. Verfahren nach Anspruch 6, bei dem der Iodlieferant Iod oder ein Iodsalz ist und der Elektrolyt ein Tetrafluoroborat ist.
  8. Verfahren nach Anspruch 1, bei dem R für I steht.
  9. Verfahren nach Anspruch 6, bei dem der Elektrolyt besteht aus HBF₄, (Me)₄NBF₄, (Et)₄NBF₄, (Pr)₄NBF₄, oder (Bu)₄NBF₄; und bei dem das Lösungsmittel besteht aus Methanol, Ethanol, Acetonitril, Tetrahydrofuran, Dimethylformamid, Dimethylsulfoxid, Dimethylether, Diethylether oder Essigsäure.
  10. Verfahren nach Anspruch 1, bei dem die Elektronen spendenden Gruppen bestehen aus Alkyl, Hydroxy, Thiol, -OR', -SR', wobei R' steht für ein C₁-C₆-Alkyl oder Phenyl; wobei ferner der Separator eine Membran ist und die Kathode aufgebaut ist aus Platin, Kohlenstoff, Kupfer, Blei, Zinn, Palladium oder rostfreiem Stahl.
  11. Verfahren nach Anspruch 1, bei dem die Ausbeute an dem para-substituierten Iodobenzolderivat größer ist als die Ausbeute an einem ortho-substituierten Iodobenzolderivat.
  12. Verfahren nach Anspruch 11, bei dem das Mol-Verhältnis von para-substituiertem Iodobenzolderivat zu dem ortho-substituierten Iodobenzolderivat nach der Reaktion größer als 1 : 1 bis etwa 100 : 1 ist.
  13. Verfahren nach Anspruch 1, das kontinuierlich durchgeführt wird.
  14. Elektrolytisches Verfahren zur Herstellung eines para-Diiodobenzols gemäß Anspruch 1, bei dem die mono-substituierte Verbindung Iodobenzol ist und bei dem die Verhältnisse der Materialien, die elektrische Spannung und die anderen Bedingungen so ausgewählt werden, daß sie wirksam zur Erzeugung von para-Diiodobenzol sind.
  15. Verfahren nach Anspruch 14, bei dem die angelegte elektrische Spannung bei etwa 1,5 bis etwa 2,5 Volt liegt, und die Spannung etwa 1 bis etwa 25 Stunden lang angelegt wird, bei einer Temperatur von etwa 25° bis etwa 100°C und bei einem Druck von etwa 1 atm bis etwa 10 atm.
  16. Verfahren nach Anspruch 14, bei dem das Gewichtsverhältnis des Iodlieferanten zum Iodobenzol zur Anolyt-Lösung bei etwa 1,25 : 2,0 : 100 bis etwa 2,5 : 1 : 100 liegt und das Gewichtsverhältnis von Tetrafluoroborat zu Acetonitril bei etwa 1 : 10 bis etwa 1 : 100 liegt.
  17. Verfahren nach Anspruch 16, bei dem der Iodlieferant Iod ist und der Elektrolyt HBF₄, (Me)₄NBF₄, (Et)₄NBF₄, (Pr)₄NBF₄ oder (Bu)₄NBF₄.
  18. Verfahren nach Anspruch 16, bei dem der Separator eine Membran ist, und bei dem die Kathode aufgebaut ist aus Platin, Kohlenstoff, Kupfer, Blei, Zinn, Palladium oder rostfreiem Stahl.
  19. Verfahren nach Anspruch 16, bei dem die Ausbeute an para-Diiodobenzol größer ist als die Ausbeute an ortho-Diiodobenzol.
  20. Verfahren nach Anspruch 19, bei dem das Mol-Verhältnis von para-Diiodobenzol zu ortho-Diiodobenzol nach der Reaktion bei etwa 1 : 1 bis etwa 10 : 1 liegt.
  21. Verfahren nach Anspruch 14, bei dem die Reinheit des para-Diiodobenzols größer ist als etwa 98 % nach der Isolierung nach Standard-Methoden.
  22. Kontinuierliches elektrolytisches Verfahren zur Herstellung von para-Diiodobenzol, bei dem man:
    (A) para-Diiodobenzol nach dem Verfahren von Anspruch 14 gewinnt,
    (B) die Anolyt-Lösung mit dem para-Diiodobenzol, das in Stufe (A) erzeugt worden ist, filtriert, um eine feste Masse zu erhalten, die umfaßt para-Diiodobenzol, und ein Filtrat, das umfaßt einen Elektrolyten, ein Lösungsmittel und mindestens eine Diiodobenzolverbindung der Formel:
    Figure imgb0009
    (C) das Filtrat aus der Stufe (B) in das Kathodenabteil einführt,
    (D) die Diiodobenzolverbindung in dem Kathodenabteil aus der Stufe (C) deiodiert, unter Bildung von Iodobenzol durch Anlegen einer elektrischen Spannung an die Anode und die Kathode, wobei die Katholyt-Lösung und die Diiodobenzolverbindung in Gegenwart einer katalytischen Menge von Palladium auf Kohlenstoff vorliegen; wobei die Verhältnisse der Materialien, die elektrische Spannung und andere Bedingungen so gewählt werden, daß sie ausreichend zur Bildung von Iodobenzol sind; und
    (E) das Iodobenzol, das durch die Stufe (D) erzeugt wird, als Ausgangsmaterial für die Stufe (A) recyclisiert.
EP89420454A 1988-11-25 1989-11-21 Verfahren zur elektrochemischen Jodierung von aromatischen Verbindungen Expired - Lifetime EP0376858B1 (de)

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* Cited by examiner, † Cited by third party
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WO2008111521A1 (ja) 2007-03-09 2008-09-18 Japan Science And Technology Agency ヨウ素化剤の製造方法、および芳香族ヨウ素化合物の製造方法

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US5575905A (en) * 1995-05-24 1996-11-19 Nycomed Imaging As Iodination process
US7514589B2 (en) 2005-01-06 2009-04-07 Nippoh Chemicals Co., Ltd. Method for producing aromatic iodides
EP2093206A1 (de) * 2008-02-20 2009-08-26 BRACCO IMAGING S.p.A. Verfahren zur Iodierung aromatischer Verbindungen
DK2451994T3 (da) 2009-07-07 2014-01-20 Bracco Imaging Spa Fremgangsmåde til fremstilling af et ioderende middel

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SU535271A1 (ru) * 1974-10-22 1976-11-15 Предприятие П/Я В-8046 Способ получени иодбензола
US4495036A (en) * 1983-07-11 1985-01-22 The Dow Chemical Company Electrochemical chlorination process
US4707230A (en) * 1985-09-23 1987-11-17 Tracer Technologies, Inc. Electrochemical dehalogenation of organic compounds

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008111521A1 (ja) 2007-03-09 2008-09-18 Japan Science And Technology Agency ヨウ素化剤の製造方法、および芳香族ヨウ素化合物の製造方法
EP2319959A1 (de) 2007-03-09 2011-05-11 Japan Science And Technology Agency Verfahren zur Herstellung einer aromatischen Iodverbindung

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DE68912920D1 (de) 1994-03-17
CA2002599A1 (en) 1990-05-25
EP0376858A3 (en) 1990-11-28
DE68912920T2 (de) 1994-08-18
ATE101206T1 (de) 1994-02-15
EP0376858A2 (de) 1990-07-04

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