EP0043758B1 - Procédé d'addition d'iodoperfluoroalcanes sur des composés éthyléniques ou acétyléniques - Google Patents

Procédé d'addition d'iodoperfluoroalcanes sur des composés éthyléniques ou acétyléniques Download PDF

Info

Publication number
EP0043758B1
EP0043758B1 EP81401033A EP81401033A EP0043758B1 EP 0043758 B1 EP0043758 B1 EP 0043758B1 EP 81401033 A EP81401033 A EP 81401033A EP 81401033 A EP81401033 A EP 81401033A EP 0043758 B1 EP0043758 B1 EP 0043758B1
Authority
EP
European Patent Office
Prior art keywords
process according
cathode
ethylenic
iodoperfluoroalkanes
electrocatalysis
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.)
Expired
Application number
EP81401033A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0043758A1 (fr
Inventor
Auguste André Aime Commeyras
Patrick André Marie Calas
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.)
Arkema France SA
Original Assignee
Atochem SA
Elf Atochem SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Atochem SA, Elf Atochem SA filed Critical Atochem SA
Publication of EP0043758A1 publication Critical patent/EP0043758A1/fr
Application granted granted Critical
Publication of EP0043758B1 publication Critical patent/EP0043758B1/fr
Expired legal-status Critical Current

Links

Images

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
    • C25B3/01—Products
    • C25B3/11—Halogen 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
    • C25B3/07—Oxygen containing compounds

Definitions

  • This addition can be carried out for example by radical route initiating the reaction by a rise in temperature (RN Haszeldine, J. Chem. Soc. 1953 p. 1199, USP 3 016406 and 3 016 407), by irradiation with UV rays ( article by RN Haszeldine already cited, JD Park, J. Org. Chem. 261961 p. 2086 and D. Cantacuzene J. Chem. Soc. Perkin 11977 p. 1365), via azo derivatives (NO Brac, J. Org. Chem. 271962 p. 3027 and USP 3 083 224, 3 145 222 and 3 257 407).
  • the Applicant has developed a process for adding iodoperfluoroalkanes to unsaturated alcohols by electrocatalysis, which leads to practically quantitative yields.
  • allyl alcohol for example, the corresponding polyfluorinated iodoalcohol is first obtained, then by continuing the electrolysis, the epoxide is obtained by dehydroiodidation.
  • the iodide ions produced migrate to the anode where they are oxidized with the formation of iodine which settles in the anolyte in the form of elementary iodine.
  • phase of formation of the halohydrin and that of the epoxide are successive or simultaneous depending on the density of the imposed current.
  • the process of the invention is applicable to acetylenic alcohols. This is how propargyl alcohol gives a mixture of iodo ethylenic alcohol and acetylenic alcohol:
  • Ethylenic alcohol is found in both cis and trans forms.
  • the ethylenic ethers can also fix R F I under the operating conditions described.
  • the reaction can be carried out in a solvent medium or in an aqueous emulsion depending on the cathode material used.
  • a mercury cathode the reaction will take place in DMF medium
  • a carbon fiber cathode it is possible to use an aqueous emulsion containing iodoperfluoroalkane, unsaturated alcohol and an electrolyte like the KCI.
  • type of carbon fibers which can be used as cathode mention may be made of RIGILOR AGTF 10000 bundles, long VSC fibers and RVG graphite felts which are all products of Carbone-Lorraine.
  • the Faraday yield varies with the type of cell used. It is excellent for mercury cathode cells, significantly less good for carbon fiber cathode cells. Nevertheless, the phase of formation of the R F I addition compound on the olefin or the acetylene compound is still electrocatalytic with an electrical current consumption clearly less than 1 Faraday per mole, while the epoxidation phase is not electrocatalytic and requires at least 1 Faraday per mole of product formed.
  • the ohmic drop in the cell depends closely on the geometry of the assembly and on the aqueous phase / organic phase ratio of the catholyte. However, it remains low when compared to the values encountered in organic electrochemistry. It varies from around 4 to 10 volts depending on the intensities used.
  • the anode is carbon (electrode for arc 6 mm in diameter).
  • the anolyte is a saturated KCI solution, the catholyte contains:
  • FIG. 1 shows the plan of the apparatus used.
  • R F C 4 F g.
  • Example 2 is repeated by varying the intensity of the electrolysis current. The results are given in the table below:
  • the catholyte is charged with 2 ml H 2 0 saturated with KCI, 4 ml of propargyl alcohol CH ⁇ C ⁇ CH 2 OH, 6 ml of C 4 F 9 I. A current of 0.2 A is imposed.
  • The% of A, B, C are given in molar% relative to the starting R F I: C: C 4 F 9 ⁇ C ⁇ C ⁇ CH 2 OH
  • the catholyte contains
  • the C 6 F 13 compound is obtained in an analogous manner. These compounds are soluble in acetone from which they recrystallize by slow evaporation of the solvent. Carbon 13 NMR analysis makes it possible to determine the cis-trans percentage of A (cf. NO Brace J. Org. Chem. 44 1979 p. 212).
  • the organic phase tends to consist only of this C 8 F 17 I with very little allyl alcohol, the latter preferably passing into the aqueous phase.
  • the electrolysis then does not lead to any reaction on C 8 F 17 I.
  • compositions are indicated in mol%.

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)
EP81401033A 1980-07-08 1981-06-26 Procédé d'addition d'iodoperfluoroalcanes sur des composés éthyléniques ou acétyléniques Expired EP0043758B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8015121A FR2486521A1 (fr) 1980-07-08 1980-07-08 Procede d'addition d'iodoperfluoroalcanes sur des composes ethyleniques ou acetyleniques
FR8015121 1980-07-08

Publications (2)

Publication Number Publication Date
EP0043758A1 EP0043758A1 (fr) 1982-01-13
EP0043758B1 true EP0043758B1 (fr) 1985-04-03

Family

ID=9243958

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81401033A Expired EP0043758B1 (fr) 1980-07-08 1981-06-26 Procédé d'addition d'iodoperfluoroalcanes sur des composés éthyléniques ou acétyléniques

Country Status (7)

Country Link
US (1) US4394225A (enExample)
EP (1) EP0043758B1 (enExample)
JP (1) JPS5747882A (enExample)
BR (1) BR8104338A (enExample)
CA (1) CA1148499A (enExample)
DE (1) DE3169663D1 (enExample)
FR (1) FR2486521A1 (enExample)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4650913A (en) * 1984-11-29 1987-03-17 E. I. Du Pont De Nemours And Company Sulfinate-initiated addition of perfluorinated iodides to olefins
FR2597511B1 (fr) * 1986-04-17 1990-09-07 Atochem Fonctionnalisation de iodo-polyfluoroalcanes par reduction electrochimique et nouveaux composes fluores ainsi obtenus
IT1190116B (it) * 1986-05-30 1988-02-10 Ausimont Spa Processo per la sintesi di mono o di idrossifluoroalcani
US5997716A (en) * 1998-07-09 1999-12-07 Ppg Industries Ohio, Inc. Method of electrochemically producing epoxides

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3180895A (en) * 1960-11-25 1965-04-27 Du Pont Fluorocarbon ethers
BE637692A (enExample) * 1962-09-20
FR1443994A (fr) * 1965-04-27 1966-07-01 Pechiney Saint Gobain Perfectionnements dans l'obtention d'oxydes d'oléfines
US3632489A (en) * 1969-04-24 1972-01-04 Norman Louis Weinberg Electrochemical introduction of nitrogen and oxygen functions into olefinic compounds
CH555793A (de) * 1970-08-24 1974-11-15 Ciba Geigy Ag Verfahren zur herstellung von gegebenenfalls substituierten perfluoralkyljodid-olefin- bzw.-cycloolefin-1:1-addukten.
US4097344A (en) * 1976-06-29 1978-06-27 E. I. Du Pont De Nemours And Company Electrochemical coupling of perfluoroalkyl iodides

Also Published As

Publication number Publication date
JPS6132398B2 (enExample) 1986-07-26
EP0043758A1 (fr) 1982-01-13
DE3169663D1 (en) 1985-05-09
CA1148499A (fr) 1983-06-21
FR2486521A1 (fr) 1982-01-15
JPS5747882A (en) 1982-03-18
BR8104338A (pt) 1982-03-23
US4394225A (en) 1983-07-19
FR2486521B1 (enExample) 1982-10-01

Similar Documents

Publication Publication Date Title
DE1468149B1 (de) Verfahren zur herstellung von olefinoxiden
FR2624884A1 (fr) Procede de synthese electrochimique de cetones alpha saturees
EP0043758B1 (fr) Procédé d'addition d'iodoperfluoroalcanes sur des composés éthyléniques ou acétyléniques
Tokuda et al. Regioselectivity in electrochemical allylation of carbonyl compounds. A synthesis of egomaketone by regioselective allylation
FR2486968A1 (fr) Procede electrochimique pour la synthese de composes organiques
EP0245133B1 (fr) Fonctionnalisation de iodo-polyfluoroalcanes par réduction électrochimique et nouveaux composés fluorés ainsi obtenus
Chiba et al. Stereoselective Diels-Alder reaction of electrogenerated quinones on a PTFE-fiber coated electrode in lithium perchlorate/nitromethane
EP0630428A1 (fr) Procede de preparation de derives du taxane.
WO2009071478A1 (de) Verfahren zur reduktiven hydrodimerisierung von ungesättigten organischen verbindungen mittels einer diamantelektrode
US4098657A (en) Electrolyte dehydrohalogenation of α-haloalcohols
EP0203851B1 (fr) Procédé électrochimique de préparation de dérivés organiques trifluoro(ou chlorodifluoro ou dichlorofluoro) méthylés
US4457810A (en) 4,4'-Diphenyl ether-dialdehyde-bis-dimethylacetal and a process for its preparation
JP4755458B2 (ja) ２−アルキン−１−アセタールの製造方法
CH664979A5 (fr) Procede d'electrosynthese d'acides carboxyliques.
RU1830059C (ru) Способ получени низших насыщенных или ненасыщенных фторуглеводородов
EP0370866B1 (fr) Procédé d'électrosynthèse d'aldéhydes
EP0083274A1 (fr) Procédé de préparation d'hydrocarbures acétyléniques vrais à chaîne perfluorée
EP0201365A1 (fr) Procédé d'électrosynthèse d'alcools et de composés époxydes
US3257298A (en) Method for the preparation of acetals
US3783112A (en) Manufacture of sebacic acid diesters
Köster et al. Electro-organic syntheses
US3415725A (en) Electrolytic preparation of trialkoxyalkanes and tetraalkoxyalkanes
CH628883A5 (fr) Procede de fabrication d'un disulfure de tetraalkylthiurame.
SUZUKI et al. Surface Modification of Carbon Fiber by using Electro-oxidation and-reduction Sequential Procedure
BE623657A (enExample)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19810701

AK Designated contracting states

Designated state(s): BE CH DE FR GB IT LI NL SE

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SOCIETE ATOCHEM

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE CH DE FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 3169663

Country of ref document: DE

Date of ref document: 19850509

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19890426

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19890522

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19890608

Year of fee payment: 9

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19890630

Year of fee payment: 9

Ref country code: GB

Payment date: 19890630

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19890809

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19890830

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19900626

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19900627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19900630

Ref country code: CH

Effective date: 19900630

Ref country code: BE

Effective date: 19900630

BERE Be: lapsed

Owner name: ATOCHEM

Effective date: 19900630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19910101

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19910228

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19910301

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 81401033.6

Effective date: 19910206