EP1913178A1 - Procede pour produire des derives de 1,1,4,4-tetraalcoxy-but-2-ene - Google Patents

Procede pour produire des derives de 1,1,4,4-tetraalcoxy-but-2-ene

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Publication number
EP1913178A1
EP1913178A1 EP06792613A EP06792613A EP1913178A1 EP 1913178 A1 EP1913178 A1 EP 1913178A1 EP 06792613 A EP06792613 A EP 06792613A EP 06792613 A EP06792613 A EP 06792613A EP 1913178 A1 EP1913178 A1 EP 1913178A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
aryl
formula
dialkoxy
radicals
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.)
Withdrawn
Application number
EP06792613A
Other languages
German (de)
English (en)
Inventor
Ingo Richter
Hermann Pütter
Ulrich Griesbach
Till Gerlach
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP1913178A1 publication Critical patent/EP1913178A1/fr
Withdrawn legal-status Critical Current

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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
    • C25B3/23—Oxidation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/30—Compounds having groups
    • C07C43/303—Compounds having groups having acetal carbon atoms bound to acyclic carbon atoms

Definitions

  • the present invention relates to an electrochemical process for the preparation of 1, 1, 4,4-tetraalkoxybut-2-enes from 1, 4-dialkoxy-1, 3-butadiene in the presence of a C 1 to C 6 alkyl alcohol by electrochemical oxidation.
  • EP-A 581 097 describes starting from 2,5-dimethoxydihydrofuran the production of 1,1,4,4-tetramethoxy-but-2-ene using dehydrating reagents and acid action. Electrochemical syntheses are already known for the starting material 2,5-dihydro-2,5-dimethoxyfuran used in EP-A 581 097. Starting from furans is used in this anodic methoxylation, in particular bromide as an advantageous Ox istskatalysator (mediator). Thus, DE-A-27 10 420 and DE-A-848 501 describe the anodic oxidation of furans in the presence of sodium or ammonium bromide as conductive salts.
  • radicals R 1 and R 2 independently of one another are hydrogen, C 1 - to C 6 -alkyl, C 6 - to C 12 -aryl, for example phenyl or C 1 - to C 12 -cycloalkyl or R 1 and R 2 together with the double bond to which they are bonded, a Ce to Ci2 aryl radical such as phenyl mono- or polysubstituted to C ⁇ -alkyl, halogen or alkoxy-substituted phenyl, or a mono- or polyunsaturated C5 to Ci2 -Cycloalkyl radical, R 3 , R 4 independently of one another are hydrogen, methyl, trifluoromethyl or nitrile, found in the 1, 4-dialkoxy-1, 3-butadienes of the formula II
  • radicals R 1 , R 3 and R 4 have the same meaning as in formula I, are electrochemically oxidized in the presence of a C 1 to C 6 alkyl alcohol.
  • the radical R 1 is preferably a methyl radical.
  • 1,4-dialkoxy-1,3-butadienes are substantially less expensive. Due to a higher boiling point of 1, 4-dialkoxy-1, 3-butadiene also reduces the cooling effort during the reaction and higher reaction temperatures are possible. Another significant advantage of this educt is its significantly lower toxicity. 1, 4-Dimethoxy-1, 3-butadienes are known per se. 1,1-Dimethoxy-1,3-butadiene can be prepared by methylation of 1,4-butynediol to 1,4-dimethoxy-2-butyne and its rearrangement as described, for example, in L.
  • the C 1 to C 6 alkyl alcohol based on the 1, 4-dialkoxy-1, 3-butadiene derivative of the general formula (II), equimolar or in excess of up to 1:20 used and then serves as Solvent or diluent for the compound of general formula (I) formed.
  • Solvent or diluent for the compound of general formula (I) formed.
  • the electrolysis solution is added to customary cosolvents. These are the inert solvents generally used in organic chemistry with a high oxidation potential. Examples include dimethylformamide, dimethyl carbonate, acetonitrile or propylene carbonate.
  • Conducting salts which are contained in the electrolysis solution are generally at least one compound selected from among potassium, sodium, lithium, iron, alkali, alkaline earth, tetra (C 1 -C 6 -alkyl) ammonium , preferably tri (cis-C6-alkyl) -methylammonium salts.
  • Suitable counterions are sulfate, hydrogensulfate, alkyl sulfates, aryl sulfates, halides, phosphates, carbonates, alkyl phosphates, alkyl carbonates, nitrate, alcoholates, tetrafluoroborate or perchlorate.
  • acids derived from the abovementioned anions are suitable as conductive salts.
  • MTBS methyltributylammonium methylsulfate
  • methyltriethylammonium methylsulfate methyltri-propylmethylammonium methylsulfates.
  • suitable electrolyte salts are ionic liquids. Suitable ionic liquids are described in "Lonic Liquids in Synthesis”, ed. Peter Wasserscheid, Tom Welton, Verlag Wiley VCH, 2003, Chap. 3.6, pages 103 - 126.
  • the process according to the invention can be carried out in all customary types of electrolytic cell. Preferably, one works continuously with undivided flow cells.
  • Electrolysis cells are particularly suitable in which the anode space is separated from the cathode space by a membrane or a diaphragm and very particularly suitable are undivided bipolar capillary gap cells or plate stacking cells in which the electrodes are designed as plates and are arranged plane-parallel (see Ullmann's Encyclopedia of Industrial Chemistry, 1999 electronic release, Sixth Edition, VCH-Verlag Weinheim, Volume Electrochemistry, Chapter 3.5, special cell designs and Chapter 5, Organic Electrochemistry, Subchapter 5.4.3.2 Cell Design). Such electrolysis cells are e.g. also described in DE-A-19533773.
  • the current densities at which the process is carried out are generally 1 to 20, preferably 3 to 5 mA / cm 2 .
  • the temperatures are usually -20 to 55 ° C, preferably 20 to 40 0 C. In general, working at atmospheric pressure. Higher pressures are preferably used when working at higher temperatures in order to avoid boiling of the starting compounds or cosolvents.
  • Suitable as anode materials are, for example, graphitic materials, noble metals such as platinum or metal oxides such as ruthenium or chromium oxide or mixed oxides of the type RuO x TiO x , metals such as lead or nickel or boron-doped diamond. Preference is given to graphite and platinum. Furthermore, anodes with diamond surfaces are preferred.
  • cathode materials are, for example, iron, steel, stainless steel, nickel; Lead mercury or precious metals such as platinum, boron-doped diamond and graphite or carbon materials into consideration, with graphite is preferred.
  • the system is graphite as the anode and cathode.
  • the electrolysis solution is worked up by general separation methods.
  • the electrolysis solution is generally first brought to a pH of 8 to 9, then distilled and fertilize the individual compounds are obtained separately in the form of different fractions. Further purification can be carried out, for example, by crystallization, distillation or by chromatography.
  • Electrolyte 47 g of a mixture of E 1 E, E 1 Z and Z, Z-1, 4-
  • MTBS methyltributylammonium methylsulfate
  • the electrolyte was pumped through the cell for 5 hours at a flow rate of 250 l / h via a heat exchanger.

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)

Abstract

L'invention concerne un procédé pour produire des dérivés de 1,1,4,4,-tétraalcoxy-but-2-ène de formule générale (I) dans laquelle les groupes R<SUP>1</SUP> et R<SUP>2</SUP> représentent indépendamment l'un de l'autre hydrogène, un groupe alkyle en C<SUB>1</SUB>-C<SUB>6</SUB>, un groupe aryle en C<SUB>6</SUB>-C<SUB>12</SUB> tel qu'un groupe phényle, ou un groupe cycloalkyle en C<SUB>5</SUB>-C<SUB>12</SUB>, ou R<SUP>1</SUP> et R<SUP>2</SUP> forment, avec la liaison double avec laquelle ils sont liés un groupe aryle en C<SUB>6</SUB>-C<SUB>12</SUB> tel qu'un groupe phényle, un groupe phényle substitué une ou plusieurs fois par un groupe alkyle en C<SUB>1</SUB>-C<SUB>6</SUB>, un halogène, ou un groupe alcoxy, ou un groupe cycloalkyle en C<SUB>5</SUB>-C<SUB>12</SUB> insaturé une ou plusieurs fois ; R<SUP>3</SUP>, R<SUP>4</SUP> désignent indépendamment l'un de l'autre hydrogène, méthyle, trifluorométhyle, ou nitrile. Selon l'invention, les 1,4-dialkoxy-1,3-butadiènes de formule (II), dans laquelle les groupes R<SUP>1</SUP>, R<SUP>3</SUP> et R<SUP>4</SUP> ont la même signification que dans la formule (I), sont oxydés par voie électrochimique en présence d'un alkylalcool en C<SUB>1</SUB>-C<SUB>6</SUB>.
EP06792613A 2005-08-04 2006-07-31 Procede pour produire des derives de 1,1,4,4-tetraalcoxy-but-2-ene Withdrawn EP1913178A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005036687A DE102005036687A1 (de) 2005-08-04 2005-08-04 Verfahren zur Herstellung von 1,1,4,4,-Tetraalkoxy-but-2-enderivaten
PCT/EP2006/064845 WO2007014932A1 (fr) 2005-08-04 2006-07-31 Procede pour produire des derives de 1,1,4,4-tetraalcoxy-but-2-ene

Publications (1)

Publication Number Publication Date
EP1913178A1 true EP1913178A1 (fr) 2008-04-23

Family

ID=37308952

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06792613A Withdrawn EP1913178A1 (fr) 2005-08-04 2006-07-31 Procede pour produire des derives de 1,1,4,4-tetraalcoxy-but-2-ene

Country Status (8)

Country Link
US (1) US20080228009A1 (fr)
EP (1) EP1913178A1 (fr)
JP (1) JP2009503266A (fr)
KR (1) KR20080044257A (fr)
CN (1) CN101233263A (fr)
CA (1) CA2617556A1 (fr)
DE (1) DE102005036687A1 (fr)
WO (1) WO2007014932A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3424539A1 (fr) * 2017-07-06 2019-01-09 The Procter & Gamble Company Compositions de réduction des mauvaises odeurs
CN109518211B (zh) * 2019-01-08 2020-11-06 合肥工业大学 一种芳香偶酰类化合物的电化学合成方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4223889A1 (de) * 1992-07-21 1994-01-27 Basf Ag Verfahren zur Herstellung von E,Z-Butendial-bis-dialkylacetalen
DE19944989A1 (de) * 1999-09-20 2001-03-22 Basf Ag Verfahren zur elektrolytischen Umwandlung von Furanderivaten
DE10324192A1 (de) * 2003-05-28 2004-12-23 Basf Ag Verfahren zur Herstellung von alkoxylierten 2,5-Dihydrofuran-oder tetra-1,1,4,4-alkoxylierten But-2-enderivaten

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007014932A1 *

Also Published As

Publication number Publication date
KR20080044257A (ko) 2008-05-20
CN101233263A (zh) 2008-07-30
CA2617556A1 (fr) 2007-02-08
DE102005036687A1 (de) 2007-02-08
WO2007014932A1 (fr) 2007-02-08
US20080228009A1 (en) 2008-09-18
JP2009503266A (ja) 2009-01-29

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