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EP1863781A1 - Procede pour produire des derives alkoxyles de 2,5-dihydrofurane- ou de tetra-1,1,4,4-but-2-ene - Google Patents

Procede pour produire des derives alkoxyles de 2,5-dihydrofurane- ou de tetra-1,1,4,4-but-2-ene

Info

Publication number
EP1863781A1
EP1863781A1 EP06725267A EP06725267A EP1863781A1 EP 1863781 A1 EP1863781 A1 EP 1863781A1 EP 06725267 A EP06725267 A EP 06725267A EP 06725267 A EP06725267 A EP 06725267A EP 1863781 A1 EP1863781 A1 EP 1863781A1
Authority
EP
European Patent Office
Prior art keywords
sub
derivatives
general formula
alkyl
butene
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Withdrawn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
EP06725267A
Other languages
German (de)
English (en)
Inventor
Ingo Richter
Hermann Pütter
Ulrich Griesbach
Nils Bottke
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 EP1863781A1 publication Critical patent/EP1863781A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/88—Benzo [c] furans; Hydrogenated benzo [c] furans with one oxygen atom directly attached in position 1 or 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
    • 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

Definitions

  • the invention relates to a novel process for the preparation of substituted in 3 or 4-position-2,5-Dihydrofuranderivaten each carrying a CrCe alkoxy in the 2- or in the 5-position or at both positions, or in 3- or 4-position substituted 1, 1, 4,4-tetraalkoxy-but-2-enes (DHF alkoxy derivatives).
  • 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.
  • EP-A-078 004 discloses the anodic oxidation of furans with alkoxides, halides and sulfonates as conducting salts while WO 2004/85710 describes the direct anodic oxidation of furans on specific boron-doped diamond electrodes.
  • the object was therefore to provide an electrochemical process for the preparation of alkoxylated 2,5-dihydrofuran or tetra-1,1,4,4-alkoxybut-2-ene derivatives which is economical and the desired products in high yields and with good selectivity provides.
  • radicals R 1 and R 2 are independently hydrogen, C 1 - to C 6 -alkyl, C 6 to C 12 aryl such as phenyl or C 5 - to C 12 cycloalkyl or R 1 and R 2 together with the double bond to which they are attached, a C 6 - to C 12 -aryl radical such as, for example, phenyl mono- or poly-C 1 - to C 6 -alkyl, halogen- or alkoxy-substituted phenyl, or a mono- or polyunsaturated one C 5 - to C 12 - form cycloalkyl,
  • C 1 - to Ce-monoalkyl alcohol methanol or isopropanol is preferably used.
  • the process according to the invention is particularly preferably used for the production of
  • R 1 , R 2 independently of one another are hydrogen, C 1 - to C 6 -alkyl, C 6 - to C 12 -aryl or C 5 - to C 12 -cycloalkyl,
  • R 1 and R 2 together with the double bond to which they are attached form a C 6 - to C 12 -aryl radical or a mono- or polyunsaturated C 5 - to C 12 -cycloalkyl radical
  • R 3 C 1 - to C 6 -alkyl means, by electrochemical oxidation in the presence of a C 1 - to C 6 -Monoalkylalkohols prepares from 2-butene-diol derivatives of the formula (I).
  • radicals R 1 , R 2 and R 3 have the same meaning as in the general formula (II) from 2-butene-diol derivatives of the formula (I) or a mixture thereof with DHF-alkoxy derivatives of the general formula (II)
  • R 3 is C 1 - to C 6 -alkyl, from buten-1,4-diol of the general formula (I), where R 1 and R 2 in formula (I) are hydrogen.
  • 2-butene-1,4-diol is considerably less expensive. Due to a higher boiling point of the 2-butene-1, 4-diol also reduces the cooling effort during the reaction and higher reaction temperatures are possible. An essential further advantage of this educt is its significantly lower toxicity. Cis-butene-1,4-diol or at least 20% by weight of cis-butene-1,4-diol-containing diastereomer mixtures are preferably used in the process according to the invention. Particularly suitable is the process according to the invention for the preparation of DHF-alkoxy derivatives of the general formula (IIIb),
  • radicals R 4 , R 5 , R 6 and R 7 are hydrogen, C 1 - to C 4 -alkyl, C 1 - to C 6 - alkoxy or halogen, and R 3 in the general formula (II) indicated Meaning,
  • radicals R 4 , R 5 , R 6 and R 7 are hydrogen, C 1 - to C 4 -alkyl, C 1 - to C 6 - alkoxy or halogen,
  • radicals R 4 , R 5 , R 6 and R 7 are hydrogen, C 1 - to C 4 -alkyl, C 1 - to C 6 - alkoxy or halogen, and R 3 in the general formula (II) indicated Meaning,
  • the radicals R 4 , R 5 , R 6 and R 7 are hydrogen.
  • the desired target products are a compound of the general formula (III) or (IV), starting from 2-butene-1,4-diol derivatives of the general formula (I).
  • the unwanted compound of general formula (II) is returned to the electrolysis cell and then used together with the corresponding 2-butene-1, 4-diol derivative of the general formula (I) as starting material for the preparation of the target products with the desired higher number of alkoxy radicals.
  • the C 1 - to C 6 monoalcohol based on the 2-butene-1, 4-diol derivative of the general formula (I), equimolar or used in excess of up to 1:20 and then serves at the same time as a solvent or diluent for the compound of general formula (II) and the compound of general formula (I) formed.
  • a solvent or diluent for the compound of general formula (II) and the compound of general formula (I) formed Preference is given to using a C 1 -C 6 -monoalkyl alcohol and very particularly preferably methanol.
  • the electrolysis solution is added to customary cosolvents.
  • these are the inert solvents commonly used in organic chemistry. tel with a high oxidation potential. Examples include dimethylformamide, dimethyl carbonate or propylene carbonate.
  • Conducting salts which are contained in the electrolysis solution are generally at least one compound selected from the group consisting of potassium, sodium, lithium, iron, alkali, alkaline earth metal, Te ⁇ a (C 1 - to C 6- alkyl) ammonium, preferably tri (C 1 - to C 6 alkyl) -methylammonium salts.
  • Suitable counterions are sulfate, bisulfate, 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 pH of the electrolyte is by addition of organic and inorganic acids such as citric acid, tartaric acid, sulfuric acid, phosphoric acid, sulfonic acids, C 1 - to C 6 carboxylic acids such as formic acid, acetic acid, propionic acid or by using per se known buffer systems on a pH in the range of 2 to 7, preferably 2.5 to 5 set.
  • organic and inorganic acids such as citric acid, tartaric acid, sulfuric acid, phosphoric acid, sulfonic acids, C 1 - to C 6 carboxylic acids such as formic acid, acetic acid, propionic acid or by using per se known buffer systems on a pH in the range of 2 to 7, preferably 2.5 to 5 set.
  • 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.
  • bipolar switched capillary gap cells or Plattenstapelzellen 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 Eiectrochemistry, Chapter 3.5 Special Cell Designs and Chapter 5, Organic Ectrochemistry, Subchapter 5.4.3.2 Cell Design).
  • 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 0 C, preferably 20 to 40 0 C. In general, working at atmospheric pressure. Higher pressures are preferably used when working at higher temperatures. tet is to be avoided in order to avoid boiling of the starting compounds or cosolvents.
  • Suitable anode materials are, for example, noble metals such as platinum or metal oxides such as ruthenium or chromium oxide or mixed oxides of the type RuO x TiO x . Preference is given to graphite or carbon electrodes. Furthermore, anodes with diamond surfaces are preferred.
  • cathode materials for example, iron, steel, stainless steel, nickel or precious metals such as platinum and graphite or carbon materials into consideration, with graphite is preferred. Furthermore, cathodes with diamond surfaces are preferred.
  • the system is graphite as the anode and cathode and graphite as the anode and nickel, stainless steel or steel as the cathode. Furthermore, anodes with diamond surfaces are preferred.
  • 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. If 2,5-dimethoxytetrahydrofuran is to be prepared from 2,5-dihydro-2,5-dimethoxyfuran, purification is not necessary and the crude product obtained by the process according to the invention can be used.
  • MTBS methyltributylammonium methylsulfate
  • the electrolyte was pumped through the cell for 19 h at a flow rate of 200 l / h via a heat exchanger.
  • Electrolyte 35.0 g of 1,2-benzenedimethanol

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 2,5-dihydro-furane substitués en position 3 ou 4, dotés chacun en position 2 ou 5 ou sur les deux positions d'un groupe alcoxy C<SUB>1</SUB>- à C<SUB>6</SUB> (dérivés alcoxy DHF I), ou bien des dérivés de 1,1,4,4-tétraalcoxy-but-2-ène substitués en position 3 ou 4, à partir de dérivés 2-butène-1,4-diol de formule (I), dans laquelle les restes R<SUP>1</SUP> et R<SUP>2</SUP> signifient indépendamment l'un de l'autre hydrogène, alkyle C<SUB>1 </SUB>à C<SUB>6</SUB>, aryle C<SUB>6</SUB> à C<SUB>12 </SUB>ou cycloalkylène C<SUB>5</SUB> à C<SUB>12</SUB>, ou bien R<SUP>1</SUP> et R<SUP>2</SUP> forment ensemble, avec la double liaison à laquelle ils sont reliés, un groupe aryle C<SUB>6</SUB> à C<SUB>12</SUB> ou un groupe cycloalkyle C<SUB>5</SUB> à C<SUB>12 </SUB>monoinsaturé ou polyinsaturé, ou bien à partir de leur mélange avec des dérivés de 2,5- dihydrofurane substitués en position 3 ou 4 et dotés d'un groupe alcoxy C<SUB>1</SUB> à C<SUB>6</SUB>en position 2 ou 5, par oxydation électrochimique en présence d'un alcool monoalkyle C<SUB>1</SUB> à C<SUB>6</SUB>.
EP06725267A 2005-03-24 2006-03-23 Procede pour produire des derives alkoxyles de 2,5-dihydrofurane- ou de tetra-1,1,4,4-but-2-ene Withdrawn EP1863781A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005013631A DE102005013631A1 (de) 2005-03-24 2005-03-24 Verfahren zur Herstellung von alkoxylierten 2,5-Dihydrofuran- oder tetra-1,1,4,4-alkoxylierten But-2-enderivaten
PCT/EP2006/060989 WO2006100289A1 (fr) 2005-03-24 2006-03-23 Procede pour produire des derives alkoxyles de 2,5-dihydrofurane- ou de tetra-1,1,4,4-but-2-ene

Publications (1)

Publication Number Publication Date
EP1863781A1 true EP1863781A1 (fr) 2007-12-12

Family

ID=36649870

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06725267A Withdrawn EP1863781A1 (fr) 2005-03-24 2006-03-23 Procede pour produire des derives alkoxyles de 2,5-dihydrofurane- ou de tetra-1,1,4,4-but-2-ene

Country Status (7)

Country Link
US (1) US20080110763A1 (fr)
EP (1) EP1863781A1 (fr)
JP (1) JP2008536007A (fr)
CN (1) CN101137635A (fr)
CA (1) CA2602077A1 (fr)
DE (1) DE102005013631A1 (fr)
WO (1) WO2006100289A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX2012010906A (es) * 2010-03-25 2012-10-09 Basf Se Metodo de lavado electroquimico de textiles.
CN102633754B (zh) * 2012-03-28 2014-02-05 南开大学 用改性纳米氧化铝催化剂制备高纯度2,5-二氢呋喃的方法
US20190352784A1 (en) * 2016-11-24 2019-11-21 Avantium Knowledge Centre B.V. Process for treating a furan-2,5-dicarboxylic acid composition
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
EP4540440A1 (fr) * 2022-06-15 2025-04-23 DSM IP Assets B.V. Procédé de préparation de 2,5-dihydrofurane alcoxylé
WO2024231257A1 (fr) 2023-05-05 2024-11-14 Dsm Ip Assets B.V. Procédé de préparation de 1,1,4,4-tétraalkyloxy-2-butène
CN119800382B (zh) * 2024-12-26 2025-09-26 西北工业大学 基于电催化1,4- 丁烯二醇加氢脱羟制备的3-丁烯-1-醇及其制备方法和应用

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3142626A1 (de) * 1981-10-28 1983-05-05 Basf Ag, 6700 Ludwigshafen Elektrochemisches verfahren zur herstellung von 2,5-dialkoxy-2,5-dihydrofuranen
DE19962102A1 (de) * 1999-12-22 2001-06-28 Basf Ag Verfahren zur elektrochemischen Oxidation von organischen Verbindungen
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 WO2006100289A1 *

Also Published As

Publication number Publication date
US20080110763A1 (en) 2008-05-15
DE102005013631A1 (de) 2006-09-28
CA2602077A1 (fr) 2006-09-28
JP2008536007A (ja) 2008-09-04
CN101137635A (zh) 2008-03-05
WO2006100289A1 (fr) 2006-09-28

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