EP0902846B1 - Procede pour preparer des phtalides - Google Patents

Procede pour preparer des phtalides Download PDF

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Publication number
EP0902846B1
EP0902846B1 EP97921810A EP97921810A EP0902846B1 EP 0902846 B1 EP0902846 B1 EP 0902846B1 EP 97921810 A EP97921810 A EP 97921810A EP 97921810 A EP97921810 A EP 97921810A EP 0902846 B1 EP0902846 B1 EP 0902846B1
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EP
European Patent Office
Prior art keywords
phthalic acid
alkyl
anodic
hydrogen
acid derivatives
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EP97921810A
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German (de)
English (en)
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EP0902846A1 (fr
Inventor
Hermann Pütter
Heinz Hannebaum
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BASF SE
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BASF SE
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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
    • C25B3/25—Reduction

Definitions

  • the present invention relates to a new method of manufacture of phthalides by cathodic reduction of phthalic acid or phthalic acid derivatives.
  • Phthalides are especially used as intermediates for manufacturing of pesticides needed.
  • An electrochemical process for the production of the phthalides is known from DE-A-2 144 419.
  • phthalides can be produced in satisfactory yields if you split the reduction in Electrolysis cells.
  • a disadvantage of the described method is that with the Use of apparatus connected to split electrolysis cells Effort, since 2 cell circles are required in this case. In addition is working with 2 cell circles with the following further disadvantages connected:
  • the cell circles must be separated by a membrane or a diaphragm; this means a loss of energy through ohmic heat.
  • at least one chamber is usually charged with an aqueous (> 80% H 2 O) conductive salt solution. In the case of cathodic reductions, this is the anolyte.
  • the constraint on this approach severely limits the scope for using the anode reaction. Usually only hydrogen is produced as an anode product.
  • a process for producing phthalides was carried out by cathodic reduction of phthalic acid or phthalic acid derivatives, in which the carboxy groups can be replaced by units, that can be derived from carboxy groups in a condensation reaction are and one or more of the hydrogen atoms of the o-phenylene unit phthalic acid can be substituted by inert residues, found, taking the reduction in an organic Solvent containing less than 50 wt .-% water and one undivided electrolytic cell.
  • ammonium salts and in particular the ammonium salt of phthalamic acid are particularly preferred.
  • Suitable as electrode materials (both cathode and anode) commercially available electrodes made of graphite or carbon.
  • the electrolyte is usually a 2 to 40% by weight solution of phthalic acid or a phthalic acid derivative in an organic solvent, preferably less contains more than 25, particularly preferably less than 5% by weight of water.
  • Suitable organic solvents are in particular aliphatic C 1 to C 4 alcohols, in particular methanol or ethanol, or a mixture of such alcohols with a carboxamide such as dimethylformamide or t-butylformamide.
  • the electrolytes generally contain alkyl sulfates, for example methyl sulfate, or quaternary ammonium salts, in particular tetra (C 1 -C 4 -alkyl) ammonium halogens or tetrafluoroborates, usually in amounts of 0.4 to 10% by weight, based on the electrolyte, as conductive salts .
  • alkyl sulfates for example methyl sulfate
  • quaternary ammonium salts in particular tetra (C 1 -C 4 -alkyl) ammonium halogens or tetrafluoroborates, usually in amounts of 0.4 to 10% by weight, based on the electrolyte, as conductive salts .
  • anodic Depolarizer For the anodic coupling process, it is recommended to be anodic Depolarizer to use usual organic compounds whose Suitability for electrochemical oxidation to the person skilled in the art in general is known. Some of the anodic coupling processes are preferred performed in the presence of a mediator. Possible anodic coupling processes and their mediatization for example in D. Kyriakou, Modern Electroorganic Chemistry, Springer, Berlin 1994, described in chapter 4.2.
  • the anodic coupling processes are particularly suitable Oxidations of C-O or C-N single or double bonds, e.g. the oxidation of carboxylic acids, arylmethanes, aldehydes, carboxamides, Alcohols and heterocycles, or the oxidative C-C linkage especially of naphthalenes or activated CH groups.
  • Halogen compounds are particularly suitable as mediators all bromides or iodides.
  • the type of workup of the electrolyte mixture depends in particular according to the type of anodic coupling product and can according to generally known separation methods such as distillation, precipitation or recrystallization. Can be particularly easy most of the phthalides of many in a basic, aqueous environment separate insoluble organic by-products by removing the Phthalides in ammoniacal aqueous solutions that dissolves separates aqueous phase and the phthalide by acidification the aqueous phase fails again (see also here DE-A-2 510 920).
  • Phthalides are obtained by the process according to the invention technically simple way in high yield and purity. At the same time it is possible by coupling with anodic oxidation reactions to produce different types of valuable products without the current and material yield at the cathode would decrease.
  • a solution of 500 g dimethyl phthalate (2.56 mol), 1600 g t.-butylformamide is placed in an electrolytic cell, consisting of ten bipolar graphite ring disks, area per side: 147 dm 2 , with an electrode spacing of 0.7 mm and 375 g of methanol were electrolyzed with 25 g of tetrabutylammonium tetrafluoroborate at a current of 2.5 A for 11.5 hours at 60 ° C.
  • the solvent t-butylformamide is recovered without decomposition, the anode process is methanol oxidation with the main product Methyl formate.

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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)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Claims (9)

  1. Procédé de préparation de phtalides par réduction cathodique d'acide phtalique ou de dérivés de l'acide phtalique, dans lesquels les groupes carboxy peuvent être remplacés par des motifs pouvant être obtenus à partir de groupes carboxy dans le cadre d'une réaction de condensation, et un ou plusieurs des atomes d'hydrogène du motif o-phénylène de l'acide phtalique peuvent être substitués par des radicaux inertes, procédé dans lequel on met en oeuvre la réduction dans un solvant organique qui contient moins de 50 % en poids d'eau, et dans une cellule d'électrolyse non-subdivisée.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise un acide phtalique ou des dérivés de l'acide phtalique de formule générale I
    Figure 00110001
    dans laquelle les substituants ont les significations suivantes :
    R1, R2, R3 et R4 représentent chacun indépendamment des autres un atome d'hydrogène, un groupe alkyle en C1 à C4 ou halogéno,
    R5, R6 :
    a) indépendamment l'un de l'autre, représentent chacun -COOH ou COOX, où X est un radical alkyle en C1 à C4,
    b) l'un des substituants R5 ou R6 est -COONY4, et l'autre substituant est CONH2, où Y est un radical alkyle en C1 à C4 ou un atome d'hydrogène,
    c) R5 et R6 forment ensemble -CO-O-CO-.
  3. Procédé selon la revendication 1 ou 2, dans lequel on utilise en tant que dérivés de l'acide phtalique des esters di(alkyliques en C1 à C3) de l'acide phtalique.
  4. Procédé selon les revendications 1 à 3, dans lequel on utilise des électrodes au graphite ou au charbon.
  5. Procédé selon les revendications 1 à 4, dans lequel on utilise en tant que solvant organique un alcool aliphatique en C1 à C4 ou un mélange d'un alcool de ce type avec un carboxamide.
  6. Procédé selon les revendications 1 à 5, dans lequel on utilise en tant que sel conducteur un sel de l'ammonium quaternaire.
  7. Procédé selon les revendications 1 à 6, dans lequel on utilise pour l'opération de couplage anodique, en tant que dépolarisateur anodique, un composé organique usuel convenant à l'oxydation électrochimique.
  8. Procédé selon les revendications 1 à 7, dans lequel on utilise en tant que médiateur de l'opération de couplage anodique un composé halogéné.
  9. Procédé selon la revendication 8, dans lequel on utilise en tant que médiateur un bromure ou un iodure.
EP97921810A 1996-05-10 1997-04-28 Procede pour preparer des phtalides Expired - Lifetime EP0902846B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19618854 1996-05-10
DE19618854A DE19618854A1 (de) 1996-05-10 1996-05-10 Verfahren zur Herstellung von Phthaliden
PCT/EP1997/002185 WO1997043464A1 (fr) 1996-05-10 1997-04-28 Procede pour preparer des phtalides

Publications (2)

Publication Number Publication Date
EP0902846A1 EP0902846A1 (fr) 1999-03-24
EP0902846B1 true EP0902846B1 (fr) 2000-07-26

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP97921810A Expired - Lifetime EP0902846B1 (fr) 1996-05-10 1997-04-28 Procede pour preparer des phtalides

Country Status (8)

Country Link
US (1) US6063256A (fr)
EP (1) EP0902846B1 (fr)
JP (1) JP3946260B2 (fr)
CN (1) CN1058302C (fr)
CA (1) CA2254788C (fr)
DE (2) DE19618854A1 (fr)
ES (1) ES2150770T3 (fr)
WO (1) WO1997043464A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1017688B1 (fr) * 1997-09-19 2002-04-10 Basf Aktiengesellschaft Procede de production de phtalides

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AR018507A1 (es) * 1997-09-19 2001-11-28 Basf Se Proceso de recuperacion de un compuesto derivado del acido ftalico de una mezcla de reaccion en la que se sintetiza este compuesto
DE19808296A1 (de) * 1998-02-27 1999-09-02 Basf Ag Verfahren zur selektiven Hydrolyse von Acetalen bzw. Ketalen in Gegenwart von Phthaliden
DE19944989A1 (de) 1999-09-20 2001-03-22 Basf Ag Verfahren zur elektrolytischen Umwandlung von Furanderivaten
DE19944990A1 (de) 1999-09-20 2001-03-22 Basf Ag Verfahren zur elektrolytischen Umwandlung von organischen Verbindungen
CN1182127C (zh) * 2000-06-28 2004-12-29 中国医学科学院药物研究所 新的取代的2-苯并[c]呋喃酮化合物,其制备方法以及包含它们的药物组合物
DE10057888A1 (de) * 2000-11-22 2002-05-23 Basf Ag Herstellung von Butantetracarbonsäurederivaten mittels gekoppelter Elektrosynthese
DE10058304A1 (de) * 2000-11-24 2002-05-29 Basf Ag Verfahren zur Herstellung von alkoxylierten Carbonylverbindungen durch ein anodisches Oxidationsverfahren unter Nutzung der kathodischen Koppelreaktion zur organischen Synthese
KR20150023709A (ko) * 2012-06-15 2015-03-05 바스프 에스이 친핵체 존재 하의 유기 기판의 애노드 산화

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2510920A1 (de) * 1975-03-13 1976-09-30 Basf Ag Verfahren zur elektrochemischen herstellung von phthalid
DE2630927A1 (de) * 1976-07-09 1978-01-19 Basf Ag Verfahren zur herstellung von phthalidcarbonsaeure-(5)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1017688B1 (fr) * 1997-09-19 2002-04-10 Basf Aktiengesellschaft Procede de production de phtalides

Also Published As

Publication number Publication date
CA2254788C (fr) 2005-03-01
JP2000511592A (ja) 2000-09-05
ES2150770T3 (es) 2000-12-01
DE19618854A1 (de) 1997-11-13
JP3946260B2 (ja) 2007-07-18
DE59702087D1 (de) 2000-08-31
EP0902846A1 (fr) 1999-03-24
CA2254788A1 (fr) 1997-11-20
CN1210564A (zh) 1999-03-10
US6063256A (en) 2000-05-16
WO1997043464A1 (fr) 1997-11-20
CN1058302C (zh) 2000-11-08

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