EP1362022A1 - Method for producing orthocarbonic acid trialkyl esters - Google Patents

Method for producing orthocarbonic acid trialkyl esters

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Publication number
EP1362022A1
EP1362022A1 EP01980340A EP01980340A EP1362022A1 EP 1362022 A1 EP1362022 A1 EP 1362022A1 EP 01980340 A EP01980340 A EP 01980340A EP 01980340 A EP01980340 A EP 01980340A EP 1362022 A1 EP1362022 A1 EP 1362022A1
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EP
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Prior art keywords
same meaning
alkyl
ketals
methyl
orthoester
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EP01980340A
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German (de)
French (fr)
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EP1362022B1 (en
Inventor
Andreas Fischer
Hermann Pütter
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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
    • C25B3/23—Oxidation

Definitions

  • the invention relates to a process for the preparation of orthocarboxylic acid trialkyl esters (orthoester 0) by electrochemical oxidation of alpha-beta-diketones or alpha-beta-hydroxyketones, the keto function being in the form of a ketal function derived from C 1 -C 4 -alkyl alcohols and the hydroxyl function is optionally in the form of an ether function derived from Ci to C 4 alkyl alcohols (ketals K), in the presence of Ci to C 4 alcohols (alcohols A), the molar ratio of the sum of the orthoesters in the electrolyte 0 and the ketals K to the alcohols A is 0.2: 1 to 5: 1.
  • Non-electrochemical processes for the preparation of orthocarboxylic acid trialkyl esters such as trimethyl orthoforate (TMOF) are e.g. known from DE-A-3606472, wherein chloroform is reacted together with sodium methylate.
  • the object on which the invention is based was therefore to provide an electrochemical process for making orthocarboxylic acid trialkyl esters accessible economically and in particular in high current and product yields and with high selectivity.
  • R 1 hydrogen, C 1 ⁇ to C 2 n-alkyl, C - to C 0 -alkenyl,
  • R 2 , R 3 C 1 -C 20 -alkyl, C 3 - to C 12 -cycloalkyl, and C 4 - to C o-cycloalkyl-alkyl or R 2 and R 3 together form a C 2 - to cio-alkylene
  • R 4 Cx to C 4 alkyl.
  • R5, RIO the same meaning as R 1
  • R 6 , R 7 the same meaning as R 2
  • R 8 hydrogen under the condition that R 9 has the same meaning as R 1 or the same meaning as R2
  • R 9 the same meaning as R 1 or -0- R 2 .
  • R 13 , R 14 the same meaning as R 1
  • ketals II which are those in which R 9 has exclusively the same meaning as R 1 .
  • R 17 , R 20 the same meaning as R 4 ,
  • R 19 the same meaning as R 2 and
  • XC 2 - to -C 2 alkylene means (orthoester la)
  • R 21 , R 22 the same meaning as R 2
  • R 23 the same meaning as R 8
  • R 24 the same meaning as R 9 and
  • the ketals used according to the invention are accessible by generally known production processes. If these are functional groups, the easiest way to prepare them is to start from a precursor that has a CC double bond at the location of the desired functional group. fertilizer and then functionalized using standard methods (see Synthesis, (1981) 501 - 522).
  • the process according to the invention can also be used particularly advantageously for the production of orthoesters Ib, which are compounds in which
  • R 1 hydrogen, C ⁇ -C o-alkyl, C 3 -C ⁇ cycloalkyl or
  • R 2 , R 3 Ci to C 20 alkyl, C 3 - to -C 2 cycloalkyl, and C 4 - bis
  • R 4 Ci to C alkyl (orthoester Ib)
  • R 5 , R 10 the same meaning as R 1 in orthoester Ib
  • R 6 to R 9 the same meaning as R 2 or R 3 in orthoester Ib (ketals Ilb)
  • the process according to the invention can be used in particular for the production of orthoesters Ic in which
  • R 1 hydrogen, C 1 -C 5 -alkyl
  • R 2 , R 3 , R 4 methyl or ethyl (orthoester Ic)
  • R 5 , R 10 the same meaning as R 1 in Orthoester Ic
  • R 6 to R 9 the same meaning as R 2 or R 3 in Orthoester Ic (Ketale IIc).
  • radicals R 5 and R 10 preferably have the same meaning.
  • TMOF orthoformic acid methyl ester
  • ethyl ester or orthoacetic acid ethyl ester or ethyl ester orthoester Id
  • TAE 1,1,2,2-tetramethoxyethane
  • TAE 1, 1, 2, 2-tetraethoxyethane
  • the molar ratio of the sum of the orthoesters 0 and the ketals K to the alcohols A is 0.2: 1 to 5: 1, preferably 0.2: 1 - 2: 1 and particularly preferably 0.3: 1 to 1: 1.
  • the conductive salts contained in the electrolysis solution are generally alkali, tetra (C ⁇ bis
  • C 6 alkyl ammonium or tri (-C ⁇ to C 6 alkyl) benzyl ammonium salts.
  • Sulfate, hydrogen sulfate, alkyl sulfates, aryl sulfates, halides, phosphates, carbonates, alkyl phosphates, alkyl carbonates, nitrate, alcoholates, tetrafluoroborate or perchlorate are suitable as counterions.
  • acids derived from the above-mentioned anions can be considered as conductive salts.
  • Methyltributylammonium methyl sulfates are preferred,
  • customary cosolvents are added to the electrolysis solution. These are the inert solvents with a high oxidation potential that are common in organic chemistry. Examples include dimethyl carbonate or propylene carbonate.
  • the process according to the invention can be carried out in all customary electrolysis cell types.
  • One preferably works continuously with undivided flow cells.
  • the feed rate of the starting materials is generally chosen so that the weight ratio of the ketals K used to the orthoesters I formed in the electrolyte is 10: 1 to 0.05: 1.
  • the current densities at which the process is carried out are generally 1 to 1000, preferably 10 to 100 mA / cm 2 .
  • the temperatures are usually -20 to 60 ° C, preferably 0 to 60 ° C.
  • normal pressure is used. Higher pressures are preferably used when working at higher temperatures 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 RuO x TiO x type .
  • Graphite or carbon electrodes are preferred.
  • cathode materials are iron, steel, stainless steel, nickel or precious metals such as platinum and graphite or carbon materials.
  • the system is preferably graphite as anode and cathode and graphite as anode and nickel, stainless steel or steel as cathode.
  • the electrolysis solution is worked up using general separation methods.
  • the electrolysis solution is generally first distilled and 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.
  • Example 3 1, 1, 2-trimethoxyethane, 320 g of methanol and 5.8 g of ammonium tetrafluoroborate are used and subjected to an electrolyte.
  • the electrolysis conditions were as described in Example 1. 9.5 GC area% formaldehyde dimethylacetal and 5.9 GC area% trimethyl orthoformate were obtained in the electrolysis discharge.
  • Example 3

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

Abstract

The invention relates to a method for producing orthocarbonic acid trialkyl esters by electrochemical oxidation of alpha-beta-diketones or alpha-beta-hydroxy ketones in the presence of C1-to C4-alcohols (alcohol A), the keto function being present in the form of a ketal function derived from C1- to C4-alykl alcohols and the hydroxyl function being optionally in the form of an ether function derived from C1- to C4-alykl alcohols (ketal K). The molar ratio of the ketal K to the alcohols A in the electrolytes is 0.2:1 to 10:1.

Description

Verfahren zur Herstellung von OrthocarbonsäuretrialkylesternProcess for the preparation of orthocarboxylic acid trialkyl esters
Beschreibungdescription
Die Erfindung betrifft ein Verfahren zur Herstellung von Orthocarbonsäuretrialkylestern (Orthoester 0) durch elektrochemische Oxidation von alpha-beta-Diketonen oder alpha-beta-Hydroxyketo- nen, wobei die Ketofunktion in Form einer von Cι~ bis C4-Alkylal- koholen abgeleiteten Ketalfunktion und die Hydroxylfunktion ggf. in Form einer von Ci- bis C4-Alkylalkoholen abgeleiteten Ether- funktion vorliegt (Ketale K) , in Gegenwart von Ci-bis C4-Alkoholen (Alkohole A) , wobei im Elektrolyten das molare Verhältnis der Summe der Orthoester 0 und der Ketale K zu den Alkoholen A 0,2 : 1 bis 5 : 1 beträgt.The invention relates to a process for the preparation of orthocarboxylic acid trialkyl esters (orthoester 0) by electrochemical oxidation of alpha-beta-diketones or alpha-beta-hydroxyketones, the keto function being in the form of a ketal function derived from C 1 -C 4 -alkyl alcohols and the hydroxyl function is optionally in the form of an ether function derived from Ci to C 4 alkyl alcohols (ketals K), in the presence of Ci to C 4 alcohols (alcohols A), the molar ratio of the sum of the orthoesters in the electrolyte 0 and the ketals K to the alcohols A is 0.2: 1 to 5: 1.
Nicht-elektrochemische Verfahren zur Herstellung von Orthocarbonsäuretrialkylestern wie Trimethylorthofor iat (TMOF) sind z.B. aus DE-A- 3606472 bekannt, wobei Chloroform zusammen mit Natrium- methylat umgesetzt wird.Non-electrochemical processes for the preparation of orthocarboxylic acid trialkyl esters such as trimethyl orthoforate (TMOF) are e.g. known from DE-A-3606472, wherein chloroform is reacted together with sodium methylate.
Weiterhin ist die Herstellung von TMOF aus Blausäure und Methanol in J. Org. Chem. 20 (1955) 1573 bekannt.The production of TMOF from hydrocyanic acid and methanol is also known in J. Org. Chem. 20 (1955) 1573.
Aus J. Amer. Chem. Soc . , (1975) 2546 und J. Org. Chem., 61 (1996) 3256 sowie Electrochim. Acta 42, (1997) 1933 sind elektrochemische Verfahren bekannt, mit denen C-C-Einfachbindungen zwischen C-Atomen, die je eine AIkoxyfunktion tragen, oxidativ gespalten werden können. Eine gezielte Bildung von Orthoesterfunktionen ist jedoch nicht beschrieben.From J. Amer. Chem. Soc. , (1975) 2546 and J. Org. Chem., 61 (1996) 3256 and Electrochim. Acta 42, (1997) 1933, electrochemical processes are known with which C-C single bonds between C atoms, each of which has an alkoxy function, can be cleaved oxidatively. A targeted formation of orthoester functions is not described.
Aus Russ. Chem. Bull., 48 (1999) 2093 ist es bekannt, vicinale Diketone, die in Form ihrer Acetale vorliegen durch anodische Oxidation unter Einsatz hoher Ladungsmengen und in Gegenwart ei- nes hohen Methanolüberschusses (vgl. S 2097, 1. Spalte, 5. Absatz) in den entsprechenden Dicarbonsäuredie ethylester zu zersetzen.From soot. Chem. Bull., 48 (1999) 2093, it is known to use vicinal diketones in the form of their acetals by anodic oxidation using large amounts of charge and in the presence of a large excess of methanol (cf. S 2097, 1st column, 5. Paragraph) in the corresponding dicarboxylic acid to decompose the ethyl ester.
In Canadian Journal of Chemistry, 50 (1972) 3424 wird die anodi- sehe Oxidation von Benzil-tetramethyldiketal zu Tri ethyl-ortho- benzoat in einem mehr als 100fachen Methanolüberschuss beschrieben. Nach Angabe der Autoren beträgt die Produktausbeute jedoch nur 62% und die Stromausbeute 5%.Canadian Journal of Chemistry, 50 (1972) 3424 describes the anodic oxidation of benzil-tetramethyldiketal to triethyl orthobenzoate in a more than 100-fold excess of methanol. According to the authors, however, the product yield is only 62% and the electricity yield 5%.
In Journ. Am. Chem. Soc, (1963), 2525 wird die elektrochemische Oxidation von dem Orthochinontetramethylketal in einer basischen Methanollösung zu dem entsprechenden Orthoester beschrieben. Die Umsetzung wurde in einer basischen Methanollösung durchgeführt, wobei die Substratkonzentration 10% betrug. Die Produktausbeute betrug 77% bei einer Stromausbeute von 6 % (16 F/mol) . Rein aliphatische Orthoester konnten auf elektrochemische Weise bisher nicht hergestellt werden.In journ. At the. Chem. Soc, (1963), 2525 describes the electrochemical oxidation of the orthoquinone tetramethyl ketal in a basic methanol solution to the corresponding orthoester. The The reaction was carried out in a basic methanol solution, the substrate concentration being 10%. The product yield was 77% with a current yield of 6% (16 F / mol). Purely aliphatic orthoesters have so far not been able to be produced electrochemically.
Die der Erfindung zugrunde liegende Aufgabe bestand somit darin, ein elektrochemisches Verfahren bereitzustellen, um wirtschaftlich und insbesondere in hohen Strom- und Produktausbeuten und mit hoher Selektivität Orthocarbonsäuretrialkylester zugänglich zu machen.The object on which the invention is based was therefore to provide an electrochemical process for making orthocarboxylic acid trialkyl esters accessible economically and in particular in high current and product yields and with high selectivity.
Demgemäß wurde das eingangs beschriebene Verfahren gefunden.Accordingly, the process described at the outset has been found.
Das erfindungsgemässe Verfahren eignet sich insbesondere zur Herstellung von Orthoestern I der allgemeinen Formel I,The process according to the invention is particularly suitable for the preparation of orthoesters I of the general formula I,
OR3 OR 3
wobei die Reste die folgende Bedeutung habenwhere the residues have the following meaning
R1: Wasserstoff, Cι~ bis C2n-Alkyl, C - bis C 0-Alkenyl,R 1 : hydrogen, C 1 ~ to C 2 n-alkyl, C - to C 0 -alkenyl,
C - bis C o-Alkinyl, C3- bis Cι -Cycloalkyl, C4- bis C n-Cycloalkyl-alkyl, C4- bis Cio-Aryl oder ggf. 1 bisC - to C o-alkynyl, C 3 - to -C -cycloalkyl, C 4 - to C n-cycloalkyl-alkyl, C 4 - to Cio-aryl or optionally 1 to
3-fach substituiert durch Ci- bis Cs-Alkoxy oder Ci- bis Cg-Alkoxycarbonyl3 times substituted by Ci to Cs alkoxy or Ci to Cg alkoxycarbonyl
R2, R3 : Ci- bis C20-Alkyl, C3- bis C12-Cycloalkyl , und C4- bis C o-Cycloalkyl-alkyl oder R2 und R3 gemeinsam eine C2- bis Cio-Alkylen bildenR 2 , R 3 : C 1 -C 20 -alkyl, C 3 - to C 12 -cycloalkyl, and C 4 - to C o-cycloalkyl-alkyl or R 2 and R 3 together form a C 2 - to cio-alkylene
R4: Cx- bis C4-Alkyl .R 4 : Cx to C 4 alkyl.
Hierfür geht man von Ketalen II der allgemeinen Formel II aus For this one starts from ketals II of the general formula II
wobei die Reste die folgende Bedeutung habenwhere the residues have the following meaning
R5, RIO; die gleiche Bedeutung wie R1 R5, RIO; the same meaning as R 1
R6, R7: die gleiche Bedeutung wie R2 R 6 , R 7 : the same meaning as R 2
R8: Wasserstoff unter der Bedingung, dass R9 die gleiche Bedeutung wie R1 hat, oder die gleiche Bedeutung wie R2R 8 : hydrogen under the condition that R 9 has the same meaning as R 1 or the same meaning as R2
R9: die gleiche Bedeutung wie R1 oder -0- R2.R 9 : the same meaning as R 1 or -0- R 2 .
Es ist gleichfalls möglich, die Orthoester I in Form einer Mischung mit Ketalen IV der allgemeinen Formel IV zu erhalten,It is also possible to obtain the orthoesters I in the form of a mixture with ketals IV of the general formula IV,
ORl OR l
wobei die Reste die folgende Bedeutung haben:where the residues have the following meaning:
Rll. die gleiche Bedeutung wie R4 R ll. the same meaning as R 4
R": die gleiche Bedeutung wie R2 R ": the same meaning as R 2
R13, R14: die gleiche Bedeutung wie R1 R 13 , R 14 : the same meaning as R 1
Hierfür geht man von Ketalen II aus, bei denen es sich um solche handelt, bei denen R9 ausschliesslich die gleiche Bedeutung wie R1 hat.For this one starts from ketals II, which are those in which R 9 has exclusively the same meaning as R 1 .
Besonders günstig läßt sich das erfindungsgemäße Verfahren zur Herstellung von Orthoestern der allgemeinen Formel la (Orthoester la) einsetzen The process according to the invention can be used particularly advantageously for the preparation of orthoesters of the general formula Ia (orthoester Ia)
bei denen die Reste die folgende Bedeutung haben:where the residues have the following meaning:
Ris, Ri6; die gleiche Bedeutung wie R2 Ris, Ri6 ; the same meaning as R 2
RlS; die gleiche Bedeutung wie R2 RIS; the same meaning as R 2
R17, R20: die gleiche Bedeutung wie R4,R 17 , R 20 : the same meaning as R 4 ,
R19 : die gleiche Bedeutung wie R2 undR 19 : the same meaning as R 2 and
X C2- bis Cι2-Alkylen bedeutet (Orthoester la)XC 2 - to -C 2 alkylene means (orthoester la)
Hierzu geht man von Ketalen der allgemeinen Formel Ha aus,To this end, ketals of the general formula Ha are used,
bei denen die Reste die folgende Bedeutung haben: where the residues have the following meaning:
R21, R22: die gleiche Bedeutung wie R2 R 21 , R 22 : the same meaning as R 2
R23: die gleiche Bedeutung wie R8 R 23 : the same meaning as R 8
R24: die gleiche Bedeutung wie R9 undR 24 : the same meaning as R 9 and
die gleiche Bedeutung wie X hat (Ketale Ha.)has the same meaning as X (Ketale Ha.)
Die erfindungsgemäß eingesetzten Ketale sind nach allgemein bekannten Herstellverfahren zugänglich. Sofern es sich um solche mit funktioneilen Gruppen handelt, lassen sich diese am einfachsten herstellen, indem man von einer Vorstufe ausgeht, die an der Stelle der gewünschten funktionellen Gruppe eine C-C-Doppelbin- düng trägt und diese anschließend nach Standardmethoden funktio- nalisiert (s. Synthesis, (1981) 501 - 522).The ketals used according to the invention are accessible by generally known production processes. If these are functional groups, the easiest way to prepare them is to start from a precursor that has a CC double bond at the location of the desired functional group. fertilizer and then functionalized using standard methods (see Synthesis, (1981) 501 - 522).
Besonders vorteilhaft läßt sich das erfindungsgemäße Verfahren auch zur Herstellung von Orthoestern Ib einsetzen, bei denen es sich um Verbindungen handelt, in denenThe process according to the invention can also be used particularly advantageously for the production of orthoesters Ib, which are compounds in which
R1: Wasserstoff, Cχ-C o-Alkyl, C3-Cι -Cycloalkyl oderR 1 : hydrogen, Cχ-C o-alkyl, C 3 -Cι cycloalkyl or
C4-C o-Cycloalkyl-alkylC 4 -C o -cycloalkyl-alkyl
R2, R3 : Ci- bis C20-Alkyl, C3- bis Cι2-Cycloalkyl, und C4- bisR 2 , R 3 : Ci to C 20 alkyl, C 3 - to -C 2 cycloalkyl, and C 4 - bis
C o-Cycloalkyl-alkyl oder R2 und R3 gemeinsam C2- bisC o-Cycloalkyl-alkyl or R 2 and R 3 together C 2 - bis
Cio-Alkylen bildenForm Cio-Alkylene
R4: Ci- bis C -Alkyl (Orthoester Ib)R 4 : Ci to C alkyl (orthoester Ib)
ausgehend von Ketalen II, bei denen die Reste die folgende Bedeutung haben:starting from ketals II, in which the residues have the following meaning:
R5, R10: die gleiche Bedeutung wie R1 in Orthoester IbR 5 , R 10 : the same meaning as R 1 in orthoester Ib
R6 bis R9 : die gleiche Bedeutung wie R2 oder R3 in Orthoester Ib (Ketalen Ilb)R 6 to R 9 : the same meaning as R 2 or R 3 in orthoester Ib (ketals Ilb)
In der Gruppe der Orthoester Ib läßt sich das erfindungsgemäße Verfahren insbesondere einsetzen zur Herstellung von Orthoestern Ic, in denenIn the group of orthoesters Ib, the process according to the invention can be used in particular for the production of orthoesters Ic in which
R1: Wasserstoff, Cι~ bis C5-Alkyl,R 1 : hydrogen, C 1 -C 5 -alkyl,
R2, R3, R4: Methyl oder Ethyl bedeutet (Orthoester Ic)R 2 , R 3 , R 4 : methyl or ethyl (orthoester Ic)
ausgehend von Ketalen II, bei denen die Reste die folgende Bedeutung haben :starting from ketals II, in which the residues have the following meaning:
R5, R10 : die gleiche Bedeutung wie R1 in Orthoester IcR 5 , R 10 : the same meaning as R 1 in Orthoester Ic
R6 bis R9 : die gleiche Bedeutung wie R2 oder R3 in Orthoester Ic (Ketale IIc) .R 6 to R 9 : the same meaning as R 2 or R 3 in Orthoester Ic (Ketale IIc).
In den Ketalen Ilb und IIc haben die Reste R5 und R10 bevorzugt die gleiche Bedeutung.In the ketals IIb and IIc, the radicals R 5 and R 10 preferably have the same meaning.
Ganz besonders günstig läßt sich das erfindungsgemäße Verfahren zur Herstellung von Orthoameisensäuremethylester (TMOF) oder -ethylester oder Orthoessigsäure ethylester oder -ethylester (Orthoester Id) einsetzen, wobei als Ausgangsverbindungen 1,1,2,2-Tetramethoxyethan bzw. 1, 1, 2 , 2-Tetraethoxyethan (TME) (Ketale Ild) dienen.The process according to the invention for the preparation of orthoformic acid methyl ester (TMOF) or ethyl ester or orthoacetic acid ethyl ester or ethyl ester (orthoester Id) can be used very particularly favorably, starting compounds 1,1,2,2-tetramethoxyethane or 1, 1, 2, 2-tetraethoxyethane (TME) (Ketale Ild) are used.
Im Elektrolyten beträgt das molare Verhältnis der Summe der Orthoester 0 und der Ketale K zu den Alkoholen A 0,2 : 1 bis 5 : 1, bevorzugt 0,2 : 1 - 2 : 1 und besonders bevorzugt 0,3 : 1 bis 1 : 1.In the electrolyte, the molar ratio of the sum of the orthoesters 0 and the ketals K to the alcohols A is 0.2: 1 to 5: 1, preferably 0.2: 1 - 2: 1 and particularly preferably 0.3: 1 to 1: 1.
Als Leitsalze, die in der Elektrolyselösung enthalten sind, han- delt es sich im Allgemeinen um Alkali, Tetra (C ~ bisThe conductive salts contained in the electrolysis solution are generally alkali, tetra (C ~ bis
C6-alkyl) ammonium- oder Tri(Cι~ bis C6-alkyl) -benzylammoniumsalze. Als Gegenion kommen Sulfat, Hydrogensulfat, Alkylsulfate, Aryl- sulfate, Halogenide, Phosphate, Carbonate, Alkylphosphate, Alkyl- carbonate, Nitrat, Alkoholate, Tetrafluorborat oder Perchlorat in Betracht.C 6 alkyl) ammonium or tri (-C ~ to C 6 alkyl) benzyl ammonium salts. Sulfate, hydrogen sulfate, alkyl sulfates, aryl sulfates, halides, phosphates, carbonates, alkyl phosphates, alkyl carbonates, nitrate, alcoholates, tetrafluoroborate or perchlorate are suitable as counterions.
Weiterhin kommen die von den vorstehend genannten Anionen abgeleiteten Säuren als Leitsalze in Betracht.Furthermore, the acids derived from the above-mentioned anions can be considered as conductive salts.
Bevorzugt sind Methyltributylammoniummethylsulfate (MTBS) ,Methyltributylammonium methyl sulfates (MTBS) are preferred,
Methyltriethylammoniummethylsulfat oder Methyl-tri-propylmethyl- ammoniummethylsulfate .Methyl triethylammonium methyl sulfate or methyl tri-propylmethyl ammonium methyl sulfate.
Gegebenenfalls setzt man der Elektrolyselösung übliche Cosolven- zien zu. Dabei handelt es sich um die in der organischen Chemie allgemein üblichen inerten Lösungsmittel mit einem hohen Oxidati- onspotential . Beispielhaft genannt seien Dimethylcarbonat oder Propylencarbonat .If necessary, customary cosolvents are added to the electrolysis solution. These are the inert solvents with a high oxidation potential that are common in organic chemistry. Examples include dimethyl carbonate or propylene carbonate.
Das erfindungsgemäße Verfahren kann in allen üblichen Elektrolysezellentypen durchgeführt werden. Vorzugsweise arbeitet man kontinuierlich mit ungeteilten Durchflusszellen.The process according to the invention can be carried out in all customary electrolysis cell types. One preferably works continuously with undivided flow cells.
Bei kontinuierlicher Durchführung des Verfahrens wählt man die Zulaufgeschwindigkeit der Einsatzstoffe im allgemeinen so, dass das Gewichtsverhältnis der eingesetzten Ketale K zu den gebildeten Orthoestern I im Elektrolyten 10 : 1 bis 0,05 : 1 beträgt.When the process is carried out continuously, the feed rate of the starting materials is generally chosen so that the weight ratio of the ketals K used to the orthoesters I formed in the electrolyte is 10: 1 to 0.05: 1.
Die Stromdichten, bei denen man das Verfahren durchführt, betra- gen im allgemeinen 1 bis 1000, bevorzugt 10 bis 100 mA/cm2. Die Temperaturen betragen üblicherweise -20 bis 60°C, bevorzugt 0 bis 60°C. Im allgemeinen wird bei Normaldruck gearbeitet. Höhere Drücke werden bevorzugt dann angewandt, wenn bei höheren Temperaturen gearbeitet werden soll, um ein Sieden der Ausgangsverbin- düngen bzw. Cosolventien zu vermeiden. Als Anodenmaterialien eignen sich beispielsweise Edelmetalle wie Platin oder Metalloxide wie Ruthenium oder Chromoxid oder Mischoxide des Typs RuOxTiOx. Bevorzugt sind Graphit oder Kohleelektroden.The current densities at which the process is carried out are generally 1 to 1000, preferably 10 to 100 mA / cm 2 . The temperatures are usually -20 to 60 ° C, preferably 0 to 60 ° C. In general, normal pressure is used. Higher pressures are preferably used when working at higher temperatures 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 RuO x TiO x type . Graphite or carbon electrodes are preferred.
Als Kathodenmaterialien kommen beispielsweise Eisen, Stahl, Edelstahl, Nickel oder Edelmetalle wie Platin sowie Graphit oder Kohlematerialien in Betracht . Bevorzugt ist das System Graphit als Anode und Kathode sowie Graphit als Anode und Nickel, Edelstahl oder Stahl als Kathode.Examples of suitable cathode materials are iron, steel, stainless steel, nickel or precious metals such as platinum and graphite or carbon materials. The system is preferably graphite as anode and cathode and graphite as anode and nickel, stainless steel or steel as cathode.
Nach Beendigung der Reaktion wird die Elektrolyselösung nach allgemeinen Trennmethoden aufgearbeitet. Hierzu wird die Elektrolyselösung im allgemeinen zunächst destilliert und die einzelnen Verbindungen werden in Form von unterschiedlichen Fraktionen getrennt gewonnen. Eine weitere Reinigung kann beispielsweise durch Kristallisation, Destillation oder chromatographisch erfolgen.After the reaction has ended, the electrolysis solution is worked up using general separation methods. For this purpose, the electrolysis solution is generally first distilled and 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.
Experimenteller TeilExperimental part
Beispiel 1:Example 1:
Es wurde eine ungeteilte Zelle mit Graphitelektroden in bipolarer Anordnung eingesetzt. Die gesamte Elektrodenfläche betrug 0,145 m2 (Anode und Kathode) . Als Elektrolyt wurde eine Lösung bestehend aus 2 Mol Methanol auf 1 Mol TME eingesetzt, welche 2 Gew.-% MTBS als Leitsalz enthielt. Die Elektrolyse erfolgte bei 300 A/m2 und es wurde eine Ladungsmenge von 2 F bezogen auf TME durch die Zelle geleitet. Die Temperatur während der Elektrolyse betrug 20°C. Nach Beendigung der Elektrolyse wurden die Elektrolysepro- dukte mittels GasChromatographie quantitativ und mittels GC-MS- Kopplung qualitativ bestimmt. Es war bei einem Umsatz an TME von 69 % TMOF mit einer Selektivität von 77 % entstanden. Die Neben- produkte waren vor allem Methylformiat sowie Methylal .An undivided cell with graphite electrodes in a bipolar arrangement was used. The total electrode area was 0.145 m 2 (anode and cathode). A solution consisting of 2 moles of methanol per 1 mole of TME, which contained 2% by weight of MTBS as the conductive salt, was used as the electrolyte. The electrolysis was carried out at 300 A / m 2 and a charge of 2 F based on TME was passed through the cell. The temperature during the electrolysis was 20 ° C. After the electrolysis had ended, the electrolysis products were determined quantitatively by means of gas chromatography and qualitatively by means of GC-MS coupling. It was created with a TME conversion of 69% TMOF with a selectivity of 77%. The by-products were primarily methyl formate and methylal.
Beispiel 2 :Example 2:
In einer Elektrolysezelle mit einer Elektrodenfläche von 316,4 cm2, sonst wie in Beispiel 1 beschrieben, wurden 240,3 gIn an electrolysis cell with an electrode area of 316.4 cm 2 , otherwise as described in Example 1, 240.3 g
1, 1, 2-Trimethoxyethan, 320 g Methanol und 5,8 g Ammoniumtetra- fluoroborat eingesetzt und einer Elektrolyde unterworfen. Die Elektrolysebedingungen waren wie in Beispiel 1 beschrieben. Man erhielt im Elektrolyseaustrag 9,5 GC-Flächen-% Formaldehyddime- thylacetal und 5,9 GC-Flächen-% Trimethylorthoformiat . Beispiel 3 :1, 1, 2-trimethoxyethane, 320 g of methanol and 5.8 g of ammonium tetrafluoroborate are used and subjected to an electrolyte. The electrolysis conditions were as described in Example 1. 9.5 GC area% formaldehyde dimethylacetal and 5.9 GC area% trimethyl orthoformate were obtained in the electrolysis discharge. Example 3:
In einer Elektrolysezelle mit einer Elektrodenfläche von 298,8 cm2, sonst wie in Beispiel 1 beschrieben, wurden 89, g 2,2,3,3-Te- tramethoxybuten (80 %ig, hergestellt aus Diacetyl und Trimethyl- orthoformiat) , 64 g Methanol und 1,7 g Ammoniumtetrafluoroborat umgesetzt. Die Elektrolysebedingungen waren wie in Beispiel 1 beschrieben. Man erhielt im Elektroiyseaustrag nach einem Stromeinsatz von 2 Faraday 1,7 GC-Flächen-% Trimethylorthoacetat, nach 8 F Stromeinsatz 18 GC-Flächen-% .In an electrolysis cell with an electrode area of 298.8 cm 2 , otherwise as described in Example 1, 89 g of 2,2,3,3-tetramethoxybutene (80%, made from diacetyl and trimethyl orthoformate), 64 g of methanol and 1.7 g of ammonium tetrafluoroborate reacted. The electrolysis conditions were as described in Example 1. In the discharge from the electrolyte, 1.7 GC area% of trimethyl orthoacetate was obtained after a current of 2 Faraday, and 18 GC area% after 8 F of current.
Beispiel 4:Example 4:
In einer kontinuierlich betriebenen Elektrolyse erhielt man bei einer Stromdichte von 310 A/m2 an Graphitelektroden und einem Zulauf von Methanol zu 1, 1, 2 , 2-Tetramethoxyethan von 1,5 mol zu 1 mol und einem MTBS-Gehalt von 8 Gew.-% im Elektroiyseaustrag bei einem Umsatz von 41 % TME eine Selektivität zu TMOF von 95 % und eine Stromausbeute für TMOF von 78 %. In a continuously operated electrolysis, a current density of 310 A / m 2 on graphite electrodes and an inflow of methanol to 1, 1, 2, 2-tetramethoxyethane of 1.5 mol to 1 mol and an MTBS content of 8% were obtained. -% in the electroysis discharge with a conversion of 41% TME, a selectivity to TMOF of 95% and a current yield for TMOF of 78%.

Claims

Patentansprücheclaims
1. Verfahren zur Herstellung von Orthocarbonsäuretrialkylestern (Orthoester 0) durch elektrochemische Oxidation von aiphabeta-Diketonen oder alpha-beta-Hydroxyketonen, wobei die Ke- tofunktion in Form einer von Cχ~ bis C4-Alkylalkoholen abgeleiteten Ketalfunktion und die Hydroxylfunktion ggf. in Form einer von Ci- bis C4-Alkylalkoholen abgeleiteten Etherfunktion vorliegt (Ketale K) , in Gegenwart von Ci-bis C4-Alkoholen (Alkohole A) , wobei im Elektrolyten das molare Verhältnis der Summe aus Orthoester O und der Ketale K zu den Alkoholen A 0,2 : 1 bis 5 : 1 beträgt.1. Process for the preparation of orthocarboxylic acid trialkyl esters (orthoester 0) by electrochemical oxidation of aiphabeta diketones or alpha-beta-hydroxyketones, the keto function being in the form of a ketal function derived from Cχ ~ to C 4 alkyl alcohols and the hydroxyl function possibly in the form an ether function derived from Ci to C 4 alkyl alcohols is present (ketals K), in the presence of Ci to C 4 alcohols (alcohols A), the molar ratio of the sum of orthoester O and the ketals K to the alcohols in the electrolyte A is 0.2: 1 to 5: 1.
2. Verfahren nach Anspruch 1, wobei es sich bei den Orthoestern I um Verbindungen der allgemeinen Formel I handelt,2. The method according to claim 1, wherein the orthoesters I are compounds of the general formula I,
OR3 OR 3
wobei die Reste die folgende Bedeutung habenwhere the residues have the following meaning
R1: Wasserstoff, Cι~ bis C2o-Alkyl-, C2- bis C2rj-Alkenyl, C2- bis C n-Alkinyl, C3- bis Cχ2-Cycloalkyl, C4- bis C 0-Cycloalkyl-alkyl, C4- bis Cι0-Aryl oder ggf. 1 bis 3-fach substituiert durch C^- bis Cs-Alkoxy oder Ci- bis Cs-AlkoxycarbonylR 1 : hydrogen, C 1 ~ to C 2 o-alkyl, C 2 - to C 2 rj-alkenyl, C 2 - to C n-alkynyl, C 3 - to Cχ 2 -cycloalkyl, C 4 - to C 0 - cycloalkyl-alkyl, C 4 - to Cι 0 aryl, or optionally 1 to 3 times substituted by C ^ - to Cs-alkoxy or Ci to Cs-alkoxycarbonyl
R2, R3: Ci- bis C20-Alkyl, C3- bis C12-Cycloalkyl, und C4- bis C o-Cycloalkyl-alkyl oder R2 und R3 gemeinsamR 2 , R 3 : Ci to C 20 alkyl, C 3 to C 12 cycloalkyl, and C 4 to C o-cycloalkylalkyl or R 2 and R 3 together
C - bis Cio-Alkylen bildenForm C - to Cio alkylene
R4: Ci- bis C4 Alkyl,R 4 : Ci to C 4 alkyl,
ausgehend von Ketalen II der allgemeinen Formel II starting from ketals II of the general formula II
wobei die Reste die folgende Bedeutung habenwhere the residues have the following meaning
R5 , R10 : die gleiche Bedeutung wie R1 R 5 , R 10 : the same meaning as R 1
R6, R7: die gleiche Bedeutung wie R2 R 6 , R 7 : the same meaning as R 2
RS: Wasserstoff unter der Bedingung, dass R9 die gleiche Bedeutung wie R1 hat, oder die gleiche Bedeu-- tung wie R2 RS : hydrogen under the condition that R 9 has the same meaning as R 1 , or the same meaning as R 2
R9: die gleiche Bedeutung wie R1 oder -O-R2.R 9 : the same meaning as R 1 or -OR 2 .
Verfahren nach Anspruch 2, wobei die Orthoester I der allgemeinen Formel I in Form einer Mischung mit Ketalen IV der allgemeinen Formel IVThe method of claim 2, wherein the orthoesters I of the general formula I in the form of a mixture with ketals IV of the general formula IV
OR13 OR 13
wobei die Reste die folgende Bedeutung haben:where the residues have the following meaning:
RU; die gleiche Bedeutung wie R4 R U ; the same meaning as R 4
R12, die gleiche Bedeutung wie R2 R 12 has the same meaning as R 2
R13 , R1 : die gleiche Bedeutung wie R1 R 13 , R 1 : the same meaning as R 1
gebildet werden, ausgehend von Ketalen II, bei denen es sich um solche handelt, bei denen R9 ausschliesslich die gleiche Bedeutung wie R1 hat .are formed, starting from ketals II, which are those in which R 9 has exclusively the same meaning as R 1 .
4. Verfahren nach Anspruch 1, wobei es sich bei den Orthoestern I um Verbindungen der allgemeinen Formel la, handelt, 4. The method according to claim 1, wherein the orthoesters I are compounds of the general formula Ia,
bei denen die Reste die folgende Bedeutung haben:where the residues have the following meaning:
R15 , R16 : die gleiche Bedeutung wie R2 R 15 , R 16 : the same meaning as R 2
iβ; die gleiche Bedeutung wie R2 i β ; the same meaning as R 2
R17 , R20: die gleiche Bedeutung wie R4,R 17 , R 20 : the same meaning as R 4 ,
Rl9: die gleiche Bedeutung wie R2 undR 19 : the same meaning as R 2 and
X C - bis Cι2-Alkylen bedeutet (Orthoester la) ,XC - to -C 2 alkylene means (orthoester la),
ausgehend von Ketalen der allgemeinen Formel Hastarting from ketals of the general formula Ha
bei denen die Reste die folgende Bedeutung haben: where the residues have the following meaning:
R21, R22 : die gleiche Bedeutung wie R2 R 21 , R 22 : the same meaning as R 2
R23: die gleiche Bedeutung wie R8 R 23 : the same meaning as R 8
R24: die gleiche Bedeutung wie R9 undR 24 : the same meaning as R 9 and
Y die gleiche Bedeutung wie X hat (Ketale Ha)Y has the same meaning as X (Ketale Ha)
Verfahren nach Anspruch 2, wobei es sich bei den Orthoestern I um Verbindungen handelt , in derThe method of claim 2, wherein the orthoesters I are compounds in which
Rl: Wasserstoff, Cι~ bis C6-Alkyl, R2, R3, R4: Methyl oder Ethyl (Orthoester Ic) ,R l : hydrogen, C 1 -C 6 -alkyl, R 2 , R 3 , R 4 : methyl or ethyl (orthoester Ic),
ausgehend von Ketalen II, bei denen die Reste die folgende Bedeutung haben: 5starting from ketals II, in which the residues have the following meaning: 5
R5, R10 : die gleiche Bedeutung wie R1 in Orthoester IcR 5 , R 10 : the same meaning as R 1 in Orthoester Ic
R6 bis R9 : die gleiche Bedeutung wie R2 oder R1 in Orthoester Ic (Ketale IIc) . 10R 6 to R 9 : the same meaning as R 2 or R 1 in Orthoester Ic (Ketale IIc). 10
6. Verfahren nach Anspruch 5, wobei es sich bei den Orthoestern I um Orthoameisensäuremethyl- oder ethylester oder Orthoes- sigsäuremethyl- oder ethylester (Orthoester Id) handelt, ausgehend von 1, 1, 2 , 2-Tetramethoxyethan bzw. 1, 1, 2 , 2-Tetraetho-6. The method according to claim 5, wherein the orthoesters I are ortho formic acid methyl or ethyl ester or ortho formate or methyl or ethyl ester (ortho ester Id), starting from 1, 1, 2, 2-tetramethoxyethane or 1, 1, 2 , 2-tetraetho-
15 xyethan (Ketale Ild) bzw. 1, 1, 2 , 2-Tetramethoxypropan bzw. 1, 1, 2 , 2-Tetraethoxypropan, bzw. 2 , 2 , 3 , 3-Tetramethoxybutan bzw. 2,2,3,3-Tetraethoxybutan.15 xyethane (Ketale Ild) or 1, 1, 2, 2-tetramethoxypropane or 1, 1, 2, 2-tetraethoxypropane, or 2, 2, 3, 3-tetramethoxybutane or 2,2,3,3- Tetraethoxybutan.
7. Verfahren nach den Ansprüchen 1 bis 6, wobei man das Verfah- 20 ren in einem Elektrolyten ausführt, der als Leitsalz Tetra7. The method according to claims 1 to 6, wherein one carries out the process in an electrolyte which is used as the conductive salt tetra
(Ci- bis C6-alkyl) ammonium- oder Tri(Cι- bis Cg-alkyl) -benzyl- ammoniumsalze mit Sulfat, Hydrogensulfat, Alkylsulfaten, Arylsulfaten, Halogeniden, Phosphaten, Carbonaten, Alkyl- phosphaten, Alkylcarbonaten, Nitrat, Alkoholaten, Tetrafluor- 25 borat oder Perchlorat als Gegenion.(Ci to C6 alkyl) ammonium or tri (Cι- to Cg-alkyl) -benzyl-ammonium salts with sulfate, hydrogensulfate, alkyl sulfates, phosphates, arylsulfates, halides, phosphates, carbonates, alkyl, alkyl carbonates, nitrate, alcoholates, Tetrafluoroborate or perchlorate as counter ion.
8. Verfahren nach den Ansprüchen 1 bis 7, wobei man als Leitsalz Methyltributyammoniumethylsulfat , Methyl-tripropylammoniumme- thylsulfat, Methyltriethylammoniummethylsulfat oder Tetrame-8. The method according to claims 1 to 7, wherein the main salt is methyl tributyammonium ethyl sulfate, methyl tripropylammonium methyl sulfate, methyl triethylammonium methyl sulfate or tetrame-
30 thylammonium ethylsulfat einsetzt.30 uses thylammonium ethyl sulfate.
9. Verfahren nach den Ansprüchen 1 bis 8 , wobei man das Verfahren in einer ungeteilten Elektrolysezelle ausführt.9. The method according to claims 1 to 8, wherein the method is carried out in an undivided electrolytic cell.
35 10. Verfahren nach den Ansprüchen 1 bis 9, wobei die Ladungsmenge pro Mol umgesetztem alpha-beta-Diketon oder alpha-beta-Hydro- xyketon 2 bis 4 F beträgt.35 10. The method according to claims 1 to 9, wherein the amount of charge per mole of converted alpha-beta-diketone or alpha-beta-hydroxy-ketone is 2 to 4 F.
4040
45 45
EP01980340A 2000-09-06 2001-09-05 Method for producing orthocarbonic acid trialkyl esters Expired - Lifetime EP1362022B1 (en)

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DE10043789A DE10043789A1 (en) 2000-09-06 2000-09-06 Electrochemical oxidation production of orthocarboxylic acid trialkyl esters from diketones or hydroxyketones in presence of alkanols is effected at specified molar ratios to improve yield and selectivity
PCT/EP2001/010216 WO2002020446A1 (en) 2000-09-06 2001-09-05 Method for producing orthocarbonic acid trialkyl esters

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CN107473945B (en) * 2016-06-08 2020-09-01 中国科学院大连化学物理研究所 Method for preparing tetramethoxymethane by catalyzing direct oxidation esterification of methanol
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