EP0152801A2 - Process for manufacturing benzaldehyde dialkylacetals - Google Patents

Process for manufacturing benzaldehyde dialkylacetals Download PDF

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Publication number
EP0152801A2
EP0152801A2 EP85100746A EP85100746A EP0152801A2 EP 0152801 A2 EP0152801 A2 EP 0152801A2 EP 85100746 A EP85100746 A EP 85100746A EP 85100746 A EP85100746 A EP 85100746A EP 0152801 A2 EP0152801 A2 EP 0152801A2
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Prior art keywords
electrolyte
electrolysis
benzaldehyde
alkanol
electrolyte contains
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German (de)
French (fr)
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EP0152801B1 (en
EP0152801A3 (en
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Dieter Dr. Degner
Eckhard Roske
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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

  • This invention relates to a new process for the preparation of benzaldehyde dialkyl acetals by electrooxidation of benzyl alkyl ethers.
  • the electrochemical oxidation of toluene derivatives in the presence of an alkanol to the corresponding benzaldehyde dialkyl acetals is e.g. from J. Chem. Soc. Perkin 1 (1978) 708 to 715, DE-PS 28 48 397 or EP-PS 12 240 known.
  • the benzaldehyde dialkyl acetals are only obtained with good selectivity if the toluene derivative used has a substituent with electron donor properties in the 4-position.
  • the unsubstituted toluene can only be converted into the dialkylacetals of benzaldehyde in very poor selectivities under the conditions of electrooxidation (see FR-PS 2 351 932).
  • the process according to the invention can be carried out in electrolysis cells which are conventional per se.
  • An undivided flow cell with a bipolar electrode arrangement is particularly suitable.
  • Precious metals such as Pt or metal oxides such as Pb0 2 or Ru0 2 are suitable as anode materials.
  • the preferred anode material is graphite.
  • the electrolyte consists of the benzyl alkyl ether, the alcohol and a basic electrolyte.
  • Bases, neutral salts and acids can be used as the basic electrolyte.
  • Bases are, for example, alkali hydroxides, such as NaOH or KOH, and alkali alcoholates, such as NaOCH 3 .
  • Fluorides such as KF, sulfonates such as KS0 3 C 6 H 5 or alkyl sulfates such as (CH 3 ) 4 N + SO 4 CH - are used as neutral salts.
  • acids used are sulfuric acids or sulfonic acids, such as CH 3S 0 3H or C 6 H 5 SO 3 H.
  • acidic or neutral electrolytes are preferably used.
  • the electrolyte composition can be varied within wide limits.
  • An electrolyte is preferably used which has a content of 10 to 50% by weight of the benzyl alkyl ether and 50 to 90% by weight of the alcohol, the electrolyte additionally also 0.1 to 5% by weight, based on the mixture from benzyl alkyl ether and alcohol, an acid or a neutral salt.
  • Electrolysis is carried out at current densities of, for example, 0.5 to 20 A / dm 2 , preferably 2 to 10 A / dm 2.
  • the temperatures during the electrolysis can likewise be chosen within wide limits.
  • Electrolysis is preferably carried out at temperatures up to 5 ° C. below the boiling point of the alkanol.
  • a great advantage of the process is that more than 50% of the benzylalkyl ethers can be converted without reducing the selectivity of the electrooxidation.
  • the alkanols which also serve as solvents, can be returned to the electrolysis without any intermediate cleaning, without the electrolysis being adversely affected by the formation of deposits on the electrodes, as is frequently observed in industrial organic electrolysis.
  • the method can thus also be carried out continuously in a simple manner.
  • the benzaldehyde alkyl acetals obtained by the process are valuable fragrances.
  • the electrolyte is pumped through the cell at 200 l / h during the electrolysis.
  • the electrolyte is pumped through the cell at 200 l / h during the electrolysis.
  • Electrosynthesis of benzaldehyde dimethyl acetal (basic electrolyte) The electrolyte is pumped through the cell at 200 l / h during the electrolysis.
  • the electrolyte is pumped through the cell at 200 l / h during the electrolysis.
  • the electrolysis discharge is first neutralized with NaOH. Then ethanol is distilled off at normal pressure and 75 to 90 ° C. The precipitated salt is separated off on a suction filter and the filtrate is fractionated at 80 to 100 ° C. and 10 to 20 torr. This gives 123.6 g of benzyl ethyl ether and 262.5 g of benzaldehyde diethylacetal. This results in a conversion of benzyl ethyl ether of 64.2 Z, a yield of benzaldehyde diethylacetal of 57.5% and a selectivity for benzaldehyde diethylacetal of 89.6%.

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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)

Abstract

1. A process for the preparation of a benzaldehyde dialkylacetal of the general formula see diagramm : EP0152801,P4,F3 where R is methyl or ethyl, wherein a benzyl alkylether of the general formula see diagramm : EP0152801,P4,F4 is oxidized electrochemically in the absence of toluene and in the presence of an alcohol of the formula ROH and of a base electrolyte.

Description

Diese Erfindung betrifft ein neues Verfahren zur Herstellung von Benzaldehyddialkylacetalen durch Elektrooxidation von Benzylalkylethern.This invention relates to a new process for the preparation of benzaldehyde dialkyl acetals by electrooxidation of benzyl alkyl ethers.

Die elektrochemische Oxidation von Toluolderivaten in Gegenwart eines Alkanols zu den entsprechenden Benzaldehyddialkylacetalen ist z.B. aus J. Chem. Soc. Perkin 1 (1978) 708 bis 715, DE-PS 28 48 397 oder EP-PS 12 240 bekannt. Bei diesen Verfahren werden die Benzaldehyddialkylacetale nur dann in guter Selektivität erhalten, wenn das eingesetzte Toluolderivat in 4-Stellung einen Substituenten mit Elektronendonatoreigenschaften aufweist. Das unsubstituierte Toluol läßt sich unter den Bedingungen der Elektrooxidation nur in sehr schlechten Selektivitäten in die Dialkylacetale des Benzaldehyds überführen (s. FR-PS 2 351 932).The electrochemical oxidation of toluene derivatives in the presence of an alkanol to the corresponding benzaldehyde dialkyl acetals is e.g. from J. Chem. Soc. Perkin 1 (1978) 708 to 715, DE-PS 28 48 397 or EP-PS 12 240 known. In these processes, the benzaldehyde dialkyl acetals are only obtained with good selectivity if the toluene derivative used has a substituent with electron donor properties in the 4-position. The unsubstituted toluene can only be converted into the dialkylacetals of benzaldehyde in very poor selectivities under the conditions of electrooxidation (see FR-PS 2 351 932).

Es wurde nun gefunden, daß man Benzaldehyddialkylacetale der allgemeinen Formel

Figure imgb0001
in der R eine Methyl- oder Ethylgruppe bedeutet, mit sehr guter Selektivität erhält, wenn man Benzylalkylether der allgemeinen Formel
Figure imgb0002
 It has now been found that benzaldehyde dialkyl acetals of the general formula
Figure imgb0001
 in which R represents a methyl or ethyl group, with very good selectivity, if benzyl alkyl ethers of the general formula
Figure imgb0002

in Gegenwart eines Alkohols der Formel ROH elektrochemisch oxidiert.electrochemically oxidized in the presence of an alcohol of the formula ROH.

Das erfindungsgemäße Verfahren läßt sich in an sich üblichen Elektrolysezellen durchführen. Besonders gut eignet sich eine ungeteilte Durchflußzelle mit bipolarer Elektrodenanordnung. Als Anodenmaterialien kommen Edelmetalle, wie Pt oder Metalloxide, wie Pb02 oder Ru02 in Betracht. Bevorzugtes Anodenmaterial ist Graphit.The process according to the invention can be carried out in electrolysis cells which are conventional per se. An undivided flow cell with a bipolar electrode arrangement is particularly suitable. Precious metals such as Pt or metal oxides such as Pb0 2 or Ru0 2 are suitable as anode materials. The preferred anode material is graphite.

Als Kathodenmaterialien lassen sich z.B. Edelmetalle, wie Platin, andere Metalle, wie Nickel oder Eisen bzw. Metallegierungen, wie Stahl einsetzen. Auch Graphit ist als Kathodenmaterial geeignet. Der Elektrolyt setzt sich aus dem Benzylalkylether, dem Alkohol und einem Grundelektrolyten zusammen. Als Grundelektrolyt kommen Basen, Neutralsalze und Säuren in Frage. Basen sind z.B. Alkalihydroxide, wie NaOH oder KOH sowie Alkalialkoholate wie NaOCH3. Als Neutralsalze werden Fluoride, wie KF, Sulfonate, wie KS03C6H5 oder Alkylsulfate wie (CH3)4N+ SO4CH- eingesetzt. Als Säuren dienen beispielsweise Schwefelsäuren oder Sulfonsäuren, wie CH3S03H oder C6H5SO3H. Bei dem erfindungsgemäßen Verfahren werden bevorzugt saure oder neutrale Elektrolyte eingesetzt. Die Elektrolytzusammensetzung kann in weiten Grenzen variiert werden. Vorzugsweise wird ein Elektrolyt verwendet, der einen Gehalt an dem Benzylalkylether von 10 bis 50 Gew.% und an dem Alkohol von 50 bis 90 Gew.X aufweist, wobei der Elektrolyt außerdem noch 0,1 bis 5 Gew.X, bezogen auf das Gemisch aus Benzylalkylether und Alkohol, einer Säure oder eines Neutralsalzes enthält.For example, noble metals such as platinum, other metals such as nickel or iron or metal alloys such as steel can be used as cathode materials. Graphite is also suitable as the cathode material. The electrolyte consists of the benzyl alkyl ether, the alcohol and a basic electrolyte. Bases, neutral salts and acids can be used as the basic electrolyte. Bases are, for example, alkali hydroxides, such as NaOH or KOH, and alkali alcoholates, such as NaOCH 3 . Fluorides such as KF, sulfonates such as KS0 3 C 6 H 5 or alkyl sulfates such as (CH 3 ) 4 N + SO 4 CH - are used as neutral salts. Examples of acids used are sulfuric acids or sulfonic acids, such as CH 3S 0 3H or C 6 H 5 SO 3 H. In the process according to the invention, acidic or neutral electrolytes are preferably used. The electrolyte composition can be varied within wide limits. An electrolyte is preferably used which has a content of 10 to 50% by weight of the benzyl alkyl ether and 50 to 90% by weight of the alcohol, the electrolyte additionally also 0.1 to 5% by weight, based on the mixture from benzyl alkyl ether and alcohol, an acid or a neutral salt.

Man elektrolysiert bei Stromdichten von z.B. 0,5 bis 20 A/dm2, bevorzugt bei 2 bis 10 A/dm2. Die Temperaturen während der Elektrolyse können ebenfalls in weiten Grenzen gewählt werden. Vorzugsweise elektrolysiert man bei Temperaturen bis zu 5°C unterhalb des Siedepunktes des Alkanols. Ein großer Vorteil des Verfahrens ist es, daß die Benzylalkylether zu über 50 % umgesetzt werden können, ohne daß die Selektivität der Elektrooxidation absinkt. Weiterhin können die Alkanole, die zugleich als Lösungsmittel dienen, ohne jegliche Zwischenreinigung zur Elektrolyse rückgeführt werden, ohne daß es, wie häufig bei technischen organischen Elektrolysen beobachtet, durch Belagsbildung auf den Elektroden zu einer Beeinträchtigung der Elektrolyse kommt. Das Verfahren ist somit auch kontinuierlich auf einfache Weise durchführbar.Electrolysis is carried out at current densities of, for example, 0.5 to 20 A / dm 2 , preferably 2 to 10 A / dm 2. The temperatures during the electrolysis can likewise be chosen within wide limits. Electrolysis is preferably carried out at temperatures up to 5 ° C. below the boiling point of the alkanol. A great advantage of the process is that more than 50% of the benzylalkyl ethers can be converted without reducing the selectivity of the electrooxidation. Furthermore, the alkanols, which also serve as solvents, can be returned to the electrolysis without any intermediate cleaning, without the electrolysis being adversely affected by the formation of deposits on the electrodes, as is frequently observed in industrial organic electrolysis. The method can thus also be carried out continuously in a simple manner.

Die nach dem Verfahren erhaltenen Benzaldehydalkylacetale sind wertvolle Riechstoffe.The benzaldehyde alkyl acetals obtained by the process are valuable fragrances.

Das erfindungsgemäße Verfahren wird an folgenden Beispielen weiter verdeutlicht.The process according to the invention is further illustrated in the following examples.

Beispiel 1example 1

Elektrosynthese von Benzaldehyddimethylacetal (neutraler Elektrolyt-

Figure imgb0003
Electrosynthesis of benzaldehyde dimethyl acetal (neutral electrolyte
Figure imgb0003

Der Elektrolyt wird während der Elektrolyse mit 200 1/h durch die Zelle gepumpt.The electrolyte is pumped through the cell at 200 l / h during the electrolysis.

Aufarbeitung: Zunächst wird Methanol bei Normaldruck und 60 bis 70°C abdestilliert, dann das ausgefallene Leitsalz KF über eine Drucknutsche abgetrennt und das erhaltene Filtrat bei 80 bis 120°C und 10 bis 30 Torr reindestilliert. Hierbei erhält man neben 56,6 g Benzylmethylether (kann mit CH30H/KF zur Elektrolyse rückgeführt werden) 207,2 g Benzaldehyddimethylacetal. Hieraus ergibt sich ein Umsatz an Benzylmethylether von 78,1 X, eine Ausbeute an Benzaldeyhddimethylacetal von 64,4 % und eine Selektivität für Benzaldehyddimethylacetal von 82,6 %.Working up: First, methanol is distilled off at normal pressure and 60 to 70 ° C., then the precipitated conductive salt KF is separated off using a pressure filter and the filtrate obtained is distilled in at 80 to 120 ° C. and 10 to 30 torr. In addition to 56.6 g of benzyl methyl ether (can be recycled to CH 3 0H / KF for electrolysis), 207.2 g of benzaldehyde dimethyl acetal are obtained. This results in a conversion of benzyl methyl ether of 78.1 X, a yield of benzaldehyde dimethyl acetal of 64.4% and a selectivity for benzaldehyde dimethyl acetal of 82.6%.

Beispiel 2Example 2

Elektrosynthese von Benzaldeyhddimethylacetal (saurer Elektrolyt)Electrosynthesis of benzaldehyde dimethyl acetal (acid electrolyte)

Figure imgb0004
Der Elektrolyt wird während der Elektrolyse mit 200 1/h durch die Zelle gepumpt.
Figure imgb0004
 The electrolyte is pumped through the cell at 200 l / h during the electrolysis.

Aufarbeitung: Der Elektrolyseaustrag wird mit NaOCH3 neutralisiert und dann analog Beispiel 1 aufgearbeitet. Hierbei erhält man 21,2 g Benzylmethylether und 355,7 g Benzaldehyddimethylacetal. Hieraus ergibt sich ein Umsatz an Benzylmethylether von 95,4 %, eine Ausbeute an Benzaldehyddialkylacetal von 62,5 % und eine Selektivität für Benzaldehyddialkylacetal von 65,5 %.Workup: The electrolysis discharge is neutralized with NaOCH 3 and then worked up analogously to Example 1. This gives 21.2 g of benzyl methyl ether and 355.7 g of benzaldehyde dimethyl acetal. This results in a conversion of benzyl methyl ether of 95.4%, a yield of benzaldehyde dialkyl acetal of 62.5% and a selectivity for benzaldehyde dialkyl acetal of 65.5%.

Beispiel 3Example 3

Elektrosynthese von Benzaldehyddimethylacetal (basischer Elektrolyt)

Figure imgb0005
Der Elektrolyt wird während der Elektrolyse mit 200 1/h durch die Zelle gepumpt.Electrosynthesis of benzaldehyde dimethyl acetal (basic electrolyte)
Figure imgb0005
 The electrolyte is pumped through the cell at 200 l / h during the electrolysis.

Aufarbeitung: Der Elektrolyseaustrag wird analog Beispiel 1 aufgearbeitet. Man erhält 115,1 g Benzylmethylether und 138,7 g Benzaldehyddimethylacetal. Hieraus ergibt sich ein Umsatz an Benzylmethylether von 68,0 %, eine Ausbeute an Benzyladehyddimethylacetal von 30,9 Z und eine Selektivität für Benzaldehyddimethylacetal von 45,5 %.Working up: The electrolysis discharge is worked up analogously to Example 1. 115.1 g of benzyl methyl ether and 138.7 g of benzaldehyde dimethyl acetal are obtained. This results in a conversion of benzyl methyl ether of 68.0%, a yield of benzyladehyddimethylacetal of 30.9 Z and a selectivity for benzaldehyde dimethyl acetal of 45.5%.

Beispiel 4Example 4

Elektrosynthese von Benzaldehyddiethylacetal

Figure imgb0006
Electrosynthesis of benzaldehyde diethylacetal
Figure imgb0006

Der Elektrolyt wird während der Elektrolyse mit 200 1/h durch die Zelle gepumpt.The electrolyte is pumped through the cell at 200 l / h during the electrolysis.

Aufarbeitung: Der Elektrolyseaustrag wird zunächst mit NaOH neutralisiert. Dann wird Ethanol bei Normaldruck und 75 bis 90°C abdestilliert. Das ausgefallene Salz wird über eine Drucknutsche abgetrennt und das Filtrat bei 80 bis 100°C und 10 bis 20 Torr fraktioniert. Hierbei erhält man 123,6 g Benzylethylether und 262,5 g Benzaldehyddiethylacetal. Hieraus ergibt sich ein Umsatz an Benzylethylether von 64,2 Z, eine Ausbeute an Benzaldehyddiethylacetal von 57,5 % und eine Selektivität für Benzaldeyhddiethylacetal von 89,6 %.Processing: The electrolysis discharge is first neutralized with NaOH. Then ethanol is distilled off at normal pressure and 75 to 90 ° C. The precipitated salt is separated off on a suction filter and the filtrate is fractionated at 80 to 100 ° C. and 10 to 20 torr. This gives 123.6 g of benzyl ethyl ether and 262.5 g of benzaldehyde diethylacetal. This results in a conversion of benzyl ethyl ether of 64.2 Z, a yield of benzaldehyde diethylacetal of 57.5% and a selectivity for benzaldehyde diethylacetal of 89.6%.

Claims (8)

1. Verfahren zur Herstellung von Benzaldehyddialkylacetalen der allgemeinen Formel
Figure imgb0007
in der R eine Methyl- oder Ethylgruppe bedeutet, dadurch gekennzeichnet, daß man Benzylalkylether der allgemeinen Formel
Figure imgb0008
in Gegenwart eines Alkohols der Formel ROH elektrochemisch oxidiert.1. Process for the preparation of benzaldehyde dialkyl acetals of the general formula
Figure imgb0007
 in which R represents a methyl or ethyl group, characterized in that benzylalkyl ethers of the general formula
Figure imgb0008
 electrochemically oxidized in the presence of an alcohol of the formula ROH. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Elektrolyse in einer ungeteilten Durchflußzelle an Graphitanoden durchführt.2. The method according to claim 1, characterized in that one carries out the electrolysis in an undivided flow cell on graphite anodes. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Elektrolyt Neutralsalze enthält.3. The method according to claim 1, characterized in that the electrolyte contains neutral salts. 4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Elektrolyt Kaliumfluorid oder Kaliumbenzosulfonat enthält.4. The method according to claim 1, characterized in that the electrolyte contains potassium fluoride or potassium benzosulfonate. 5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Elektrolyt Säuren enthält.5. The method according to claim 1, characterized in that the electrolyte contains acids. 6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Elektrolyt Schwefelsäure, Methylschwefelsäure oder Benzolsulfonsäure enthält.6. The method according to claim 1, characterized in that the electrolyte contains sulfuric acid, methyl sulfuric acid or benzenesulfonic acid. 7. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man einen Elektrolyten verwendet, der einen Gehalt an Benzylalkylether von 10 bis 50 Gew.% und einem Gehalt an Alkanol von 90 bis 50 Gew.X aufweist, und der zusätzlich, bezogen auf das Gemisch aus Benzylalkylether und Alkanol, 0,1 bis 5 Gew.% einer Säure oder eines Neutralsalzes enthält.7. The method according to claim 1, characterized in that one uses an electrolyte which has a benzyl alkyl ether content of 10 to 50 wt.% And an alkanol content of 90 to 50 wt. X, and additionally, based on the mixture from benzyl alkyl ether and alkanol, contains 0.1 to 5% by weight of an acid or a neutral salt. 8. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Elektrolysen bei Stromdichten von 0,5 bis 20 A/dm2 und Temperaturen bis zu 5°C unterhalb der Siedetemperatur des Alkanols durchführt.8. The method according to claim 1, characterized in that one carries out the electrolysis at current densities of 0.5 to 20 A / dm 2 and temperatures up to 5 ° C below the boiling point of the alkanol.
EP85100746A 1984-02-03 1985-01-25 Process for manufacturing benzaldehyde dialkylacetals Expired EP0152801B1 (en)

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DE19843403789 DE3403789A1 (en) 1984-02-03 1984-02-03 METHOD FOR PRODUCING BENZALDEHYDDIALKYL ACETALES
DE3403789 1984-02-03

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EP0152801A2 true EP0152801A2 (en) 1985-08-28
EP0152801A3 EP0152801A3 (en) 1985-09-25
EP0152801B1 EP0152801B1 (en) 1987-05-27

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0283807A1 (en) * 1987-03-14 1988-09-28 BASF Aktiengesellschaft Process for the preparation of methoxyacetaldehyde dialkyl acetals
EP0393668A2 (en) * 1989-04-21 1990-10-24 BASF Aktiengesellschaft Method of preparation of benzaldehyde dialkyl acetals and new benzaldehyde dialkyl acetals
EP0554564A1 (en) * 1992-01-22 1993-08-11 BASF Aktiengesellschaft Process for preparing benzaldehyde acetals

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0011712A2 (en) * 1978-11-08 1980-06-11 BASF Aktiengesellschaft Preparation of benzaldehyde dialkyl acetals substituted in the 4-position

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0011712A2 (en) * 1978-11-08 1980-06-11 BASF Aktiengesellschaft Preparation of benzaldehyde dialkyl acetals substituted in the 4-position

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0283807A1 (en) * 1987-03-14 1988-09-28 BASF Aktiengesellschaft Process for the preparation of methoxyacetaldehyde dialkyl acetals
EP0393668A2 (en) * 1989-04-21 1990-10-24 BASF Aktiengesellschaft Method of preparation of benzaldehyde dialkyl acetals and new benzaldehyde dialkyl acetals
EP0393668A3 (en) * 1989-04-21 1991-01-23 BASF Aktiengesellschaft Method of preparation of benzaldehyde dialkyl acetals and new benzaldehyde dialkyl acetals
US5078838A (en) * 1989-04-21 1992-01-07 Basf Aktiengesellschaft Preparation of benzaldehyde dialkyl acetals and novel benzaldehyde dialkyl acetals and benzyl esters
EP0554564A1 (en) * 1992-01-22 1993-08-11 BASF Aktiengesellschaft Process for preparing benzaldehyde acetals

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EP0152801B1 (en) 1987-05-27
DE3403789A1 (en) 1985-08-08
EP0152801A3 (en) 1985-09-25
DE3560200D1 (en) 1987-07-02

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