EP0164705B1 - Process for manufacturing phthalaldehydacetals - Google Patents
Process for manufacturing phthalaldehydacetals Download PDFInfo
- Publication number
- EP0164705B1 EP0164705B1 EP85107063A EP85107063A EP0164705B1 EP 0164705 B1 EP0164705 B1 EP 0164705B1 EP 85107063 A EP85107063 A EP 85107063A EP 85107063 A EP85107063 A EP 85107063A EP 0164705 B1 EP0164705 B1 EP 0164705B1
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- Prior art keywords
- bis
- benzene
- electrolysis
- alkanol
- phthalaldehyde
- 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.)
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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 electrochemical process for the production of phthalaldehyde acetals.
- Phthalaldehyde acetals can e.g. B. by reacting phthalaldehydes with o-esters (J. Chem. Soc. Perkin II, 1975, 1656).
- the phthalaldehydes required as starting materials are provided, for. B. by the Sommelet process from bis (chloromethyl) benzenes and hexamethylenetetramine. This z. B. in J. Chem. Soe.
- the process described in 1950, 2141 to 2145 provides only moderate yields and is not very environmentally friendly.
- phthalaldehyde acetals of the general formula in which R is an alkyl radical having 1 to 4 carbon atoms can advantageously be prepared by alkoxymethylbenzenes of the general formula
- alkoxymethylbenzenes of formula II such.
- B called: 1,2-, 1,3- or 1,4-bis (methoximethyl) benzene, 1,2-, 1,3- or 1,4-bis (ethoximethyl) benzene, 1, 2-, 1,3- or 1,4-bis (propoximethyl) benzene, 1,2-, 1,3- or 1,4-bis (isopropoximethyl) benzene and 1,2-, 1,3 - or 1,4-bis (tert. butoxmethyl) benzene.
- Alcohols of the formula ROH are e.g. B. methanol, ethanol, propamol and butanol.
- the electrochemical oxidation according to the invention can be carried out in technically customary electrolysis cells. Undivided flow cells are particularly suitable.
- a solution of the bis- (alkoxymethyl) benzene of the formula II in the alkanol is expediently used as the electrolyte, which solution may contain an auxiliary electrolyte to improve the conductivity.
- auxiliary electrolytes z.
- B. bases such as alkali metal alcoholates, neutral salts such as fluorides, tetrafluoroborates, sulfonates and sulfates and acids such as alkyl sulfonic acids, alkanesulfonic acids and sulfuric acid.
- Neutral auxiliary electrolytes such as KF and KSO 3 C 6 H 5 or acidic auxiliary electrolytes such as H Z S0 4 , CH 3 S0 3 H or C 6 H 5 S0 3 H are preferably used.
- anodes in the electrolysis according to the invention for. B. precious metals, metal oxides such as Ru0 2 and Pb0 2 or graphite.
- the preferred anode material is graphite.
- the current densities are 0.1 to 20 A / dm 3 , current densities between 2 and 8 A / dm 2 are preferred.
- the temperatures are advantageously at least 5'C below the boiling point of the alkanol used, provided the electrolysis is carried out without pressure. For example, electrolysis is carried out at -5 to 55 ° C, preferably 10 to 50 ° C.
- the electrolysis is carried out with 4 to 12 F / mol of bis (alkoxymethyl) benzene. It is preferably electrolyzed with 7 to 10 F / mol of bis (alkoxymethyl) benzene, so that the bis (alkoxymethyl) benzene is largely reacted.
- the electrolysis can be carried out batchwise or continuously.
- the electrolysis discharges are preferably worked up by distillation. Unreacted alkanol can be returned to the electrolysis without purification. Electrode inactivations or electrode corrosion are not observed even when the electrolyte is reused many times.
- the phthalaldehyde acetals obtainable by the process of the invention are intermediates e.g. B. for the production of dyes and optical brighteners and also serve for the synthesis of special polymers.
- the electrolyte was pumped through the cell at a flow rate of 200 l / h via a heat exchanger. After the electrolysis had ended, the electrolysis discharge was neutralized with sodium methylate. Then methanol was distilled off at normal pressure and 65 to 75 ° C. and the precipitated salt was separated off at 60 to 70 ° C. using a pressure filter. The residue was pure distilled at 100 to 120 ° C and 3 mbar. This gave 3.5 g of 1,4-bis (methoxymethyl) benzene and 222.2 g of terephthalaldialdehyde tetramethyl acetal.
- the electrolyte was pumped through the cell at a flow rate of 200 l / h via a heat exchanger.
- the electrolysis discharge was carried out as described in Example 1, but without adding sodium methylate.
- Working up gave 0.4 g of 1,4-bis (methoxymethyl) benzene and 158.2 g of terephthalaldehyde tetramethyl acetal. From this, a conversion of 1,4-bis (methoxymethyl) benzene of 99.7%, a yield of terephthalaldehyde tetramethyl acetal of 80.1% and a selectivity for terephthalaldehyde tetramethyl acetal of 80.4% are calculated.
- the recovered methanol and potassium benzene sulfonate could be used again for electrolysis.
- the electrolyte was pumped through the cell at a flow rate of 200 l / h via a heat exchanger. After the electrolysis had ended, methanol was distilled off from the electrolysis discharge at atmospheric pressure and 65 to 80 ° C. The precipitated potassium benzene sulfonate was separated off on a pressure filter and the filtrate was fractionally distilled at 100 to 120 ° C. and 5 mbar. This gave 3.8 g of 1,2-bis (methoxymethyl) benzene and 230.3 g of o-phthalaldehyde tetramethyl acetal.
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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)
Description
Diese Erfindung betrifft ein neues elektrochemisches Verfahren zur Herstellung von Phthalaldehydacetalen.This invention relates to a new electrochemical process for the production of phthalaldehyde acetals.
Phthalaldehydacetale lassen sich z. B. durch Umsetzung von Phthalaldehyden mit o-Estern herstellen (J. Chem. Soc. Perkin II, 1975, 1656). Die als Ausgangsstoffe benötigten Phthalaldehyde stellt man z. B. nach dem Sommelet-Verfahren aus Bis-(chlormethyl)-benzolen und Hexamethylentetramin her. Dieses z. B. in J. Chem. Soe. 1950, 2141 bis 2145 beschriebene Verfahren liefert nur mäßige Ausbeuten und ist wenig umweltfreundlich. Aus der DE-OS 31 08 790 ist ein Verfahren zur Herstellung von Phthalaldehydacetalen bekannt, bei dem man a, a, a', a'- Tetrahalogenxylole mit Alkalialkoholaten umsetzt. Von Nachteil ist bei dieser Synthese die schlechte Zugänglichkeit der Tetrahalogenxylole, die bei der Halogenierung von Xylolen nur in schlechten Selektivitäten im Gemisch mit Xylolen verschiedenen Halogenierungsgrads entstehen.Phthalaldehyde acetals can e.g. B. by reacting phthalaldehydes with o-esters (J. Chem. Soc. Perkin II, 1975, 1656). The phthalaldehydes required as starting materials are provided, for. B. by the Sommelet process from bis (chloromethyl) benzenes and hexamethylenetetramine. This z. B. in J. Chem. Soe. The process described in 1950, 2141 to 2145 provides only moderate yields and is not very environmentally friendly. From DE-OS 31 08 790 a process for the preparation of phthalaldehyde acetals is known, in which a, a, a ', a'-tetrahalo-xylenes are reacted with alkali metal alcoholates. A disadvantage of this synthesis is the poor accessibility of the tetrahalogen xylenes, which arise in the halogenation of xylenes only in poor selectivities in a mixture with xylenes of different degrees of halogenation.
Es wurde nun gefunden, daß man Phthalaldehydacetale der allgemeinen Formel
in Gegenwart eines Alkamols der Formel ROH, wobei R die obengenannte Bedeutung hat, elektrochemisch oxidiert. Es ist besonders überraschend, daß man nach dem Verfahrem der Erfindung gezielt die Oxidationsstufe der Dialdehyde in hoher Selektivität erreicht.electrochemically oxidized in the presence of an alkamol of the formula ROH, where R has the meaning given above. It is particularly surprising that the oxidation stage of the dialdehydes can be selectively achieved by the process of the invention.
Als Alkoxymethylbenzole der Formel II seien z. B. genannt: 1,2-, 1,3-oder 1,4-Bis-(methoximethyl)-benzol, 1,2-, 1,3- oder 1,4-Bis-(ethoximethyl)-benzol, 1,2-, 1,3- oder 1,4-Bis-(propoximethyl)-benzol, 1,2-, 1,3-oder 1,4-Bis-(isopropoximethyl)-benzol und 1,2-, 1,3- oder 1,4-Bis-(tert. butoxmethyl)-benzol. Alkohole der Formel ROH sind z. B. Methanol, Ethanol, Propamol und Butanol.As alkoxymethylbenzenes of formula II such. B. called: 1,2-, 1,3- or 1,4-bis (methoximethyl) benzene, 1,2-, 1,3- or 1,4-bis (ethoximethyl) benzene, 1, 2-, 1,3- or 1,4-bis (propoximethyl) benzene, 1,2-, 1,3- or 1,4-bis (isopropoximethyl) benzene and 1,2-, 1,3 - or 1,4-bis (tert. butoxmethyl) benzene. Alcohols of the formula ROH are e.g. B. methanol, ethanol, propamol and butanol.
Die erfindungsgemäße elektrochemische Oxidation kann in technisch üblichen Elektrolysezellen durchgeführt werden. Besonders gut geeignet sind ungeteilte Durchflußzellen. Als Elektrolyt wird zweckmäßigerweise eine Lösung des Bis-(alkoxymethyl)-benzols der Formel II in dem Alkanol eingesetzt, die zur Verbesserung der Leitfähigkeit einen Hilfselektrolyten enthalten kann. Als Hilfselektrolyte sind z. B. Basen, wie Alkalialkoholate, Neutralsalze wie Fluoride, Tetrafluoroborate, Sulfonate und Sulfate und Säuren wie Alkylsulfonsäuren, Alkansulfonsäuren und Schwefelsäure geeignet. Bevorzugt werden neutrale Hilfselektrolyte wie KF und KSO3C6H5 oder saure Hilfselektrolyte wie HZS04, CH3S03H oder C6H5S03H eingesetzt.The electrochemical oxidation according to the invention can be carried out in technically customary electrolysis cells. Undivided flow cells are particularly suitable. A solution of the bis- (alkoxymethyl) benzene of the formula II in the alkanol is expediently used as the electrolyte, which solution may contain an auxiliary electrolyte to improve the conductivity. As auxiliary electrolytes z. B. bases such as alkali metal alcoholates, neutral salts such as fluorides, tetrafluoroborates, sulfonates and sulfates and acids such as alkyl sulfonic acids, alkanesulfonic acids and sulfuric acid. Neutral auxiliary electrolytes such as KF and KSO 3 C 6 H 5 or acidic auxiliary electrolytes such as H Z S0 4 , CH 3 S0 3 H or C 6 H 5 S0 3 H are preferably used.
Der Elektrolyt hat beispielsweise folgende Zusammensetzung:
- 2 bis 30 Gew.% Bis-(alkoxymethyl)-benzol,
- 65 bis 98 Gew.% Alkanol
- 0,1 bis 5 Gew.% Hilfselektrolyt.
- 2 to 30% by weight of bis (alkoxymethyl) benzene,
- 65 to 98% by weight alkanol
- 0.1 to 5% by weight of auxiliary electrolyte.
Als Anoden werden bei der erfindungsgemäßen Elektrolyse z. B. Edelmetalle, Metalloxide, wie Ru02 und Pb02 oder Graphit eingesetzt. Bevorzugtes Anodenmaterial ist Graphit. Als Kathodenmaterialien kommeu z. B. Stahl, Eisen, Nickel, Blei oder Graphit in Betracht. Die Stromdichten betragen 0,1 bis 20 A/dm3, bevorzugt werden Stromdichten zwischen 2 und 8 A/dm2. Die Temperaturen liegen zweckmäßigerweise mindestens 5'C unter dem Siedepunkt des eingesetzten Alkanols, sofern die Elektrolyse drucklos durchgeführt wird. Beispielsweise elektrolysiert man bei -5 bis 55°C, vorzugsweise 10 bis 50°C. Die Elektrolyse wird mit 4 bis 12 F/Mol Bis-(alkoxymethyl)-benzol durchgeführt. Man elektrolysiert vorzugsweise mit 7 bis 10 F/Mol Bis-(alkoxymethyl)-benzol, so daß das Bis-(alkoxymethyl)-benzol weitgehend umgesetzt wird. Die Elektrolyse kann sowohl diskontinuierlich als auch kontinuierlich durchgeführt werden.As anodes in the electrolysis according to the invention, for. B. precious metals, metal oxides such as Ru0 2 and Pb0 2 or graphite. The preferred anode material is graphite. Come as cathode materials z. B. steel, iron, nickel, lead or graphite. The current densities are 0.1 to 20 A / dm 3 , current densities between 2 and 8 A / dm 2 are preferred. The temperatures are advantageously at least 5'C below the boiling point of the alkanol used, provided the electrolysis is carried out without pressure. For example, electrolysis is carried out at -5 to 55 ° C, preferably 10 to 50 ° C. The electrolysis is carried out with 4 to 12 F / mol of bis (alkoxymethyl) benzene. It is preferably electrolyzed with 7 to 10 F / mol of bis (alkoxymethyl) benzene, so that the bis (alkoxymethyl) benzene is largely reacted. The electrolysis can be carried out batchwise or continuously.
Die Aufarbeitung der Elektrolyseausträge erfolgt vorzugsweise destillativ. Nicht umgesetztes Alkanol kann ohne Reinigung zur Elektrolyse rückgeführt werden. Elektrodeninaktivierungen oder Elektrodenkorrosion werden auch bei vielfacher Wiederverwendung des Elektrolyten nicht beobachtet.The electrolysis discharges are preferably worked up by distillation. Unreacted alkanol can be returned to the electrolysis without purification. Electrode inactivations or electrode corrosion are not observed even when the electrolyte is reused many times.
Die nach dem Verfahren der Erfindung erhältlichen Phthalaldehydacetale sind Zwischenprodukte z. B. für die Herstellung von Farbstoffen und optischen Aufhellern und dienen auch zur Synthese spezieller Polymerer.The phthalaldehyde acetals obtainable by the process of the invention are intermediates e.g. B. for the production of dyes and optical brighteners and also serve for the synthesis of special polymers.
Elektrosynthese von Terephthaldialdehydtetramethylacetal
Bei der Elektrolyse unter den angegebenen Bedingungen wurde der Elektrolyt mit einer Strömungsgeschwindigkeit von 200 I/h über einen Wärmetauscher durch die Zelle gepumpt. Nach Beendigung der Elektrolyse wurde der Elektrolyseaustrag mit Natriummethylat neutralisiert. Dann wurde Methanol bei Normaldruck und 65 bis 75°C abdestilliert und das ausgefallene Salz bei 60 bis 70°C über eine Drucknutsche abgetrennt. Der Rückstand wurde bei 100 bis 120°C und 3 mbar reindestilliert. Hierbei wurden 3,5 g 1,4-Bis-(methoxymethyl)-benzol und 222,2 g Terephthaldialdehydtetramethylacetal erhalten. Hieraus errechnet sich ein Umsatz an 1,4-Bis-(methoxymethyl)-benzol von 98,7 %, eine Ausbeute an Terephthaldialdehydtetramethylacetal von 62,1 % und eine Selektivität für Terephthaldialdehydtetramethylacetal von 62,9 %. Das zurückgewonnene 1,4-Bis-(methoxymethyl)-benzol ließ sich erneut für eine Elektrolyse verwenden.During the electrolysis under the specified conditions, the electrolyte was pumped through the cell at a flow rate of 200 l / h via a heat exchanger. After the electrolysis had ended, the electrolysis discharge was neutralized with sodium methylate. Then methanol was distilled off at normal pressure and 65 to 75 ° C. and the precipitated salt was separated off at 60 to 70 ° C. using a pressure filter. The residue was pure distilled at 100 to 120 ° C and 3 mbar. This gave 3.5 g of 1,4-bis (methoxymethyl) benzene and 222.2 g of terephthalaldialdehyde tetramethyl acetal. From this, a conversion of 1,4-bis (methoxymethyl) benzene of 98.7%, a yield of terephthalaldehyde tetramethyl acetal of 62.1% and a selectivity for terephthalaldehyde tetramethyl acetal of 62.9% are calculated. The recovered 1,4-bis (methoxymethyl) benzene could be used again for electrolysis.
Elektrosynthese von TerephthaldialdehydtetramethylacetalElectrosynthesis of terephthalaldehyde tetramethyl acetal
Bei der Elektrolyse unter den angegebenen Bedingungen wurde der Elektrolyt mit einer Strömungsgeschwindigkeit von 200 I/h über einen Wärmetauscher durch die Zelle gepumpt. Der Elektrolyseaustrag wurde wie in Beispiel 1 beschrieben, jedoch ohne Zugabe von Natriummethylat aufgearbeitet. Bei der Aufarbeitung wurden 0,4 g 1,4-Bis-(methoxymethyl)-benzol und 158,2 g Terephthalaldehydtetramethylacetal erhalten. Hieraus errechnet sich ein Umsatz an 1,4-Bis-(methoxymethyl)-benzol von 99,7 %, eine Ausbeute an Terephthaldialdehydtetramethylacetal von 80,1 % und eine Selektivität für Terephthaldialdehydtetramethylacetal von 80,4 %. Das zurückgewonnene Methanol und Kaliumbenzolsulfonat ließen sich erneut für eine Elektrolyse verwenden.During the electrolysis under the specified conditions, the electrolyte was pumped through the cell at a flow rate of 200 l / h via a heat exchanger. The electrolysis discharge was carried out as described in Example 1, but without adding sodium methylate. Working up gave 0.4 g of 1,4-bis (methoxymethyl) benzene and 158.2 g of terephthalaldehyde tetramethyl acetal. From this, a conversion of 1,4-bis (methoxymethyl) benzene of 99.7%, a yield of terephthalaldehyde tetramethyl acetal of 80.1% and a selectivity for terephthalaldehyde tetramethyl acetal of 80.4% are calculated. The recovered methanol and potassium benzene sulfonate could be used again for electrolysis.
Elektrosynthese von o-PhthaldialdehydtetramethylacetalElectrosynthesis of o-phthaldialdehyde tetramethyl acetal
Bei der Elektrolyse unter den angegebenen Bedingungen wurde der Elektrolyt mit einer Strömungsgeschwindigkeit von 200 I/h über einen Wärmetauscher durch die Zelle gepumpt. Nach Beendigung der Elektrolyse wurde vom Elektrolyseaustrag Methanol bei Normaldruck und 65 bis 80°C abdestilliert. Das ausgefallene Kaliumbenzolsulfonat wurde über eine Drucknutsche abgetrennt und das Filtrat bei 100 bis 120°C und 5 mbar fraktioniert destilliert. Hierbei wurden 3,8 g 1,2-Bis-(methoxymethyl)-benzol und 230,3 g o-Phthaldialdehydtetramethylacetal erhalten. Hieraus errechnet sich ein Umsatz an 1,2-Bis-(methoxymethyl)-benzol von 98,6 %, eine Ausbeute an o-Phthaldialdehydtetramethylacetal von 64,3 % und eine Selektivität für o-Phthaldialdehydtetramethylacetal von 65,3 %. Zurückgewonnenes Kaliumbenzolsulfonat und Methanol ließen sich ermeut für eine Elektrolyse verwenden.During the electrolysis under the specified conditions, the electrolyte was pumped through the cell at a flow rate of 200 l / h via a heat exchanger. After the electrolysis had ended, methanol was distilled off from the electrolysis discharge at atmospheric pressure and 65 to 80 ° C. The precipitated potassium benzene sulfonate was separated off on a pressure filter and the filtrate was fractionally distilled at 100 to 120 ° C. and 5 mbar. This gave 3.8 g of 1,2-bis (methoxymethyl) benzene and 230.3 g of o-phthalaldehyde tetramethyl acetal. From this, a conversion of 1,2-bis (methoxymethyl) benzene of 98.6%, a yield of o-phthalaldehyde tetramethyl acetal of 64.3% and a selectivity for o-phthalaldehyde tetramethyl acetal of 65.3% are calculated. Recovered potassium benzene sulfonate and methanol could only be used for electrolysis.
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3421976 | 1984-06-14 | ||
| DE19843421976 DE3421976A1 (en) | 1984-06-14 | 1984-06-14 | METHOD FOR PRODUCING PHTHALALDEHYDACETALES |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0164705A2 EP0164705A2 (en) | 1985-12-18 |
| EP0164705A3 EP0164705A3 (en) | 1986-04-23 |
| EP0164705B1 true EP0164705B1 (en) | 1987-09-02 |
Family
ID=6238274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85107063A Expired EP0164705B1 (en) | 1984-06-14 | 1985-06-07 | Process for manufacturing phthalaldehydacetals |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0164705B1 (en) |
| JP (1) | JPH0647746B2 (en) |
| DE (2) | DE3421976A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3913166A1 (en) * | 1989-04-21 | 1990-10-25 | Basf Ag | METHOD FOR PRODUCING BENZALDEHYDDIALKYLACETALS AND NEW BENZALDEHYDDIALKYLACETALS AND BENZYL ESTERS |
| DE4122314A1 (en) * | 1991-07-05 | 1993-01-07 | Basf Ag | O-PHTHALDIALDEHYDTETRAALKYLACETALES, THEIR PREPARATION AND THEIR USE AS DEPOT CONNECTIONS |
| DE4201544A1 (en) * | 1992-01-22 | 1993-07-29 | Basf Ag | METHOD FOR THE PRODUCTION OF BENZALDEHYDACETALES |
| DE4308846A1 (en) * | 1993-03-19 | 1994-09-22 | Basf Ag | Process for the preparation of terephthalaldehyde tetraalkylacetals |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4318783A (en) * | 1978-11-30 | 1982-03-09 | Bayer Aktiengesellschaft | Process for the preparation of optionally substituted benzaldehyde dialkyl acetals |
| DE3048992A1 (en) * | 1980-12-24 | 1982-07-15 | Hoechst Ag, 6000 Frankfurt | 4,4'-DIPHENYL ETHER-DIALDEHYDE-BIS-DIMETHYL ACETAL AND A METHOD FOR THE PRODUCTION THEREOF |
| DE3108790A1 (en) * | 1981-03-07 | 1982-09-16 | Dynamit Nobel Ag, 5210 Troisdorf | Process for the preparation of bis(dialkoxymethyl)benzenes |
-
1984
- 1984-06-14 DE DE19843421976 patent/DE3421976A1/en not_active Withdrawn
-
1985
- 1985-06-07 DE DE8585107063T patent/DE3560532D1/en not_active Expired
- 1985-06-07 EP EP85107063A patent/EP0164705B1/en not_active Expired
- 1985-06-14 JP JP60128382A patent/JPH0647746B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0647746B2 (en) | 1994-06-22 |
| DE3421976A1 (en) | 1985-12-19 |
| EP0164705A3 (en) | 1986-04-23 |
| JPS6112886A (en) | 1986-01-21 |
| EP0164705A2 (en) | 1985-12-18 |
| DE3560532D1 (en) | 1987-10-08 |
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