EP0212512A1 - Process for manufacturing carbamic-acid esters - Google Patents
Process for manufacturing carbamic-acid esters Download PDFInfo
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- EP0212512A1 EP0212512A1 EP86111022A EP86111022A EP0212512A1 EP 0212512 A1 EP0212512 A1 EP 0212512A1 EP 86111022 A EP86111022 A EP 86111022A EP 86111022 A EP86111022 A EP 86111022A EP 0212512 A1 EP0212512 A1 EP 0212512A1
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- Prior art keywords
- acid esters
- electrolysis
- carbamic
- alkyl
- manufacturing
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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 present invention relates to a new process for the preparation of carbamic acid esters.
- Carbamic acid esters as is generally known, have been prepared from phosgene by reaction with alcohols to form chloroformic acid esters and subsequent aminolysis. Dealing with the highly toxic and corrosive preliminary and intermediate products requires considerable technical effort. HCl or halogen-containing waste salts are also obtained in these processes, the separation of which is often technically very complex (cf. Ullmann, Enzyklopadie der techn. Chemie, Vol. 9, p. 118 ff.).
- the invention was based on the object of finding a process for the preparation of carbamic esters which is technically simple and economical and is distinguished by particular environmental friendliness.
- carbamic acid esters of the general formula (I) R1NHCOOR2 (I), in which R1 is hydrogen or an alkyl, cycloalkyl or alkaryl radical and R2 is a low molecular weight alkyl radical, can be prepared particularly advantageously if formamides of the general formula (II) R1NHCHO (II) electrochemically oxidized in the presence of alcohols of the formula R2OH and in the presence of an ionogenic halide.
- Suitable cycloalkyl radicals are those having 3 to 8, in particular 5 and 6, carbon atoms.
- R1 can be alkylaryl radicals having 7 to 12, in particular 7 to 8, carbon atoms, e.g. represent benzyl or phenylethyl radicals.
- radicals mentioned can still carry substituents which are inert under the reaction conditions, e.g. C1-C4 alkyl or alkoxy groups, halogen or nitrile groups.
- the following formamides can be implemented: methylformamide, ethylformamide, n- and iso-propylformamide, n-butylformamide, n-octylformamide, cyclohexyl- or cyclopentylformamide, benzylformamide and the unsubstituted formamide.
- R2 represents a low molecular weight alkyl radical, in particular an alkyl radical having 1 to 5 carbon atoms, preferably a methyl or ethyl radical.
- R2 represents a low molecular weight alkyl radical, in particular an alkyl radical having 1 to 5 carbon atoms, preferably a methyl or ethyl radical.
- n- or iso-propanol, n-butanol, n-propanol and in particular methanol, ethanol can be used.
- Suitable ionogenic halides are salts of hydrogen iodide, hydrobromic acid and hydrochloric acid. Salts of hydrobromic acid, such as alkali, alkaline earth bromides and quaternary ammonium, especially tetraalkylammonium bromides are particularly preferred.
- the cation does not play an essential role in the invention, therefore other ionic metal halides can also be used, but one becomes advantageous choose cheap halides. Examples include sodium, potassium, calcium and ammonium bromide, and di-, tri- and tetramethyl- or tetraethylammonium bromide.
- the method according to the invention does not require a special electrolysis cell. It can advantageously be carried out in an undivided flow cell.
- All anode materials which are customary per se and are stable under the electrolysis conditions, such as noble metal, for example gold or platinum or metal oxides such as NiO x, can be used as anodes.
- the preferred anode material is graphite.
- the cathode material consists, for example, of metals such as lead, iron, steel, nickel or precious metals such as platinum.
- the preferred cathode material is also graphite.
- the composition of the electrolyte can be chosen within wide limits.
- the electrolyte consists of 10-80 wt% R1NHCHO 10 - 80% by weight. R2OH 0.1 - 10% by weight halide.
- a solvent can be added to the electrolyte, for example to improve the solubility of the formamide or the halide.
- examples include nitriles such as acetonitrile, carbonates such as dimethyl carbonates and ethers such as tetrahydrofuran.
- the current density is not a limiting factor for the method according to the invention, it is e.g. 1 to 25 A / dm2, preferably 3 to 12 A / dm2.
- the temperature is expediently chosen so that it is at least 5 to 10 ° C. below the boiling point of the electrolyte.
- electrolysis is preferably carried out at temperatures of 20 to 30 ° C.
- the process according to the invention offers the possibility of largely converting the formamides without there being any deterioration in yield.
- the current yields are also unusually high in the process according to the invention.
- the formamide is already fully converted in electrolysis with 2 to 2.5 F / mol formamide.
- the electrolysis discharges can be worked up by methods known per se.
- the electrolysis discharge is expediently worked up by distillation. Excess alkanol and any cosolvent used are first distilled off, the halides are separated in a known manner, for example by filtration or extraction, and the carbamic acid esters are distilled or recrystallized. Alkanol, possibly unreacted formamide and cosolvent as well as halides can advantageously be returned to electrolysis.
- the process according to the invention can be carried out batchwise or continuously.
- the carbamic acid esters produced by the process according to the invention are versatile intermediates for the synthesis of isocyanates, crop protection agents and auxiliaries, e.g. for finishing textiles.
- the electrooxidation was carried out in an undivided electrolysis cell with graphite anodes and cathodes at temperatures of 20 to 25 ° C.
- the electrolyte which contains sodium bromide as the conductive salt, was pumped through the cell at 200 l / h via a heat exchanger.
- the composition of the electrolyte is shown in Table 1.
- the work-up was carried out in such a way that the alcohol was distilled off at atmospheric pressure up to a bottom temperature of 120 to 130 ° C. and the remaining residue was distilled in at 5 to 40 mbar.
- the purification was carried out by recrystallization from ethyl acetate.
- the residue was filtered hot after separating the alcohol at 80-100 ° C. (separation of NaBr); the urethanes then crystallized from the filtrate at 20-30 ° C. in spectroscopic (1 H-NMR) pure form.
- the carbamic acid esters were obtained at a conversion of 100% in yields of 57 to 88%, based on the starting material (II).
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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
Herstellung von Carbamidsäureestern (I) R¹NHCOOR² (I) (mit R¹ = H, Alkyl, Cycloalkyl, Alkylaryl; R² = Alkyl) durch Elektrooxidation von Formamiden (II) R¹NHCHO (II) in Gegenwart von Alkoholen R²OH und in Anwesenheit eines ionogenen Halogenids.Preparation of carbamic acid esters (I) R¹NHCOOR² (I) (with R¹ = H, alkyl, cycloalkyl, alkylaryl; R² = alkyl) by electrooxidation of formamides (II) R¹NHCHO (II) in the presence of alcohols R²OH and in the presence of an ionogenic halide.
Description
Die vorliegende Erfindung betrifft ein neues Verfahren zur Herstellung von Carbamidsäureestern.The present invention relates to a new process for the preparation of carbamic acid esters.
Carbamidsäureester wurden bisher, wie allgemein bekannt, ist aus Phosgen durch Umsetzung mit Alkoholen zu Chlorameisensäureestern und anschließende Aminolyse hergestellt. Der Umgang mit den hochtoxischen und korrosiven Vor- und Zwischenprodukten erfordert technisch einen erheblichen Aufwand. Weiterhin fallen bei diesen Verfahren HCl oder halogenhaltige Abfallsalze an, deren Abtrennung häufig technisch sehr aufwendig ist (vgl. Ullmann, Enzyklopädie der techn. Chemie, Bd. 9, S. 118 ff.).Carbamic acid esters, as is generally known, have been prepared from phosgene by reaction with alcohols to form chloroformic acid esters and subsequent aminolysis. Dealing with the highly toxic and corrosive preliminary and intermediate products requires considerable technical effort. HCl or halogen-containing waste salts are also obtained in these processes, the separation of which is often technically very complex (cf. Ullmann, Enzyklopadie der techn. Chemie, Vol. 9, p. 118 ff.).
In phosgenfreien Alternativverfahren wird Harnstoff mit Alkanolen umgesetzt. Nachteilig hierbei sind hohe Reaktionstemperaturen und lange Reaktionszeiten sowie der technisch aufwendige Umgang mit Feststoffen (vgl. z.B. Houben-Weyl, Methoden d. org. Chemie, Bd. 8, S. 111 ff.).In phosgene-free alternative processes, urea is reacted with alkanols. Disadvantages here are high reaction temperatures and long reaction times as well as the technically complex handling of solids (see e.g. Houben-Weyl, Methods of Organic Chemistry, Vol. 8, p. 111 ff.).
Der Erfindung lag nun die Aufgabe zugrunde, ein Verfahren zur Herstellung von Carbamidsäurestern zu finden, das technisch einfach und ökonomisch ist und sich durch besondere Umweltfreundlichkeit auszeichnet.The invention was based on the object of finding a process for the preparation of carbamic esters which is technically simple and economical and is distinguished by particular environmental friendliness.
Demgemäß wurde gefunden, daß man Carbamidsäureester der allgemeinen Formel (I),
R¹NHCOOR² (I),
in der R¹ Wasserstoff oder einen Alkyl-, Cycloalkyl- oder Alkarylrest bedeutet und R² für einen niedermolekularen Alkylrest steht, besonders vorteilhaft herstellen kann, wenn man Formamide der allgemeinen Formel (II)
R¹NHCHO (II)
in Gegenwart von Alkoholen der Formel R²OH und in Anwesenheit eines ionogenen Halogenids elektrochemisch oxidiert.Accordingly, it has been found that carbamic acid esters of the general formula (I)
R¹NHCOOR² (I),
in which R¹ is hydrogen or an alkyl, cycloalkyl or alkaryl radical and R² is a low molecular weight alkyl radical, can be prepared particularly advantageously if formamides of the general formula (II)
R¹NHCHO (II)
electrochemically oxidized in the presence of alcohols of the formula R²OH and in the presence of an ionogenic halide.
Der Erfolg des Verfahrens ist überraschend, da seit langem bekannt ist, daß die elektrochemische Umsetzung von Formamiden in Alkoholen in Gegenwart von Leitsalzen wie Tetraalkylammoniumtetrafluoroborat stets zu Alkoxiformamiden führt (vgl. z.B. L. Eberson und K. Nyberg; Tetrahedron 32 (1976), 2185-2206), wie folgende Reaktionsgleichung verdeutlicht:
Bevorzugt werden Alkylreste mit 1 bis 12, insbesondere 1 bis 8, vorzugsweise 1 bis 4 Kohlenstoffatomen, z.B. Methyl-, Ethyl-, n- und iso--Propyl-, n-Butyl- oder tert. Butylreste.Alkyl radicals having 1 to 12, in particular 1 to 8, preferably 1 to 4 carbon atoms, e.g. Methyl, ethyl, n and iso - propyl, n-butyl or tert. Butyl residues.
Als Cycloalkylreste kommen solche mit 3 bis 8, insbesondere 5 und 6 Kohlenstoffatomen in Betracht. Weiterhin kann R¹ für Alkylarylreste mit 7 bis 12, insbesondere 7 bis 8 Kohlenstoffatomen, z.B. für Benzyl- oder Phenylethylreste stehen.Suitable cycloalkyl radicals are those having 3 to 8, in particular 5 and 6, carbon atoms. Furthermore, R1 can be alkylaryl radicals having 7 to 12, in particular 7 to 8, carbon atoms, e.g. represent benzyl or phenylethyl radicals.
Die genannten Reste können noch unter den Reaktionsbedingungen inerte Substituenten tragen, z.B. C₁-C₄-Alkyl- oder Alkoxigruppen, Halogen oder Nitrilgruppen.The radicals mentioned can still carry substituents which are inert under the reaction conditions, e.g. C₁-C₄ alkyl or alkoxy groups, halogen or nitrile groups.
Beispielsweise können folgende Formamide umgesetzt werden: Methylformamid, Ethylformamid, n- und iso-Propylformamid, n-Butylformamid, n-Octylformamid, Cyclohexyl- oder Cyclopentylformamid, Benzylformamid sowie das unsubstituierte Formamid.For example, the following formamides can be implemented: methylformamide, ethylformamide, n- and iso-propylformamide, n-butylformamide, n-octylformamide, cyclohexyl- or cyclopentylformamide, benzylformamide and the unsubstituted formamide.
In den Alkoholen der Formel R²OH steht R² für einen niedermolekularen Alkylrest, insbesondere für einen Alkylrest mit 1 bis 5 Kohlenstoffatomen, vorzugsweise für einen Methyl- oder Ethylrest. Beispielsweise können n- oder iso-Propanol, n-Butanol, n-Propanol und insbesondere Methanol, Ethanol verwendet werden.In the alcohols of the formula R²OH, R² represents a low molecular weight alkyl radical, in particular an alkyl radical having 1 to 5 carbon atoms, preferably a methyl or ethyl radical. For example, n- or iso-propanol, n-butanol, n-propanol and in particular methanol, ethanol can be used.
Als ionogene Halogenide kommen Salze der Iodwasserstoff-, Bromwasserstoff- und Chlorwasserstoffsäure in Betracht. Besonders bevorzugt sind Salze der Bromwasserstoffsäure, wie Alkali-, Erdalkalibromide sowie quaternäre Ammonium-, insbesondere Tetraalkylammoniumbromide. Das Kation spielt keine erfindungswesentliche Rolle, es können daher auch andere ionogene Metallhalogenide verwendet werden, vorteilhaft wird man jedoch billige Halogenide wählen. Beispielsweise seien Natrium-, Kalium-, Calcium- und Ammoniumbromid sowie Di-, Tri- und Tetramethyl- oder Tetraethylammoniumbromid genannt.Suitable ionogenic halides are salts of hydrogen iodide, hydrobromic acid and hydrochloric acid. Salts of hydrobromic acid, such as alkali, alkaline earth bromides and quaternary ammonium, especially tetraalkylammonium bromides are particularly preferred. The cation does not play an essential role in the invention, therefore other ionic metal halides can also be used, but one becomes advantageous choose cheap halides. Examples include sodium, potassium, calcium and ammonium bromide, and di-, tri- and tetramethyl- or tetraethylammonium bromide.
Das erfindungsgemäße Verfahren erfordert keine besondere Elektrolysezelle. Vorteilhaft kann man es in einer ungeteilten Durchflußzelle durchführen. Als Anoden können alle an sich üblichen Anodenmaterialien verwendet werden, die unter den Elektrolysebedingungen stabil sind, wie Edelmetall, z.B. Gold oder Platin oder Metalloxide wie NiOx. Bevorzugtes Anodenmaterial ist Graphit. Das Kathodenmaterial besteht z.B. aus Metallen wie Blei, Eisen, Stahl, Nickel oder Edelmetallen wie Platin. Bevorzugtes Kathodenmaterial ist ebenfalls Graphit.The method according to the invention does not require a special electrolysis cell. It can advantageously be carried out in an undivided flow cell. All anode materials which are customary per se and are stable under the electrolysis conditions, such as noble metal, for example gold or platinum or metal oxides such as NiO x, can be used as anodes. The preferred anode material is graphite. The cathode material consists, for example, of metals such as lead, iron, steel, nickel or precious metals such as platinum. The preferred cathode material is also graphite.
Die Zusammensetzung des Elektrolyten kann in weiten Grenzen gewählt werden. So besteht der Elektrolyt beispielsweise aus
10 - 80 Gew.% R¹NHCHO
10 - 80 Gew%. R²OH
0,1 - 1O Gew.% Halogenid.The composition of the electrolyte can be chosen within wide limits. For example, the electrolyte consists of
10-80 wt% R¹NHCHO
10 - 80% by weight. R²OH
0.1 - 10% by weight halide.
Dem Elektrolyten kann so gewünscht ein Lösungsmittel, etwa zur Verbesserung der Löslichkeit des Formamids oder des Halogenids zugesetzt werden. Beispiele hierfür sind Nitrile, wie Acetonitril, Carbonate, wie Dimethylcarbonate und Ether, wie Tetrahydrofuran. Die Stromdichte ist kein begrenzender Faktor für das erfindungsgemäße Verfahren, sie beträgt z.B. 1 bis 25 A/dm², vorzugsweise wird mit 3 bis 12 A/dm² elektrolysiert. Die Temperatur wird bei druckloser Fahrweise der Elektrolyse zweckmäßigerweise so gewählt, daß sie zumindest 5 bis 10°C unter dem Siedepunkt des Elektrolyten liegt. Bei Verwendung von Methanol oder Ethanol wird vorzugsweise bei Temperaturen von 20 bis 30°C elektrolysiert. Es wurde überraschend festgestellt, daß das erfindungsgemäße Verfahren die Möglichkeit bietet die Formamide weitgehend umzusetzen, ohne daß es zu Ausbeuteverschlechterungen kommt. Auch die Stromausbeuten sind bei dem erfindungsgemäßen Verfahren ungewöhnlich hoch. So ist das Formamid bei Elektrolyse mit 2 bis 2,5 F/Mol Formamid bereits vollständig umgesetzt.If desired, a solvent can be added to the electrolyte, for example to improve the solubility of the formamide or the halide. Examples include nitriles such as acetonitrile, carbonates such as dimethyl carbonates and ethers such as tetrahydrofuran. The current density is not a limiting factor for the method according to the invention, it is e.g. 1 to 25 A / dm², preferably 3 to 12 A / dm². When the electrolysis is operated without pressure, the temperature is expediently chosen so that it is at least 5 to 10 ° C. below the boiling point of the electrolyte. When using methanol or ethanol, electrolysis is preferably carried out at temperatures of 20 to 30 ° C. It was surprisingly found that the process according to the invention offers the possibility of largely converting the formamides without there being any deterioration in yield. The current yields are also unusually high in the process according to the invention. For example, the formamide is already fully converted in electrolysis with 2 to 2.5 F / mol formamide.
Die Aufarbeitung der Elektrolyseausträge kann man nach an sich bekannten Methoden vornehmen. Zweckmäßigerweise wird der Elektrolyseaustrag destillativ aufgearbeitet. Überschüssiges Alkanol und evtl. eingesetztes Kolösungsmittel werden zunächst abdestilliert, die Halogenide werden in bekannter Weise z.B. durch Filtration oder Extraktion abgetrennt, und die Carbamidsäureester werden reindestilliert bzw. umkristallisiert. Alkanol, evtl. unumgesetztes Formamid und Kolösungsmittel sowie Halogenide können vorteilhaft zur Elektrolyse zurückgeführt werden. Das erfindungsgemäße Verfahren kann sowohl diskontinuierlich als auch kontinuierlich durchgeführt werden.The electrolysis discharges can be worked up by methods known per se. The electrolysis discharge is expediently worked up by distillation. Excess alkanol and any cosolvent used are first distilled off, the halides are separated in a known manner, for example by filtration or extraction, and the carbamic acid esters are distilled or recrystallized. Alkanol, possibly unreacted formamide and cosolvent as well as halides can advantageously be returned to electrolysis. The process according to the invention can be carried out batchwise or continuously.
Die nach dem erfindungsgemäßen Verfahren hergestellten Carbamidsäureester sind vielfältig einsetzbare Zwischenprodukte für die Synthese von Isocyanaten, Pflanzenschutzmitteln und Hilfsmitteln, z.B. für die Ausrüstung von Textilien.The carbamic acid esters produced by the process according to the invention are versatile intermediates for the synthesis of isocyanates, crop protection agents and auxiliaries, e.g. for finishing textiles.
Die Elektrooxidation wurde in einer ungeteilten Elektrolysezelle mit Graphitanoden und -kathoden bei Temperaturen von 20 bis 25°C durchgeführt. Während der Elektrolyse wurde der Elektrolyt, der als Leitsalz Natriumbromid enthält, mit 200 l/h über einen Wärmeaustauscher durch die Zelle gepumpt. Die Zusammensetzung des Elektrolyten ist Tabelle 1 zu entnehmen.The electrooxidation was carried out in an undivided electrolysis cell with graphite anodes and cathodes at temperatures of 20 to 25 ° C. During the electrolysis, the electrolyte, which contains sodium bromide as the conductive salt, was pumped through the cell at 200 l / h via a heat exchanger. The composition of the electrolyte is shown in Table 1.
Nach Beendigung der Elektrolyse erfolgte die Aufarbeitung in der Weise, daß man den Alkohol bei Normaldruck bis zu einer Sumpftemperatur von 120 bis 130°C abdestillierte und den verbleibenden Rückstand bei 5 bis 40 mbar reindestillierte. Im Fall des unsubstituierten Carbamidsäuremethylesters (Beispiel 7) erfolgte die Reinigung durch Umkristallisieren aus Essigester. In den Beispielen 8 und 9 wurde der Rückstand nach Abtrennung des Alkohols bei 80-100°C heiß filtriert (Abtrennung von NaBr); die Urethane kristallisierten dann bei 20-30°C in spektroskopisch (¹H-NMR) reiner Form aus dem Filtrat aus. Die Carbamidsäureester wurden bei einem Umsatz von 100 % in Ausbeuten von 57 bis 88 %, bezogen auf den Ausgangsstoff (II), erhalten.After the electrolysis had ended, the work-up was carried out in such a way that the alcohol was distilled off at atmospheric pressure up to a bottom temperature of 120 to 130 ° C. and the remaining residue was distilled in at 5 to 40 mbar. In the case of the unsubstituted carbamic acid methyl ester (Example 7), the purification was carried out by recrystallization from ethyl acetate. In Examples 8 and 9 the residue was filtered hot after separating the alcohol at 80-100 ° C. (separation of NaBr); the urethanes then crystallized from the filtrate at 20-30 ° C. in spectroscopic (1 H-NMR) pure form. The carbamic acid esters were obtained at a conversion of 100% in yields of 57 to 88%, based on the starting material (II).
Die Beispiele 1 bis 9 sind in Tabelle 1 zusammengefaßt.
Claims (4)
R¹NHCOOR² (I),
in der R¹ Wasserstoff oder eine Alkyl-, Cycloalkyl- oder Alkarylrest bedeutet und R² für einen niedermolekularen Alkylrest steht, dadurch gekennzeichnet, daß man Formamide der allgemeinen Formel (II)
R¹NHCHO (II)
in Gegenwart von Alkoholen der Formel R²OH und in Anwesenheit eines ionogenen Halogenids elektrochemisch oxidiert.1. Process for the preparation of carbamic acid esters of the general formula (I)
R¹NHCOOR² (I),
in which R¹ is hydrogen or an alkyl, cycloalkyl or alkaryl radical and R² is a low molecular weight alkyl radical, characterized in that formamides of the general formula (II)
R¹NHCHO (II)
electrochemically oxidized in the presence of alcohols of the formula R²OH and in the presence of an ionogenic halide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19853529531 DE3529531A1 (en) | 1985-08-17 | 1985-08-17 | METHOD FOR PRODUCING CARBAMID ACID ESTERS |
| DE3529531 | 1985-08-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0212512A1 true EP0212512A1 (en) | 1987-03-04 |
| EP0212512B1 EP0212512B1 (en) | 1988-11-17 |
Family
ID=6278769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86111022A Expired EP0212512B1 (en) | 1985-08-17 | 1986-08-09 | Process for manufacturing carbamic-acid esters |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US4661217A (en) |
| EP (1) | EP0212512B1 (en) |
| JP (1) | JPH076075B2 (en) |
| CN (1) | CN1013887B (en) |
| AU (1) | AU587849B2 (en) |
| CA (1) | CA1275066A (en) |
| DE (2) | DE3529531A1 (en) |
| DK (1) | DK388786A (en) |
| FI (1) | FI86715C (en) |
| HU (1) | HU199109B (en) |
| IL (1) | IL79645A (en) |
| NO (1) | NO163965C (en) |
| ZA (1) | ZA866150B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0308744A1 (en) * | 1987-09-12 | 1989-03-29 | BASF Aktiengesellschaft | Process for the preparation of imidazolidinones and oxazolidinones |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3606478A1 (en) * | 1986-02-28 | 1987-09-03 | Basf Ag | METHOD FOR PRODUCING BISCARBAMATES AND NEW BISCARBAMATES |
| US5214169A (en) * | 1988-04-25 | 1993-05-25 | Merrell Dow Pharmaceuticals Inc. | N-(2,3-epoxycyclopentyl) carbamate derivatives |
| JP3168031B2 (en) * | 1990-11-16 | 2001-05-21 | トヨタ自動車株式会社 | Heat-resistant herapatite and method for producing the same |
| CN107964668B (en) * | 2016-10-19 | 2019-08-16 | 中国科学院上海有机化学研究所 | C (sp in compound3)-H key is converted into C (sp3)-O key method and the compound that is prepared |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE676746A (en) * | 1965-02-19 | 1966-08-18 | ||
| FR2298614A1 (en) * | 1975-01-25 | 1976-08-20 | Hoechst Ag | PROCESS FOR PREPARING N- (A-ALCOXYETHYL) -CARBOXAMIDES |
| EP0067463A1 (en) * | 1981-06-05 | 1982-12-22 | Shell Internationale Researchmaatschappij B.V. | A process for the preparation of isocyanates and/or derivatives thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3459643A (en) * | 1967-02-03 | 1969-08-05 | Sprague Electric Co | Alkoxylation of n-methyl-n-hydrocarbylamides |
| US3464960A (en) * | 1967-12-15 | 1969-09-02 | Us Army | Mixture for rapid polymerization |
| DE2336976A1 (en) * | 1973-07-20 | 1975-02-13 | Hoechst Ag | PROCESS FOR THE PRODUCTION OF N- (ALPHAALCOXYAETHYL) CARBONIC ACID AMIDES |
| US4138408A (en) * | 1975-12-20 | 1979-02-06 | Hoechst Aktiengesellschaft | ω-Alkoxy derivatives of lactams and process for their manufacture |
| DE2655741A1 (en) * | 1976-12-09 | 1978-06-15 | Hoechst Ag | METHOD FOR PRODUCING CARBAMID ACID ESTERS OF HIGH-BOILING ALCOHOLS |
| DE2919756A1 (en) * | 1979-05-16 | 1980-11-27 | Hoechst Ag | METHOD FOR PRODUCING N-ALPHA -ALKOXYETHYL-CARBONIC ACID AMIDES |
| DE3233309A1 (en) * | 1982-09-08 | 1984-03-08 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING N-SUBSTITUTED CARBAMATES |
| EP0106352B1 (en) * | 1982-10-19 | 1989-06-14 | Mitsubishi Rayon Co., Ltd. | Novel polymer composition |
| US4457813A (en) * | 1983-03-04 | 1984-07-03 | Monsanto Company | Electrolysis cells and electrolytic processes |
| DE3435388A1 (en) * | 1984-09-27 | 1986-04-03 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING AROMATIC CARBONIC ACID ESTERS |
| US4588482A (en) * | 1985-06-10 | 1986-05-13 | Basf Aktiengesellschaft | Preparation of phthalaldehyde acetals |
-
1985
- 1985-08-17 DE DE19853529531 patent/DE3529531A1/en not_active Withdrawn
-
1986
- 1986-08-06 IL IL79645A patent/IL79645A/en not_active IP Right Cessation
- 1986-08-08 CA CA000515607A patent/CA1275066A/en not_active Expired - Lifetime
- 1986-08-08 FI FI863246A patent/FI86715C/en not_active IP Right Cessation
- 1986-08-09 EP EP86111022A patent/EP0212512B1/en not_active Expired
- 1986-08-09 DE DE8686111022T patent/DE3661202D1/en not_active Expired
- 1986-08-11 US US06/895,173 patent/US4661217A/en not_active Expired - Lifetime
- 1986-08-13 JP JP61188798A patent/JPH076075B2/en not_active Expired - Lifetime
- 1986-08-13 CN CN86105208A patent/CN1013887B/en not_active Expired
- 1986-08-15 AU AU61507/86A patent/AU587849B2/en not_active Ceased
- 1986-08-15 HU HU863599A patent/HU199109B/en not_active IP Right Cessation
- 1986-08-15 ZA ZA866150A patent/ZA866150B/en unknown
- 1986-08-15 DK DK388786A patent/DK388786A/en not_active Application Discontinuation
- 1986-08-15 NO NO863297A patent/NO163965C/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE676746A (en) * | 1965-02-19 | 1966-08-18 | ||
| FR2298614A1 (en) * | 1975-01-25 | 1976-08-20 | Hoechst Ag | PROCESS FOR PREPARING N- (A-ALCOXYETHYL) -CARBOXAMIDES |
| EP0067463A1 (en) * | 1981-06-05 | 1982-12-22 | Shell Internationale Researchmaatschappij B.V. | A process for the preparation of isocyanates and/or derivatives thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0308744A1 (en) * | 1987-09-12 | 1989-03-29 | BASF Aktiengesellschaft | Process for the preparation of imidazolidinones and oxazolidinones |
Also Published As
| Publication number | Publication date |
|---|---|
| FI863246A (en) | 1987-02-18 |
| US4661217A (en) | 1987-04-28 |
| CN86105208A (en) | 1987-02-18 |
| NO163965B (en) | 1990-05-07 |
| AU6150786A (en) | 1987-02-19 |
| AU587849B2 (en) | 1989-08-31 |
| NO163965C (en) | 1990-08-15 |
| FI86715C (en) | 1992-10-12 |
| NO863297L (en) | 1987-02-18 |
| IL79645A (en) | 1990-07-12 |
| HUT43032A (en) | 1987-09-28 |
| JPS6240389A (en) | 1987-02-21 |
| HU199109B (en) | 1990-01-29 |
| DE3661202D1 (en) | 1988-12-22 |
| CN1013887B (en) | 1991-09-11 |
| FI863246A0 (en) | 1986-08-08 |
| FI86715B (en) | 1992-06-30 |
| DK388786D0 (en) | 1986-08-15 |
| ZA866150B (en) | 1987-04-29 |
| EP0212512B1 (en) | 1988-11-17 |
| DE3529531A1 (en) | 1987-02-26 |
| NO863297D0 (en) | 1986-08-15 |
| IL79645A0 (en) | 1986-11-30 |
| JPH076075B2 (en) | 1995-01-25 |
| DK388786A (en) | 1987-02-18 |
| CA1275066A (en) | 1990-10-09 |
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