EP0971937A1 - Process for preparing alkyl-1-alkoxyethylphosphinous acids - Google Patents
Process for preparing alkyl-1-alkoxyethylphosphinous acidsInfo
- Publication number
- EP0971937A1 EP0971937A1 EP98910711A EP98910711A EP0971937A1 EP 0971937 A1 EP0971937 A1 EP 0971937A1 EP 98910711 A EP98910711 A EP 98910711A EP 98910711 A EP98910711 A EP 98910711A EP 0971937 A1 EP0971937 A1 EP 0971937A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- acetaldehyde
- acids
- general formula
- alkoxyethylphosphinous
- 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.)
- Withdrawn
Links
- 239000002253 acid Substances 0.000 title claims abstract description 14
- 150000007513 acids Chemical class 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- -1 alkyl dichlorophosphanes Chemical class 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011541 reaction mixture Substances 0.000 claims abstract description 5
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N acetaldehyde dimethyl acetal Natural products COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 claims description 8
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 7
- 150000001241 acetals Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- JHNJGLVSPIMBLD-UHFFFAOYSA-N dichloro(ethyl)phosphane Chemical compound CCP(Cl)Cl JHNJGLVSPIMBLD-UHFFFAOYSA-N 0.000 claims description 3
- LSMMTQDEKKQXAG-UHFFFAOYSA-N dichloro(propan-2-yl)phosphane Chemical compound CC(C)P(Cl)Cl LSMMTQDEKKQXAG-UHFFFAOYSA-N 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- CDPKWOKGVUHZFR-UHFFFAOYSA-N dichloro(methyl)phosphane Chemical compound CP(Cl)Cl CDPKWOKGVUHZFR-UHFFFAOYSA-N 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- HVFIQVINDMYLRU-UHFFFAOYSA-N 1-ethoxyethyl(methyl)phosphinic acid Chemical compound CCOC(C)P(C)(O)=O HVFIQVINDMYLRU-UHFFFAOYSA-N 0.000 description 1
- IACYCGGYWPYWFH-UHFFFAOYSA-N 1-methoxyethyl(methyl)phosphinic acid Chemical compound COC(C)P(C)(O)=O IACYCGGYWPYWFH-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- CJYWQTOGKMPYEW-UHFFFAOYSA-N ethyl(1-methoxyethyl)phosphinic acid Chemical compound CCP(O)(=O)C(C)OC CJYWQTOGKMPYEW-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
Definitions
- the invention relates to a process for the preparation of alkyl-1-alkoxyethylphosphinic acids.
- Alkyl 1-alkoxyethylphosphinic acids are valuable intermediates for the production of flame retardants. These acids are usually prepared by hydrolysis of the corresponding acid chlorides, which are prepared by reacting alkyldichlorophosphanes with acetaldehyde acetals (Tsivunin et al., Zh. Obshch. Khim. 40 (102) 1970, 12, 2560). The unsatisfactory yields are disadvantageous in this process, since the acid chlorides are obtained in yields of 60-70% of theory. Technically simple production processes for alkyl-1-alkoxyethylphosphinic acids are therefore sought.
- the invention relates to a process for the preparation of alkyl-1-alkoxyethylphosphinic acids of the general formula (I)
- R 1 represents a straight-chain or branched alkyl radical having 1 to 6 carbon atoms, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl and R 2 represents a straight-chain or branched alkyl radical having 1 to 4 carbon - Atoms, preferably methyl or ethyl, characterized in that alkyl dichlorophosphanes of the general formula (II)
- Suitable starting materials of the general formula (II) are, for example, dichloromethylphosphine, dichloroethylphosphane and dichloroisopropylphosphine. Dichloromethylphosphine is preferred.
- Suitable starting materials of the general formula (III) are in particular acetaldehyde dimethyl acetal and acetaldehyde diethylacetyl.
- the reactants are used in a molar ratio of alkyl dichlorophosphane to acetaldehyde dialkyl acetal from 1: 1 to 1: 2, preferably from 1: 1 to 1: 1, 2.
- the components are mixed slowly with cooling.
- the reaction temperatures are -20 to 150 ° C, preferably -15 to 60 ° C.
- the resulting reaction mixture can, if appropriate, be freed of low boilers and water is then added without further purification measures.
- the molar ratio of alkyl di chlorophosphine to water must be at least 1: 1. Excesses are possible and especially useful if the crude acid is to be processed directly without further purification.
- the method of the present invention can also be designed continuously.
- a distillation process can in particular be carried out as a cleaning operation for the acids according to the invention.
- Transition temperature of 146-151 ° C gave 140 g of 1-methoxyethyl-ethylphosphinic acid. This corresponds to a yield of 89% of theory.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
Alkyl-1-alkoxyethylphosphinous acids are produced by reacting alkyl dichlorophosphanes with acetaldehyde dialkylacetals, then adding water to the reaction mixture. This process gives high yields and is easy to carry out.
Description
Beschreibungdescription
Verfahren zur Herstellung von Alkyl-1-alkoxyethylphosphinsäurenProcess for the preparation of alkyl-1-alkoxyethylphosphinic acids
Die Erfindung betrifft ein Verfahren zur Herstellung von Alkyl-1-alkoxyethylphosphin- säuren.The invention relates to a process for the preparation of alkyl-1-alkoxyethylphosphinic acids.
Alkyl-1-alkoxyethylphosphinsäuren sind wertvolle Zwischenprodukte zur Herstellung von Flammschutzmitteln. Die Herstellung dieser Säuren erfolgt gewöhnlich durch Hydrolyse der entsprechenden Säurechloride, die durch Umsetzung von Alkyldi- chlorphosphanen mit Acetaldehydacetalen hergestellt werden (Tsivunin et al., Zh. Obshch. Khim. 40 (102) 1970, 12, 2560). Nachteilig bei diesem Verfahren sind die unbefriedigenden Ausbeuten, da die Säurechloride mit Ausbeuten von 60 - 70 % der Theorie anfallen. Gesucht sind daher technisch einfache Herstellverfahren für die Alkyl-1-alkoxyethyl- phosphinsäuren.Alkyl 1-alkoxyethylphosphinic acids are valuable intermediates for the production of flame retardants. These acids are usually prepared by hydrolysis of the corresponding acid chlorides, which are prepared by reacting alkyldichlorophosphanes with acetaldehyde acetals (Tsivunin et al., Zh. Obshch. Khim. 40 (102) 1970, 12, 2560). The unsatisfactory yields are disadvantageous in this process, since the acid chlorides are obtained in yields of 60-70% of theory. Technically simple production processes for alkyl-1-alkoxyethylphosphinic acids are therefore sought.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Alkyl-1-alkoxyethyl- phosphinsäuren der allgemeinen Formel (I)The invention relates to a process for the preparation of alkyl-1-alkoxyethylphosphinic acids of the general formula (I)
worinwherein
R1 für einen geradkettigen oder verzweigten Alkylrest mit 1 bis 6 Kohlenstoffato- men, vorzugsweise Methyl, Ethyl, n-Propyi, iso-Propyl, n-Butyl oder tert-Butyl steht und R2 für einen geradkettigen oder verzweigten Alkylrest mit 1 bis 4Kohlenstoff- atomen, vorzugsweise Methyl oder Ethyl steht, dadurch gekennzeichnet, daß
man Alkyl-dichlorphosphane der allgemeinen Formel (II)R 1 represents a straight-chain or branched alkyl radical having 1 to 6 carbon atoms, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl and R 2 represents a straight-chain or branched alkyl radical having 1 to 4 carbon - Atoms, preferably methyl or ethyl, characterized in that alkyl dichlorophosphanes of the general formula (II)
R1PCI2 (II)R 1 PCI 2 (II)
worin R1 die obengenannte Bedeutung hat, mit Acetaldehyddialkylacetalen der allgemeinen Formel (III)wherein R 1 has the meaning given above, with acetaldehyde dialkyl acetals of the general formula (III)
CH3-CH(OR2)2 (III)CH 3 -CH (OR 2 ) 2 (III)
worin R2 die obengenannte Bedeutung hat, umsetzt und das Reaktionsgemisch anschließend mit Wasser umsetzt.wherein R 2 has the meaning given above, and the reaction mixture is then reacted with water.
Überraschenderweise liegen bei diesem Verfahren die Ausbeuten erheblich höher als bei dem bekannten Verfahren nach Tsivunin et al., das die Isolierung der Säure- Chloride vorschreibt.Surprisingly, the yields in this process are considerably higher than in the known process according to Tsivunin et al., Which prescribes the isolation of the acid chlorides.
Als Ausgangsstoffe der allgemeinen Formel (II) kommen beispielsweise Dichlor- methylphosphan, Dichlor-ethylphosphan und Dichlor-isopropylphosphan in Frage. Dichlor-methylphosphan ist bevorzugt.Suitable starting materials of the general formula (II) are, for example, dichloromethylphosphine, dichloroethylphosphane and dichloroisopropylphosphine. Dichloromethylphosphine is preferred.
Als Ausgangsstoffe der allgemeinen Formel (III) kommen insbesondere Acetalde- hyddimethylacetal und Acetaldehyddiethylacetyl in Frage.Suitable starting materials of the general formula (III) are in particular acetaldehyde dimethyl acetal and acetaldehyde diethylacetyl.
Die Reaktanten werden im Molverhältnis Alkyl-dichlorphosphan zu Acetaldehyddial- kylacetal von 1 :1 bis 1 :2 eingesetzt, bevorzugt von 1 :1 bis 1 :1 ,2.The reactants are used in a molar ratio of alkyl dichlorophosphane to acetaldehyde dialkyl acetal from 1: 1 to 1: 2, preferably from 1: 1 to 1: 1, 2.
Die Komponenten werden unter Kühlung langsam vermischt. Die Reaktionstemperaturen betragen -20 bis 150°C, vorzugsweise -15 bis 60°C. Nach beendeter Reaktion kann das anfallende Reaktionsgemisch gegebenenfalls von Leichtsiedem befreit werden und wird dann ohne weitere Reinigungsmaßnahmen mit Wasser versetzt. Dabei soll das Molverhältnis von eingesetztem Alkyl-di-
chlorphosphan zu Wasser mindestens 1 :1 betragen. Überschüsse sind möglich und insbesondere dann zweckmäßig, wenn die anfallende Rohsäure ohne weitere Reinigung direkt weiterverarbeitet werden soll.The components are mixed slowly with cooling. The reaction temperatures are -20 to 150 ° C, preferably -15 to 60 ° C. After the reaction has ended, the resulting reaction mixture can, if appropriate, be freed of low boilers and water is then added without further purification measures. The molar ratio of alkyl di chlorophosphine to water must be at least 1: 1. Excesses are possible and especially useful if the crude acid is to be processed directly without further purification.
Das Verfahren der vorliegenden Erfindung kann auch kontinuierlich gestaltet werden.The method of the present invention can also be designed continuously.
Als Reinigungsoperation für die anfallenden erfindungsgemäßen Säuren kann insbesondere ein Destillationsprozeß durchgeführt werden.A distillation process can in particular be carried out as a cleaning operation for the acids according to the invention.
Beispiel 1example 1
In 135,7 g (1.036 mol) Dichlor-ethylphosphan wurden bei 25°C innerhalb von 1,5 Stunden 93,4 g (1.037 mol) Acetaldehyddimethylacetal unter Rühren und Kühlen eingetropft. Dann wurde nachgerührt und anschließend die Leichtsieder bei 18 mbar bis zu einer Badtemperatur von 100°C über eine 30 cm-Vigreux-Kolonne abdestilliert. Nach dem Abkühlen auf Raumtemperatur wurden unter lebhaftem Rühren in das verbliebene Reaktionsgemisch langsam 56 ml (3.1 mol) Wasser eingetropft, wobei die Temperatur bis 50°C anstieg. Nach beendeter exothermer Reaktion wurde für drei Stunden nachgerührt und anschließend bei 0,25 mbar destilliert. Bei einerIn 135.7 g (1,036 mol) of dichloro-ethylphosphane, 93.4 g (1,037 mol) of acetaldehyde dimethyl acetal were added dropwise at 25 ° C. with stirring and cooling. The mixture was then stirred and then the low boilers were distilled off at 18 mbar up to a bath temperature of 100 ° C. using a 30 cm Vigreux column. After cooling to room temperature, 56 ml (3.1 mol) of water were slowly added dropwise to the remaining reaction mixture with vigorous stirring, the temperature rising to 50 ° C. After the exothermic reaction had ended, stirring was continued for three hours and then distilled at 0.25 mbar. At a
Übergangstemperatur von 146 - 151°C erhielt man 140 g 1-Methoxyethyl-ethylphos- phinsäure. Das entspricht einer Ausbeute von 89 % der Theorie.Transition temperature of 146-151 ° C gave 140 g of 1-methoxyethyl-ethylphosphinic acid. This corresponds to a yield of 89% of theory.
Ergebnis der Analyse: C5H13O3P (152) berechnet: 39,47 % C 8,55 % H 20,39 % P gefunden: 39,40 % C 8,45 % H 20,20 % PResult of the analysis: C 5 H 13 O 3 P (152) calculated: 39.47% C 8.55% H 20.39% P found: 39.40% C 8.45% H 20.20% P
Beispiel 2Example 2
In 351 g (3.0 mol) Dichlor-methylphosphan wurden bei 25 - 40°C innerhalb von 3In 351 g (3.0 mol) of dichloromethylphosphine at 25 - 40 ° C within 3
Stunden 270,4 g (3.0 mol) Acetaldehyddimethylacetal unter Rühren und Kühlen ein-
getropft. Nach beendeter Reaktion wurde 3 Stunden nachgerührt und anschließend bei 18 mbar bis zu einer Innentemperatur von 80°C die Leichtsieder entfernt. Nach dem Abkühlen auf Raumtemperatur wurde unter lebhaftem Rühren 135 ml (7.5 mol) Wasser vorsichtig eingetropft. Dabei stieg unter Kühlung die Temperatur bis auf ma- ximal 50°C. Anschließend wurde nachgerührt und bei 0,15 mbar destilliert. Man erhielt bei einer Übergangstemperatur von 132 - 136°C 370 g 1 -Methoxyethyl-methyl- phosphinsäure. Dies entspricht einer Ausbeute von 89 % der Theorie.Hours 270.4 g (3.0 mol) acetaldehyde dimethyl acetal with stirring and cooling dripped. After the reaction was stirred for 3 hours and then the low boilers were removed at 18 mbar up to an internal temperature of 80 ° C. After cooling to room temperature, 135 ml (7.5 mol) of water were carefully added dropwise with vigorous stirring. With cooling, the temperature rose to a maximum of 50 ° C. The mixture was then stirred and distilled at 0.15 mbar. 370 g of 1-methoxyethyl-methylphosphinic acid were obtained at a transition temperature of 132-136 ° C. This corresponds to a yield of 89% of theory.
Ergebnis der Elementaranalyse: C4H11O3P (138) berechnet: 34,78 % C 7,97 % H 22,46 % P gefunden: 34,70 % C 7,90 % H 22,70 % PElemental analysis result: C 4 H 11 O 3 P (138) calculated: 34.78% C 7.97% H 22.46% P found: 34.70% C 7.90% H 22.70% P
Beispiel 3Example 3
Dichlor-methylphosphan und Acetaldehyddiethylacetal wurden analog Beispiel 2 umgesetzt. Nach Hydrolyse des Rohproduktes erhielt man in 93 %iger Ausbeute die 1-Ethoxyethyl-methylphosphinsäure mit einem Siedepunkt von 147 - 148°C bei 1 ,6 mbar.Dichloromethylphosphine and acetaldehyde diethylacetal were reacted analogously to Example 2. After hydrolysis of the crude product, 1-ethoxyethyl-methylphosphinic acid with a boiling point of 147-148 ° C. at 1.6 mbar was obtained in 93% yield.
Ergebnis der Elementaranalyse: C5H13OP (152) berechnet: 39,47 % C 8,55 % H 20,39 % P gefunden: 39,35 % C 8,40 % H 20,10 % P
Elemental analysis result: C 5 H 13 OP (152) calculated: 39.47% C 8.55% H 20.39% P found: 39.35% C 8.40% H 20.10% P
Claims
1. Verfahren zur Herstellung von Alkyl-1-alkoxyethylphosphinsäuren der allgemeinen Formel1. Process for the preparation of alkyl-1-alkoxyethylphosphinic acids of the general formula
worinwherein
R1 für einen geradkettigen oder verzweigten Alkylrest mit 1 bis 6 Kohlen- stoffatomen, vorzugsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl oder tert-Butyl steht undR 1 represents a straight-chain or branched alkyl radical having 1 to 6 carbon atoms, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl and
R2 für einen geradkettigen oder verzweigten Alkylrest mit 1 bis 4 Kohlenstoffatomen, vorzugsweise Methyl oder Ethyl steht, dadurch gekennzeichnet, daß man Alkyl-dichlorphosphane der allgemeinen FormelR 2 represents a straight-chain or branched alkyl radical having 1 to 4 carbon atoms, preferably methyl or ethyl, characterized in that alkyl dichlorophosphines of the general formula
R1PCI2 (II)R 1 PCI 2 (II)
worin R1 die obengenannte Bedeutung hat, mit Acetaldehyddialkylacetalen der allgemeinen Formelwherein R 1 has the meaning given above, with acetaldehyde dialkyl acetals of the general formula
CH3-CH(OR2)2 (III)CH 3 -CH (OR 2 ) 2 (III)
worin R2 die obengenannte Bedeutung hat, umsetzt und das Reaktionsgemisch anschließend mit Wasser umsetzt.wherein R 2 has the meaning given above, and the reaction mixture is then reacted with water.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß als Alkyl-dichlorphosphan Dichlor-methylphosphan, Dichlor-ethylphosphan oder Dichlor-iso- propylphosphan und/oder als Acetaldehyddialkylacetal Acetaldehyddimethy-
lacetal oder Acetaldehyddiethylacetal verwendet wird.2. The method according to claim 1, characterized in that as the alkyl dichlorophosphane dichloromethylphosphine, dichloroethylphosphane or dichloro-isopropylphosphane and / or as acetaldehyde dialkyl acetal acetaldehyde dimethyl lacetal or acetaldehyde diethylacetal is used.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß Alkyl-dichlorphosphan und Acetaldehyddialkylacetal im Molverhältnis 1 :1 bis 1 :2 eingesetzt wird.
3. The method according to claim 1 or 2, characterized in that alkyl dichlorophosphane and acetaldehyde dialkyl acetal is used in a molar ratio of 1: 1 to 1: 2.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19708722 | 1997-03-04 | ||
| DE19708722A DE19708722A1 (en) | 1997-03-04 | 1997-03-04 | Process for the preparation of alkyl-1-alkoxyethylphosphinic acids |
| PCT/EP1998/000985 WO1998039340A1 (en) | 1997-03-04 | 1998-02-20 | Process for preparing alkyl-1-alkoxyethylphosphinous acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0971937A1 true EP0971937A1 (en) | 2000-01-19 |
Family
ID=7822164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98910711A Withdrawn EP0971937A1 (en) | 1997-03-04 | 1998-02-20 | Process for preparing alkyl-1-alkoxyethylphosphinous acids |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0971937A1 (en) |
| JP (1) | JP2001513787A (en) |
| DE (1) | DE19708722A1 (en) |
| WO (1) | WO1998039340A1 (en) |
| ZA (1) | ZA981771B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2736914B1 (en) | 2011-07-29 | 2016-07-06 | Straitmark Holding AG | Method for the manufacture of compounds containing an alpha-oxy phosphorus group by using p-x components |
| EP2567961A1 (en) * | 2011-09-08 | 2013-03-13 | Straitmark Holding AG | Method for the manufacture of compounds containing an alpha-oxyphosphorus group by using an activator |
-
1997
- 1997-03-04 DE DE19708722A patent/DE19708722A1/en not_active Withdrawn
-
1998
- 1998-02-20 EP EP98910711A patent/EP0971937A1/en not_active Withdrawn
- 1998-02-20 JP JP53810698A patent/JP2001513787A/en active Pending
- 1998-02-20 WO PCT/EP1998/000985 patent/WO1998039340A1/en not_active Application Discontinuation
- 1998-03-03 ZA ZA981771A patent/ZA981771B/en unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9839340A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA981771B (en) | 1998-09-04 |
| JP2001513787A (en) | 2001-09-04 |
| WO1998039340A1 (en) | 1998-09-11 |
| DE19708722A1 (en) | 1998-09-10 |
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