DE1153022B - Process for the preparation of AEthylenimin-N-ethylphosphonic acid dialkyl esters - Google Patents
Process for the preparation of AEthylenimin-N-ethylphosphonic acid dialkyl estersInfo
- Publication number
- DE1153022B DE1153022B DEF30457A DEF0030457A DE1153022B DE 1153022 B DE1153022 B DE 1153022B DE F30457 A DEF30457 A DE F30457A DE F0030457 A DEF0030457 A DE F0030457A DE 1153022 B DE1153022 B DE 1153022B
- Authority
- DE
- Germany
- Prior art keywords
- preparation
- ethylphosphonic acid
- aethylenimin
- dialkyl esters
- acid dialkyl
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 6
- 150000002148 esters Chemical class 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title description 3
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 5
- ZTWTYVWXUKTLCP-UHFFFAOYSA-L ethenyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-L 0.000 claims description 4
- DREPONDJUKIQLX-UHFFFAOYSA-N 1-[ethenyl(ethoxy)phosphoryl]oxyethane Chemical compound CCOP(=O)(C=C)OCC DREPONDJUKIQLX-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- YFEWYGFTFNHSQF-UHFFFAOYSA-N 1-[ethenyl(propoxy)phosphoryl]oxypropane Chemical compound CCCOP(=O)(C=C)OCCC YFEWYGFTFNHSQF-UHFFFAOYSA-N 0.000 description 1
- -1 alkali metal alkoxides Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/564—Three-membered rings
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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Verfahren zur Herstellung von Äthylenimin-N-äthylphosphonsäuredialkylestern Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Äthylenimin-N-äthylphosphonsäuredialkylestern. Erfindungsgemäß werden diese Verbindungen erhalten, indem man Vinylphosphonsäuredialkylester mit Äthylenimin, gegebenenfalls in Gegenwart von basischen Katalysatoren, umsetzt. Process for the preparation of Äthylenimin-N-ethylphosphonic acid dialkyl esters The invention relates to a process for the preparation of ethyleneimine-N-ethylphosphonic acid dialkyl esters. According to the invention, these compounds are obtained by adding dialkyl vinylphosphonate with ethyleneimine, optionally in the presence of basic catalysts, is reacted.
Als Vinylphosphonsäuredialkylester werden z. B. der Vinylphosphonsäurediäthylester, Vinylphosphonsäuredi-n-propylester oder Vinylphosphonsäuredin-butylester verwendet. As dialkyl vinylphosphonate z. B. the vinylphosphonic acid diethyl ester, Di-n-propyl vinylphosphonate or din-butyl vinylphosphonate is used.
Als Katalysatoren, die gegebenenfalls für die vorstehend genannte Reaktion eingesetzt werden, eignen sich beispielsweise Alkalimetallalkoholate, Alkalimetallphenolate oder die Alkalimetalle selbst. Die Katalysatoren werden hierbei vorzugsweise in Mengen bis zu 1001o, bezogen auf eingesetztes Äthylenimin, angewendet. As catalysts, which may be used for the above Reaction are used, for example, alkali metal alkoxides, alkali metal phenates are suitable or the alkali metals themselves. The catalysts are preferably used in Amounts up to 1001o, based on the ethyleneimine used, applied.
Die Durchführung des erfindungsgemäßen Verfahrens erfolgt im allgemeinen dergestalt, daß molare Mengen Vinylphosphonsäureester und Äthylenimin, vorzugsweise ein geringer Überschuß der letzteren Komponente, d. h. etwa 1,1 bis 1,3 Mol Äthylenimin pro Mol Vinylphosphonsäuredialkylester, gegebenenfalls in Gegenwart obenerwähnter Katalysatoren, unter Ausschluß von Kohlendioxyd in einem Druckgefäß, je nach Art der eingesetzten Komponenten mehrere Stunden erwärmt werden. The process according to the invention is generally carried out such that molar amounts of vinyl phosphonic acid ester and ethylene imine, preferably a slight excess of the latter component, d. H. about 1.1 to 1.3 moles of ethyleneimine per mole of dialkyl vinylphosphonate, optionally in the presence of the abovementioned Catalysts, with exclusion of carbon dioxide in a pressure vessel, depending on the type the components used are heated for several hours.
Im allgemeinen kommen hierbei Reaktionszeiten von 15 bis 25 Stunden sowie Temperaturen von 40 bis 600C, vorzugsweise 50 bis 55"C, in Betracht.In general, reaction times of 15 to 25 hours come here as well as temperatures of 40 to 60 ° C., preferably 50 to 55 ° C., are possible.
Die Verwendung von Lösungsmitteln ist in den meisten Fällen nicht erforderlich. Nach beendetem Umsatz wird das Reaktionsprodukt im Vakuum unter inerter Gasatmosphäre mehrmals der fraktionierten Destillation unterworfen.The use of solvents in most cases is not necessary. After the conversion has ended, the reaction product is in vacuo under inert Gas atmosphere subjected to fractional distillation several times.
Die nach dem erfindungsgemäßen Verfahren erhaltenen Produkte stellen in reiner Form beständige Verbindungen dar, die als Flammschutzmittel verwendbar sind. The products obtained by the process according to the invention represent in their pure form stable compounds that can be used as flame retardants are.
Beispiel 1 12 g Äthylenimin und 41 g Vinylphosphonsäurediäthylester werden mit 0,1 g Natriummethylat unter Stickstoff in ein Druckrohr eingeschmolzen und 20 Stunden auf 50 bis 55"C erwärmt. Anschließend wird das Reaktionsprodukt im Vakuum in inerter Atmosphäre mehrfach der fraktionierten Destillation unterworfen. Dabei werden zunächst 16,5 g oder 40% der eingesetzten Menge Vinylphosphonsäurediäthylester zurückerhalten. Anschließend gehen 17 g Äthylenimin-N-äthylphosphonsäurediäthylester vom Kp. 59 bis 600 C bei 0,01 bis 0,05 Torr über, entsprechend einer Ausbeute von 55010 der Theorie unter Berücksichtigung der zurückgewonnenen Menge Vinylphosphonsäurediäthylester. Bei der Destillation hinterbleibt ein sirupöser Rest.example 1 12 g of ethyleneimine and 41 g of diethyl vinylphosphonate are melted in a pressure tube with 0.1 g of sodium methylate under nitrogen and heated to 50 to 55 ° C. for 20 hours , 5 g or 40% of the amount of diethyl vinylphosphonate used are then recovered. 17 g of ethylenimine-N-ethylphosphonic acid diethyl ester with a bp Amount of diethyl vinylphosphonate. A syrupy residue remains after the distillation.
Beispiel 2 Zu 5,2 g Äthylenimin werden 0,3 g in Scheiben geschnittenes metallisches Natrium gegeben. Anschließend läßt man unter Stickstoff und unter Rühren bei Zimmertemperatur langsam 12 g Vinylphosphonsäurediäthylester zutropfen. Dabei erwärmt sich der Ansatz allmählich und nimmt eine dunkelgelbe Färbung an. Nach dem Abklingen der Reaktionswärme wird noch 3 Stunden auf 45 bis 55"C erwärmt. Danach ist die Lösung kirschrot gefärbt. Example 2 0.3 g of cut into slices are added to 5.2 g of ethyleneimine metallic sodium given. It is then left under nitrogen and with stirring Slowly add dropwise 12 g of diethyl vinylphosphonate at room temperature. Included the approach warms up gradually and takes on a dark yellow color. After this After the heat of reaction has subsided, the mixture is heated to 45 to 55 ° C. for a further 3 hours the solution is cherry-red in color.
Die Aufarbeitung erfolgt, wie im Beispiel 1 beschrieben, durch fraktionierte Destillation, nachdem vom restlichen Natrium abgetrennt worden ist Dabei geht sofort reiner Äthylenimin-N-äthylphosphonsäure-diäthylester über. Ausbeute 10,6g (7O0!o der Theorie). Es hinterbleibt ein geringer undestillierbarer Rest. The work-up is carried out, as described in Example 1, by fractionated Distillation after the remaining sodium has been separated off. This goes immediately pure ethylenimine-N-ethylphosphonic acid diethyl ester over. Yield 10.6 g (7O0! O the theory). A small amount of undistilled residue remains.
Claims (1)
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL260849D NL260849A (en) | 1960-02-04 | ||
| DEF35799A DE1191966B (en) | 1960-02-04 | 1960-02-04 | Process for the production of polymers containing phosphorus and nitrogen |
| DEF30460A DE1160183B (en) | 1960-02-04 | 1960-02-04 | Process for the production of copolymers of ethyleneimine compounds serving as amphoteric ion exchangers |
| DE1960F0036151 DE1300293B (en) | 1960-02-04 | 1960-02-04 | Process for the production of phenol condensation resins suitable as amphoteric exchangers |
| DEF30457A DE1153022B (en) | 1960-02-04 | 1960-02-04 | Process for the preparation of AEthylenimin-N-ethylphosphonic acid dialkyl esters |
| DEF36150A DE1168078B (en) | 1960-02-04 | 1960-02-04 | Process for the production of amphoteric ion exchangers |
| FR851318A FR1278553A (en) | 1960-02-04 | 1961-02-01 | Amphoteric ion exchange resins |
| GB54263A GB976567A (en) | 1960-02-04 | 1961-02-02 | A process for the production of amphoteric ion exchange resins |
| GB54363A GB976568A (en) | 1960-02-04 | 1961-02-02 | A process for the production of amphoteric ion exchange resins |
| GB54463A GB976569A (en) | 1960-02-04 | 1961-02-02 | A process for the preparation of diesters of n-dihydroxy-phosphinylethyl ethylene imine |
| GB3602163A GB976570A (en) | 1960-02-04 | 1961-02-02 | Amphoteric ion exchange resins |
| GB402261A GB976566A (en) | 1960-02-04 | 1961-02-02 | Amphoteric ion exchange resins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF30457A DE1153022B (en) | 1960-02-04 | 1960-02-04 | Process for the preparation of AEthylenimin-N-ethylphosphonic acid dialkyl esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1153022B true DE1153022B (en) | 1963-08-22 |
Family
ID=7093773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF30457A Pending DE1153022B (en) | 1960-02-04 | 1960-02-04 | Process for the preparation of AEthylenimin-N-ethylphosphonic acid dialkyl esters |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1153022B (en) |
-
1960
- 1960-02-04 DE DEF30457A patent/DE1153022B/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2525442C3 (en) | Process for the preparation of geminal dihalides | |
| DE1153022B (en) | Process for the preparation of AEthylenimin-N-ethylphosphonic acid dialkyl esters | |
| EP0090213B1 (en) | Process for the preparation of derivatives of vinylphosphonic or vinylpyrophosphonic acids | |
| DE1568945C3 (en) | Process for the production of unsaturated phosphonic acid dichlorides | |
| DE2129583C3 (en) | Process for the production of phosphinic anhydrides | |
| DE3503262A1 (en) | Process for working up halosilane mixtures generated in the course of producing silicon | |
| DE2345360A1 (en) | PROCESS FOR THE PRODUCTION OF TRANSCHRYSANTHEMUM MONOCARBONIC ACID AND ALKYLESTERS THEREOF | |
| EP0074582B1 (en) | Process for preparing dialkylphosphinic-acid halides | |
| DE1075584B (en) | Process for the preparation of tertiary aliphatic esters of phosphorous acid | |
| DE2609126C2 (en) | Process for the preparation of [2- (haloformyl) vinyl] organyl phosphinic acid halides | |
| DE912810C (en) | Process for the preparation of monomeric vinyl esters | |
| EP0005502B1 (en) | Process for preparing halides of halomethyl phosphinic acids | |
| DE1227911B (en) | Process for the preparation of diaryl carbonates | |
| DE1543483C3 (en) | Process for the preparation of chlorine- and bromine-containing cyclic phosphonic acid esters | |
| DE1116660B (en) | Process for the preparation of dialkyl aluminum fluorides | |
| EP0071783B1 (en) | Process for preparing alkyl or arylthiophosphonic-acid chlorides | |
| DE1197883B (en) | Process for the production of phosphonic acid esters | |
| DE859157C (en) | Process for the production of organic isocyanates | |
| DE1231714B (en) | Process for the production of bis-2- (1, 3, 2-dioxaborolane), bis-2- (1, 3, 2-dioxaborinane) or bis-2- (1, 3, 2-dioxabenzoborol) | |
| DE2514871A1 (en) | PROCESS FOR THE PRODUCTION OF CYCLIC PHOSPHIC ACID ESTERS | |
| DEF0016621MA (en) | ||
| DE1027669B (en) | Process for the production of tetraaryl tin | |
| EP0262394A2 (en) | Process for preparing vinylphosphonic acid dichloride | |
| DE1159935B (en) | Process for the production of Arylthiolphosphorsäuredichloriden | |
| DE1162364B (en) | Process for the production of organic phosphines |