DE1918204A1 - Diphosphacyclopentenone derivs. prepn. - from dimalonates and phosphorus dihalide derivs. - Google Patents
Diphosphacyclopentenone derivs. prepn. - from dimalonates and phosphorus dihalide derivs.Info
- Publication number
- DE1918204A1 DE1918204A1 DE19691918204 DE1918204A DE1918204A1 DE 1918204 A1 DE1918204 A1 DE 1918204A1 DE 19691918204 DE19691918204 DE 19691918204 DE 1918204 A DE1918204 A DE 1918204A DE 1918204 A1 DE1918204 A1 DE 1918204A1
- Authority
- DE
- Germany
- Prior art keywords
- phosphorus
- compounds
- derivs
- halogen atoms
- atom
- 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- Withdrawn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
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 28
- 239000011574 phosphorus Substances 0.000 title claims description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 18
- 125000005843 halogen group Chemical group 0.000 claims abstract description 10
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 7
- 125000004429 atom Chemical group 0.000 claims abstract description 5
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 125000001424 substituent group Chemical group 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 17
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- -1 malonic acid diester Chemical class 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000004437 phosphorous atom Chemical group 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000000575 pesticide Substances 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 2
- VGUWZCUCNQXGBU-UHFFFAOYSA-N 3-[(4-methylpiperazin-1-yl)methyl]-5-nitro-1h-indole Chemical compound C1CN(C)CCN1CC1=CNC2=CC=C([N+]([O-])=O)C=C12 VGUWZCUCNQXGBU-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- CARIEMHHHBHFJG-UHFFFAOYSA-N Br.Br.CCCCP Chemical compound Br.Br.CCCCP CARIEMHHHBHFJG-UHFFFAOYSA-N 0.000 description 1
- 102000010029 Homer Scaffolding Proteins Human genes 0.000 description 1
- 108010077223 Homer Scaffolding Proteins Proteins 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- ASWXNYNXAOQCCD-UHFFFAOYSA-N dichloro(triphenyl)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(Cl)(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 ASWXNYNXAOQCCD-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- RBQWPHPZIUSRTB-UHFFFAOYSA-N phenoxyphosphane dihydrochloride Chemical compound Cl.Cl.POC1=CC=CC=C1 RBQWPHPZIUSRTB-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/535—Organo-phosphoranes
- C07F9/5352—Phosphoranes containing the structure P=C-
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
Description
Verfahren zur Herstellung von Derivaten des 1,2-Diphosphacyclopenten-(5)-on-(4) Die vom fünfwertigen Phosphor abgeleitete Verbindung Triphenylphosphindichlorid reagiert mit Verbindungen, die eine aktivierte Methylengruppe enthalten, zu beständigen Derivaten des Triphenylphosphindimethylens. Dabei setzt sich jeweils ein Molekül der Phosphorverbindung mit einem Molekül der Methylenkomponente um. Als Methylenverbindungen kommen Malonester, Cyanessigester, Malonsäuredinitril und Bisbenzolsulfonyl-methan (Bisphenylsulfon-methan) in Betracht. So ergibt z.B, die Reaktion von Triphenylphosphin-dichlorid mit Malonsäurediäthylester Triphenylphosphin-dicarbäthoxymethylen. Diese Verbindung ist durch eine Doppelbindung zwischen dem fünfwertigen Phosphoratom und einem Kohlenstoffatom charakterisiert (vergl. Homer, Oediger, Chem, Ber. 19 (1958), Seite 437 ff). Process for the preparation of derivatives of 1,2-diphosphacyclopenten- (5) -one- (4) The compound triphenylphosphine dichloride derived from pentavalent phosphorus reacts with compounds that contain an activated methylene group to persist Derivatives of triphenylphosphine dimethylene. One molecule settles in each case the phosphorus compound with a molecule of the methylene component. As methylene compounds come malonic esters, cyanoacetic esters, malonic acid dinitrile and bisbenzenesulfonyl methane (Bisphenylsulfon-methane) into consideration. For example, the reaction of triphenylphosphine dichloride results with diethyl malonate triphenylphosphine-dicarbethoxymethylene. This connection is through a double bond between the pentavalent phosphorus atom and a carbon atom characterized (see Homer, Oediger, Chem, Ber. 19 (1958), page 437 ff).
Einen völlig anderen Verlauf nimmt die Reaktion, wenn man von der entsprechenden Dichlorverbindung des dreiwertigen Phosphors, dem Phenylphosphindichlorid, ausgeht. Setzt man diese e Verbindung mit Malonsäurediäthylester um, dann treten überraschenderweise gleichzeitig jeweils zwei Moleküle Phenylphosphindichlorid und zwei Moleküle des Esters miteinander in Reaktion Hierbei entsteht die Verbindung 1-Ätoxy-1,2-diphenyl-[1,2-diphosphacyclopenten-(5)-on-(4)]-trcarbonsäure-(3,3,5)-triäthylester der folgende Struktur zukommt: und die sich von dem bisher unbekannten fünfglieärigen heterocyclischen Ringsystem 1,2-Diphosphacyclopenten-(5)-on-(4) ableitet. Das neue heterocyclische Ringsystem ist durch die Bachbarschaft zweier Phosphoratome und das Vorhadenssin einer Doppelbindung zwischen einem Phosphor- und einem Kohlenstoffatom gekennzeichnet. Es hat sich gezeigt, daß diese Umsetzung nicht auf Phenylphasphindichlorid und Malonsäurediäthylester als Ausgangsstoffe beschränkt ist, sondern daß ganz allgemein Verbindingen des dreiwertigen Phosphors, die mindestens zwei unmittelbar an das Phosphoratom gebundene, zur Umsetzung mit Wasserstoff befähigte Halogenatome enthalten sowie Ester der Malonsäure mit den verschiedensten Alkoholen eingesetzt werden können.The reaction takes a completely different course if one starts from the corresponding dichloro compound of trivalent phosphorus, phenylphosphine dichloride. If this compound is reacted with diethyl malonate, then, surprisingly, two molecules of phenylphosphine dichloride and two molecules of the ester react with one another at the same time. on- (4)] -trcarboxylic acid- (3,3,5) -triethyl ester has the following structure: and which is derived from the previously unknown five-membered heterocyclic ring system 1,2-diphosphacyclopenten- (5) -one- (4). The new heterocyclic ring system is characterized by the presence of two phosphorus atoms and the presence of a double bond between one phosphorus and one carbon atom. It has been shown that this reaction is not limited to phenylphasphine dichloride and malonic acid diethyl ester as starting materials, but that, in general, compounds of trivalent phosphorus which contain at least two halogen atoms which are directly bonded to the phosphorus atom and capable of reacting with hydrogen, as well as esters of malonic acid with a wide variety of Alcohols can be used.
Es wurde gefunden, daß man zur Herstellung von Derivaten des 1,2-Diphosphacyclopenten-(5)-on-(4) in der Weise arbeitet, daß man in Gegenwart einer Base Malonsäurediester mit solchen Verbindungen des dreiwertigen Phosphors zur Reaktion briugt, die mindestens zwe unmittelbar an das Phosphoratom gebundene, zur Umsetzung mit Wasserstoff befähigte Halogenatome enthalten Bevorzugt wendet man dabei den Diester und die Phosphorverbindung in einem Molverhältnis von etwa 1 : 1 an.It has been found that for the preparation of derivatives of 1,2-diphosphacyclopenten- (5) -one- (4) works in such a way that in the presence of a base malonic acid diester with such Compounds of trivalent phosphorus cause at least two bound directly to the phosphorus atom, capable of reacting with hydrogen Containing halogen atoms. Preference is given to using the diester and the phosphorus compound in a molar ratio of about 1: 1.
Nach einer besonderen Ausführungsform des Verfabrens der Erz in dung setzt man als Verbindungen des dreiwertigen Phosphors, die mindestens zwei unmittelbar an das Phosphoratom gebundene> zur Umsetzung mit Wasserstoff befähigte Halogenatome enthalten, Verbindungen der allgemeinen Formel ein, wobei X gleiche oder verschiedene Halogenatome bedeutet, R einen aliphatischen, cycloaliphatischen, heterocyclischen oder aromatischen Rest darstellt9 der gegebenenfalls solche Substituenten trägt, die mit den an Phosphor gebundenen Halogenatomen nicht in Reaktion treten können, Ä Brückenatome sind, die wahlweise Sauerstoff, Schwefel, Stickstoff oder Phosphor darstellen und für n die Werte 0 oder 1, im Fall von Schwefel, Stickstoff oder Phosphor als Brückenatom für n auch der Wert 2 stehen kann. Beispiele für derartige Verbindungen sind Phenylphosphindichlorid, Butylphosphindibromid, Phenoxyphosphindichlorid, N-Methylanilin-N-phosphindichlorid.According to a particular embodiment of the ore in manure, compounds of the general formula are used as compounds of trivalent phosphorus which contain at least two halogen atoms which are directly bonded to the phosphorus atom and which are capable of reacting with hydrogen where X is the same or different halogen atoms, R is an aliphatic, cycloaliphatic, heterocyclic or aromatic radical9 which may have those substituents that cannot react with the halogen atoms bonded to phosphorus, Ä are bridge atoms that can optionally be oxygen, sulfur, Represent nitrogen or phosphorus and for n the values 0 or 1, in the case of sulfur, nitrogen or phosphorus as bridging atom for n also the value 2 can stand. Examples of such compounds are phenylphosphine dichloride, butylphosphine dibromide, phenoxyphosphine dichloride, N-methylaniline-N-phosphine dichloride.
Die Umsetzung zwischen den Reaktionspartnern verläuft bereits bei Raumtemperatur oder wenig erhöhter Temperatur. Zweckmäßig arbeitet man bei 40 bis 6001 In speziellen Fällen, z.B, bei sterisch gehinderten Reaktionspartnern, können Jedoch auch höhere Temperaturen erforderlich sein. Zweckmäßig führt man die Reaktion unter Feuchtigkeitsauhluß und in Inertgasatmosphäre durch.The implementation between the reactants is already taking place at Room temperature or slightly elevated temperature. It is best to work at 40 to 6001 In special cases, e.g. with sterically hindered reaction partners, However, higher temperatures may also be required. The reaction is expediently carried out under moisture and in an inert gas atmosphere.
Der Zusatz einer Base zum Reaktionsgemisch dient der laufenden Entfernung des während der Reaktion entstehenden Halogenwasserstoffs. Dementsprechend wird die Base mindestens in einer Menge angewendet, die zur Bindung von 2 Molen Halogenwasserstoff ausreicht. Nach einer bevorzugten Ausführungsform des Verfahrens der Erfindung verwendet man als Base tertiare Amine, insbesondere Triäthylamin.The addition of a base to the reaction mixture is used for ongoing removal of the hydrogen halide formed during the reaction. Accordingly, will the base is used in at least an amount sufficient to bind 2 moles of hydrogen halide sufficient. Used in a preferred embodiment of the method of the invention tertiary amines, especially triethylamine, are used as the base.
Die Aufarbeitung des Reaktionsproduktes ist davon abhängig, ob unter Verwendung eines Lösungsmittels gearbeitet wurde und welchen Aggregatzustand die heterocyclische phosphorhaltige Verb in dung aufweist. Verwendet man als Reaktionsmedium ein inertes Lösungsmittel, aus dem die heterocyclische phosphorhaltige Verbindung während der Umsetzung ausfällt, so filtriert man zweckmäßig nach beendeter Reaktion ab und gewinnt die reine Substanz durch Extration aus dem Rückstand.The work-up of the reaction product depends on whether under Use of a solvent was worked and what state of aggregation the having heterocyclic phosphorus-containing compound. Used as a reaction medium an inert solvent that makes up the heterocyclic phosphorus-containing compound If precipitates during the reaction, it is expediently filtered after the reaction has ended and the pure substance is obtained by extraction from the residue.
Falls die organische phosphorhaltige Verbindung in dem Reaktionsmedium lölich ist, kann z.B., gegebenenfalls nach Abfilieren unlöslicher Nebenprodukte, das Löeungsmittel abdestilliert und die hierbei anfallende Verbindung durch Emkristallisieren oder Destillieren gereinigt werden.If the organic phosphorus-containing compound is in the reaction medium is soluble, e.g., if necessary after filtering off insoluble by-products, the solvent is distilled off and the resulting connection be purified by recrystallization or distillation.
Bei Durchführuhg der Reaktion in Abwesenheit eines Lösungsmittels wird die organische phosphorhaltige Verbindung zweckmäßig aus dem Umsetzungsprodukt durch Extraktion mit einem inerten organischen Lösungsmittel gewonnen und- nach Entfernung des Extr;hionsmediums ebenfalls durch Umkristallisieren oder Destillieren in reiner Form dargestellt.When carrying out the reaction in the absence of a solvent the organic phosphorus-containing compound is expediently obtained from the reaction product obtained by extraction with an inert organic solvent and - after Removal of the extrusion medium also by recrystallization or distillation presented in pure form.
Auf Grund der Anwesenheit eines Phosphoratomes mit freiem Elektronenpaar sind die Verbindungen Elektronendonatoren und deshalb zur Komplexbildung mit Übergangsmetallen und deren Verbindungen befähigt.Due to the presence of a phosphorus atom with a free electron pair the compounds are electron donors and therefore form complexes with transition metals and enable their connections.
Die nach dem Verfahren der Erfindung zugänglichen Verbindungen haben sich als Schädlingsbekämpfungsmittel, als Bestandteil von Katalysatoren sowie als Zwischenprodukte fur technisch durchgeführte Synthesen bewährt.Have the compounds obtainable by the method of the invention as a pesticide, as a component of catalysts and as Intermediate products have been tried and tested for technical syntheses.
Beispiele Die in der nachfolgenden Tabelle zusammengestellten Verbindungen wurden nach folgendem Verfahren hergestellt: Zu jeweils 0,1 Mol der in Spalte 1 angegebenen Reaktionspartner, die in etwa der 5-fachen Gewichtsmenge Benzol gelöst waren, wurden in Stickstoffatmosphäre bei 500 unter Rühren 0,2 Mol Triäthylamin getropft. Anschließend wurde zwei Stunden gerührt und ausgefallenes Triätllylammoniumhalogenid abfiltriert. Das Lösungsmittel wurde abdestilliert und das verbleibende Reaktionsprodukt entweder mit Äther gewaschen und aus absolutem Methanol lçmkristalo lisiert oder, falls es sich um eine Flüssigkeit handelte, zur Reinigung destilliert.Examples The compounds compiled in the table below were prepared according to the following process: To 0.1 mol each of the in column 1 specified reactants, which dissolved in about 5 times the amount by weight of benzene were, 0.2 mol of triethylamine were in a nitrogen atmosphere at 500 with stirring dripped. The mixture was then stirred for two hours and precipitated trietllylammonium halide filtered off. The solvent was distilled off and the remaining reaction product either washed with ether and crystallized from absolute methanol or, if it was a liquid, distilled to clean it.
Tabelle
Claims (3)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT680168A AT282644B (en) | 1968-07-15 | 1968-07-15 | Process for the preparation of the new 1,2-diphosphacyclopenten- (5) -one- (4) derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1918204A1 true DE1918204A1 (en) | 1970-09-17 |
Family
ID=3589877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19691918204 Withdrawn DE1918204A1 (en) | 1968-07-15 | 1969-04-10 | Diphosphacyclopentenone derivs. prepn. - from dimalonates and phosphorus dihalide derivs. |
Country Status (4)
| Country | Link |
|---|---|
| AT (1) | AT282644B (en) |
| BR (1) | BR6910732D0 (en) |
| DE (1) | DE1918204A1 (en) |
| NL (1) | NL6910891A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016170060A1 (en) | 2015-04-21 | 2016-10-27 | Covestro Deutschland Ag | Process for producing polyisocvanurate plastics having functionalized surfaces |
| US10590226B2 (en) | 2015-04-21 | 2020-03-17 | Covestro Deutschland Ag | Solids based on polyisocyanurate polymers produced under adiabatic conditions |
| US10597484B2 (en) | 2015-04-21 | 2020-03-24 | Covestro Deutschland Ag | Polyisocyanurate plastics having high thermal stability |
| US10717805B2 (en) | 2015-04-21 | 2020-07-21 | Covestro Deutschland Ag | Process for producing polyisocyanurate plastics |
| US10752723B2 (en) | 2015-04-21 | 2020-08-25 | Covestro Deutschland Ag | Polyisocyanurate polymer and process for the production of polyisocyanurate polymers |
-
1968
- 1968-07-15 AT AT680168A patent/AT282644B/en not_active IP Right Cessation
-
1969
- 1969-04-10 DE DE19691918204 patent/DE1918204A1/en not_active Withdrawn
- 1969-07-15 BR BR21073269A patent/BR6910732D0/en unknown
- 1969-07-15 NL NL6910891A patent/NL6910891A/xx unknown
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016170060A1 (en) | 2015-04-21 | 2016-10-27 | Covestro Deutschland Ag | Process for producing polyisocvanurate plastics having functionalized surfaces |
| US10590226B2 (en) | 2015-04-21 | 2020-03-17 | Covestro Deutschland Ag | Solids based on polyisocyanurate polymers produced under adiabatic conditions |
| US10597484B2 (en) | 2015-04-21 | 2020-03-24 | Covestro Deutschland Ag | Polyisocyanurate plastics having high thermal stability |
| US10717805B2 (en) | 2015-04-21 | 2020-07-21 | Covestro Deutschland Ag | Process for producing polyisocyanurate plastics |
| US10752724B2 (en) | 2015-04-21 | 2020-08-25 | Covestro Deutschland Ag | Process for producing polyisocvanurate plastics having functionalized surfaces |
| US10752723B2 (en) | 2015-04-21 | 2020-08-25 | Covestro Deutschland Ag | Polyisocyanurate polymer and process for the production of polyisocyanurate polymers |
| US11390707B2 (en) | 2015-04-21 | 2022-07-19 | Covestro Deutschland Ag | Polyisocyanurate polymers and process for the production of polyisocyanurate polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| AT282644B (en) | 1970-07-10 |
| NL6910891A (en) | 1970-01-19 |
| BR6910732D0 (en) | 1973-01-02 |
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