DE1200295B - Process for the preparation of Triarylphosphinopropionsaeurebetainen - Google Patents
Process for the preparation of TriarylphosphinopropionsaeurebetainenInfo
- Publication number
- DE1200295B DE1200295B DEF42214A DEF0042214A DE1200295B DE 1200295 B DE1200295 B DE 1200295B DE F42214 A DEF42214 A DE F42214A DE F0042214 A DEF0042214 A DE F0042214A DE 1200295 B DE1200295 B DE 1200295B
- Authority
- DE
- Germany
- Prior art keywords
- acrylic acid
- reaction
- acid
- triphenylphosphine
- heated
- 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 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 7
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 7
- 229960003237 betaine Drugs 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GAWAYYRQGQZKCR-REOHCLBHSA-N (S)-2-chloropropanoic acid Chemical compound C[C@H](Cl)C(O)=O GAWAYYRQGQZKCR-REOHCLBHSA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- ASLOMEPLDWVVRG-UHFFFAOYSA-N 3-phenylprop-2-enoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=CC1=CC=CC=C1 ASLOMEPLDWVVRG-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- RIZPLDXMQXJTTJ-UHFFFAOYSA-N phosphane;prop-2-enoic acid Chemical compound [PH4+].[O-]C(=O)C=C RIZPLDXMQXJTTJ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- -1 β -carboxyethyl-triphenylphosphonium halides Chemical class 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
-
- 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
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/50—Phosphorus bound to carbon only
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int. Cl.:Int. Cl .:
C07fC07f
Deutsche KL: 12 ο-26/01German KL: 12 ο-26/01
Nummer: 1200 295Number: 1200 295
Aktenzeichen: F 42214IV b/12 οFile number: F 42214IV b / 12 ο
Anmeldetag: 5. März 1964Filing date: March 5, 1964
Auslegetag: 9. September 1965Opening day: September 9, 1965
Es ist bekannt, Trioxytrimethylphosphin mit Acrylsäure zu einer phosphororganischen Verbindung umzusetzen, welche die Struktur des /WrioXytrimethylphosphinopropionsäurebetains besitzt. Es ist weiterhin bekannt, Acrylsäure und deren Derivate mit Triphenylphosphin zu phosphororganischen Verbindungen umzusetzen. Diese Umsetzung soll nur in Gegenwart von äquimolaren Mengen einer starken Säure (Halogenwasserstoffsäure) gelingen und führt zu β - Carboxyäthyl - Triphenylphosphoniumhalogeniden (H. H ο f f m a η η, Chem. Berichte, 94,1961, S. 1331). In dieser Arbeit heißt es wörtlich unter Bezugnahme auf die obengenannte Umsetzung mit Trioxytrimethylphosphin: »Mit dem sehr viel weniger aktiven Triphenylphosphin und schwächer polaren Verbindungen« (worunter sinngemäß Acrylsäure und ihre Derivate zu verstehen sind) »können beständige Addukte nicht isoliert werden«. Die gleiche Auffassung über das Reaktionsvermögen der Triarylphosphine gegenüber Verbindungen mit Kohlenstoff-Kohlenstoff-Doppelbindungen wird auch inHouben — Weyl, »Methoden der Organischen Chemie«, Bd. XII/1, S. 92 und 111, vertreten.It is known that trioxytrimethylphosphine can be reacted with acrylic acid to form an organophosphorus compound which has the structure of WrioXytrimethylphosphinopropionic acid betaine. It is also known that acrylic acid and its derivatives can be reacted with triphenylphosphine to form organophosphorus compounds. This reaction should only succeed in the presence of equimolar amounts of a strong acid (hydrohalic acid) and leads to β -carboxyethyl-triphenylphosphonium halides (H. H ο ffma η η, Chem. Reports, 94, 1961, p. 1331). With reference to the above-mentioned reaction with trioxytrimethylphosphine, this work says literally: "With the much less active triphenylphosphine and weaker polar compounds" (which is understood to mean acrylic acid and its derivatives) "stable adducts cannot be isolated". The same view of the reactivity of the triarylphosphines towards compounds with carbon-carbon double bonds is also represented in Houben-Weyl, "Methods of Organic Chemistry", Vol. XII / 1, pp. 92 and 111.
Überraschenderweise wurde nun gefunden, daß man bereits in der Kälte Triarylphosphinopropionsäurebeataine unter exothermer Umsetzung mit guten Ausbeuten dadurch erhält, daß man Acrylsäure oder deren a-Alkylderivate und Triarylphosphine, gegebenenfalls im Gemisch mit Lösungsmitteln, unter Vermischen umsetzt, gegebenenfalls das erhaltene Reaktionsgemisch erwärmt und das erhaltene Reaktionsprodukt abtrennt.Surprisingly, it has now been found that triarylphosphinopropionic acid ataine can be obtained even in the cold obtained under exothermic reaction with good yields that acrylic acid or their α-alkyl derivatives and triarylphosphines, if appropriate in a mixture with solvents, reacts with mixing, optionally the obtained The reaction mixture is heated and the reaction product obtained is separated off.
Verfahren zur Herstellung von
TriarylphosphinopropionsäurebetainenProcess for the production of
Triarylphosphinopropionic acid betaines
Anmelder:Applicant:
Farbenfabriken Bayer Aktiengesellschaft,
1.0 LeverkusenPaint factories Bayer Aktiengesellschaft,
1.0 Leverkusen
Als Erfinder benannt:Named as inventor:
Dr. Erich Einers, Krefeld-BockumDr. Erich Einers, Krefeld-Bockum
Im Falle der Reaktion mit Triphenylphosphin wurde ein Produkt erhalten, das sich als identisch mit der von Denney.J. org. Chem. (1962), 27, S. 3404,In the case of the reaction with triphenylphosphine, a product was obtained which was found to be identical to that of Denney.J. org. Chem. (1962), 27, p. 3404,
so durch Umsatz von Chlorpropionsäure mit Triphenylphosphin und anschließende Chlorwasserstoffabspaltung erhaltenen Verbindung erwies. Bei der Bestimmung des Schmelzpunktes zeigte es sich, daß das Reaktionsprodukt bei schnellem Aufheizen den auchso by the reaction of chloropropionic acid with triphenylphosphine and subsequent elimination of hydrogen chloride proved. In determining of the melting point, it was found that the reaction product also with rapid heating
as von Denney gefundenen Schmelzpunkt von 169 bis 1700C zeigte. Bei langsamem Aufheizen sintert das Betain bereits unter seinem Schmelzpunkt bei 150 bis 1600C unter Zersetzung zu einem farblosen Harz. Bei dieser Temperatur findet die auch von Denney bei 2000C beobachtete Zersetzung in Acrylsäure und Triphenylphosphin statt, und zwar vermutlich unter intermediärer Bildung des Phosphoniumacrylates:The melting point found by Denney showed 169 to 170 ° C. When heated slowly, the betaine already sinters below its melting point at 150 to 160 ° C. with decomposition to form a colorless resin. At this temperature, the decomposition into acrylic acid and triphenylphosphine, also observed by Denney at 200 ° C., takes place, presumably with intermediate formation of the phosphonium acrylate:
2R3P© —CH2-CH2-C = O2R 3 P © -CH 2 -CH 2 -C = O
IR3P® — CH2-CH2 — C — OHJ O — C CH = CH2 + R3PIR 3 P® - CH 2 -CH 2 - C - OHJ O - C CH = CH 2 + R 3 P
Bei 180 bis 2000C zerfällt das Reaktionsprodukt aus Acrylsäure und Triphenlphosphin im Vakuum nahezu quantitativ in die beiden Komponenten Triphenylphosphin und Acrylsäure in Übereinstimmung mit dem Verhalten des von Denney hergestellten Betains. Die gleiche Übereinstimmung des erfindungsgemäß herstellbaren mit dem von Denney hergestellten Betain zeigt sich auch beim Kochen mit Äthanol und konzentrierter Salzsäure, wobei sich /S-Carbäthoxyäthyltriphenylphosphoniumchlorid vom Schmelzpunkt 113 0C bildet, und beim Erhitzen mit Äthyljodid in Alkohol, wobei sich /3-Carbäthoxyäthyltriphenylphosphoniumjodid vom Schmelzpunkt 111°C bildet.At 180 to 200 0 C, the reaction product of acrylic acid and Triphenlphosphin in vacuo disintegrates almost quantitatively in the two components of triphenylphosphine and acrylic acid in accordance with the behavior of the betaine produced by Denney. The same coincidence of the present invention produced with the produced Denney betaine is also reflected by boiling with ethanol and concentrated hydrochloric acid, with / S-Carbäthoxyäthyltriphenylphosphoniumchlorid forms of melting point 113 0 C, and when heated with ethyl iodide in alcohol in order to / 3 Carbäthoxyäthyltriphenylphosphoniumjodid with a melting point of 111 ° C.
Zur Herstellung der Betaine wird die Acrylsäure — Zimtsäure und Crotonsäure reagieren bemerkenswerterweise nicht — erfindungsgemäß in An- oder Abwesenheit von Lösungsmitteln mit dem Triarylphosphin umgesetzt. Als Lösungsmittel kommen vorzugsweise solche Flüssigkeiten in Frage, in denen sowohl das Triarylphosphin als auch die Acrylsäure gut löslich sind, das Reaktionsprodukt dagegen unlöslich ist. Solche Lösungsmittel sind z. B. Dioxan, Tetrahydrofuran, Essigester, Acetonitril und Aceton. Aus diesenAcrylic acid - cinnamic acid and crotonic acid react remarkably to produce betaines not - according to the invention in the presence or absence of solvents with the triarylphosphine implemented. Liquids that are preferably used as solvents are those in which both the triarylphosphine and acrylic acid are readily soluble, whereas the reaction product is insoluble. Such solvents are e.g. B. dioxane, tetrahydrofuran, ethyl acetate, acetonitrile and acetone. From these
509 660/515509 660/515
Lösungsmitteln fällt das Betain während der Umsetzung aus und kann durch Filtrieren abgetrennt werden, während nicht umgesetztes Triphenylphosphin in Lösung bleibt. Die Acrylsäure kann in reiner Form oder in Form der technisch leicht zugänglichen wäßrigen Lösung verwendet werden. Die allgemein gebräuchlichen Stabilisierungsmittel für Acrylsäure, wie Methylenblau oder Hydrochinon, stören die Umsetzung nicht und brauchen nicht entfernt zu werden, falls sich deren Anwesenheit nicht störend auf den geplanten Verwendungszweck des Betains auswirkt.Solvents the betaine precipitates during the reaction and can be separated by filtration while unreacted triphenylphosphine remains in solution. The acrylic acid can be in pure form or in the form of the technically easily accessible aqueous solution. The general Common stabilizers for acrylic acid, such as methylene blue or hydroquinone, interfere with the reaction not and need not be removed if their presence does not interfere with the intended use of the betaine.
Als Triarylphosphine kommen z. B. in Frage: Triphenylphosphin, Tritolylphosphin und Tri-ß-chlorphenylphosphin. As triaryl phosphines, for. B. in question: triphenylphosphine, tritolylphosphine and tri-ß-chlorophenylphosphine.
Wenngleich die Umsetzung bereits bei Zimmertemperatur einsetzt, empfiehlt es sich doch, das Reaktionsgemisch zur Vervollständigung der Reaktion einige Zeit, z. B. etwa 1 bis 10 Stunden, auf höhere Temperaturen zu erwärmen. Geeignete Temperaturen liegen z. B. im Bereich von etwa 60 bis 8O0C oder höher. Bei Temperaturen zwischen etwa 140 und 1600C führt die Reaktion nur zu einem teilweisen Umsatz, da in diesem Bereich bereits die Rückspaltung des Reaktionsproduktes beginnt. Man erhält dann eine wesentlich geringere Ausbeute an Betain neben viel unverändertem Triphenylphosphin und carboxylgruppenhaltigen Harzen, wobei es sich vermutlich um polymere Acrylsäure handelt.Although the reaction starts at room temperature, it is advisable to let the reaction mixture complete the reaction for some time, e.g. B. about 1 to 10 hours to heat to higher temperatures. Suitable temperatures are e.g. Example in the range of about 60 to 8O 0 C or higher. At temperatures between about 140 and 160 0 C, the reaction leads only to a partial conversion, since in this area already the cleavage of the reaction product begins. A significantly lower yield of betaine is then obtained, in addition to much unchanged triphenylphosphine and resins containing carboxyl groups, which are presumably polymeric acrylic acid.
Die Phosphinobetaine können als Beschleuniger beim Aushärten ungesättigter Polyesterharze, als Flammschutzmittel und Schädlingsbekämpfungsmittel für Holz, Textilien und Kunststoffe verwendet werden.The phosphinobetaines can be used as accelerators in the curing of unsaturated polyester resins Flame retardants and pesticides can be used for wood, textiles and plastics.
52,4 g Triphenylphosphin werden in der gleichen Menge Dioxan gelöst. Über die Lösung wird Stickstoff geleitet. Dann wird die Lösung auf 6O0C erwärmt. Nach Erreichen der Temperatur von 6O0C wird unter Rühren innerhalb einer Stunde eine -. Lösung von 14,4 g Acrylsäure in der gleichen Menge Dioxan zugetropft Während des, Zutropfens trübt sich die anfangs, klare Reaktionslösung, Es fällt ein weißer Niederschlag aus. Nach Beendigung des Zutropfens wird noch 5 Stunden auf 60 bis 8O0C erhitzt. Nach Abkühlen auf Zimmertemperatur wird der teilweise pulvrige, feinkristalline Niederschlag abgesaugt und mit Aceton nachgewaschen. Aus dem auf —5°C abgekühlten Filtrat wird nach längerem Stehenlassen noch eine weitere Menge Reaktionsprodukt gewonnen. Das Produkt wild bei HO0C getrocknet und hat einen Schmelzpunkt von 169 bis 1700C. Es zeigt beim Titrieren mit Natronlauge gegen Phenolphthalein eine Säurezahl von 2 bis 3, welche durch Spuren mitgerissener, nicht umgesetzter Acrylsäure bedingt sein dürfte. Nach dem Eindampfen des Acetonfiltrates bleibt eine harzige Masse zurück, aus der beim Behandeln mit Benzol 4,8 g nicht umgesetztes Triphenylphosphin isoliert werden. Die Gesamtausbeute an Phosphinobetain beträgt 57 g = 85 % der Theorie.52.4 g of triphenylphosphine are dissolved in the same amount of dioxane. Nitrogen is passed over the solution. Then, the solution is heated to 6O 0 C. After reaching the temperature of 6O 0 C is with stirring within one hour -. A solution of 14.4 g of acrylic acid in the same amount of dioxane was added dropwise. During the dropwise addition, the initially clear reaction solution became cloudy. A white precipitate formed. After completion of dropping a further 5 hours is heated to 60 to 8O 0 C. After cooling to room temperature, the partially powdery, finely crystalline precipitate is filtered off with suction and washed with acetone. A further amount of reaction product is recovered from the filtrate, which has been cooled to -5 ° C. after standing for a long time. The product dried wild at HO 0 C and has a melting point of 169 to 170 0 C. When titrated with sodium hydroxide solution against phenolphthalein, it shows an acid number of 2 to 3, which is likely to be due to traces of entrained, unreacted acrylic acid. After evaporation of the acetone filtrate, a resinous mass remains, from which 4.8 g of unreacted triphenylphosphine are isolated on treatment with benzene. The total yield of phosphinobetaine is 57 g = 85% of theory.
52,4 g Triphenylphosphin werden mit 14,4 g Acrylsäure unter Rühren 2 Stunden auf 140° C erhitzt. Beim Abkühlen zerfällt das Reaktionsgemisch in zwei Schichten. Die obere Schicht (20,5 g) besteht aus Triphenylphosphin. Diese Schicht wird durch Lösen mit Benzol entfernt. Die verbleibende untere Schicht stellt ein hellgefärbtes Harz dar und wird mehrmals mit Aceton aufgekocht. Dabei scheidet sich das Phosphinobetain in feinkristalliner Form ab und wird abfiltriert. Das Produkt wird bei 1100C getrocknet. Die Ausbeute beträgt 34,5 g = 51,6 % der Theorie. Beim Eindampfen des Acetonfiltrates bleiben 8 g einer harzigen Masse zurück, welche eine Säurezahl von 121 zeigt.52.4 g of triphenylphosphine are heated with 14.4 g of acrylic acid at 140 ° C. for 2 hours while stirring. On cooling, the reaction mixture breaks down into two layers. The top layer (20.5 g) consists of triphenylphosphine. This layer is removed by dissolving with benzene. The remaining lower layer is a light-colored resin and is boiled several times with acetone. The phosphinobetaine separates out in fine crystalline form and is filtered off. The product is dried at 110 0 C. The yield is 34.5 g = 51.6% of theory. When the acetone filtrate is evaporated, 8 g of a resinous mass remain, which has an acid number of 121.
Claims (1)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF42214A DE1200295B (en) | 1964-03-05 | 1964-03-05 | Process for the preparation of Triarylphosphinopropionsaeurebetainen |
| CH64565A CH437279A (en) | 1964-03-05 | 1965-01-18 | Process for the preparation of triarylphosphinopropionic acid betaines |
| NL6501547A NL6501547A (en) | 1964-03-05 | 1965-02-08 | |
| AT130465A AT250989B (en) | 1964-03-05 | 1965-02-15 | Process for the preparation of triphenylphosphinopropionic acid betaine |
| FR7042A FR1434364A (en) | 1964-03-05 | 1965-02-25 | Process for the preparation of betaines of triarylphosphinopropionic acids |
| GB908265A GB1036265A (en) | 1964-03-05 | 1965-03-03 | Process for the production of triaryl-phosphino-propionic acid betaines |
| BE660600D BE660600A (en) | 1964-03-05 | 1965-03-04 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF42214A DE1200295B (en) | 1964-03-05 | 1964-03-05 | Process for the preparation of Triarylphosphinopropionsaeurebetainen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1200295B true DE1200295B (en) | 1965-09-09 |
Family
ID=7098990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF42214A Pending DE1200295B (en) | 1964-03-05 | 1964-03-05 | Process for the preparation of Triarylphosphinopropionsaeurebetainen |
Country Status (7)
| Country | Link |
|---|---|
| AT (1) | AT250989B (en) |
| BE (1) | BE660600A (en) |
| CH (1) | CH437279A (en) |
| DE (1) | DE1200295B (en) |
| FR (1) | FR1434364A (en) |
| GB (1) | GB1036265A (en) |
| NL (1) | NL6501547A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2540260A1 (en) * | 1975-09-10 | 1977-03-17 | Hoechst Ag | PHOSPHORUS BETAINS AND PROCESS FOR THEIR PRODUCTION |
| DE2540232A1 (en) * | 1975-09-10 | 1977-03-24 | Hoechst Ag | PHOSPHORUS BETAINS AND PROCESS FOR THEIR PRODUCTION |
-
1964
- 1964-03-05 DE DEF42214A patent/DE1200295B/en active Pending
-
1965
- 1965-01-18 CH CH64565A patent/CH437279A/en unknown
- 1965-02-08 NL NL6501547A patent/NL6501547A/xx unknown
- 1965-02-15 AT AT130465A patent/AT250989B/en active
- 1965-02-25 FR FR7042A patent/FR1434364A/en not_active Expired
- 1965-03-03 GB GB908265A patent/GB1036265A/en not_active Expired
- 1965-03-04 BE BE660600D patent/BE660600A/xx unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2540260A1 (en) * | 1975-09-10 | 1977-03-17 | Hoechst Ag | PHOSPHORUS BETAINS AND PROCESS FOR THEIR PRODUCTION |
| DE2540232A1 (en) * | 1975-09-10 | 1977-03-24 | Hoechst Ag | PHOSPHORUS BETAINS AND PROCESS FOR THEIR PRODUCTION |
Also Published As
| Publication number | Publication date |
|---|---|
| AT250989B (en) | 1966-12-12 |
| FR1434364A (en) | 1966-04-08 |
| NL6501547A (en) | 1965-09-06 |
| CH437279A (en) | 1967-06-15 |
| GB1036265A (en) | 1966-07-20 |
| BE660600A (en) | 1965-07-01 |
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