DE1126379B - Process for the preparation of isocyanatoaryl-phosphoric acid or -thiophosphoric acid derivatives - Google Patents

Process for the preparation of isocyanatoaryl-phosphoric acid or -thiophosphoric acid derivatives

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Publication number
DE1126379B
DE1126379B DEF24991A DEF0024991A DE1126379B DE 1126379 B DE1126379 B DE 1126379B DE F24991 A DEF24991 A DE F24991A DE F0024991 A DEF0024991 A DE F0024991A DE 1126379 B DE1126379 B DE 1126379B
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Prior art keywords
acid
thiophosphoric
phosphoric acid
aryl
preparation
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DEF24991A
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German (de)
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Dr Hans Holtschmidt
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Bayer AG
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Bayer AG
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Priority to NL112815D priority Critical patent/NL112815C/xx
Priority to NL235813D priority patent/NL235813A/xx
Application filed by Bayer AG filed Critical Bayer AG
Priority to DEF24991A priority patent/DE1126379B/en
Priority to FR785838A priority patent/FR1225715A/en
Priority to CH6922859A priority patent/CH417585A/en
Priority to GB427359A priority patent/GB891654A/en
Priority to US143284A priority patent/US3136806A/en
Publication of DE1126379B publication Critical patent/DE1126379B/en
Pending legal-status Critical Current

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    • 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
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/242—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/717—Monoisocyanates or monoisothiocyanates containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/776—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur phosphorus
    • 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
    • C08K5/5398—Phosphorus bound to sulfur

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  • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Verfahren zur Herstellung von Isocyanatoaryl-phosphors äure-oder -thiophosphorsäure-Derivaten Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von Isocyanatoarylphosphorsäure- oder -thiophosphorsäure-Derivaten mit einer oder mehreren Isocyanat-Gruppen. Es wurde nämlich gefunden, daß man Aminoarylphosphorsäure- oder -thiophosphorsäureester bzw. Aminoarylphosphorsäure- oder -thiophosphorsäureamide in glatter Reaktion und guter Ausbeute in die entsprechenden Isocyanate überführen kann, wenn man die Amino-Verbindungen in einem inerten Lösungsmittel in an sich bekannter Weise mit Phosgen umsetzt. Die als Ausgangsmaterial zu verwendenden Amino-Verbinzungen besitzen die allgemeine Formel In der Formel bedeutet R = O oder S; X = O-Aryl, O-Aralkyl, O-Cycloalkylaryl, S-Aryl, S-Aralkyl, S-Cycloalkylaryl, N-(Aryl)2, N-Alkylaryl oder N-Cyclo alkylaryl; Y und Z haben die gleiche Bedeutung wie X oder können O-Alkyl, O-Cycloalkyl, S-Alkyl, S-Cycloalkyl, N-(Alkyl)2 oder N-(Cycloalkyl)2 sein; X, Y und Z können gleich oder verschieden, gegebenenfalls auch ungesättigt sein und/oder weitere Substituenten, wie Halogen-, Alkoxy- oder Carbonsäureester-Gruppen, enthalten; mindestens einer der aromatischen Substituenten enthält schließlich mindestens eine aromatisch gebundene Amino-Gruppe.Process for the preparation of isocyanatoarylphosphoric acid or thiophosphoric acid derivatives The present invention relates to a process for the preparation of isocyanatoarylphosphoric acid or thiophosphoric acid derivatives with one or more isocyanate groups. It has been found that aminoarylphosphoric acid or thiophosphoric acid esters or aminoarylphosphoric acid or thiophosphoric acid amides can be converted into the corresponding isocyanates in a smooth reaction and good yield if the amino compounds are reacted with phosgene in an inert solvent in a manner known per se . The amino compounds to be used as starting material have the general formula In the formula, R = O or S; X = O-aryl, O-aralkyl, O-cycloalkylaryl, S-aryl, S-aralkyl, S-cycloalkylaryl, N- (aryl) 2, N-alkylaryl or N-cycloalkylaryl; Y and Z have the same meaning as X or can be O-alkyl, O-cycloalkyl, S-alkyl, S-cycloalkyl, N- (alkyl) 2 or N- (cycloalkyl) 2; X, Y and Z can be identical or different, optionally also unsaturated and / or contain further substituents, such as halogen, alkoxy or carboxylic acid ester groups; Finally, at least one of the aromatic substituents contains at least one aromatically bound amino group.

Die als Ausgangsmaterial dienenden Aminoarylphosphorsäure- oder -thiophosphorsäure-Derivate lassen sich beispielsweise nach dem Verfahren der deutschen Patentanmeldung F 249591V bit 2 q (deutsche Auslegeschrift 1122 075) herstellen. Eine weitere Möglichkeit zur Herstellung der Ausgangsmaterialien ist in der belgischen Patentschrift 594 194 beschrieben. The aminoarylphosphoric acid or thiophosphoric acid derivatives used as starting material can be, for example, according to the method of the German patent application F 249591V bit 2 q (German interpretation 1122 075). One more way for the preparation of the starting materials is in Belgian patent specification 594 194 described.

Verbindungen der vorgenannten Formel, welche erfindungsgemäß mit Phosgen in die entsprechenden Monoisocyanate, Diisocyanate, Triisocyanate oder auch höherwertigen Isocyanate übergeführt werden können, sind beispielsweise: Phosphorsäure-(p-aminophenyl)-triester, Thiophosphorsäure-(p-aminophenyl)-triester, Phosphorsäure-diäthyl-p-aminophenyl-triester, Thiophosphorsäure-diäthyl-p-aminophenyltriester, Phosphorsäure-monocycloalkyl-mono-p-aminophenyl-diester-dimethylamid, Thiophosphorsäure-monocycloalkyl-monop-aminophenyl-diester-dimethylamid, Phosphorsäure-monoäthyl-monovinyl-monoaminonaphthyl-triester, Thiophosphorsäure-monoäthyl-monovinylmonoaminonaphthyl-triester, Phosphorsäure-monoäthylester-bis-(N-methyl-N-p-aminophenylamid), Thiophosphorsäure-monoäthylester-bis-(N-methyl-N-p-aminophenylamid), Phosphorsäure-(3-amino-5-methylphenyl)-triester, Thiophosphorsäure-(3-amino-5-methylphenyl)-triester.Compounds of the aforementioned formula, which according to the invention with phosgene into the corresponding monoisocyanates, diisocyanates, triisocyanates or higher valued ones Isocyanates can be converted, for example: phosphoric acid (p-aminophenyl) triester, Thiophosphoric acid (p-aminophenyl) triester, phosphoric acid diethyl p-aminophenyl triester, Thiophosphoric acid diethyl-p-aminophenyl triester, phosphoric acid monocycloalkyl-mono-p-aminophenyl-diester-dimethylamide, Thiophosphoric acid-monocycloalkyl-monop-aminophenyl-diester-dimethylamide, phosphoric acid-monoethyl-monovinyl-monoaminonaphthyl-triester, Thiophosphoric acid monoethyl monovinylmonoaminonaphthyl triester, phosphoric acid monoethyl ester bis (N-methyl-N-p-aminophenylamide), Thiophosphoric acid monoethyl ester bis (N-methyl-N-p-aminophenylamide), phosphoric acid (3-amino-5-methylphenyl) triester, Thiophosphoric acid (3-amino-5-methylphenyl) triester.

Ferner sei beispielhaft genannt die Verbindung der Formel Nach einer abgeänderten besonderen Ausführungsform lassen sich auch solche Aminoarylphosphorsäure-oder -thiophosphorsäure-Derivate dem erfindungsgemäßen Verfahren unterwerfen, die mehrere Phosphorsäurereste im Molekül enthalten, mit anderen Worten solche Derivate, in denen die Gruppen Y und/oder Z zwei oder mehrere Phosphorsäurereste gemäß obenstehender Formel miteinander verbinden.The compound of the formula may also be mentioned by way of example According to a modified particular embodiment, those aminoarylphosphoric acid or thiophosphoric acid derivatives which contain several phosphoric acid residues in the molecule, in other words those derivatives in which the groups Y and / or Z have two or more phosphoric acid residues according to the above formula, can also be subjected to the process according to the invention connect with each other.

In solchen Fällen bedeuten Y und/oder Z Reste von zwei- oder mehrwertigen Alkoholen, zwei- oder mehrwertigen Aminen, linearen oder verzweigten Polyestern, Polyäthern, Polyamiden, Polyesteramiden u. dgl., welche über O-, S- und/oder N-Atome zwei oder mehrere Arylphosphorsäure- oder -thiophosphorsäurereste verknüpfen.In such cases, Y and / or Z represent radicals of bivalent or polyvalent ones Alcohols, di- or polyvalent amines, linear or branched polyesters, Polyethers, polyamides, polyester amides and the like like., which over O-, S and / or N atoms two or more aryl phosphoric acid or thiophosphoric acid residues link.

Die Phosgenierung der Aminoarylphosphorsäure-oder -thiophosphorsäure-Derivate erfolgt in an sich bekannter Weise nach den üblichen technischen Methoden der Phosgenierung, z. B. durch eine Kaltphasen-Heißphasen-Phosgenierung, oder aber auch nach dem Hydrochlorid-Verfahren, wobei das entsprechende Aminhydrochlorid phosgeniert wird. Sie kann kontinuierlich oder diskontinuierlich ausgeführt werden, wobei man sich vorzugsweise eines inerten Lösungsmittels bedient, etwa Chlorbenzol, o-Dichlorbenzol oder Nitrobenzol. Zur Erzielung einer guten Ausbeute ist es in vielen Fällen zweckmäßig, die Temperatur bei der Phosgenierung nicht zu hoch zu wählen. Aus diesem Grunde ist üblicherweise die Kaltphasen-Heißphasen-Phosgenierung dem Hydrochlorid-Verfahren vorzuziehen, da in ersterem Fall das Gemisch aus Carbaminsäurechlorid und Aminhydrochlorid in einer derartig feinen Suspension anfällt, daß die Heißphasen-Phosgenierung schon bei Temperaturen zwischen 80 und 120"C in kurzer Zeit beendet ist. The phosgenation of aminoarylphosphoric acid or thiophosphoric acid derivatives takes place in a manner known per se using the customary technical methods of phosgenation, z. B. by a cold phase-hot phase phosgenation, or by the hydrochloride process, the corresponding amine hydrochloride being phosgenated. You can be continuous or carried out batchwise, preferably an inert one Solvent used, such as chlorobenzene, o-dichlorobenzene or nitrobenzene. To the To achieve a good yield, it is advisable in many cases to adjust the temperature not to be chosen too high in the phosgenation. For this reason it is common to prefer cold-phase-hot-phase phosgenation to the hydrochloride process, since in the former case the mixture of carbamic acid chloride and amine hydrochloride in such a fine suspension is obtained that the hot phase phosgenation already occurs at temperatures between 80 and 120 "C is completed in a short time.

Die erfindungsgemäß hergestellten Isocyanate fallen schon in einer derart reinen Form an, daß eine besondere Reinigung durch Umkristallisieren oder Destillieren nicht notwendig ist. Ein kurzes Erwärmen des Reaktionsgutes im Vakuum unterhalb des Siedepunktes bzw. ein Ausblasen mit einem indifferenten Gas bei erhöhten Temperaturen zur Zerstörung etwa noch vorhandener Carbaminsäurechloride oder zur Entfernung von überschüssigem Phosgen reicht völlig aus. The isocyanates prepared according to the invention fall in one such pure form that a special purification by recrystallization or Distilling is not necessary. Briefly heating the reaction mixture in vacuo below the boiling point or blowing out with an inert gas at increased Temperatures for the destruction of any carbamic acid chlorides still present or for Removal of excess phosgene is sufficient.

Das erfindungsgemäße Verfahren verläuft überraschend einfach und glatt, wobei die Verfahrensprodukte meist in Ausbeuten von über 80°/o erhalten werden. Ein derartiges Ergebnis war nach dem Stand der Technik nicht zu erwarten. Es stand vielmehr zu befürchten, daß durch die Einwirlcung eines Säurechlorids, nämlich des Phosgens oder des während der Phosgenierung gebildeten Chlorwasserstoffs, eine Spaltung der Phosphorester bzw. Phosphoramid-Bindungen eintreten würde. (Am. Soc., 80, 1958, S. 735 und G. M. Kosolapoff, »Organo Phosphorus Compounds«, New York, John Wiley and Sons, Inc., 1950, S. 214). Ester- bzw. Amid-Spaltprodukte treten aber selbst in kleinen Mengen als Nebenprodukte nicht in Erscheinung. The inventive method is surprisingly simple and smooth, the process products mostly being obtained in yields of over 80%. Such a result was not to be expected according to the prior art. It stood rather, it is to be feared that the induction of an acid chloride, namely the Phosgene or the hydrogen chloride formed during the phosgenation, a cleavage the phosphoric ester or phosphoramide bonds would occur. (Am. Soc., 80, 1958, P. 735 and G. M. Kosolapoff, "Organo Phosphorus Compounds", New York, John Wiley and Sons, Inc., 1950, p. 214). Ester or amide cleavage products occur themselves not apparent in small quantities as by-products.

Die Verfahrensprodukte sind wertvolle Vulkanisationsmittel, insbesondere zum Vulkanisieren von Butylkautschuk. Sie finden ferner Verwendung als Hydrophobiermittel zum Ausrüsten von Textilien. Sie dienen ebenfalls als Ausgangsmaterialien für die Herstellung von Kunststoffen. Diejenigen, die noch polymensierbare ungesättigte Bindungen im Molekül enthalten, lassen sich in Polymerisate überführen, die Thiophosphorsäure-Gruppen im Molekül eingebaut und darüber hinaus noch freie Isocyanat-Gruppen enthalten. The products of the process are valuable vulcanizing agents, in particular for vulcanizing butyl rubber. They are also used as water repellants for finishing textiles. They also serve as starting materials for the Manufacture of plastics. Those that are still polymerizable unsaturated Bonds contained in the molecule can be converted into polymers, the thiophosphoric acid groups built into the molecule and also contain free isocyanate groups.

Beispiel 1 In einen 3-1-Kolben werden 1,5 1 trockenes Chlorbenzol gegeben, auf -10"C gekühlt und anschließend 800 g Phosgen eingeleitet und kondensiert. Dann werden bei gleicher Temperatur 371 g feingepulvertes 4,4',4"-Triamino-triphenylphosphat portionsweise hinzugegeben. Man rührt 4 Stunden in der Kälte nach und läßt über Nacht bei Raumtemperatur stehen. Example 1 In a 3-1 flask are 1.5 l dry chlorobenzene given, cooled to -10 "C and then introduced 800 g of phosgene and condensed. Then 371 g of finely powdered 4,4 ', 4 "-Triamino-triphenylphosphate are added at the same temperature added in portions. The mixture is then stirred in the cold for 4 hours and leaves overnight stand at room temperature.

Anschließend wird zwischen 90 und 110°C so lange ein kräftiger Phosgen strom eingeleitet, bis eine homogene Lösung vorliegt. Die Chlorbenzollösung wird dann mit Stickstoff ausgeblasen und das Chlorbenzol im Vakuum abdestilliert. Der Rückstand wird anschließend noch 1 Stunde bei 1600 C im Hochvakuum nachbehandelt, um restliche Spuren Carbaminsäurechlorid zu zerstören.A vigorous phosgene then forms between 90 and 110 ° C. for so long current initiated until a homogeneous solution is present. The chlorobenzene solution will then blown out with nitrogen and the chlorobenzene is distilled off in vacuo. Of the The residue is then aftertreated for a further 1 hour at 1600 C in a high vacuum, to destroy remaining traces of carbamic acid chloride.

Das zurückbleibende, gelbe Öl ist 4,4',4"-Triisocyanatophenylphosphat. Es kristallisiert nach einigen Tagen als analysenreine wachsartige weiße Masse aus. The yellow oil that remains is 4,4 ', 4 "-triisocyanatophenyl phosphate. After a few days it crystallizes out as an analytically pure, waxy white mass.

Ausbeute: 380 g = 850/o der Theorie; F. 78 bis 80°C.Yield: 380 g = 850 / o of theory; M.p. 78 to 80 ° C.

C2lHl2N3oxP (Molekulargewicht 449,3): Berechnet C56,1, H2,68, N9,36, P6,91, NCO28,10/0; gefunden C 55,74, H 2,60, N 9,70, P 6,95, NCO 28,3%.C2lHl2N3oxP (molecular weight 449.3): calculated C56.1, H2.68, N9.36, P6.91, NCO28.10 / 0; found C 55.74, H 2.60, N 9.70, P 6.95, NCO 28.3%.

Beispiel 2 354 g Thlophosphorsäure-(p-aminophenyl)-triester werden langsam bei -5 bis 0°C in eine Lösung von 600 g Phosgen in 2,51 Chlorbenzol eingetragen. Die Mischung läßt man über Nacht in der Kälte stehen. Example 2 354 g of thlophosphoric acid (p-aminophenyl) triester slowly added at -5 to 0 ° C in a solution of 600 g of phosgene in 2.51 chlorobenzene. The mixture is left in the cold overnight.

Anschließend wird unter weiterem Einleiten von Phosgen die Temperatur erhöht. Nach etwa 6 Stunden ist bei einer Phosgenierungstemperatur von 100 bis 110°C bis auf einen geringen schleimigen Rückstand alles gelöst, von dem unter Zusatz von trockener Aktivkohle abfiltriert wird. Es hinterbleibt eine hellgelbe Schmelze, die alsbald kristallin erstarrt. Ausbeute: 380 g = 97°/0 der Theorie; F. 84 bis 86"C.The temperature is then increased with further introduction of phosgene elevated. After about 6 hours, the phosgenation temperature is from 100 to 110.degree apart from a small slimy residue, everything dissolved, from which added is filtered off by dry activated carbon. A light yellow melt remains, which soon solidifies in crystalline form. Yield: 380 g = 97% of theory; F. 84 to 86 "C.

Analyse: Berechnet C 54,1, H 2,6, N 9,05, P 6,7, S 6,9 O/o; gefunden C53,9, H2,8, N9,1, P6,9, S7,3%.Analysis: Calculated C 54.1, H 2.6, N 9.05, P 6.7, S 6.9 O / o; found C53.9, H2.8, N9.1, P6.9, S7.3%.

Beispiel 3 In 1,5 1 Chlorbenzol werden bei -10"C 700 g Phosgen verflüssigt. Anschließend wird eine Lösung von 475 g Thiophosphorsäure-diäthyl-mono-p-aminophenyl-triester, gelöst in 11 Chlorbenzol, so eingetropft, daß die Temperatur nicht über 0°C ansteigt. Example 3 700 g of phosgene are liquefied in 1.5 l of chlorobenzene at -10 "C. Then a solution of 475 g of thiophosphoric acid diethyl mono-p-aminophenyl triester, dissolved in 11 chlorobenzene, added dropwise so that the temperature does not rise above 0 ° C.

Nach Stehen in der Kälte über Nacht wird bei 100 bis 110° C weiteres Phosgen eingeleitet, bis nach 4 Stunden eine helle, klare Lösung entstanden ist. Es wird wie im Beispiel 2 aufgearbeitet. Man erhält als Rückstand 472 g des schwachbraungefärbten öligen Isocyanates.After standing in the cold overnight at 100 to 110 ° C, further Phosgene was passed in until a pale, clear solution had formed after 4 hours. It is worked up as in Example 2. 472 g of the pale brown color are obtained as residue oily isocyanates.

Kp.1 147 bis 149"C (unter leichter Zersetzung).Bp. 1 147 to 149 "C (with slight decomposition).

Analyse: Berechnet ... N 5,2, P 11,4, S 11,8%; gefunden ... N 5,3, P 11,0, S 11,0 °/o.Analysis: Calculated ... N 5.2, P 11.4, S 11.8%; found ... N 5.3, P 11.0, S 11.0%.

Claims (2)

PATENTANSPRÜCHE: 1. Verfahren zur Herstellung von Isocyanatoaryl-phosphorsäure- oder -thiophosphorsäure-Derivaten, dadurch gekennzeichnet, daß man Verbindungen der allgemeinen Formel in an sich bekannter Weise mit Phosgen umsetzt, wobei in der Formel R = O oder S; X = O-Aryl, O-Aralkyl, O-Cycloalkylaryl, S-Aryl, S-Aralkyl, S-Cycloalkylaryl, N-(Aryl)2, N-Alkylaryl oder N-Cycloalkylaryl; Y und Z die gleichen Substituenten wie X oder auch O-Alkyl, O-Cycloalkyl, S-Alkyl, S-Cycloalkyl, N-(Alkyl)2, N-(Cycloalkyl)2 bedeuten und wobei X, Y und Z gleich oder verschieden, gegebenenfalls auch ungesättigt sein und/oder weitere Substituenten, wie Halogen-, Alkoxy- oder Carbonsäureester-Gruppen, enthalten können und wobei mindestens einer der aromatischen Substituenten mindestens eine aromatisch gebundene Amino-Gruppe enthält.PATENT CLAIMS: 1. Process for the preparation of isocyanatoaryl-phosphoric acid or -thiophosphoric acid derivatives, characterized in that compounds of the general formula is reacted with phosgene in a manner known per se, where in the formula R = O or S; X = O-aryl, O-aralkyl, O-cycloalkylaryl, S-aryl, S-aralkyl, S-cycloalkylaryl, N- (aryl) 2, N-alkylaryl or N-cycloalkylaryl; Y and Z denote the same substituents as X or also O-alkyl, O-cycloalkyl, S-alkyl, S-cycloalkyl, N- (alkyl) 2, N- (cycloalkyl) 2 and where X, Y and Z are identical or different , may optionally also be unsaturated and / or contain further substituents, such as halogen, alkoxy or carboxylic acid ester groups, and wherein at least one of the aromatic substituents contains at least one aromatically bound amino group. 2. Abgeänderte Ausführungsform des Verfahrens nach Anspruch 1, gekennzeichnet durch die Verwendung von solchen Arylphosphorsäure- oder -thiophosphorsäure-Derivaten, in denen die Gruppen Y und/oder Z zwei oder mehrere Phosphorsäurereste gemäß Formel miteinander verbinden. 2. Modified embodiment of the method according to claim 1, characterized through the use of such arylphosphoric acid or thiophosphoric acid derivatives, in which the groups Y and / or Z have two or more phosphoric acid residues according to the formula connect with each other.
DEF24991A 1958-02-06 1958-02-06 Process for the preparation of isocyanatoaryl-phosphoric acid or -thiophosphoric acid derivatives Pending DE1126379B (en)

Priority Applications (7)

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NL112815D NL112815C (en) 1958-02-06
NL235813D NL235813A (en) 1958-02-06
DEF24991A DE1126379B (en) 1958-02-06 1958-02-06 Process for the preparation of isocyanatoaryl-phosphoric acid or -thiophosphoric acid derivatives
FR785838A FR1225715A (en) 1958-02-06 1959-02-05 Aromatic isocyanates derived from phosphoric acid and thiophosphoric acid and process for their preparation
CH6922859A CH417585A (en) 1958-02-06 1959-02-06 Process for the production of phosphoric acid or thiophosphoric acid derivatives
GB427359A GB891654A (en) 1958-02-06 1959-02-06 Isocyanatoaryl esters and amides of phosphoric and thiophosphoric acids
US143284A US3136806A (en) 1958-02-06 1961-10-06 Polyphosphate phenyl esters containing isocyanate radicals

Applications Claiming Priority (1)

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DEF24991A DE1126379B (en) 1958-02-06 1958-02-06 Process for the preparation of isocyanatoaryl-phosphoric acid or -thiophosphoric acid derivatives

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DE1126379B true DE1126379B (en) 1962-03-29

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DEF24991A Pending DE1126379B (en) 1958-02-06 1958-02-06 Process for the preparation of isocyanatoaryl-phosphoric acid or -thiophosphoric acid derivatives

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DE (1) DE1126379B (en)
FR (1) FR1225715A (en)
GB (1) GB891654A (en)
NL (2) NL112815C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4870206A (en) * 1987-07-08 1989-09-26 Bayer Aktiengesellschaft Aromatic polyisocyanates, their preparation and use as components for adhesives

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103265573B (en) * 2013-05-30 2015-08-05 四川理工学院 The preparation method of O, O '-two (phenmethyl) phosphorodithioic acid benzyl ester and the application in metal pickle liquor thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4870206A (en) * 1987-07-08 1989-09-26 Bayer Aktiengesellschaft Aromatic polyisocyanates, their preparation and use as components for adhesives

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NL235813A (en)
GB891654A (en) 1962-03-14
NL112815C (en)
CH417585A (en) 1966-07-31

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