DE1075611B - Process for the production of new nitrogen-containing organic phosphorus compounds - Google Patents
Process for the production of new nitrogen-containing organic phosphorus compoundsInfo
- Publication number
- DE1075611B DE1075611B DENDAT1075611D DE1075611DA DE1075611B DE 1075611 B DE1075611 B DE 1075611B DE NDAT1075611 D DENDAT1075611 D DE NDAT1075611D DE 1075611D A DE1075611D A DE 1075611DA DE 1075611 B DE1075611 B DE 1075611B
- Authority
- DE
- Germany
- Prior art keywords
- dichloride
- mole
- amine
- production
- phosphorus compounds
- 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
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- 238000000034 method Methods 0.000 title claims description 7
- -1 nitrogen-containing organic phosphorus compounds Chemical class 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 150000001412 amines Chemical class 0.000 claims description 10
- 150000004985 diamines Chemical class 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 150000003949 imides Chemical class 0.000 description 4
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- XBWIAVHZEWSRJI-UHFFFAOYSA-N Cl.Cl.OP(O)(=O)OC1=CC=CC=C1 Chemical compound Cl.Cl.OP(O)(=O)OC1=CC=CC=C1 XBWIAVHZEWSRJI-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- BGMIRDHBNWQSGE-UHFFFAOYSA-N hypochlorous acid;pyridine Chemical compound ClO.C1=CC=NC=C1 BGMIRDHBNWQSGE-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JBCSOBKDUKAJHR-UHFFFAOYSA-N ClO.NC1=CC=CC=C1 Chemical compound ClO.NC1=CC=CC=C1 JBCSOBKDUKAJHR-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- KTDQSZZNGSRIGL-UHFFFAOYSA-N cyclohexanamine hypochlorous acid Chemical compound ClO.C1(CCCCC1)N KTDQSZZNGSRIGL-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 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
- 150000002605 large molecules Chemical class 0.000 description 1
- MGJXBDMLVWIYOQ-UHFFFAOYSA-N methylazanide Chemical compound [NH-]C MGJXBDMLVWIYOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VCAFTIGPOYBOIC-UHFFFAOYSA-N phenyl dihydrogen phosphite Chemical compound OP(O)OC1=CC=CC=C1 VCAFTIGPOYBOIC-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing 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
- C07F9/06—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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/6587—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having two phosphorus atoms as ring hetero atoms in the same ring
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
Verfahren zur Herstellung neuer stickstoffhaltiger organischer Phosphorverbindungen Die Erfindung betrifft ein Verfahren zur Herstellung neuer stickstoffhaltiger organischer Phosphorverbindungen, das dadurch gekennuzeichnet ist, daß man ein mit einem gegebenenfalls substituierten aromatischen Rest verestertes Dichlorid der Orthophosphorsäure mit primären gegebenenfalls substituierten Mono- oder Diaminen bei erhöhter Temperatur in der Weise umsetzt, daß man in Gegenwart eines inerten organischen Lösungsmittels entweder das Amin in einer solchen Menge zum Dichlorid zulaufen läßt oder unter Druck Amin und Dichlorid in einer solchen Menge reagieren läßt, daß sich unter Abspaltung beider Chloratome entweder 1 Mol des Dichlorids mit 1 Mol des Monoamins oder 2 Mol des Dichlorids mit 1 Mol des Diamins in Gegenwart des gleichen oder eines tertiären Amins als säurebindendes Mittel umsetzen. Process for the production of new nitrogen-containing organic phosphorus compounds The invention relates to a process for the production of new nitrogen-containing organic Phosphorus compounds, which is characterized in that one with an optionally substituted aromatic radical esterified dichloride of orthophosphoric acid with primary optionally substituted mono- or diamines at elevated temperature reacted in such a way that one in the presence of an inert organic solvent either the amine can run in such an amount to the dichloride or below Pressure amine and dichloride can react in such an amount that they split off both chlorine atoms either 1 mole of the dichloride with 1 mole of the monoamine or 2 moles of the dichloride with 1 mole of the diamine in the presence of the same or a tertiary Implement amine as an acid-binding agent.
Die Verfahrensprodukte entsprechen unter Anwendung von primären Monoaminen monomolekular formuliert dem Typ und bimolekular formuliert dem Typ oder unter Anwendung von primären Diaminen dem Typ worin R einen gegebenenfalls substituierten aromatischen Rest, Z einen aliphatischen, aromatischen, araliphatischen oder cycloaliphatischen, gegebenenfalls substituierten Rest und n eine ganze Zahl darstellt.The products of the process correspond to the type, formulated monomolecularly, using primary monoamines and bimolecularly formulated the type or using primary diamines of the type where R is an optionally substituted aromatic radical, Z is an aliphatic, aromatic, araliphatic or cycloaliphatic, optionally substituted radical and n is an integer.
Die Herstellung der Phosphorsäurearylesterimide bzw. Diimide erfolgt durch Umsetzen von 1 Mol des obigen Phosphorsäurearylesterdichlorids mit t Mol eines obigen Monoamins bzw. 1/2 Mol eines obigen Diamins unter Erwärmen in einem Lösungsmittel bei Siedetemperatur bzw. im Druckgefäß unter Zufügung von zwei weiteren Molen des gleichen Mono- bzw. The aryl phosphoric ester imides or diimides are produced by reacting 1 mole of the above aryl phosphoric ester dichloride with t moles of one above monoamine or 1/2 mole of above diamine with heating in a solvent at boiling point or in the pressure vessel with the addition of two further moles of des same mono or
1 Mol oder gleichen Diamins oder 2 Mol eines tertiären Amins zur Bindung der frei werdenden 2 Mol Chlorwasserstoff. Je nach Art des zur Imidbildung verwendeten Amins müssen gegebenenfalls verschiedene Reaktionstemperaturen verwendet werden, was am besten durch die Wahl eines niedriger- oder höhersiedenden Lösemittels erfolgt. Als derartige Lösemittel kommen z. B. Benzol und Benzinarten bis zu Siedepunkten von 1600 C in Frage. Dabei scheidet sich das entstandene Aminchlorhydrat teilweise aus, oder es bleibt nach dem Verdampfen des Lösemittels auch ganz im Reaktionsprodukt gelöst. Das Chlorhydrat kann durch Auswaschen entfernt werden, im allgemeinen lohnt dies aber nicht, da es bei den Umsetzungen, denen die Imide dienen, nicht stört. Auch wenn auf eine Reindarstellung der Imide verzichtet wird, ist ihre Konstitution aus der Zusammensetzung der Umsetzungsprodukte abzuleiten.1 mole or the same diamine or 2 moles of a tertiary amine for bonding of the released 2 moles of hydrogen chloride. Depending on the type of imide used Amine, different reaction temperatures may have to be used, which is best done by choosing a lower or higher boiling solvent. Such solvents come, for. B. Benzene and types of gasoline up to boiling points of 1600 C in question. The amine chlorohydrate formed partially separates out or it remains entirely in the reaction product after the solvent has evaporated solved. The chlorohydrate can be removed by washing it out, which is generally worthwhile but not, since it does not interfere with the reactions that the imides serve. Even if the imides are not shown in pure form, their constitution is the same derived from the composition of the reaction products.
Beispiel 1 bzw. (C6H5 OP= NC C Zu einer am Rückfluß siedenden Lösung von 1 Mol Phosphorsäurephenylesterdichlorid in Benzol läßt man unter Rühren bei Feuchtigkeitsausschluß eine Lösung von 3 Mol wasserfreies Methylamin zutropfen und erhitzt nach Beendigung des Umsatzes noch 1/2 Stunde unter Rückfluß weiter. Das Reaktionsprodukt wird nach Abdestillieren des Benzols in Chloroform gelöst und mehrmals mit Wasser ausgeschüttelt. Das nach Verdampfen des Chloroforms verbleibende Reaktionsprodukt stellt eine zähe, nicht kristallisierende, bernsteinfarbige Masse dar, löslich in Äther, Chloroform, Methanol, Methanol, Aceton, Benzol, Toluol, unlöslich in Wasser und Petroläther.example 1 or (C6H5 OP = NC C) A solution of 3 mol of anhydrous methylamine is added dropwise to a refluxing solution of 1 mol of phenyl phosphoric ester dichloride in benzene with stirring and with exclusion of moisture, and after the conversion has ended, the mixture is heated under reflux for a further 1/2 hour After the benzene has been distilled off, the reaction product is dissolved in chloroform and extracted several times with water. The reaction product remaining after the chloroform has evaporated is a viscous, non-crystallizing, amber-colored mass, soluble in ether, chloroform, methanol, methanol, acetone, benzene, toluene, insoluble in water and petroleum ether.
Es ist Bis-(phosphorsäurephenylestermethylimid); Berechnet: N 8,28, P 18,31; gefunden: N8,50, P 18,19.It is bis (phosphoric acid phenyl ester methylimide); Calculated: N 8.28, P 18.31; found: N8.50, P 18.19.
Ausbeute 40 bis 50o.Yield 40 to 50o.
Beispiel 2 C18H22 O4N2 P2; Molgewicht 392,3.Example 2 C18H22 O4N2 P2; Molecular weight 392.3.
Man erhitzt 2 Mol Phosphorsäurephenylesterdichlorid mit 1 Mol Hexamethylendiamin in 4 Mol Pyridin im Bombenrohr erst 3 Stunden auf 1500 C und anschließend 3 Stunden auf 1800 C. Nach dem Abkühlen des Bombenrohres befinden sich in demselben zwei Schichten, von denen die obere in der Hauptsache aus Pyridinchlorhydrat besteht, während die unter eine gelbbraune, leicht klebrige Masse darstellt. Um das in der Masse eingeschlossene Pyridin bzw. Pyridinchlorhydrat zu entfernen, wird dieselbe in Methanol gelöst und diese Lösung in dünnem Strahl in Wasser gegossen, wobei das Reaktionsprodukt sofort ausfällt. Dieser Reinigungsvorgang wird bis zum Ausbleiben der Chloridreaktion mit Silbernitratlösung mehrmals wiederholt. Nach Entfernung des Pyridinchlorhydrats wird das Produkt nochmals in Methanol gelöst und in Lösung mittels entwässerten Natriumsulfats getrocknet. Nach Abdestillieren des Lösungsmittels hinterbleibt das noch nicht analysenreine Bis- (phosphorsäurephenylester) -hexamethylendiimid als sprödes, bernsteinfarbenes Harz. 2 moles of phosphoric acid phenyl ester dichloride are heated with 1 mole of hexamethylenediamine in 4 moles of pyridine in a sealed tube first at 1500 C for 3 hours and then for 3 hours to 1800 C. After the bomb tube has cooled down there are two layers in it, of which the upper consists mainly of pyridine chlorohydrate, while the under a yellow-brown, slightly sticky mass. To that included in the crowd To remove pyridine or pyridine chlorohydrate, the same is dissolved in methanol and this solution is poured into water in a thin stream, the reaction product immediately fails. This cleaning process continues until the chloride reaction does not occur Silver nitrate solution repeated several times. After removal of the pyridine chlorohydrate the product is redissolved in methanol and dehydrated in solution Dried sodium sulfate. After the solvent has been distilled off, this remains Bis- (phosphoric acid phenyl ester) -hexamethylene diimide as yet not analytically pure brittle, amber-colored resin.
Um ein analysenreines Produkt zu erhalten, löst man das gereinigte Reaktionsprodukt erneut in Methanol und behandelt es viermal mit Aktivkohle (Carboraffin). Nach Entfernung des Lösemittels resultiert chemisch reines Bis- (phosphorsäurephenylester) -hexamethylendiimid, Die Ausbeute beträgt 30 bis 40°/o. In order to obtain an analytically pure product, the purified one is dissolved Reaction product in methanol again and treated four times with activated carbon (carboraffin). After removing the solvent, chemically pure bis (phosphoric acid phenyl ester) results -hexamethylene diimide, the yield is 30 to 40%.
Die Verbindung ist löslich in Methanol, Äthanol, Aceton, Dioxan, Tetrahydrofuran, Chloroform, Dimethylformamid, Eisessig und unlöslich in Wasser, Äther, Essigester, Benzol, Chlorbenzol, Tetrachlorkohlenstoff. The compound is soluble in methanol, ethanol, acetone, dioxane, Tetrahydrofuran, chloroform, dimethylformamide, glacial acetic acid and insoluble in water, Ether, ethyl acetate, benzene, chlorobenzene, carbon tetrachloride.
Berechnet: N 7,14°/o, P 15,8o/o; gefunden: N7,100/o, P 15,9°/o; Molgewicht: Berechnet: 392,3; gefunden: 419,5 (in Eisessig). Calculated: N 7.14%, P 15.8o / o; found: N7.100 / o, P 15.9 ° / o; Molecular weight: Calculated: 392.3; found: 419.5 (in glacial acetic acid).
Beispiel 3 bzw. (C6 H5 O = P (O) =N-C0H11)2.Example 3 or (C6 H5 O = P (O) = N-COH11) 2.
Es wird wie im Beispiel 1 verfahren, nur werden an Stelle von 3 Mol Methylamin 3 Mol Cyclohexylamin verwendet. Nach Beendigung der Reaktion kristallisieren ca. 87 0/o der Theorie Cyclohexylaminchlorhydrat aus, der Rest bleibt im Rohprodukt gelöst. Er kann durch Ausschütteln der benzolischen Lösung mit Wasser entfernt werden. Das reine Bis-(phosphörsäurephenylestercyclohexylimid) ist eine zähe, nicht kristallisierende, bernsteinfarbene Substanz, löslich in Äther, Chloroform, Tetrachlorkohlenstoff, Methanol, Äthanol, Benzol, Toluol, unlöslich in Wasser und Petroläther. Ausbeute 60 bis 70 o. The procedure is as in Example 1, only instead of 3 mol Methylamine 3 moles of cyclohexylamine used. Crystallize when the reaction is complete about 87 0 / o of theory cyclohexylamine chlorohydrate, the remainder remains in the crude product solved. It can be removed by shaking the benzene solution with water. The pure bis (phosphorous acid phenyl ester cyclohexylimide) is a tough, non-crystallizing, amber colored substance, soluble in ether, chloroform, carbon tetrachloride, Methanol, ethanol, benzene, toluene, insoluble in water and petroleum ether. yield 60 to 70 o.
Berechnet: N 5,910/o; gefunden: N 5,74°/o. Calculated: N 5.910 / o; found: N 5.74%.
Molgewicht: Berechnet: 474; gefunden: 489 (in Eisessig).Molecular Weight: Calculated: 474; found: 489 (in glacial acetic acid).
Beispiel 4 bzw. (C6H5O-P [Oj =N-CH2 C6H5)2 bzw. C6 H5 O-P (0) N-C H2-C6 H5.Example 4 and (C6H5O-P [Oj = N-CH2 C6H5) 2 and C6 H5 OP (0) NC H2-C6 H5, respectively.
1 Mol Phosphorsäurephenylesterdichlorid wird wie im Beispiel 1 und 3 mit 3 Mol Benzylamin zur Reaktion gebracht, wobei wie in den anderen Beispielen 2 Mol des Amins zur Säurebindung dienen. In diesem Fall wird aber an Stelle von Benzol ein Benzin vom Siedepunkt 1600 C verwendet, da bei niedrigeren Temperaturen die Reaktion nicht zur Bildung des Imids führt. Es entsteht ein zähes braunes Harz, das noch das entstandene Aminchlorhydrat enthält, sich aber bei Umsatzreaktionen als das gesuchte Phosphorsäurephenylesterbenzylimid erweist. Ausbeute 30 bis 400/o. Beispiel 5 Man erhitzt 1 Mol Phosphorsäurephenylesterdichlorid mit 3 Mol frisch destillierten Anilins in 250 ccm Cumol im Druckgefäß 5 Stunden auf 2500 C.1 mol of phosphoric acid phenyl ester dichloride is reacted with 3 mol of benzylamine as in Examples 1 and 3, 2 mol of the amine serving for acid binding as in the other examples. In this case, however, a gasoline with a boiling point of 1600 C is used instead of benzene, since the reaction does not lead to the formation of the imide at lower temperatures. A tough brown resin is formed which still contains the amine chlorohydrate that has formed, but turns out to be the phenyl ester benzylimide sought after in conversion reactions. Yield 30 to 400 / o. Example 5 1 mol of phosphoric acid phenyl ester dichloride is heated with 3 mol of freshly distilled aniline in 250 cc of cumene in a pressure vessel at 2500 ° C. for 5 hours.
Nach dem Erkalten erhält man eine schwarzgrüne Reaktionsmasse, die in Aceton aufgenommen wird, wobei die Hauptmenge des bei der Reaktion entstandenen Anilinchlorhydrats ungelöst bleibt und das Phosphorsäurephenylesteranil in Lösung geht. Nach dem Abdestillieren des Acetons erhält man das Rohanil als sehr dunkle, zähe Masse, die ohne jede weitere Reinigung für Anlagerungsreaktionen verwendet werden kann.After cooling, a black-green reaction mass is obtained, which is taken up in acetone, the majority of which is formed in the reaction Aniline chlorohydrate remains undissolved and the phenyl ester anil in solution goes. After the acetone has been distilled off, the crude oil is obtained as a very dark, viscous mass that can be used for attachment reactions without any further purification can be.
Das vom Anilinchlorhydrat vollkommen befreite und in Acetonlösung viermal mit Aktivkohle ge- reinigte Phosphorsäurephenylesteranil ergibt bei der Analyse einen Stickstoffwert von 6,29 0/o gegenüber der Theorie von 6,06°/o Stickstofl5. Ausbeute 30 bis 40%. The completely freed from the aniline chlorohydrate and in acetone solution four times with activated carbon purified phosphoric acid phenylester anil results in the analysis a nitrogen value of 6.29% compared to the theory of 6.06% nitrogen5. Yield 30 to 40%.
Die oben beschriebenen Umsetzungsprodukte sollen als Grundlage für gemischte anorganisch-organische Kunststoffe dienen, indem sie bei geeigneten Temperaturen und unter Zusatz passender Katalysatoren in hochmolekulare Verbindungen besonderer Thermostabilität umgewandelt werden. The conversion products described above are intended as a basis for Mixed inorganic-organic plastics are used by keeping them at suitable temperatures and with the addition of suitable catalysts in high molecular weight compounds Thermostability can be converted.
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