DE3739799A1 - Fluorine-containing compounds based on 4,4'-bis[2-(4-hydroxyphenyl)hexafluoroisopropyl] diphenyl ether, their preparation and their use - Google Patents

Fluorine-containing compounds based on 4,4'-bis[2-(4-hydroxyphenyl)hexafluoroisopropyl] diphenyl ether, their preparation and their use

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DE3739799A1
DE3739799A1 DE19873739799 DE3739799A DE3739799A1 DE 3739799 A1 DE3739799 A1 DE 3739799A1 DE 19873739799 DE19873739799 DE 19873739799 DE 3739799 A DE3739799 A DE 3739799A DE 3739799 A1 DE3739799 A1 DE 3739799A1
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Prior art keywords
hydrogen
compounds
bis
hexafluoroisopropyl
diphenyl ether
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DE19873739799
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German (de)
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Juergen Dr Lau
Guenter Dr Siegemund
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Hoechst AG
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Hoechst AG
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Priority to DE19873739799 priority Critical patent/DE3739799A1/en
Priority to EP88119069A priority patent/EP0317882B1/en
Priority to DE8888119069T priority patent/DE3882658D1/en
Priority to JP63293756A priority patent/JPH01165552A/en
Priority to CA000583836A priority patent/CA1331018C/en
Priority to KR1019880015403A priority patent/KR890008077A/en
Priority to US07/276,194 priority patent/US4978790A/en
Publication of DE3739799A1 publication Critical patent/DE3739799A1/en
Priority to US07/569,615 priority patent/US5081315A/en
Withdrawn legal-status Critical Current

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    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
    • C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
    • C07C205/38—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. nitrodiphenyl ethers
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/20—Pyrrones

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

Abstract

Compounds of the formula <IMAGE> in which R<1> and R<2> are different from each other and are hydrogen, NO2 or -NH2, R<3> is hydrogen or halogen, with the proviso that R<1> is hydrogen if R<2> is NO2 or -NH2 and R<2> is hydrogen if R<1> is -NO2 or -NH2, process for their preparation by reacting aromatic nitro compounds with a suitable dihydroxy compound and, if appropriate, subsequent reduction and use of the amino compounds for the preparation of polycondensates which are stable at high temperatures.

Description

Die Erfindung bezieht sich auf neue fluorhaltige Verbindungen auf Basis von 4,4′-Bis[2-(4-hydroxyphenyl)hexafluorisopropyl] diphenylether, Verfahren zu ihrer Herstellung und ihre Verwendung, wobei die Verbindungen zwei Hexafluorisopropylidengruppen aufweisen.The invention relates to new fluorine-containing Compounds based on 4,4′-bis [2- (4-hydroxyphenyl) hexafluoroisopropyl] diphenyl ether, process for their Manufacture and its use, the compounds two Have hexafluoroisopropylidene groups.

Fluorhaltige Verbindungen, speziell fluorhaltige Diaminoverbindungen auf Basis von 2,2-Bis[3- bzw. 4-Aminophenoxy) phenyl]hexafluorpropan sind bekannt (US 41 11 906 bzw. EP-A 01 92 480). Ebenfalls sind Verbindungen bekannt, die in 2-Stellung am Phenoxykern ein Halogenatom aufweisen (US 45 21 623). Diese Verbindungen, die eine einzige Hexafluorisopropylidengruppe aufweisen, werden zur Herstellung von Polyimiden und Polyamiden mit günstigen Eigenschaften wie thermische Stabilität, Widerstand gegen Bestrahlung und mechanische Festigkeit eingesetzt. Es war daher überraschend, daß aus Verbindungen, die zwei Hexafluorisopropylidengruppen im Molekül tragen, Polymerisate hergestellt werden können, die verbesserte Eigenschaften aufweisen.Fluorine-containing compounds, especially fluorine-containing ones Diamino compounds based on 2,2-bis [3- or 4-aminophenoxy) phenyl] hexafluoropropane are known (US 41 11 906 or EP-A 01 92 480). Connections are also known which have a halogen atom in the 2-position on the phenoxy nucleus (US 45 21 623). These connections, the one Have hexafluoroisopropylidene group are used for the preparation of polyimides and polyamides with favorable properties such as thermal stability, resistance to radiation and mechanical strength used. So it was surprising that from compounds that have two hexafluoroisopropylidene groups carry in the molecule, polymers can be produced, which have improved properties.

Gegenstand der Erfindung sind neue Verbindungen auf der Basis von 4,4′-Bis[2-(4-hydroxyphenyl)hexafluorisopropyl]- diphenylether der FormelThe invention relates to new compounds on the Base of 4,4′-bis [2- (4-hydroxyphenyl) hexafluoroisopropyl] - diphenyl ether of the formula

in der R¹ und R² verschieden voneinander sind und Wasserstoff, -NO₂ oder -NH₂ bedeuten, R³ Wasserstoff oder Halogen ist mit der Maßgabe, daß R¹ Wasserstoff ist, wenn R² -NO₂ oder -NH₂ ist und R² Wasserstoff ist, wenn R¹ -NO₂ oder NH₂ ist.in which R¹ and R² are different from one another and Is hydrogen, -NO₂ or -NH₂, R³ is hydrogen or Halogen is provided that R1 is hydrogen if R² is -NO₂ or -NH₂ and R² is hydrogen when R¹ -NO₂ or NH₂.

Gegenstand der Erfindung ist auch ein Verfahren zur Herstellung der Verbindungen der Formel (I) und die Verwendung der daraus enthaltenen Diaminoverbindungen.The invention also relates to a method for Preparation of the compounds of formula (I) and the Use of the contained diamino compounds.

Als Ausgangsmaterial für die neuen, fluorhaltigen Verbindungen der Formel (I) dient der 4,4′-Bis [2-(4- hydroxyphenyl)hexafluorisopropyl]diphenylether, der mit aromatischen halogenhaltigen Nitroverbindungen zu den entsprechenden Dinitroverbindungen umgesetzt wird. Chlor ist als Halogen bevorzugt. Als aromatische Nitroverbindungen werden vorzugsweise 4-Chlornitrobenzol, 3,4-Dichlornitrobenzol und 1,3-Dinitrobenzol eingesetzt. Das Verhältnis von Diphenylether zu den aromatischen Nitroverbindungen beträgt im allgemeinen 1 : 2 bis 3, vorzugsweise 1 : 2,1 bis 2,4, bezogen auf molare Mengen. Die eingesetzte 4-Hydroxyphenylverbindung ist nach einem Verfahren erhältlich, das in der am selben Tage eingereichten deutschen Patentanmeldung P 37 39 795.8, Titel: "Teilfluorierte Diphenylether, Verfahren zu ihrer Herstellung und ihre Verwendung" beschrieben worden ist.As a starting material for the new, fluorine-containing Compounds of the formula (I) are used in the 4,4′-bis [2- (4- hydroxyphenyl) hexafluoroisopropyl] diphenyl ether, which with aromatic halogen-containing nitro compounds to the corresponding dinitro compounds is implemented. Is chlorine preferred as halogen. As aromatic nitro compounds 4-chloronitrobenzene, 3,4-dichloronitrobenzene and 1,3-dinitrobenzene are used. The ratio of diphenyl ether to aromatic Nitro compounds is generally 1: 2 to 3, preferably 1: 2.1 to 2.4, based on molar amounts. The used 4-hydroxyphenyl compound is after a Procedure available in the same day German patent application P 37 39 795.8, Title: "Partially fluorinated diphenyl ethers, process for their Manufacture and its use "has been described.

Die Umsetzung wird in organischen Lösungsmitteln durchgeführt, und zwar in dipolaren aprotischen Lösungsmitteln wie Dimethylformamid, Dimethylacetamid, Dimethylsulfoxid, Dimethylsulfon, Sulfolan, 1-Methyl-2- pyrrolidinon.The reaction is carried out in organic solvents carried out, namely in dipolar aprotic Solvents such as dimethylformamide, dimethylacetamide, Dimethyl sulfoxide, dimethyl sulfone, sulfolane, 1-methyl-2- pyrrolidinone.

Mindestens stöchiometrische Mengen einer basischen Verbindung, z. B. Alkalihydroxide, Ammoniumhydroxid, Alkalihydride, Alkali- oder Erdalkalicarbonate oder -hydrogencarbonate sowie Alkalialkoholate werden bei der Umsetzung eingesetzt. Die Molverhältnisse betragen im allgemeinen 1 : 2 bis 4, vorzugsweise 1 : 2,1 bis 3, bezogen auf den Diphenylether.At least stoichiometric amounts of a basic Connection, e.g. B. alkali hydroxides, ammonium hydroxide, Alkali hydrides, alkali or alkaline earth carbonates or -hydrogen carbonates and alkali alcoholates are used in the  Implementation. The molar ratios are in general 1: 2 to 4, preferably 1: 2.1 to 3, based on the diphenyl ether.

Die Reaktionstemperatur beträgt im allgemeinen 50 bis 200°C, vorzugsweise 100 bis 180°C.The reaction temperature is generally 50 to 200 ° C, preferably 100 to 180 ° C.

Die neuen, in erster Stufe erhaltenen Dinitroverbindungen können nach üblichen katalytischen Methoden mit Hydrierkatalysatoren oder nach stöchiometrischen Methoden, z. B. mit Zinn(II)-chlorid-Eisessig, in einer zweiten Reaktionsstufe zu den entsprechenden Diaminoverbindungen reduziert werden.The new dinitro compounds obtained in the first stage can with the usual catalytic methods Hydrogenation catalysts or by stoichiometric methods, e.g. B. with tin (II) chloride glacial acetic acid, in a second Reaction step to the corresponding diamino compounds be reduced.

Als Katalysatoren für die katalytische Reduktion können beispielsweise Platinmetalle, Kupfer, Eisen, Kobalt, Nickel, Mischungen daraus oder Metalloxide bei atmosphärischem oder erhöhtem Druck eingesetzt werden. Palladium wird bevorzugt. Die Katalysatoren können als Metall selbst oder in feinverteilter Form auf Oberflächen wie Kohle, Bariumsulfat, Silikagel, Aluminium und Zeolith verwendet werden. Bekannt ist auch die Verwendung von Raney-Nickel. Die Reduktion findet in organischen Lösungsmitteln, z. B. Alkoholen wie Methanol, Ethanol und Isopropylalkohol, Glykolen wie Ethylenglykol und Propylenglykol, Ethern die Diethylether, Dioxan, Tetrahydrofuran und Ethylenglykolmonoethylether, aliphatischen Kohlenwasserstoffen wie Hexan und Cyclohexan, aromatischen Kohlenwasserstoffen wie Benzol, Toluol und Xylol, Estern wie Ethylacetat und Butylacetat, halogenierten Kohlenwasserstoffen sowie Dimethylformamid und Dimethylsulfoxid statt. Die Temperaturen bei dieser Reaktion liegen im allgemeinen zwischen 10 und 130°C, vorzugsweise zwischen 20 bis 80°C.Can be used as catalysts for catalytic reduction for example platinum metals, copper, iron, cobalt, Nickel, mixtures thereof or metal oxides atmospheric or increased pressure. Palladium is preferred. The catalysts can be used as Metal itself or in finely divided form Surfaces such as coal, barium sulfate, silica gel, aluminum and zeolite can be used. The is also known Use of Raney nickel. The reduction takes place in organic solvents, e.g. B. alcohols such as methanol, Ethanol and isopropyl alcohol, glycols such as ethylene glycol and propylene glycol, ethers the diethyl ether, dioxane, Tetrahydrofuran and ethylene glycol monoethyl ether, aliphatic hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and Xylene, esters such as ethyl acetate and butyl acetate, halogenated hydrocarbons and dimethylformamide and dimethyl sulfoxide instead. The temperatures at this Reaction are generally between 10 and 130 ° C, preferably between 20 to 80 ° C.

Die in zweiter Stufe erhaltenen Diaminoverbindungen eignen sich zur Herstellung von hochtemperaturbeständigen Polykondensaten. Durch Umsetzung mit Tetracarbonsäuren oder deren Derivaten werden Polyimide erhalten. Andererseits ergibt die Reaktion mit Dicarbonsäurechloriden Polyamide. Beispielsweise weisen die Polyimide niedrige Dielektrizitätskonstanten auf. Weiterhin können neue Monomere und Oligomere erhalten werden, beispielsweise durch Reaktion mit Dianhydriden. Die erhaltenen Imidmonomeren und Oligomeren können durch Additionsreaktionen gehärtet werden. Die erfindungsgemäßen Diamide sind weiterhin geeignet zur Herstellung von polymeren Vorprodukten, Epoxidharzhärtern, Matrixharzen, Laminaten, Filmen, Fasern, Klebstoffen, Beschichtungen, Fotoresists und Formkörpern.The diamino compounds obtained in the second stage are suitable to manufacture high temperature resistant  Polycondensates. By reaction with tetracarboxylic acids or their derivatives are obtained polyimides. On the other hand gives the reaction with dicarboxylic acid chlorides polyamides. For example, the polyimides are low Dielectric constant. Furthermore, new ones Monomers and oligomers are obtained, for example by reaction with dianhydrides. The received Imide monomers and oligomers can by Addition reactions are hardened. The invention Diamides are also suitable for the production of polymeric precursors, epoxy resin hardeners, matrix resins, Laminates, films, fibers, adhesives, coatings, Photoresists and moldings.

BeispieleExamples 1) 4,4′-Bis[2-(4-(4-nitrophenoxy)phenyl)hexafluorisopropyl]- diphenylether1) 4,4'-bis [2- (4- (4-nitrophenoxy) phenyl) hexafluoroisopropyl] - diphenyl ether

13,1 g 4,4′-Bis[2-(4-hydroxyphenyl)hexafluorisopropyl]- diphenylether, 50 ml Dimethylacetamid, 20 ml Toluol, 1,8 g NaOH und 3 ml Wasser wurden solange unter Rückfluß erhitzt, bis kein Wasser mehr am Wasserabscheider abgeschieden wurde. Anschließend wurde das Toluol abdestilliert und die Reaktionsmischung nach der Zugabe von 7,1 g 4-Chlornitrobenzol 24 Stunden unter Rückfluß erhitzt. Nach dem Erkalten der Reaktionsmischung auf 25°C wurde der Feststoffanteil abfiltriert und verworfen. Aus dem Filtrat wurde das Dimethylacetamid destillativ im Vakuum abgetrennt und der Rückstand aus Acetonitril umkristallisiert. Es verblieben 12,5 g (71% d.Th.) eines beigefarbenen Feststoffes, der bei 160°C schmolz.13.1 g 4,4'-bis [2- (4-hydroxyphenyl) hexafluoroisopropyl] - diphenyl ether, 50 ml dimethylacetamide, 20 ml toluene, 1.8 g NaOH and 3 ml of water were heated under reflux until until no more water has been separated on the water separator. The toluene was then distilled off and the Reaction mixture after the addition of 7.1 g 4-Chloronitrobenzene heated under reflux for 24 hours. To the reaction mixture was cooled to 25 ° C. Filtered solids and discarded. From the filtrate the dimethylacetamide was removed by distillation in vacuo and the residue was recrystallized from acetonitrile. It 12.5 g (71% of theory) of a beige color remained Solid that melted at 160 ° C.

Die kernresonanzspektroskopische Analyse ergab folgende Werte:
¹H-NMR (CDCl₃)δ (ppm) : 8,2-8,3 m 4H, 7,15-7,5 m 8H, 7,0-7,1 m 12H;
¹⁹F-NMR (CDCl₃)δ (ppm): -64,4 s.The nuclear magnetic resonance analysis showed the following values:
1 H-NMR (CDCl₃) δ (ppm): 8.2-8.3 m 4H, 7.15-7.5 m 8H, 7.0-7.1 m 12H;
¹⁹F-NMR (CDCl₃) δ (ppm): -64.4 s.

Analyse für C₂₄H₂₄F₁₂N₂O₇:
ber.:
C 56,26, H 2,70, F 25,43, N 3,13, O 12,49;
gef.:
C 55,70, H 2,60, F 25,30, N 2,90, O 12,40.Analysis for C₂₄H₂₄F₁₂N₂O₇:
calc .:
C 56.26, H 2.70, F 25.43, N 3.13, O 12.49;
found:
C 55.70, H 2.60, F 25.30, N 2.90, O 12.40.

2) 4,4′-Bis[2-(4-(4-aminophenyl)phenyl)hexafluorisopropyl]- diphenylether2) 4,4'-bis [2- (4- (4-aminophenyl) phenyl) hexafluoroisopropyl] - diphenyl ether

19 g 4,4′-Bis[2-(4-(4-nitrophenoxy)phenyl)- hexafluorisopropyl]diphenylether wurden in 250 ml Essigsäureethylester gelöst und unter Zusatz von 1 g Palladium auf Kohle (5% Pd-Anteil) in einem 1-l-Autoklaven mit Wasserstoff (100 bar) bei 25-30°C reduziert. Nach der Reduktion wurde der Katalysator abfiltriert und das Lösungsmittel abdestilliert. Das Rohprodukt (18,1 g) wurde in der Wärme in einer Lösung aus Oktan/Toluol (19/1) gelöst und mit 3 g Aktivkohle behandelt. Die blaßgelbe Lösung wurde nochmals vollständig eingeengt und der Rückstand aus Toluol umkristallisiert. Ausbeute: 15,4 g (85% d. Th.) blaßgelber Feststoff, Fp.: 91-93°C.19 g 4,4'-bis [2- (4- (4-nitrophenoxy) phenyl) - hexafluoroisopropyl] diphenyl ether was added in 250 ml  Dissolved ethyl acetate and with the addition of 1 g Palladium on carbon (5% Pd content) in a 1 liter autoclave reduced with hydrogen (100 bar) at 25-30 ° C. After The catalyst was filtered off and the reduction Distilled off solvent. The crude product (18.1 g) was dissolved in heat in a solution of octane / toluene (19/1) and treated with 3 g activated carbon. The pale yellow solution was again completely concentrated and the residue Recrystallized toluene. Yield: 15.4 g (85% of theory) pale yellow solid, m.p .: 91-93 ° C.

Kernresonanzspektroskopie:
¹H-NMR (CDCl₃)δ (ppm): 7,4-6,6 m 24 H, 3,5 breites s 4H;
¹⁹F-NMR (CDCl₃)w (ppm): -64,6 s.Nuclear magnetic resonance spectroscopy:
1 H-NMR (CDCl₃) δ (ppm): 7.4-6.6 m 24 H, 3.5 broad s 4H;
¹⁹F-NMR (CDCl₃) w (ppm): -64.6 s.

Analyse für C₂₄H₂₈F₁₂N₂O₃:
ber.:
C 60,29, H 3,37, F 27,25, N 3,35, O 5,74;
gef.:
C 60,20, H 3,20, F 26,80, N 3,50, O 5,80.Analysis for C₂₄H₂₈F₁₂N₂O₃:
calc .:
C 60.29, H 3.37, F 27.25, N 3.35, O 5.74;
found:
C 60.20, H 3.20, F 26.80, N 3.50, O 5.80.

3) 4,4′-Bis[2-(4-(3-nitrophenoxy)phenyl)hexafluorisopropyl]- diphenylether3) 4,4'-bis [2- (4- (3-nitrophenoxy) phenyl) hexafluoroisopropyl] - diphenyl ether

196 g 4,4′-Bis[2-(4-hydroxyphenyl)- hexafluorisopropyl]diphenylether wurden in 1000 ml Dimethylformamid gelöst und nach der Zugabe von 120 g 1,3-Dinitrobenzol sowie 114 g Kaliumcarbonat 8 Stunden unter Rückfluß erhitzt. Die erkaltete Reaktionsmischung wurde in 10 l Wasser eingetragen und nach der Zugabe von 10 ml konz. Salzsäure filtriert. Der abgetrennte Feststoff wurde intensiv mit Wasser gewaschen. Ausbeute: 217 g (81% d. Th.) hellbrauner Feststoff, Fp.: 105-107°C.196 g 4,4'-bis [2- (4-hydroxyphenyl) - hexafluoroisopropyl] diphenyl ether were added in 1000 ml Dimethylformamide dissolved and after the addition of 120 g 1,3-dinitrobenzene and 114 g of potassium carbonate under 8 hours Heated to reflux. The cooled reaction mixture was in 10 l of water entered and after adding 10 ml of conc. Hydrochloric acid filtered. The separated solid became washed intensively with water. Yield: 217 g (81% of theory) of a light brown solid, Mp .: 105-107 ° C.

Kernresonanzspektroskopie:
¹H-NMR (CDCl₃)δ (ppm): 7,0-7,1 m 8H, 7,3-7,5 m 12 H, 7,9-8,0 m 4H;
¹⁹F-NMR (CDCl₃)δ (ppm): -64,47 s. Nuclear magnetic resonance spectroscopy:
1 H-NMR (CDCl₃) δ (ppm): 7.0-7.1 m 8H, 7.3-7.5 m 12 H, 7.9-8.0 m 4H;
¹⁹F-NMR (CDCl₃) δ (ppm): -64.47 s.

4) 4,4′-Bis[2-(4-(3-aminophenoxy)phenyl)hexafluorisopropyl]- diphenylether4) 4,4′-bis [2- (4- (3-aminophenoxy) phenyl) hexafluoroisopropyl] - diphenyl ether

89 g 4,4′-Bis[2-(4-(3-nitrophenoxy)- phenyl)hexafluorisopropyl]diphenylether wurden in 3000 ml Ethanol gelöst und in einem Stahlautoklaven nach der Zugabe von 2 g Palladiumkohle (5%ig) bei 50°C mit Wasserstoff (100 bar) reduziert. Nach dem Abfiltrieren des Katalysators wurde das Lösungsmittel vollständig abdestilliert. Das Rohprodukt wurde in Methanol gelöst und in der Siedehitze mehrmals mit Aktivkohle behandelt. Ausbeute: 54 g (64% d. Th.) blaßgelber Feststoff, Fp.: 74-77°C.89 g 4,4'-bis [2- (4- (3-nitrophenoxy) - phenyl) hexafluoroisopropyl] diphenyl ether were dissolved in 3000 ml Dissolved ethanol and in a steel autoclave after the addition of 2 g palladium-carbon (5%) at 50 ° C with hydrogen (100 bar) reduced. After filtering off the catalyst the solvent was distilled off completely. The Crude product was dissolved in methanol and at the boiling point treated several times with activated carbon. Yield: 54 g (64% of theory) of a pale yellow solid, Mp .: 74-77 ° C.

Kernresonanzspektroskopie:
¹H-NMR (CDCl₃)δ (ppm): 3,6 breites s 4H, 6,4-6,5 m 6H, 6,9-7,1 m 12H, 7,2-7,4 m 6H;
¹⁹F-NMR (CDCl₃)δ (ppm): -64,5 s.Nuclear magnetic resonance spectroscopy:
1 H-NMR (CDCl₃) δ (ppm): 3.6 broad s 4H, 6.4-6.5 m 6H, 6.9-7.1 m 12H, 7.2-7.4 m 6H;
¹⁹F-NMR (CDCl₃) δ (ppm): -64.5 s.

Analyse für C₄₂H₂₈F₁₂N₂O₃:
ber.:
C 60,29, H 3,27, F 27,25, N 3,35, O 5,74;
gef.:
C 60,70, H 3,30, F 26,80, N 3,60, O 6,20.Analysis for C₄₂H₂₈F₁₂N₂O₃:
calc .:
C 60.29, H 3.27, F 27.25, N 3.35, O 5.74;
found:
C 60.70, H 3.30, F 26.80, N 3.60, O 6.20.

5) 4,4′-Bis[2-(4-(2-chloro-4-nitrophenoxy)phenyl)- hexafluorisopropyl]diphenylether5) 4,4'-bis [2- (4- (2-chloro-4-nitrophenoxy) phenyl) - hexafluoroisopropyl] diphenyl ether

39.2 g 4,4′-Bis[2-(4-hydroxyphenyl)- hexafluorisopropyl]diphenylether wurden in 250 ml Dimethylformamid gelöst und nach der Zugabe von 25 g 3,4-Dichlornitrobenzol sowie 22 g Kaliumkarbonat 4 Stunden unter Rückfluß erhitzt. Die erkaltete Reaktionsmischung wurde in 1000 ml Wasser getropft und nach der Zugabe von 10 ml konz. Salzsäure filtriert. Der abgetrennte Feststoff wurde mit Wasser gewaschen und nach dem Trocknen aus Acetonitril umkristallisiert. Ausbeute: 37 g (64% d.Th.), Fp.: 154-156°C.39.2 g 4,4'-bis [2- (4-hydroxyphenyl) - hexafluoroisopropyl] diphenyl ether was added in 250 ml Dimethylformamide dissolved and after the addition of 25 g 3,4-dichloronitrobenzene and 22 g potassium carbonate Heated under reflux for 4 hours. The cooled Reaction mixture was dropped into 1000 ml of water and after the addition of 10 ml conc. Hydrochloric acid filtered. The separated solid was washed with water and after recrystallized from drying from acetonitrile. Yield: 37 g (64% of theory), mp .: 154-156 ° C.

Kernresonanzspektroskopie:
¹H-NMR (CDCl₃)δ (ppm): 7,0-7,1 m 1 OH, 7,4-7,5 m 8H, 8,1-8,2 2d 2H, 8,4 d 2H;
¹⁹F-NMR (CDCl₃)δ (ppm): -64,5 s.Nuclear magnetic resonance spectroscopy:
1 H-NMR (CDCl₃) δ (ppm): 7.0-7.1 m 1 OH, 7.4-7.5 m 8H, 8.1-8.2 2d 2H, 8.4 d 2H;
¹⁹F-NMR (CDCl₃) δ (ppm): -64.5 s.

6) 4,4′-Bis[2-(4-(4-amino-2-chlorphenoxy)phenyl)- hexafluorisopropyl]diphenylether6) 4,4'-bis [2- (4- (4-amino-2-chlorophenoxy) phenyl) - hexafluoroisopropyl] diphenyl ether

29 g 4,4′-Bis[2-(4-(2-chloro-4-nitrophenoxy)- phenyl)hexafluorisopropyl]diphenylether wurden in 300 ml Essigester gelöst und nach der Zugabe von 1 g Palladiumkohle (5%ig) in einem Stahlautoklaven mit Wasserstoff (100 bar) bei 50°C reduziert. Nach der Abtrennung des Katalysators wurde der Essigester am Rotationsverdampfer vollständig abgetrennt. Das Rohprodukt wurde in 30 ml verd. Salzsäure eingetragen und aus Ethanol umkristallisiert, wobei die Lösung in der Siedehitze mit Aktivkohle behandelt wird. Nach dem Abkühlen der Reaktionsmischung auf +10° wurde der ausgefallene weiße Niederschlag abfiltriert, mit Wasser gewaschen und in 400 ml Wasser suspendiert. Die Suspension wurde mit verd. Ammoniak-Lösung neutralisiert, der Feststoff anschließend abfiltriert und mit Wasser gewaschen. Ausbeute: 21 g (72% d.Th.) weißer Feststoff, Fp.: 93-95°C.29 g 4,4'-bis [2- (4- (2-chloro-4-nitrophenoxy) - phenyl) hexafluoroisopropyl] diphenyl ether were dissolved in 300 ml Dissolved ethyl acetate and after the addition of 1 g Palladium-carbon (5%) in a steel autoclave with Hydrogen (100 bar) reduced at 50 ° C. After The catalyst was separated off on the ethyl acetate Rotary evaporator completely separated. The raw product was added to 30 ml of dilute hydrochloric acid and from ethanol recrystallized, the solution at the boiling point with Activated carbon is treated. After cooling the Reaction mixture at + 10 ° became the precipitated white The precipitate is filtered off, washed with water and in 400 ml of water suspended. The suspension was diluted with Ammonia solution neutralized, the solid subsequently filtered off and washed with water. Yield: 21 g (72% of theory) of white solid, mp: 93-95 ° C.

Kernresonanzspektroskopie:
¹H-NMR (CDCl₃)δ (ppm): 3,5 breites s 4H, 6,5-6,6 2d 2H, 6,8-7,4 m 2OH;
¹⁹F-NMR (CDCl₃)δ (ppm): -64,5 s.Nuclear magnetic resonance spectroscopy:
1 H-NMR (CDCl₃) δ (ppm): 3.5 broad s 4H, 6.5-6.6 2d 2H, 6.8-7.4 m 2OH;
¹⁹F-NMR (CDCl₃) δ (ppm): -64.5 s.

Claims (9)

1. Verbindung der Formel in der R¹ und R² verschieden voneinander sind und Wasserstoff, -NO₂ oder -NH₂ bedeuten, R³ Wasserstoff oder Halogen ist mit der Maßgabe, daß R¹ Wasserstoff ist, wenn R² -NO₂ oder -NH₂ ist und R² Wasserstoff ist, wenn R¹ -NO₂ oder -NH₂ ist.1. Compound of the formula in which R¹ and R² are different from each other and denote hydrogen, -NO₂ or -NH₂, R³ is hydrogen or halogen with the proviso that R¹ is hydrogen when R² is -NO₂ or -NH₂ and R² is hydrogen when R¹ is -NO₂ or -NH₂ is. 2. Verbindung nach Anspruch 1, dadurch gekennzeichnet, daß das Halogen Chlor ist. 2. Compound according to claim 1, characterized in that the halogen is chlorine. 6. Verfahren zur Herstellung von Verbindungen gemäß einem oder mehreren der Ansprüche 1 bis 5 durch Umsetzung von aromatischen Nitroverbindugnen mit einer entsprechenden Dihydroxyverbindung und gegebenenfalls anschließender Reduktion, dadurch gekennzeichnet, daß 4,4′-Bis [2-(4- hydroxyphenyl)hexafluorisopropyl]diphenylether in einem dipolaren aprotischen Lösungsmittel gelöst und in Gegenwart von mindestens stöchiometrischen Mengen einer basischen Verbindung mit Halogennitrobenzol, Dihalogennitrobenzol oder Dinitrobenzol bei Temperaturen von 50 bis 200°C zur Reaktion gebracht und das Reaktionsprodukt isoliert oder nach Isolierung in einer zweiten Stufe katalytisch oder stöchiometrisch hydriert wird.6. Process for the preparation of compounds according to one or more of claims 1 to 5 by implementing aromatic nitro compounds with a corresponding Dihydroxy compound and optionally subsequent Reduction, characterized in that 4,4′-bis [2- (4- hydroxyphenyl) hexafluoroisopropyl] diphenyl ether in one Dipolar aprotic solvent dissolved in Presence of at least stoichiometric amounts of one basic compound with halogen nitrobenzene, Dihalogenitrobenzene or dinitrobenzene at temperatures reacted from 50 to 200 ° C and that Reaction product isolated or after isolation in a second stage catalytically or stoichiometrically hydrogenated becomes. 7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß 4-Chlornitrobenzol, 3,4-Dichlornitrobenzol oder 1,3-Dinitrobenzol eingesetzt werden.7. The method according to claim 6, characterized in that 4-chloronitrobenzene, 3,4-dichloronitrobenzene or 1,3-dinitrobenzene can be used. 8. Verfahren nach Anspruch 6 oder 7, dadurch gekennzeichnet, daß als aprotische Lösungsmittel Dimethylformamid, Dimethylacetamid, Dimethylsulfoxid, Dimethylsulfon, Sulfolan oder 1-Methyl-2-pyrrolidinon einzeln oder im Gemisch eingesetzt werden.8. The method according to claim 6 or 7, characterized characterized in that as an aprotic solvent Dimethylformamide, dimethylacetamide, dimethyl sulfoxide, Dimethyl sulfone, sulfolane or 1-methyl-2-pyrrolidinone used individually or in a mixture. 9. Verfahren nach einem oder mehreren der Ansprüche 6 bis 8, dadurch gekennzeichnet, daß als basische Verbindungen Alkalihydroxide, Ammoniumhydroxid, Alkalihydroxid, Alkali- oder Erdalkalicarbonate oder -hydrogencarbonate sowie Alkalialkoholate eingesetzt werden.9. The method according to one or more of claims 6 to 8, characterized in that as basic compounds Alkali hydroxides, ammonium hydroxide, alkali hydroxide, Alkali or alkaline earth carbonates or bicarbonates as well as alkali alcoholates are used. 10. Verfahren nach einem oder mehreren der Ansprüche 6 bis 9, dadurch gekennzeichnet, daß für die katalytische Hydrierung Metallkatalysatoren aus der Gruppe der Platinmetalle, Kupfer, Eisen, Kobalt, Nickel, Mischungen daraus sowie Metalloxide bei Temperaturen von 10 bis 130°C eingesetzt werden. 10. The method according to one or more of claims 6 to 9, characterized in that for the catalytic Hydrogenation metal catalysts from the group of Platinum metals, copper, iron, cobalt, nickel, mixtures therefrom as well as metal oxides at temperatures from 10 to 130 ° C can be used.   11. Verwendung der Aminoverbindungen gemäß den Ansprüchen 1 bis 5 zur Herstellung von hochtemperaturbeständigen Polykondensaten.11. Use of the amino compounds according to the claims 1 to 5 for the production of high temperature resistant Polycondensates. 12. Verwendung nach Anspruch 11 zur Herstellung von Polyimiden und Polyamiden.12. Use according to claim 11 for the production of Polyimides and polyamides.
DE19873739799 1987-11-24 1987-11-24 Fluorine-containing compounds based on 4,4'-bis[2-(4-hydroxyphenyl)hexafluoroisopropyl] diphenyl ether, their preparation and their use Withdrawn DE3739799A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
DE19873739799 DE3739799A1 (en) 1987-11-24 1987-11-24 Fluorine-containing compounds based on 4,4'-bis[2-(4-hydroxyphenyl)hexafluoroisopropyl] diphenyl ether, their preparation and their use
EP88119069A EP0317882B1 (en) 1987-11-24 1988-11-17 Fluor containing compounds based on 4,4'-bis[2-(4-hydroxy-phenyl)hexafluorisopropyl]diphenylether, process for their preparation and use
DE8888119069T DE3882658D1 (en) 1987-11-24 1988-11-17 FLUORIC COMPOUNDS BASED ON 4,4'-BIS (2- (4-HYDROXY-PHENYL) HEXAFLUORISOPROPYL) DIPHENYL ETHER, METHOD FOR THEIR PRODUCTION AND THEIR USE.
JP63293756A JPH01165552A (en) 1987-11-24 1988-11-22 Fluorine-containing compound based on 4, 4'-bis (2-(4-hydroxyphenyl)hexafluoroisopropyl) diphenyl ether, and its production and use
CA000583836A CA1331018C (en) 1987-11-24 1988-11-23 Fluoro-containing compounds based on 4,4'-bis [2-(4-hydroxyphenyl)hexafluoroisopropyl]diphenylether, processes for their preparation and their use
KR1019880015403A KR890008077A (en) 1987-11-24 1988-11-23 Fluoro-containing compounds based on 4,4'-bis [2- (4-hydroxyphenyl) hexafluoroisopropyl] diphenyl ether, methods for their preparation and uses thereof
US07/276,194 US4978790A (en) 1987-11-24 1988-11-23 4,4'-bis[2-(4-hydroxy-amino-phenyl)hexafluoroisopropyl]-diphenylethers and their use
US07/569,615 US5081315A (en) 1987-11-24 1990-08-20 Fluoro-containing compounds based on 4,4'-bis[2-(4-hydroxyphenyl) hexafluoroisopropyl]diphenyl ether, processes for their preparation and their use

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DE19873739799 DE3739799A1 (en) 1987-11-24 1987-11-24 Fluorine-containing compounds based on 4,4'-bis[2-(4-hydroxyphenyl)hexafluoroisopropyl] diphenyl ether, their preparation and their use

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