DD275079A1 - PROCESS FOR PREPARING PERFLUORIZED DICYCLIC AMINE - Google Patents

Abstract

The invention relates to the preparation of partially novel perfluorinated dicyclic amines of the general formula wherein the rings A and B may be 5-, 6- and 7-membered and may contain further N and / or O atoms. By electrofluorination of the corresponding enamines you get the partially new dicyclic amines that are applicable as Sauerstoffuebertraeger in medicine and biology. formula

Description

Field of application of the invention

The invention relates to a novel process for the preparation of perfluorinated dicyclic amines. The produced perfluorinated amines are suitable for the preparation of emulsions which can be used for gas transport purposes in biology and medicine.

Characteristic of the Prior Art Perfluorinated dicyclic amines of the general formula I

Λ C - N B J

are known (see, for example, JP 58-96061).

They are characterized by good emulsifiability and are already being used in medicine (Z. vses., In his Mendelejeva 30 [1185], 387).

They are obtained by the known electrochemical fluorination reaction of the corresponding acyclic amines in liquid, anhydrous hydrogen fluoride. The disadvantage of this method is that the required dicyclic amines u.a. by reactive alkylation of secondary amines with Caroonylvorbindungen or by alkylation with Cycloalkylhalogeniden must.

Object of the invention

The aim of the invention is to develop a simplified process for the production of new or known perforated diamines, in which the electrochemical fluorination is used as the perfluorination step and which proceeds from readily available starting materials, wherein a wide range of variation is to be achieved.

C setting of the essence of the invention

The invention is based on the object of developing a novel process for the preparation of perfluorinated amines and of providing new perfluorinated amines. This object is achieved by the electrofluorination of enamines of general formula II,

in the R, to R _{4 can be} hydrogen or alkyl having 1 to 2 carbon atoms. The rings Α _Ί and B | may be 5- to 7-membered rings, wherein 1 or 2 carbon atoms of the rings may be replaced by nitrogen and / or oxygen atoms. The preparation of the enamines is carried out in a known manner very easily and in good yields from cyclic ketones and cyclic secondary amines. Preferably, both rings Ai and Bi are five to seven members, and any combinations of the rings A ₁ and B _{1 are} possible. The ring A) preferably has a heteroatom, optionally also the ring B | another heteroatom, which may be nitrogen or oxygen. Both rings A _t and B ₁ in the combination preferably contain a maximum of three heteroatoms, which is due to the synthesis of the enamines. The rings A and B can be perfluoroalkyl-substituted, alone or in combination, where R 1 to R _{4 can have} one to two perfluorinated C atoms. Most preferably, the new compound is perfluoro-4-cycloheptyl-morpholine. Further preferred perfluorinated dicyclic amines according to the invention are:

Perfluoro-i-cyclopentyl-pyrrolidin

PerfluoM-cyclopentyl-morpholine

PerfluoM-cyclehexyl-morpholine

Perfl'jor-i-cycloheptyl-piperidine

PerfJ'joM-cycloheptyl-morpholine

Perfluoro-1-cyclol. 'Otyl-azepan

Perfluoro-4- (2-methylcyclohexyl) -pipcridin

Perfluoro-4- (2-methyl-cyclohexyl) -morpholin

Porfluor-4- (4-mothyl-cyclohexyl) -morpholin

The electrochemical fluorination and work-up of the perfluorinated crude product is carried out in a Simons cell to nickel anodes in anhydrous, liquid hydrogen fluoride at 4.5V to 9V, preferably 5V to 8V, with current densities of 0.05A / dm ² to 8A / dm ', preferably at 0.1 A / dm ² to 3A / dm ² , and at -20X to + 4O ⁰ C, preferably at ^{0 0} C to + 10 ⁰ C.

While the starting compounds are readily soluble in liquid hydrogen fluoride to give solutions of good electrical conductivity, the perforated dicyclic amines precipitate as a liquid hydrogen fluoride immiscible liquid phase at the bottom of the fluorination blocks. The fluorination product discharged at the bottom of the fluorination cell is washed neutral with bicarbonate solution and distilled water. For further purification, it can then be refluxed with 5n KOH / dibutylamine (1: 1) for 5 days, washed again neutral, washed with half-concentrated HjSO _4, washed again neutral and then distilled. From the perfluoroaminoether a preparative GLC (20% squalane on Chromosorb W-HHDS) for the analytical characterization of a high purity sample can be obtained. The identification of the perfluoroamino ethers obtained is carried out by means of MS, ¹⁹ F-NMR and elcmentaranalytisch. The absence of hydrogen-containing compounds is confirmed by ¹ H-NMR. The process of the invention makes it possible to use the additional process step of alkylating suitable starting materials, which must be selectively carried out, with enamines which are very readily available starting materials. In addition, the new method allows a wide range of variations in the production of perfluorinated compounds.

embodiments

The invention will be explained in more detail by examples.

example 1

73.5 g of 4-cyclohept-1-enyl-morpholine were dissolved in a Teflon cell in 0.7 liters of anhydrous hydrogen fluoride and electrofurbated at 0 to 5 ⁰ C with 6 to 7 volts of nickel electrodes 130 hours. Thereafter, 103 g of the enamine and fluorine water were released off and then electrofluorinated for another 2 hours at 7 volts. The perfluorinated product (277 g) was left out of the cell ib, neutralized with bicarbonai, and the perfluoro compounds were distilled off together with water. After separation of the Perfluorverbindi'ngen was heated for 8 hours with stirring with 200ml 8 N sodium hydroxide solution at reflux and the process repeated with fresh sodium hydroxide solution. After washing with dilute sulfuric acid and water, the product from bp 140-145T was separated by preparative gas chromatography ('0% Fomblin 425 on Chromosorb PAW) and perfluoro-4-cyclo-streptyl-morpholine by MS and ¹⁹ F-Kemresonani in the structure approved.

Example 2

179 g (1 mol) of 1- (2-methyl-cyclohex-1-enyl) -piperidine were electrofluorinated in 1 liter of anhydrous hydrogen fluoride dissolved in a Tefion cell on nickel anodes at 0 ° C to 5 ° C and 6 to 8V. After 150 hours, 180 g of fluorination product were drained off and worked up as in Example 1. This gives 120 g of a double bond and anhydrous mixture, which after GLC (squalane) in 50-m capillary 707oPerfluor-1- (2-methyl-cyclohexyl) piperidinone held.

Claims (9)

1. Process for the preparation of perfluorinated dicyclic amines of the general formula I ₁ R. wherein A and B are 5- to 7-membered rings, wherein 1 or 2 C atoms can be replaced by N and / or O atoms, and which can have a maximum of 2 perfluoro-cycloalkyl substituents having at most 2 C atoms each, characterized in that Ena.nine of general formula II, in which R ₁ to R _{4 may be} hydrogen or alkyl having 1 to 2 C atoms, the rings A ₁ and B _{1 are} five to seven-membered rings, wherein 1 or 2 C-atoms are replaced by N and / or O atoms can be electrochemically perfluorinated in anhydrous, liquid hydrogen fluoride. 2. The method according to claim 1, characterized in that both rings A ₁ and B ₁ may be 5-7gliedrig and all combinations of the rings A ₁ and B _{1 are} possible. 3. The method according to claim 1, characterized in that ring A ₁ may contain a heteroatom or ring B ₁ another heteroatom such as nitrogen or oxygen. 4. The method according to claim!, Characterized in that both rings in the combination can contain a maximum of three heteroatoms. 5. The method according to claim 1 to 4, characterized in that the rings A ₁ and B ₁ may be perfluoralkylsubstituiert alone or in combination, wherein Ri to R contains ₄ to 2 perfluorinated carbon atoms. 6. The method according to claim 1 to 3, characterized in that one produces perfluoro-4-cycloheptylmorpholine, perfluoro-1-cycloheptyl-piperidine and perfluoro-1-cycloheptyl-pyrrolidine. 7. The method according to claim 3 and 4, characterized in that one produces perfluoro-1-methyl-4- (1-piperidinyl-piperidine and Pörfluor-4- (1-methyl-4-piperidinyl) -morpholine. 8. The method according to claim 1 to 5, characterized in that one produces perfluoro-1- (2-methylcyclohexyl) -piperidine and perfluoro-4- (2-methyl-cyclohexyl) -morpholine. 9. The method according to claim 1, characterized in that one produces perfluoro-1- (4-methyl-cyclohexyl) -piperidine.