DD282715A5 - PROCESS FOR PREPARING PERFLUORIZED 1,3-OXAZOOLIDINES - Google Patents

Abstract

The invention relates to a new production process of new perfluorinated 1,3-oxazolidines. The new compounds can be used for gas transport reactions in medicine, biology and electronics and can be well emulsified with water. According to the invention, compounds of the general formula I are obtained in which R.sup.2 and R.sup.2 are each fluorine or an alkyl radical or together form a 5- to 7-membered ring by electrofluorination of caprolactams of the general formula II in which R is an alkyl radical having 2 to 10 carbon atoms or a cycloalkyl radical having 5 to 7 carbon atoms. {perfluorinated compounds; 1,3-oxazolidines; caprolactam; electrofluorination; Gasuebertraeger; Sauerstoffuebertraeger; emulsions}

Description

(II) - R

in which R is a straight-chain or branched alkyl radical having 2 to 10 carbon atoms or may be a cycloalkyl radical having a 5 to 7-membered ring, are electrochemically perfluorinated in anhydrous liquid hydrogen fluoride.

2. The method according to claim 1, characterized in that R _F , and R _F , each represents fluorine.

3. The method according to claim 1, characterized in that R _{Fi is} fluorine and R _{Fj is} trifluoromethyl.

4. The method according to claim 1, characterized in that R is _F , fluorine and R _F , pentafluoroethyl.

5. The method according to claim 1, characterized in that the preferred number of carbon atoms in the total molecule is 8-12.

6. The method according to claim 1-5, characterized in that perfluoro-8-oxa-iazabicyclo [5,3,0] decane, perfluoro-g-methyl-S-oxa-i-azabicycloiB.S.Ojdecanund perfluoro-g ethyl-S-oxa-i-azabicycloIö.SiOldecanherstellt.

7. The method according to claim 1, characterized in that perfluoro-2-oxa-9-azatricyclo (8,4,0,0 ³ⁱ⁹ ] tetradecane and perfluoro ^ -oxa ^ -azatricyclolS ^ AO ^ Jtridecan produces.

Field of application of the invention

The invention relates to a novel process for preparing novel perforated 1,3-oxazolidines. The produced perfluorinated 1,3-oxazolidines are distinguished by their excellent emulsifiability and can be used, for example, for gas transport reactions in medicine.

Characteristic of the known state of the art

A large number of perfluorinated compounds are already known, including heterocyclic compounds which contain nitrogen and oxygen as ring members. For example, perfluorinated N-substituted morpholines could be prepared by electrofluorination of the analogous perhydro-morpholines (Zhs obs Khim. 35 [1965] 485-489). Perfluoro-1,3-oxazolidines are also known, they could be obtained by pyrolysis of nonafluoroporpholine (RE Banks, ED Burling, J. Chem. Soc. 1965, 6077-83) or by electrofluorination of carbamoyl chlorides (JA Young, TCSimmons FW Hoffman, J. Amer. Chem. Soc., 78 [1956]. The pel fluorinated 1,3-oxazolidines thus depicted are exclusively monocycles.

Object of the invention

The aim of the invention is to find Wettere perfluorinated heterocycles, the dio gas-carrying properties and to develop new ways to process it.

Essence of the invention

The object of the invention is to develop a process for the manufacture of perfluorinated 1,3-oxazolidines. This object is achieved by the electrofluoriete of caprolactams of the general formula II,

NO

in which R is a straight-chain or branched alkyl radical having 2 to 10 carbon atoms or is a cycloalkyl radical, where the

Cycloalkyl may be a 5- to 7-membered ring. According to the invention, perfluorinated bicyclic or tricyclic 1,3-oxazolidines of general formula I are obtained.

rr

in which Rf ₁ and Rf ₁ each fluorine or a straight-chain or branched Perf luoralkylrest with at most 4

Represent carbon atoms, or wherein Rf ₁ and R _{F |} can be linked to a S to 7-membered ring. These compounds have not been described. Also, the manufacturing process of these compounds is new. Normally, electrofluorination is used when using perfluorinated compounds from the structural analogues Wants to produce starting products. A structural change during electrofluorination is generally not

predictable. Surprisingly, it has been found in the present invention that the used

Caprolactamstrukturen form a five-membered ring during the electrofluorination over the ring-bound residue. These Structural changes to 1,3-oxazolidines were unpredictable. The new compounds are very emulsifiable with water and are suitable because of their particularly good

gas carrying properties especially for use in medicine, biology and electronics.

Preferred 1,3-oxazolidines have a total carbon number in the molecule of 8 to 12. Especially preferred is the new one Compound perfluoro-SJ-ethyl-S-oxa-i-azabicycloB ^ oldecane. Further preferred 1,3-oxazolidines according to the invention are perfluoro-1-methyl-S-oxa-1-azabicycloIB ^ oldecane Perfluoro-e-oxa-i azabicyclolBAOIdecan Perfluoro ^ oxa-S-azatricyclole ^ ^ .O.O ltetradecan Perfluoro-2-oxa-9-azatricyclo [8,3,0,0 ^3il ] tridecane. The electrochemical fluorination is carried out in a Si-ZeIIe, wherein the corresponding caprolactam derivative in

anhydrous liquid hydrogen fluoride is dissolved and the resulting solution at 4.5-9 V, with current densities of 0.1-10 A / dm ² and 0-10 ⁰ C of nickel anodes is subjected to the electrolysis. The compounds of formula I differ on

Bottom of the cell as they are not soluble in liquid hydrogen fluoride. The isolation and purification of perfluorinated Compound is made by washing with bicarbonate solution and refluxing with 8N potassium hydroxide / dibutylamine for 5 days

(1: 1), whereby partially fluorinated compounds are destroyed. After cooling, the lower layer becomes the desired

Perfluor / compounds contained, separated, washed with water, half-concentrated sulfuric acid and again with water. It is then fractionally distilled. For analytical characterization, preparative gas chromatography was used

(20% squalene on Chromosorb) obtained a pure sample. The identification of the perfluoro-1,3-oxazolidines was carried out by MS and ¹³ F-NMR.

embodiments The invention will be explained in more detail by examples. example 1

163 g (1 mol) of N-butylcaprolactam were dissolved in 1 liter of anhydrous hydrogen fluoride in a Telion cell and electrofluorinated at 0-5 ° C with 6-7V on nickel electrodes for 200 hours.

Thereafter, the perfluorinated product was let out of the cell, neutralized with bicarbonate and heated with stirring for 5 days Reflux with 200ml 8N KOH / 200ml dibutylamine. After cooling, the lower layer was separated, with half-concentrated Sulfuric acid and then washed with water and distilled. This gave 71 g of a product of boiling point 145-150 ° C.

By fractional distillation, which consisted of 50% of a perfluoro-9-ethyl-8-oxa-1-azabicyclo [5,3,0] decane, corresponds to one

Yield of 7%. By preparative gas chromatography 620% Fomblin 425 on Chromosorb PAW) became the product

and the structure confirmed by MS and ¹⁹ F nuclear resonance.

belspiel2

195 (1 mol) of N-cyclohexylcaprolactam were dissolved in 1 liter of anhydrous hydrogen fluoride and electrofluorinated in a Teflon cell on nickel electrodes at 4-12 ⁰ C and 6-7 volts for 200 hours. 63 g of fluorination product were removed, which was worked up as in Example 1. The obtained 46 g distillate with a boiling point of 155-160 contained by GLC (squalene) in 50-m capillary acid 60% perfluoro ^ -oxa-g-azatricycloie ^ .OO ³⁹ ] tetradecane (corresponding to a yield of 4.8%), whose structure was confirmed after isolation by preparative GCL (20% Fomblin 425 on Chormosorb PAW) by MS and ¹⁹ F-NMR.

Claims (1)

1. A process for the preparation of perfluorinated 1,3-oxazolidines of the general formula I. "O-f ^F 2 N ¹ ^ Rp in which R _Fl and R _{F] are} each fluorine or a straight-chain or branched perfluoroalkyl radical having at most 4 carbon atoms, or R _F , and R _F , are linked to form a 5- to 7-membered ring, characterized in that caprolactams of the general formula II