JPS58194877A - Novel perfluorospiro compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (Rf is trifluoromethyl or pentafluoroethyl). EXAMPLE:Perfluoro(3-methyl-1-oxaspiro[4,5]decane). USE:Very useful as an inert solvent having the thermal and chemical stability, further physiologically stable, and useful as an artificial blood material having a high dissolving ability for oxygen gas and gaseous carbon dioxide. PROCESS:A reactive derivative of a carboxylic acid expressed by formula II(R is methyl or ethyl), e.g. an acid halide or ester, is electrolyzed in hydrogen fluoride, and the compound of formula I is isolated from the resultant reaction mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel perfluorospiro compounds, and more particularly to perfluoro(3-alkyl-1-oxaspiro[4,5]decane).

In general, perfluorocyclic ethers are thermally and chemically stable, have been widely used as inert solvents, are physiologically stable, and have a high ability to dissolve oxygen gas and carbon dioxide gas. Because of its large size, its use as an artificial blood material in the life science field has recently been developed, and its usefulness has been attracting attention.

Conventionally, various production methods have been proposed for monocyclic perfluoroether compounds and perfluorobiccycloether compounds, but for perfluorospiro compounds, perfluoro(1-oxaspiro[4, 4] Nonane) is only known (Japanese Unexamined Patent Publication No. 5'4-12).
8566, Japanese Patent Publication No. 55-44071).

By the way, when perfluorocyclic ether compounds are used for the above-mentioned purposes, it is necessary to select an appropriate compound according to the purpose and conditions of use, and therefore there is a demand for the development of other perfluorocyclic ether compounds. .

The present inventors have conducted extensive research into the development of new perfluorocyclic ether compounds in order to meet these demands, and have found that by electrolytically fluorinating specific carboxylic acids substituted with nclohexyl/yl groups, they can be used together with various fluorinated compounds. ,
It was discovered that a novel perfluorospiro compound can be obtained, and the present invention was completed.

That is, the present invention provides perfluoro(3-alkyl-1-oxaspiro[4,5]decane) represented by the general formula (wherein Rf id is a fluoromethyl group or a pentafluoroethyl group) It is something to do.

The perfluorospiro compound of the present invention is one that has not yet been published in the literature, and includes, for example, a reactive derivative of a carboxylic acid represented by the general formula (R in the formula is a methyl group or an ethyl group), such as an acid halide or an ester, with hydrogen fluoride. The target compound is isolated from the reaction mixture.

The perfluoro(3-methyl-1
-Oxaspiro[4,5]tecan has a boiling point of 127-127
．． Perfluoro(3-ethyl-1), a colorless transparent liquid at 5°C.
-Oxaspiro[4)5]decane) has a boiling point of 140-14
It is a colorless and transparent liquid at 1°C.

The reactive derivative of carboxylic acid used as a raw material in the present invention is derived from a carboxylic acid having a structure represented by the above general formula (■), and is, for example, 2-methyl-3-cyclohequinlepropio 11-noic acid. Examples include methyl, 2-methyl-3-cyclohexylpropionic acid chloride, methyl 2-ethyl-3-cyclohexylpropionic acid chloride, and 2-ethyl-3-cyclohexylpropionic acid chloride.

Electrolytic fluorination in this method can be performed using an electrolytic cell commonly used in the field of conventional electrolytic fluorination, and usually has a current density of 2.0 to 5. OA/dm', bath temperature 3~
8°C, and if carried out batchwise, the electrolytic voltage is at least 8°C.
It is best to continue until v is reached.

In fact, it is preferable that a reactive derivative of carboxylic acid (d) as a raw material, hydrogen fluoride, be present in an amount of 0.1 to 0.3 mol.

According to the method of the present invention, the perfluorospiro compound represented by the general formula (1) of the present invention is a perfluorospiro compound represented by the general formula (II) of the raw material.
10 to reactive derivatives of carboxylic acids represented by
This perfluorospiro compound, obtained with a theoretical yield of 22, is thermally and chemically stable, making it extremely useful as an insoluble solvent, and is also physiologically stable.
In addition, it is useful as an artificial blood material because it has a high ability to dissolve oxygen gas and carbon dioxide gas.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 The electrolytic cell was made of Monel metal with a capacity of 1 ton, had 8 nickel anodes and 9 negative electrodes arranged alternately, had an effective anode area of 9.2 d, m'', and had a reflux condenser on the top of the tank. 1 ton of hydrogen fluoride was introduced into this electrolytic cell.
, trace amounts of impurities (moisture and sulfuric acid) due to preliminary electrolysis
:Removed. Then, 0174 mol of 2-methyl-3-cyclohexylpropionic acid methyl ester was dissolved in hydrogen fluoride, and a helium sludge was added at a flow rate of 100 me/mi.
Anode current density 3.5A/d while passing from the bottom of the tank at n
m'', a voltage of 5.5 to 6.5 V, and a bath temperature of 5 to 6° C., and electrolysis was performed for 225 Ahr until the electrolytic voltage reached 8.1 V.

After electrolysis, open the cock at the bottom of the electrolytic tank and pour out 48.7L of high boiling point fluorocarbons. 'I pulled it out. After adding a small amount of pelleted molecular tube 5A to remove the remaining trace amount of hydrogen fluoride, gas chromatography was performed.
[Carrier helium, liquid phase 1,6-bis(Ll,
Analysis using 12-1-lihydroberfluorodote/roxy)hexane revealed that it was colorless and transparent, with a boiling point of 127-12
Compound 11.57 was obtained at 7.5°C. This product was developed based on the results of instrumental analyzes such as infrared absorption spectra, 1.9F nuclear magnetic resonance spectra, and mass spectra, as well as the fact that α,α-dichloroperfluoroether compounds can be reacted with anhydrous aluminum chloride. (3-methyl-1-oxaspiro C4,5E decane). At this time, perfluoro(2-
Methyl-3-chlorohexylpropionic acid fluoride)
is 11.5 y.

After the shredded gas was passed through thorium pellets for fluoridation, it was introduced into a trap cooled with dry ice and acetone, where it was liquefied and collected, yielding a 5.72 fluorocarbon mixture. Analyzing this using gas chromatography, it was colorless and transparent with a boiling point of 127.2-12.
Compound 0.8f at 7.5°C was obtained. This product was analyzed in the same manner as above and was confirmed to be perfluoro(3-methyl-1-oxaspiro[4,5]tecan). The total yield of perfluoro(3-methyl=1-oxaspiro[4,5]tecane), which was the target product, was 14.8%.

Example 2 Using the same electrolytic cell as in Example 1, 2-methyl-3-7
Electrolytic fluorination was performed under the same conditions and method as in Example 1, except that 170 A hr electrolysis was performed using 0.150 mol of chlorhexylpropionic acid chloride and the electrolytic voltage reached 8.1 V.

After electrolysis is complete, open the drain cock at the bottom of the electrolytic tank and
．． 311 fluorocarbon mixture was extracted. Still in the cold trap, 3.12% of the fluorocarbon mixture was obtained. When these were treated and analyzed in the same manner as in Example 1, perfluoro(3-methyl-1-
7.1 f (yield: 9.9%) of oxaspiro[4,5]decane) was obtained. At the same time, perfluoro(
2-Methyl-3-7=17 clohekiflupropionic acid fluoride) is 6.57
Obtained.

Example 3 Using the same electrolytic cell as in Example 1, 2-ethyl-3-'
/Chloheki/lupropionic acid trimethyl ester 0177
220 A when the electrolytic voltage reaches 7.9 ■ using moles.
Electrolytic fluorination was performed under the same conditions and method as in Example 1, except that hr electrolysis was performed. After electrolysis was completed, the drain cock at the bottom of the electrolytic cell was opened and the 52.12 fluorocarbon mixture was taken out. This was treated in the same manner as in Example 1, and analysis revealed that perfluoro(3-ethyl-1-oxaspiro[4,5]tecan) (boiling point 140-141°C)
)-Uzg, 2q (yield 9.8%) was obtained. At the same time, 7.42% of perfluoro(2-ethyl-3-cyclohexylpropionic acid fluoride) was obtained as the corresponding perfluorocarboxylic acid fluoride. In addition,
In this case, the fluorocarbon mixture in the cold trap 2
．． The target perfluorospiro compound was not present in Sample No. 32.

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Claims (1)

[Scope of Claims] 1. Perfluoro(3-alkyl-1-oxaspiro[4,s]decane) represented by the general formula (wherein Rf is a trifluoromethyl group or a pentafluoroethyl group).