JPH0360812B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to novel nitrogen-containing perfluoropropenes and a method for producing the same. More specifically, the present invention provides novel perfluorinated (2
-dialkylaminopropene) and a method for efficiently producing the same using readily available raw materials. Background Art In recent years, fluorine-containing olefin compounds have been in the spotlight as synthetic intermediates and raw materials for various fluorine-containing products. It is widely used as a monomer for producing fluorine polymer compounds. In addition, various perfluoroalkyl iodides have recently attracted attention as materials for iodine photodissociation lasers (solar pump lasers), and the carbon atoms to which iodine is bonded to are tertiary rather than secondary. Furthermore, as a substituent, a perfluoroamino group is more desirable than a perfluoroalkyl group because it can shift the ultraviolet absorption maximum to the longer wavelength side and also suppress side reactions on the amount of light. By the way, perfluoroolefins having a perfluoro (N, N-dialkylamino) group, which is a type of fluorine-containing olefin, have a double bond as a reaction site, so it is difficult to use this compound as an intermediate raw material. Therefore, it is possible to produce various useful compounds having the perfluoro(N,N-dialkylamino) group. In addition, by copolymerizing the perfluoroolefin with other fluoroolefins and introducing a perfluoro (N,N-dialkylamino) group into the polymer, it is possible to reduce the crystallinity of the polymer and improve the mechanical properties. Improvements are possible. As described above, perfluoroolefins having a perfluoro(N,N-dialkylamino) group are extremely useful compounds as synthetic intermediates and monomers for producing fluorine-containing polymer compounds. However, such perfluorinated (N,
As perfluoroolefins having N-dialkylamino) groups, for example, perfluoro(N,N-dimethylvinylamine) (U.S. Pat. No. 3,311,599), perfluoro(N-vinylmorpholine) [Journal of・Chemical Society, Parkin (J.Chem.Soc.,
Perkin), page 5 (1973)], perfluoro(N-vinylpiperidine) [J.Chem.Soc., (C)]
No. 2608 (1968)], perfluoro(N-vinylpyrrolidine) (Japanese Patent Application No. 162632-1982), and perfluoro(N-vinylhexamethyleneimine) (Japanese Patent Application No. 166889-1989). vinylamines) are only known.
The scope of their use has been limited, and there has been a demand for newer perfluorinated compounds. Problems to be Solved by the Invention Under these circumstances, the present invention provides a method for synthesizing various fluorine-containing compounds, which can be produced from easily available raw materials in a high yield through simple processing. The purpose of this invention is to provide novel perfluoro(2-dialkylaminopropenes) useful as intermediates or fluorine-containing polymeric monomers. Means for Solving the Problems As a result of extensive research in order to develop a new polymerizable perfluoro compound, the present inventors discovered that a perfluoro compound having a perfluoro (N, N-dialkylamino) group at the 3-position was used as a raw material. By using fluoride or salt of (n-butyric acid) and heat-treating it at a specific temperature, we unexpectedly discovered that a new perfluoro(2-dialkylaminopropene) could be obtained. The invention was completed. That is, the present invention provides the general formula (R ₁ and R ₂ in the formula are each a perfluoroalkyl group having 1 to 5 carbon atoms, and both are bonded directly or through an oxygen atom or a nitrogen atom, and together with the nitrogen atom to which they are bonded, five The present invention provides perfluoro(2-dialkylaminopropene) represented by formula [R ₁ and R ₂ in the formula have the same meanings as above,
A perfluoro(3-dialkylamino-n-butyric acid) derivative represented by It can be manufactured by heat treatment at a certain temperature. The present invention will be explained in detail below. The compound represented by the above general formula () of the present invention is a new compound that has not been described in any literature, and is

As an example of [formula],

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[Formula] (n and m in the formula are integers of 1 to 5). In the present invention, in order to produce the compound, perfluoro(3-dialkylamino-n-butyric acid) represented by the general formula () is used as a raw material.
Derivatives are used. This one is, for example, the general formula (R ₃ and R ₄ in the formula are each an alkyl group having 1 to 5 carbon atoms, and both are bonded directly or through an oxygen atom or a nitrogen atom, and together with the nitrogen atom to which they are bonded, they are five-membered. A reactive derivative of 3-dialkylamino-n-butyric acid, such as an acid halide or an ester, is electrolyzed in hydrogen fluoride. It can be easily manufactured by fluorinating it. Also, perfluoro(3-dialkylamino-
The n-butyric acid) salt can be obtained by reacting the perfluoro(3-dialkylamino-n-butyric acid fluoride) obtained as described above with an alkali metal or alkaline earth metal hydroxide. In the present invention, perfluoro(3-dialkylamino-n-
Perfluoro(2-dialkylaminopropene) represented by the general formula () can be easily produced by simply heat-treating a (butyric acid) derivative at a temperature in the range of 100 to 500°C. At this time, as a raw material, perfluoro(3-dialkylamino-
Preference is given to using perfluoro(sodium 3-dialkylamino-n-butyrate), perfluoro(potassium 3-dialkylamino-n-butyrate). The thermal decomposition reaction temperature is 100-500℃, preferably
It is necessary to choose a temperature within the range of 200 to 300℃. This temperature
Below 100℃, the conversion rate is too low to be practical;
If the temperature exceeds 500°C, undesirable side reactions such as decomposition are likely to occur. Further, the reaction time depends on the treatment temperature, but is usually within the range of 10 seconds to 2 hours. When the treatment temperature is high, the reaction time becomes short, whereas when the treatment temperature is low, the reaction time becomes long, so it is desirable to adopt appropriate conditions as appropriate. In this thermal decomposition reaction, the reaction pressure is not an important factor, and the reaction can be carried out under reduced pressure, atmospheric pressure, or increased pressure, but the reaction products are relatively easy to recover. From this point of view, it is preferable to carry out the reaction under atmospheric pressure or reduced pressure.
In addition, depending on the reaction form, the thermal decomposition reaction may include nitrogen,
Inert gas such as helium, argon, carbon dioxide, polyether, tetrachloroethylene, n-
It may be carried out using an aprotic liquid compound such as heptane or powdered potassium fluoride as a diluent. In this case, the dilution ratio is preferably 100 times or less. In the method of the present invention, perfluoro(3-dialkylamino-n-butyric acid fluoride) is used as a raw material.
When using a metal salt or metal oxide, it is preferable to carry out the thermal decomposition reaction in the presence of a metal salt or metal oxide. In this case, the desired general formula (
A perfluoro(2-dialkylaminopropene) represented by is obtained. There are no particular restrictions on the material of the pyrolysis reactor, but stainless steel or Hastelloy is usually used. There is no particular restriction on the type of the packed bed, and any type such as a fixed bed, moving bed, or fluidized bed can be used. Examples of the metal salts include sodium carbonate, potassium carbonate, lithium carbonate, sodium phosphate, potassium phosphate, barium carbonate,
Calcium carbonate, magnesium carbonate, potassium sulfate, sodium sulfate, etc., and metal oxides include zinc oxide, cadmium oxide, etc. Among these, solid bases such as sodium carbonate and potassium carbonate are It is particularly suitable because it can decompose the toxic COF ₂ produced. Effects of the Invention According to the method of the present invention, novel perfluorinated (2
This method is useful as an industrial method for producing perfluoro(2-dialkylaminopropenes) since it can be obtained in high yield by an extremely simple process from readily available raw materials. In addition, the perfluoro(2-dialkylaminopropenes) are new compounds that have not been described in the literature, and are used for the synthesis of fluorine-containing products such as surfactants, agricultural chemicals, pharmaceuticals, and materials for iodine photodissociation lasers (solar pump lasers). It has extremely high industrial value as an intermediate or a polymer monomer. For example, perfluoro(2
-dialkylaminopropene) can be induced into perfluorocarboxylic acid fluoride, and further into a novel tertiary perfluoroalkyl iodide, which is excellent as an iodine photodissociation laser material, as shown in the reaction formula below. As described above, the compound of the formula () of the present invention is tertiary and contains a perfluoroamino group, and as described above as the prior art, both the carbon atom to which iodine is bonded and the substituent are iodine-resistant. It meets the preferred conditions of a synthetic intermediate for producing a dissociated laser material and provides higher performance. Examples Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. Example 1 The product obtained by electrolytic fluorination of 3-(dimethylamino)-n-butyric acid methyl ester as a raw material was distilled, and the remaining crude product after distilling off most of the low-boiling point compounds was used. . The content of perfluoro(3-dimethylamino-n-butyric acid fluoride) in the crude product was 33.7% by weight. First, 30 ml of water was poured into a 200 ml three-neck flask equipped with a reflux condenser and a dropping funnel, and while stirring under ice cooling, 26.0 g of the crude product [perfluoro(3-dimethylamino-n-butyric acid fluoride)] was added. of
8.76 g] was gradually added dropwise. After the dropping was completed, stirring was continued for about 1 hour. Next, after adding phenolphthalene as an indicator, stir the mixture under ice cooling until it becomes slightly alkaline.
A concentrated aqueous potassium hydroxide solution was added dropwise to neutralize. Next, transfer the contents to a 300ml beaker,
After evaporating most of the water on a hot plate, it was further transferred to a 100 ml flask and vacuum-dried for 16 hours. After pulverizing the pale yellow solid substance in the flask obtained in this way and connecting a gas introduction pipe to the upper part of the flask, the flask was heated in an oil bath while flowing helium gas at a rate of 100 ml/min. The temperature was raised from 155°C to 200°C over a period of 18 minutes, and from 200°C to 250°C over a further 45 minutes to carry out a thermal decomposition reaction. The product was condensed and collected in a trap cooled to -78°C. The amount of fluorocarbon collected was 7.0 g. This material was subjected to gas chromatography [liquid phase:
1,6-bis(1,1,12-trihydroperfluorododecyloxy)hexane, carrier: 60-80 mesh chromosop PAW, carrier: helium], IR, ¹⁹ FNMR, Mass, etc. analysis revealed that perfluoro( It contained 0.84 g of N,N-dimethylvinylamine) and 3.73 g of perfluoro(2-dimethylaminopropene). The yield of perfluoro(2-dimethylaminopropene) is
It was 52.5% (mol%, hereinafter referred to as mol%). Perfluoro(2-dimethylaminopropene)
is a colorless transparent liquid with a boiling point of 34-36°C, and its spectroscopic data are as follows. ^19F NMR data Chemical shift (ppm, CFCl ₃ standard) -58.5 -65.8 -72.5 -71.3 Coupling constant (Hz) -=18.1, -=15.2 Mass spectrometry data m/z 283M ⁺ 264 [M-F] ⁺ 195 C ₄ F ₇ N ⁺ infrared absorption spectrum data 1749 cm ^-1 (C=C) Example 2 An instantaneous evaporator for vaporizing the raw material and a dilution gas flow rate control device are connected to the inlet side, and the reaction product is condensed at the outlet side. A stainless steel tube with a length of 48.0 cm and an inner diameter of 2.5 cm, equipped with a cold trap for collection, was used as a horizontally mounted pyrolysis reactor. Into this, 86.3 g of powdered sodium carbonate was filled horizontally to almost the middle of the reactor, and metal wool was packed at both ends. 100ml of He/
Keep it at 300℃ for about 2 hours while flowing at a rate of 1 minute.
Dry the sodium carbonate. As a raw material, a product obtained by electrolytically fluorinating methyl 3-(pyrrolidino)-n-butyrate (celdrain compound) was used as it was. The product contained 30.7% by weight of perfluoro[3-(pyrrolidino)-n-butyric acid fluoride]. First, the reactor was kept at 220°C and helium gas was allowed to flow at 100 ml/min, and the fluorocarbon mixture containing 6.91 g [containing 2.12 g of perfluoro[3-(pyrrolidino)-n-butyric acid fluoride]]
was supplied to the flash evaporator using a micro-metering pump over a period of 34 minutes, vaporized and mixed with helium gas which was quantitatively fed, and then introduced into the reactor. When the reaction product was condensed and collected in a trap cooled to -78°C on the outlet side, 4.33 g of a fluorocarbon mixture was obtained. When this product was analyzed in the same manner as in Example 1, it was found that perfluoro[2-(pyrrolidino)propene]
It contained 1.33g (yield 87.4%). The conversion rate was 100%. The physical properties of perfluoro[2-(pyrrolidino)-propene] are shown in the following table. Example 3 Example 2 except that the same reactor as in Example 2 was used, and a product obtained by electrolytic fluorination of methyl 3-(morpholino)-n-butyrate (celdrain compound) was used as the raw material. The reaction was carried out in the same manner. The product contained 36.8% by weight of perfluoro[3-(morpholino)-n-butyric acid fluoride]. 5.94 g of the above fluorocarbon mixture [perfluoro[3-(morpholino)-n-butyric acid fluoride]
[containing 2.19g] was fed to the reactor over a period of 30 minutes,
Pyrolysis yielded 4.05 g of fluorocarbon in the cooling trap. When this product was analyzed in the same manner as in Example 1,
Perfluoro [2-(morpholino)-propene]
It contained 1.21g (yield 65.3%). The conversion rate is
It was 100%. The physical properties of perfluoro[2-(morpholino)-propene] are shown in the following table. Example 4 Example 4 was carried out using the same reactor as in Example 2, except that a product obtained by electrolytically fluorinating methyl 3-(piperidino)-n-butyrate (celledrain compound) was used as the raw material. The reaction was carried out in the same manner as in 2. The product contained 41.5% by weight of perfluoro[3-(piperidino)-n-butyric acid fluoride]. 5.37 g of the above fluorocarbon mixture [perfluoro[3-(piperidino)-n-butyric acid fluoride]
containing 2.23g] was fed to the reactor over a period of 30 minutes,
Pyrolysis yielded 3.17 g of fluorocarbon in the cooling trap. When this product was analyzed in the same manner as in Example 1,
Perfluoro [2-(piperidino)-propene]
1.05g (yield 55.1%) was obtained. The physical properties of perfluoro[2-(piperidino)propene] are shown in the table below. Example 5 3-(hexamethyleneimino)-n- as a raw material
The reaction was carried out in substantially the same manner as in Example 1, except that a product obtained by electrolytic fluorination of methyl butyrate (celledrain compound) was used. The product includes:
Perfluoro[3-(methylpiperazino)-n-butyric acid fluoride] was 27.7% by weight and perfluoro[3-(methylpiperazino)-n-butyric acid fluoride]
-(hexamethyleneimino)-n-butyric acid fluoride] was contained in an amount of 23.4% by weight. 26.0 g of the above fluorocarbon mixture [containing 7.20 g of perfluoro[3-(methylpiperazino)-n-butyric acid fluoride] and 6.10 g of perfluoro[3-(hexamethyleneimino)-n-butyric acid fluoride]] was treated in the same manner as in Example 1. 17.10 g of dry pale yellow solid material was prepared. The thermal decomposition reaction was carried out under reduced pressure (3 mmHg). That is, the pulverized pale yellow solid substance mentioned above was
A trap was connected to the flask, and the pressure was reduced to 3 mmHg using a vacuum pump. next,
The flask was heated from 150°C to 200°C in an oil bath for 13 minutes, then to 220°C for an additional 15 minutes for pyrolysis, and 9.48 g of fluorocarbon was found in the trap cooled to -78°C. It was captured. When this product was analyzed in the same manner as in Example 1,
Perfluoro[2-(methylpiperidino)propene] 3.73g (yield 59.5%) and perfluoro[2-
(hexamethyleneimino)propene] 6.23 g (yield 52.2%) was obtained. The physical properties of perfluoro[2-(hexamethyleneimino)propene] are shown in the following table.

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Claims (1)

[Claims] 1. General formula (R ₁ and R ₂ in the formula are each a perfluoroalkyl group having 1 to 5 carbon atoms, and both are bonded directly or through an oxygen atom or a nitrogen atom, and together with the nitrogen atom to which they are bonded, five perfluoro(2-dialkylaminopropene), which may form a heterocyclic ring, a six-membered ring, or a seven-membered ring. 2 General formula [In the formula, R ₁ and R ₂ are each a perfluoroalkyl group having 1 to 5 carbon atoms, and both are bonded directly or through an oxygen atom or a nitrogen atom, and together with the nitrogen atom to which they are bonded, It may form a heterocyclic ring, a six-membered ring, or a seven-membered ring, and
is a fluorine atom or OM (where M is a monovalent alkali metal or alkaline earth metal)] A perfluoro(3-dialkylamino-n-butyric acid) derivative represented by A general formula characterized by heating with (R ₁ and R ₂ in the formula have the same meanings as above)
A method for producing perfluoro(2-dialkylaminopropene) represented by