JP2587380B2 - Method for producing fluorine-containing amine compound having hydrogen - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a fluorine-containing amine compound having hydrogen in a molecule, which is useful in the fields of refrigerants, foaming agents, detergents and the like. It has become clear that chlorofluorocarbons, which have been awarded in the above fields, reach the stratosphere and destroy the ozone layer, and have been internationally determined to be totally abolished for the protection of the global environment. Furthermore, production of hydrochlorofluorocarbon, which has been developed as a substitute for chlorofluorocarbon, has been decided to be banned by 2030 because of its ability to deplete the ozone layer. For this reason, there is a demand for the development of a substitute that does not destroy the ozone layer and has less impact on global warming. Compounds consisting only of carbon, fluorine, hydrogen and nitrogen do not contain chlorine, so It has no destructive potential and is expected to have very little impact on global warming, and is expected to be provided. The present invention relates to an efficient method for producing such a fluorine-containing amine compound having hydrogen.

[0002]

2. Description of the Related Art With respect to a method for producing a compound consisting only of carbon, fluorine, hydrogen and nitrogen, for example, when a perfluorotrialkylamine is produced by electrolytically fluorinating an alkylamine such as trimethylamine, N, N-dimethylethylamine or the like. It is known that it was slightly isolated as a by-product [Journal of Fluor
ine Chemistry (Journal of Fluorin Chemistry) 17 (1981) p65-7
4]. On the other hand, there has been proposed a method for producing a monohydrylated perfluorotertiary amine in a high yield by subjecting a perfluoronitrogen-containing carboxylic acid or a reactive derivative thereof to heat treatment in a protic solvent (Japanese Patent Application Laid-Open No. H11-157572). JP-A-5-132451).

[0003]

DISCLOSURE OF THE INVENTION The inventors of the present application disclose a fluorine-containing amine compound having a hydrogen atom in the molecule,
In particular, as a result of intensive research on a method capable of producing a fluorine-containing amine compound having a small amount of hydrogen atom in the molecule in high yield, a trialkylamine which is a completely different solvent from the proton-based solvent in the prior art, They have found that they are effective, and have completed the present invention.

[0004]

The present invention is characterized in that a trialkylamine is used as a reaction solvent to decarboxylate a perfluoroaminocarboxylic acid represented by the following chemical formula (1). This is a method for producing a fluorinated amine compound having the formula (hereinafter, referred to as the present compound).

[0005]

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(However, x is an integer of 1 to 3, y is an integer of 1 to 3, and z is 1 or 2.)

[0007]

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(However, x, y or z are the same as those in [Formula 1].)

Hereinafter, the present invention will be described in more detail. The starting compounds in the present invention are as shown in [Chemical Formula 1]. C _X F _{2 X + 1} or _Cy F _{2 y} in Chemical Formula 1 is a linear or branched perfluoroalkyl group or perfluoroalkylene group, respectively, and can produce the compound of the present invention in high yield. In this regard, preferred x is 1 and y is 2 or 3.

[0010] Specific examples of the starting _{compound, 1) (CF 3) 2} NCF 2 COOH 2) CF 3 N (CF 2 COOH) 2 3) (CF 3) 2 NCF 2 CF 2 COOH 4) (CF ₃ ) ₂ NCF (CF ₃ ) COOH 5) (CF ₃ ) ₂ NCF ₂ CF ₂ CF ₂ COOH 6) (CF ₃ ) ₂ NCF (CF ₃ ) CF ₂ COOH 7) CF ₃ CF ₂ (CF ₃ ) NCF _{2 CF 2 COOH 8) CF 3 CF} 2 (CF 3) NCF (CF 3) COO
H and others. Among them, preferred starting compounds are (CF ₃ ) ₂ NCF ₂ CF ₂ COOH and (CF ₃ ) ₂ NCF ₂ CF ₂ CF ₂ COOH.

The compound produced by the present invention is represented by the above-mentioned [Chemical Formula 2]. Specifically, 1. (CF ₃ ) ₂ NCF ₂ H 2. CF ₃ N (CF ₂ H) ₂ 3. _{(CF 3) 2 NCF 2 CF} 2 H 4. (CF ₃ ) ₂ NCFHCF ₃ 5. _{(CF 3) 2 NCF 2 CF} 2 CF 2 H 6. (CF ₃ ) ₂ NCF (CF ₃ ) CF ₂ H7. 7. CF ₃ CF ₂ (CF ₃ ) NCF ₂ CF ₂ H CF ₃ CF ₂ (CF ₃ ) NCFHCF ₃ and the like. The present invention is particularly suitable as a method for producing (CF ₃ ) ₂ NCF ₂ CF ₂ H and (CF ₃ ) ₂ NCF ₂ CF ₂ CF ₂ H.

The trialkylamine (hereinafter referred to as amine solvent) used as a reaction solvent in the present invention includes:
For example, tripropylamine, tri-n-butylamine, triisobutylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, etc. Tri-n-butylamine is suitable.

In the present invention, the starting compound and the amine-based solvent can be supplied to the reaction system by either a batch system or a continuous system. In the case of a batch system, the ratio of the raw material compound and the amine solvent is preferably 2 to 15 times the molar amount of the raw material compound. If the amount of the amine-based solvent is less than 2 moles, the decarboxylation reaction may be delayed. If the amount is more than 15 moles, it is not economically advantageous. When both are supplied in a continuous manner, the starting compound is added in an amount of from 0.05 to 1 mol / min of the amine-based solvent.
0.2 mol / min is preferred. If the supply rate is too slow, it is not efficient, and if it is too fast, the reaction may not proceed smoothly.

In the present invention, the temperature of the decarboxylation reaction is 4
The temperature is preferably from 0 ° C to 300 ° C, and may be appropriately selected depending on the type of the starting compound. In general, if the temperature is lower than 40 ° C., the decarboxylation reaction may not proceed sufficiently, which may lead to a decrease in the yield. Creatures may increase.

The reaction product solution obtained as described above contains, in addition to the above-mentioned fluorine-containing amine compound having hydrogen represented by the following chemical formula 2, olefinic compounds such as perfluoroalkyleneamine compounds and other by-products. Is slightly contained as an impurity, and these impurities can be easily separated and removed by a simple distillation method utilizing a difference in boiling point.

[0016]

Example 1 A 100 ml flask equipped with a Dimroth condenser, a thermometer, and a dropping funnel was charged with 30.0 g (0.162 mol) of tri-n-butylamine, and 5.0 g (0.017 mol) of a starting compound was prepared. ) Of (CF ₃ ) ₂ NC
F ₂ CF ₂ COOH was added dropwise. After the whole amount was dropped, the mixture was heated in an oil bath while being stirred with a magnetic stirrer. As the internal temperature rose to 150 ° C., mild generation of carbon dioxide was recognized. While maintaining the temperature of 150 ° C., the reaction was continued until the foaming was completed. Then
A distillation head was attached to the flask, and the reaction product was separated and recovered by simple distillation. For the separated reaction product, ¹⁹ F
As a result of confirming the structure of the component by -NMR, ¹ H-NMR and IR spectrum, the main component was (CF ₃ ) ₂ NCF ₂ CF ₂ H which was the target compound, and the yield was 83%. . The reaction product also contains 3% (CF ₃ ) ₂ NCFH (CF ₃ ), 13% CF ₂ ＣC
It was found to contain F ₂ and 2% of (CF ₃ ) ₂ NCF = CF ₂ .

Examples 2 to 4 The starting compounds were prepared by using (CF ₃ ) ₂ NCF ₂ CF ₂ C of Example 1.
From OOH, (1) (CF ₃ ) ₂ NCF ₂ COOH (Example 2) (2) CF ₃ N (CF ₂ COOH) ₂ (Example 3) (3) (CF ₃ ) ₂ NCF ₂ CF ₂ CF ₂ The reaction was carried out in the same manner as in Example 1 except that COOH (Example 4) was used and the reaction temperature was as shown in Table 1. Table 1 shows the obtained target products and their yields.

[0018]

[Table 1]

[0019]

The present invention is a method for easily producing a fluorine-containing amine compound having hydrogen in a molecule, which is useful in the fields of a refrigerant, a foaming agent, a detergent, and the like, in a high yield.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Akira Sekiya 1-1-1, Higashi, Tsukuba, Ibaraki Pref., National Institute of Advanced Industrial Science and Technology (72) Inventor Masami Iwasaki 2-40-17 Hongo, Hongo 2-chome, Bunkyo-ku, Tokyo Wakai Bldg., 6th floor Inside the Research Institute of Innovative Technology for the Earth (72) Yukio Sato 2-40-17 Hongo, Bunkyo-ku, Tokyo Hongo 6th floor of the Wakai Building, Examiner, Yamamoto, Japan Masahiro (56) References JP-A-5-132451 (JP, A) JP-A-62-22747 (JP, A) JP-A-64-25737 (JP, A) CHEMISTRY LETTER S, NO. 11P. 1887-1890 (1988) CHEMISTRY LETTER S, NO. 5P. 905-908 (1989)

Claims (1)

(57) [Claims] 1. A method for producing a hydrogen-containing fluorinated amine compound represented by the following chemical formula 2, wherein the perfluoroaminocarboxylic acid represented by the chemical formula 1 is decarboxylated using a trialkylamine as a reaction solvent. Method. Embedded image (Where x is an integer of 1 to 3, y is an integer of 1 to 3, and z is 1 or 2). (However, x, y, and z are the same as in Chemical formula 1.)