JP3177649B2 - N-fluoroalkyl perfluorocyclic amines and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel chlorofluorocarbon (CFC) substitute and a method for producing the same, and more particularly, to a method for destroying ozone in an ozone layer by eliminating chlorine atoms in a molecule. The present invention relates to a novel polyfluorocyclic amine which is considered to have a low greenhouse effect due to the presence of a hydrogen atom and a method for producing the same.

[0002]

2. Description of the Related Art Chlorofluorocarbons (CFCs) are thermally and chemically stable, have low toxicity, are nonflammable, and have excellent properties such as refrigerants, foaming agents, and solvents and cleaning agents. And other industries.

[0003] However, while CFCs have excellent properties, chlorine atoms contained in the molecules generate radicals in the stratosphere and are thought to destroy the ozone layer by a chain reaction with ozone. Has been designated as a controlled substance by various organizations.

In order to solve such global environmental problems, CFCs have excellent properties such as being usable as a refrigerant, a foaming agent, and a solvent / cleaning agent, and are released into the atmosphere. Even in such a case, there is an urgent need for the development of a new CFC substitute that has little risk of destruction of the ozone layer or has no effect on the ozone layer.

[0005] At present, hydrochlorofluorocarbons (HCFCs) and fluorinated ethers are known as CFC substitutes, but those having a nitrogen atom, especially polyfluorocyclic amines, have hardly been studied. is the current situation.

As a method for producing polyfluorocyclic amines, there is a method of producing perfluoro-N-propylpiperidine and perfluoro-N- (1,3-dimethylbutyl) isopropylpiperidine by light irradiation reaction of perfluoro-N-fluoropiperidine. Journal of Chemical Society (J. Chem. Soc., Perkin I) "No. 109
8 (1972)], formation of perfluoro-N-methylpiperidine by electrolytic fluorination of methyl piperidinoacetate [Journal of Florin Chemistry
(J. Fluorine Chem.), Vol. 50, p. 173 (1
990)], formation of N-methyloctafluoropyrrolidine by reacting nonafluoro-2,3,4,5-tetrahydropyridine with iodomethane in acetonitrile in the presence of cesium fluoride [Journal of Florin Chemistry (J. Fluorine Chem.)
5, 289 (1980)], and so on. However, these methods can be applied to a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms as a substituent or an alkyl group not containing a fluorine atom, but trifluoromethyl having both a hydrogen atom and a fluorine atom can be used. Adaptation for polyfluoroalkyl groups such as ethyl groups is impossible or very difficult.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for efficiently synthesizing fluorine-containing cyclic amines and a method for producing CF.
An object of the present invention is to provide a novel compound N-fluoroalkylperfluorocyclic amine useful as a C substitute.

[0008]

Means for Solving the Problems The present inventor has conducted intensive studies to achieve the above object, and as a result, the general formula (1):

[0009]

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(Wherein X represents CF ₂ , CF (CF ₃ ) or an oxygen atom, Y represents a fluorine atom or CF ₃ , and n represents 0, 1 or 2). Is reacted with an alkali metal fluoride or an alkaline earth metal fluoride in an aprotic polar solvent or in the absence of a solvent, and then reacted with a general formula (2): R ¹ -OSO ₂ -R ² (2) ( R ¹ is a number of 2 or more fluorine-containing alkyl group having a carbon, R ²
Represents an aryl group which may have a substituent or an alkyl group which may be substituted by fluorine. ) By continuously reacting with a sulfonic acid ester represented by the general formula (3):

[0011]

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(Wherein X is CF ₂ , CF (CF ₃ ) or an oxygen atom, Y is a fluorine atom or CF ₃ , R ¹ is a fluorine-containing alkyl group having 2 or more carbon atoms, and n is 0 ,
Indicates 1 or 2. The present inventors have found novel polyfluorocyclic amines represented by the formula (1) and a method for producing the same, and have completed the present invention.

In the present invention, the alkali metal fluoride or the alkaline earth metal fluoride and the sulfonic acid ester represented by the general formula (2) can be simultaneously charged. From the viewpoint of generation, it is desirable to perform a two-stage preparation of adding an alkali metal fluoride or an alkaline earth metal fluoride, reacting them for several hours or more, and then adding a sulfonic acid ester.

In the present invention, a reaction between a perfluorocyclic imine represented by the general formula (1) and an alkali metal fluoride or an alkaline earth metal fluoride, and a sulfonic acid ester represented by the general formula (2) The reaction with any of the above is performed in an aprotic polar solvent or without a solvent. Examples of the aprotic polar solvent include ethers such as monoglyme, diglyme, triglyme, tetraglyme, diethyl ether, dibutyl ether and dioxane; nitriles such as acetonitrile and adiponitrile; amides such as dimethylformamide; and sulfoxides such as dimethyl sulfoxide. But are not limited to these. Further, as for the solvent used in the reaction of the present invention, it is an essential condition to remove water as much as possible.

In the present invention, an alkali metal fluoride or an alkaline earth metal fluoride is used in order to efficiently produce an intermediate serving as a reactive species. As the alkali metal, for example, potassium fluoride, sodium fluoride, cesium fluoride, or the like is used. As the alkaline earth metal fluoride, for example, calcium fluoride or the like is used, but not limited thereto. From the viewpoint of the yield of the product polyfluorocyclic amine, an alkali metal fluoride is desirable.

The amount of the alkali metal fluoride or alkaline earth metal fluoride used in the present invention is not particularly limited, and is 0.1 to 0.1% based on the perfluorocyclic imine represented by the general formula (1). It is preferable to select from the range of 1 to 5.0 times mol, preferably 1.0 to 1.5 times mol.

The alkali metal fluorides or alkaline earth metal fluorides used in the present invention completely promote the production of an intermediate which becomes a reactive species and improve the yield in order to improve the yield. To make it anhydrous. In particular, when potassium fluoride is used, it is necessary to use a spray-dried product and further heat and dry under reduced pressure.

The proportion of the perfluorocyclic imine represented by the general formula (1) and the sulfonic acid ester represented by the general formula (2) in the reaction of the present invention is not particularly limited, and is not limited. Although the reaction can be carried out at a ratio, the boiling points of the polyfluorocyclic amines represented by the general formula (3) and the sulfonic acid esters represented by the general formula (2) are very close in many cases. Since separation is difficult, it is necessary to completely react and consume the sulfonic acid esters. Therefore, the charging ratio of the sulfonic acid ester to the perfluorocyclic imine is 0.1%.
It is preferable to select from the range of 7 to 0.9 times mol.

The reaction temperature in the reaction of the present invention, that is, the reaction temperature in the reaction with the alkali metal fluoride or the alkaline earth metal fluoride and the reaction with the sulfonic acid ester represented by the general formula (2) is as follows. The reaction is usually performed at 0 to 200 ° C., although it varies depending on the time, the molar ratio of the reagent used, and the like. Preferably, the reaction with the alkali metal fluoride or the alkaline earth metal fluoride is selected from the range of 20 to 50 ° C, and the reaction with the sulfonic acid ester is selected from the range of 40 to 80 ° C.

The reaction time in the reaction of the present invention, ie, the reaction time with an alkali metal fluoride or an alkaline earth metal fluoride, and the reaction time with a sulfonic acid ester represented by the general formula (2) are as follows: Although it depends on the temperature, the molar ratio of the reagent used, and the like, the reaction is almost completed in several hours to several tens of hours. However, considering the yield and the generation of by-products, the reaction with the alkali metal fluoride or the alkaline earth metal fluoride is 3 to 20.
The reaction time with the sulfonic acid ester is preferably in the range of 10 to 30 hours.

[0021]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

The general formula (1) mentioned here:

[0023]

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(Wherein X represents CF ₂ , CF (CF ₃ ) or an oxygen atom, Y represents a fluorine atom or CF ₃ , and n represents 0, 1 or 2). By subjecting a trifluoroacetate having a corresponding cyclic perfluoroamino group to a thermal decomposition reaction (Japanese Patent No. 2600118). Formula (2): the ^{_{R 1 -OSO 2 -R 2 ··· (}} 2) (R 1 is 2 or more fluorine-containing alkyl group having a carbon number, R ²
Represents an aryl group which may have a substituent or an alkyl group which may be substituted by fluorine. The sulfonic acid ester represented by the formula (1) is obtained by reacting the corresponding commercially available fluorinated alcohol with trifluoromethanesulfonic anhydride (“Tetrahedron”, p. 5375 (1988)), or trifluoromethanesulfonic acid. It can be easily produced by reaction with fluoride ("Journal of Organic Chemistry", p. 4322 (1965)).

Example 1 1.11 g (5.26) of perfluoro (5,6-dihydro-2H-1,4-oxazine) was obtained using a vacuum line.
mmol) was collected in a 30 ml Schlenk tube equipped with a Teflon cock and weighed. Next, 0.37 g (6.37 mmol) of potassium fluoride (spray-dried product) in a glove box so as to have an equivalent of 1.2 times this amount.
Was collected in a 50 ml round-bottom flask equipped with a Teflon cock, and the potassium fluoride was dried by connecting the round-bottom flask to a vacuum line and heating with a hot blaster. After adding 5 ml of tetraethylene glycol dimethyl ether (tetraglyme) dried with molecular sieves 4B as a solvent to the dried potassium fluoride under an argon atmosphere and suspending the suspension, the potassium fluoride is well mixed with the solvent. Heptafluoro (5,
6-dihydro-2H-1,4-oxazine) was introduced using a vacuum line. By stirring at room temperature for 5 hours, the precipitate was gradually dissolved to form a clear solution containing a small amount of unreacted potassium fluoride.

Subsequently, 1.02 g (4.39 mmol) of trifluoromethanesulfonic acid (2,2,2-trifluoroethyl) ester was added to the tetraglyme solution of the potassium salt of octafluoromorpholine using a vacuum line. Introduced. Heat the round bottom flask to 50 ° C.
Upon continued stirring for 0 hours, the reaction mixture was a mixture of a light yellow solution and a white solid. By reducing the pressure with a vacuum pump while heating to 50 ° C., the product was distilled out in a trap cooled with liquid nitrogen.

Each of the thus obtained crude products was -3
When fractionally distilled at a reduced pressure of 1 mmHg through a trap cooled to 5 ° C., −55 ° C., −78 ° C., and −173 ° C.,
1.04 g (GC purity 94%) at 55 ° C. and 0.084 g (GC purity 99% or more) of the desired N- (2,2,2-trifluoroethyl) octafluoromorpholine in a trap at −78 ° C. Is 8 based on trifluoromethanesulfonic acid (2,2,2-trifluoroethyl) ester.
Obtained in 1.5% isolated yield.

N- (2,2,2-trifluoroethyl)
The physical properties of octafluoromorpholine are as follows. bp .: 92.5-93.5 ° C, ¹ H-NMR (CDCl ₃ ) δ: 3.84 (m),
¹⁹ F-NMR (CDCl ₃ ) δ: 72.09 (m, 3F, CH ₂ CF ₃ ), 87.39 (b
rs, 4F, 2,6-F), 96.80 (br s, 4F, 3,5-F), GC-MS (m
/ z): 294 ([MF] ⁺ , 14.1), 244 ([M-CF ₃ ] ⁺ , 72.5),
216 (C ₄ H ₂ F ₈ N ⁺ , 5.1) _, 194 (C ₄ H ₂ F ₆ NO ⁺ , 6.1), 19
2 (C ₄ F ₆ NO ⁺ , 6.3), 178 (C ₄ H ₂ F ₆ N ⁺ , 5.3), 164 (C ₃ F ₆
N ⁺ , 14.5), 128 (C ₃ F ₄ O ⁺ , 27.1), 119 (C ₂ F ₅ ⁺ , 4
_{0.2), 100 (C 2 F} 4 +, 100), 78 (C 2 F 2 O +, 52.7), 69 (C
F ₃ ⁺ , 32.2), IR (cm ^-1 ): 1450,1405, 1361, 1295, 12
14, 1175, 1135, 1101, 1013, 963, 870.

Example 2 Heptafluoro (5,6-dihydro-2H-1,4-oxazine) was prepared in the same manner as in the above-mentioned N- (2,2,2-trifluoroethyl) octafluoromorpholine.
96 g (4.55 mmol), 0.32 g (5.51 mmol) of potassium fluoride (spray-dried product) and 5 ml of tetraethylene glycol dimethyl ether (tetraglyme) as a solvent are placed in a 50 ml round-bottom flask equipped with a Teflon cock, and the mixture is placed at room temperature. By reacting for 5 hours, a tetraglyme solution of an intermediate potassium salt of perfluoromorpholine was prepared.

Subsequently, 1.08 g (3.83 mmol) of trifluoromethanesulfonic acid (2,2,3,3,3-pentafluoropropyl) ester was added to the tetraglyme solution of potassium perfluoromorpholine in a vacuum line. Was introduced using. When the round bottom flask was heated to 50 ° C. and stirring was continued for 20 hours, the reaction mixture was a mixture of a light yellow solution and a white solid. 50 ℃
While heating to, by reducing the pressure with a vacuum pump,
The product was distilled in a trap cooled with liquid nitrogen.

The obtained crude products were each treated at -10 ° C.
Fractional distillation at a reduced pressure of 1 mmHg through a trap cooled to 40 ° C., −78 ° C., and −173 ° C. yields 0.79 g (GC purity 97%) in a −40 ° C. trap and 0.37 g in a −78 ° C. trap. N- (2,2,3,3,3-pentafluoropropyl) which is the target of (GC purity 97%)
Octafluoromorpholine was obtained in an isolated yield of 83.3% based on trifluoromethanesulfonic acid (2,2,3,3,3-pentafluoropropyl) ester.

The physical properties of N- (2,2,3,3,3-pentafluoropropyl) octafluoromorpholine are as follows. bp .: 108.0-109.0 ° C, ¹ H-NMR (CDCl ₃ ) δ: 3.88 (br
t, J _HF = 13.8 Hz), ¹⁹ F-NMR (CDCl ₃ ) δ: 84.88 (br s,
3F, CH ₂ CF ₂ CF ₃ ), 121.34 (m, 2F, CH ₂ CF ₂ CF ₃ ), 87.37
(br s, 4F, 2,6-F), 96.81 (br s, 4F, 3,5-F), GC-MS
(m / z): 344 ([MF] ⁺ , 14.4), 294 ([M-CF ₃ ] ⁺ , 21.
3), 244 ([MC ₂ F ₅ ] ⁺ , 100), 216 (C ₄ H ₂ F ₈ N ⁺ , 3.0),
194 (C ₄ H ₂ F ₆ NO ⁺ , 10.1), 192 (C ₄ F ₆ NO ⁺ , 11.8), 178
(C ₄ H ₂ F ₆ N ⁺ , 5.3), 164 (C ₃ F ₆ N ⁺ , 24.7), 128 (C ₃ F ₄ O
⁺ , 23.6), 119 (C ₂ F ₅ ⁺ , 61.4), 100 (C ₂ F ₄ ⁺ , 82.8),
78 (C ₂ F ₂ O ⁺ , 69.9), 69 (CF ₃ ⁺ , 52.2), IR (cm ^-1 ):
1454, 1448, 1410, 1366, 1359, 1328, 1298, 1265, 1
211, 1175, 1136, 1104, 1079, 1048,1011, 958, 866.

Example 3 Heptafluoro (5,6-dihydro-2H-1,4-oxazine) was prepared in the same manner as in the above-mentioned N- (2,2,2-trifluoroethyl) octafluoromorpholine.
94 g (4.45 mmol), 0.31 g (5.34 mmol) of potassium fluoride (spray-dried product) and 5 ml of tetraethylene glycol dimethyl ether (tetraglyme) as a solvent are placed in a 50 ml round-bottom flask equipped with a Teflon cock, and the mixture is placed at room temperature. By reacting for 5 hours, a tetraglyme solution of an intermediate potassium salt of octafluoromorpholine was prepared.

Subsequently, 0.80 g (3.74 mmol) of trifluoromethanesulfonic acid (2,2-difluoroethyl) ester was introduced into the tetraglyme solution of the potassium salt of octafluoromorpholine using a vacuum line. When the round bottom flask was heated to 50 ° C. and stirring was continued for 20 hours, the reaction mixture was a mixture of a light yellow solution and a white solid. By reducing the pressure with a vacuum pump while heating to 50 ° C., the product was distilled out in a trap cooled with liquid nitrogen.

The obtained crude products were each treated at -20.degree.
When fractionally distilled at a reduced pressure of 1 mmHg through a trap cooled to 50 ° C., −70 ° C., and −173 ° C., 1.03 g (GC purity 97%) of the target N- (2,2 -Difluoroethyl) octafluoromorpholine was obtained in an isolated yield of 93.6% based on trifluoromethanesulfonic acid (2,2-difluoroethyl) ester.

The physical properties of N- (2,2-difluoroethyl) octafluoromorpholine are as follows. bp .: 102.5-103.0 ° C, ¹ H-NMR (CDCl ₃ ) δ: 3.65 (br
t, 2H, CH ₂ CHF ₂ , J _HF = 11.1 Hz), 5.87 (br t, 1H,
CH ₂ CHF ₂ , J _HF = 55.2 Hz), ¹⁹ F-NMR (CDCl ₃ ) δ: 122.57
(m, 1F, CH ₂ CHF ₂ ), 87.22 (br s, 4F, 2,6-F), 96.89
(br s, 4F, 3,5-F), GC-MS (m / z): 294 ([MH] ⁺ , 1.3),
276 ([MF] ⁺ , 12.1), 244 ([M-CHF ₂ ] ⁺ , 100), 216
(C ₄ H ₂ F ₈ N ⁺ , 3.3), 194 (C ₄ H ₂ F ₆ NO ⁺ , 9.9), 192 (C ₄
F ₆ NO ⁺ , 11.7), 164 (C ₃ F ₆ N ⁺ , 25.0), 128 (C ₃ F ₄ O ⁺ ,
_{29.4), 119 (C 2 F} 5 +, 51.7), 100 (C 2 F 4 +, 63.5), 78
(C ₂ F ₂ O ⁺ , 92.9), 65 (CH ₂ CHF ₂ ⁺ , 69.5), IR (cm ^-1 ):
3000, 1453,1419, 1379, 1348, 1295, 1253, 1211, 11
34, 1102, 1069, 1021, 1000, 915, 862, 728, 681.

Example 4 In the same manner as in N- (2,2,2-trifluoroethyl) octafluoromorpholine described above, heptafluoro-
0.123 g of 3,4-dihydro-2H-pyrrole (0.
631 mmol), 0.05 g (0.861 mmol) of potassium fluoride (spray-dried product) and 3 ml of tetraethylene glycol dimethyl ether (tetraglyme) as a solvent are placed in a 30 ml Schlenk tube equipped with a Teflon cock, and reacted at room temperature for 5 hours. Thus, a tetraglyme solution of a potassium salt of octafluoropyrrolidine as an intermediate was prepared.

Subsequently, 0.122 g (0.526 mmol) of trifluoromethanesulfonic acid (2,2,2-trifluoroethyl) ester was added to the tetraglyme solution of the potassium salt of octafluoropyrrolidine using a vacuum line. Introduced. When the Schlenk tube was heated to 50 ° C. and stirring was continued for 20 hours, the reaction mixture was a mixture of a light yellow solution and a white solid. 50 ℃
While heating to, by reducing the pressure with a vacuum pump,
The product was distilled in a trap cooled with liquid nitrogen. ¹ H-NMR, ¹⁹ F-NMR, G
As a result of analysis by C-MS, the target N- (2,2
It was found that 2,2-trifluoroethyl) octafluoropyrrolidine was obtained at a synthesis yield of 55.3% based on trifluoromethanesulfonic acid (2,2,2-trifluoroethyl) ester.

N- (2,2,2-trifluoroethyl)
The physical properties of octafluoropyrrolidine are as follows. ¹ H-NMR (CDCl ₃ ) δ: 3.84 (br q, J _HF = 8.1 Hz), ¹⁹ F-
NMR (CDCl ₃ ) δ: 71.49 (m, 3F, CH ₂ CF ₃ ), 93.50 (br
s, 4F, 2,5-F), 131.98 (br s, 4F, 3,4-F), GC-MS (m /
z): 278 ([MF] ⁺ , 32.4), 228 ([M-CF ₃ ] ⁺ , 100), 17
8 (C ₄ H ₂ F ₆ N ⁺ , 24.7), 131 (C ₃ F ₅ ⁺ , 7.1), 114 (C ₂ F ₄ N
^{+, 5.5), 100 (C} 2 F 4 +, 25.9), 83 (CF 3 N +, 15.5),
_{78 (C 2 H 2 F 2} N +, 14.3), 69 (CF 3 +, 23.8).

Example 5 In the same manner as in N- (2,2,2-trifluoroethyl) octafluoromorpholine described above, nonafluoro-
0.258 g of 2,3,4,5-tetrahydropyridine
(1.05 mmol), 0.08 g (1.38 mmol) of potassium fluoride (spray-dried product), and 3 ml of tetraethylene glycol dimethyl ether (tetraglyme) as a solvent were placed in a 30 ml Schlenk tube equipped with a Teflon cock, and allowed to stand at room temperature for 5 hours. By reacting, a tetraglyme solution of potassium salt of decafluoropiperidine as an intermediate was prepared.

Subsequently, 0.209 g (0.90 mmol) of trifluoromethanesulfonic acid (2,2,2-trifluoroethyl) ester was added to the tetraglyme solution of the potassium salt of decafluoropiperidine using a vacuum line. Introduced. When the Schlenk tube was heated to 50 ° C. and stirring was continued for 20 hours, the reaction mixture was a mixture of a light yellow solution and a white solid. By reducing the pressure with a vacuum pump while heating to 50 ° C., the product was distilled out in a trap cooled with liquid nitrogen. ¹ H-NMR, ¹⁹ F-NMR, GC-
As a result of analysis by MS, the target N- (2,2,2
-Trifluoroethyl) decafluoropiperidine was found to be obtained at a synthetic yield of 24.0% based on trifluoromethanesulfonic acid (2,2,2-trifluoroethyl) ester.

N- (2,2,2-trifluoroethyl)
Physical properties of decafluoropiperidine are as follows. ¹ H-NMR (CDCl ₃ ) δ: 4.33 (br q, J _HF = 7.8 Hz), ¹⁹ FN
MR (CDCl ₃ ) δ: 70.05 (m, 3F, CH ₂ CF ₃ ), 95.53 (br s, 4
F, 2,6-F), 132.52 (br s, 4F, 3,5-F), 132.85 (br s,
2F, 4-F), GC-MS (m / z): 328 ([MF] ⁺ , 32.7), 27
8 ([M-CF ₃ ] ⁺ , 100), 228 (C ₅ H ₂ F ₁₀ N ⁺ , 16.9), 131 (C
^{_{3 F 5 +, 24.3),}} 100 (C 2 F 4 +, 43.9), 83 (CF 3 N +, 15.
_{0), 78 (C 2 H} 2 F 2 N +, 13.6), 69 (CF 3 +, 32.2).

Example 6 In the same manner as in N- (2,2,2-trifluoroethyl) octafluoromorpholine described above, perfluoro (2,2
1.00 g (3.21 mmol) of 6-dimethyl-5,6-dihydro-2H-1,4-oxazine) and 0.23 g (3.96 mmol) of potassium fluoride (spray-dried product)
l) and 5 ml of a solvent, tetraethylene glycol dimethyl ether (tetraglyme), were placed in a 50 ml round-bottom flask equipped with a Teflon cock, and reacted at room temperature for 5 hours to give an intermediate perfluoro (2,6-
A tetraglyme solution of potassium salt of dimethylmorpholine) was prepared.

Subsequently, 0.626 g (2.70 mm) of trifluoromethanesulfonic acid (2,2,2-trifluoroethyl) ester was added to the tetraglyme solution of the potassium salt of perfluoro (2,6-dimethylmorpholine).
ol) was introduced using a vacuum line. When the Schlenk tube was heated to 50 ° C. and stirring was continued for 20 hours, the reaction mixture was a mixture of a light yellow solution and a white solid. By reducing the pressure with a vacuum pump while heating to 50 ° C., the product was distilled out in a trap cooled with liquid nitrogen.

The obtained crude products were each treated at -20.degree.
When fractionally distilled at a reduced pressure of 1 mmHg through a trap cooled to 40 ° C., −60 ° C., and −173 ° C., 0.203 g (GC purity: 99%) of the trap at −40 ° C. and −78 ° C.
0.757 g (98% GC purity) of the desired 4- (2,2,2-trifluoroethyl) -2,6
-Bis (trifluoromethyl) octafluoromorpholine was obtained in an isolated yield of 85.9% based on trifluoromethanesulfonic acid (2,2,2-trifluoroethyl) ester.

As a raw material, perfluoro (2,6-dimethyl-5,6-dihydro-2H-1,4) having trans: cis = 1: 2.8 based on the trifluoromethyl group was used.
-Oxazine), but the synthesized 4- (2,2,
Similarly, for 2-trifluoroethyl) -2,6-bis (trifluoromethyl) octafluoromorpholine, there are cis-trans structural isomers for two trifluoromethyls, and the ratio is trans: cis =
1: 3.

The physical properties of cis-4- (2,2,2-trifluoroethyl) -2,6-bis (trifluoromethyl) octafluoromorpholine are as follows. ¹ H-NMR (CDCl ₃ ) δ: 3.88 (br q, J _HF = 7.8 Hz), ¹⁹ F-
NMR (CDCl ₃ ) δ: 72.04 (m, 3F, CH ₂ CF ₃ ), 81.04 (m, 6F,
2,6-CF ₃ ), 128.87 (m, 2F, 2,6-F), 97.22 (AB, 2F, 3,
5-F, J _FF = 204.9 Hz), 86.96 (AB, 2F, 3,5-F, J _FF
= 204.9 Hz), GC-MS (m / z): 394 ([MF] ⁺ , 24.9), 344
([M-CF ₃ ] ⁺ , 88.7), 294 (C ₆ H ₂ F ₁₀ NO ⁺ , 21.1), 292
(C ₆ F ₁₀ NO ⁺ , 10.5), 169 (C ₃ F ₇ ⁺ , 18.5), 150 (C
₃ F ₆ ⁺ , 100), 128 (C ₃ F ₄ O ⁺ , 16.8), 119 (C ₂ F ₅ ⁺ , 14.
0), 100 (C ₂ F ₄ ⁺ , 36.4), 83 (CF ₃ N ⁺ , 31.8), 78 (C ₂ F
₂ O ⁺ , 35.2), 69 (CF ₃ ⁺ , 92.8).

The physical properties of trans-4- (2,2,2-trifluoroethyl) -2,6-bis (trifluoromethyl) octafluoromorpholine are as follows. ¹ H-NMR (CDCl ₃ ) δ: 3.97 (m), ¹⁹ F-NMR (CDCl ₃ ) δ: 7
1.83 (m, 3F, CH ₂ CF ₃ ), 80.72 (m, 6F, 2,6-CF ₃ ), 124.
28 (m, 2F, 2,6-F), 93.25 (AB, 2F, 3,5-F, J _FF = 20
1.5 Hz), 78.18 (AB, 2F, 3,5-F, J _FF = 201.5 Hz), G
C-MS (m / z): 394 ([MF] ⁺ , 21.1), 344 ([M-CF ₃ ] ⁺ ,
87.8), 294 (C ₆ H ₂ F ₁₀ NO ⁺ , 23.7), 292 (C ₆ F ₁₀ NO ⁺ ,
12.8), 169 (C ₃ F ₇ ⁺ , 16.6), 150 (C ₃ F ₆ ⁺ , 75.8), 128
(C ₃ F ₄ O ⁺ , 17.4), 119 (C ₂ F ₅ ⁺ , 14.0), 100 (C ₂ F ₄ ⁺ ,
32.1), 83 (CF ₃ N ⁺ , 33.8), 78 (C ₂ F ₂ O ⁺ , 34.5), 69
(CF ₃ ⁺ , 100).

[0049]

According to the method of the present invention, N-fluoroalkyl perfluoro cyclic amines can be produced in a simple manner with high yield and high selectivity. It is extremely useful as an industrial method for Therefore, like the conventional CFC, the compound of the present invention is expected to be used as a foaming agent, a solvent, a cleaning agent, and the like, is promising as an alternative compound to CFC, and is considered to greatly contribute to the industry. Since these polyfluoroalkyl cyclic amines contain hydrogen atoms and do not contain chlorine atoms, they are easily decomposed in the troposphere and have little greenhouse effect, and at the same time have little effect on the global environment that does not destroy ozone in the ozone layer. Compound.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kunio Okuhara 2-40-17 Hongo, Bungo-ku, Tokyo Hongo Wakai Building 6F New Refrigerant Project, Indoor Research Institute for Global Environmental Technology, Inc. Yoshie Enomoto (56) References JP-A-5-132451 (JP, A) JP-A-63-208572 (JP, A) JP-A-55-51016 (JP, A) JP-A-62-22756 (JP, A) JP-A-63 -22563 (JP, A) Chem. Pharm. Bull. , Vol. 33, No. 3, p. 1221-1231 (1985) Fluorine Chem. , Vol. 66, No. 2, p. 193-202 (1994) Fluorine Chem. , Vol. 59, no. 3, p. 351-365 (1992) Fluorine Chem. , Vol. 45, no. 2, p. 293-311 (1989) Fluorine Chem. , Vol. 43, No. 1, p. 67-85 (1989) Fluorine Chem. , Vol. 26, No. 4, p. 417-434 (1984) Zh. Org. Khim. , Vol. 6, p. 1215-1224 (1974) Zh. Prikl. Khim. (Le Ningrad), Vol. 48, No. 3, p. 706-709 (1975) Zh. Obshch. Khim. , Vol. 36, No. 9, p. 1613-1618 (1966) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 207/10 C07D 211/38 C07D 223/04 C07D 265/30 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] The general formula (1): (Wherein X represents CF ₂ , CF (CF ₃ ) or an oxygen atom, Y represents a fluorine atom or CF ₃ , and n represents 0, 1 or 2). After reacting with an alkali metal fluoride or an alkaline earth metal fluoride in a non-polar solvent or in a non-solvent, a general formula (2): R 1 -OSO ₂ -R ² . . . (2) (R1 is a fluorinated alkyl group having at least 2 carbon atoms, R ²
Represents an aryl group which may have a substituent or an alkyl group which may be substituted by fluorine. Wherein the reaction with the sulfonic acid ester represented by the formula (3) is carried out continuously. (X in the formula is CF ₂ , CF (CF ₃ ) or an oxygen atom, Y is a fluorine atom or CF ₃ , R ¹ is a fluorinated alkyl group having 2 or more carbon atoms, and n is 0, 1 or 2 The method for producing novel N-fluoroalkyl perfluorocyclic amines represented by the formula: