JP2003113149A - New fluorine-containing ketone compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new fluorine-containing ketone compound, and further to provide a method for producing the compound with high efficiency. SOLUTION: This fluorine-containing ketone is represented by the general formula (wherein, R is a 1-4C lower aliphatic alkyl group; RF1 and RF2 are each a 1-3C lower aliphatic perfluoroalkyl group, or may form a 5- or 6-membered heterocycle with or without an oxygen atom). The method for producing the fluorine-containing ketone is also provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel fluorine-containing ketone compound and a method for producing the same, and more specifically, it relates to a fluorine-containing product such as a monomer for producing a fluorine-containing polymer, a surfactant, an agricultural chemical and a pharmaceutical product. Raw material, synthetic intermediate, and novel fluorine-containing ketone compound that can be used as a heat transfer medium that can substitute for chlorofluorocarbon (CFC) and hydrochlorofluorocarbon (HCFC), a cleaning agent, a fire extinguishing agent, a reaction solvent, and a method for producing the same It is about.

[0002]

Fluorine-containing ketone compounds are generally useful as raw materials and synthetic intermediates for various fluorine-containing products and can be used, for example, in the production of surfactants, agricultural chemicals, pharmaceuticals and the like. On the other hand, conventionally, a refrigerant, a heat transfer medium,
Chlorofluorocarbons (CFCs) have been widely used as foaming agents, cleaning agents, fire extinguishing agents, reaction solvents and the like.
The CFCs have been widely used in various industrial fields because they have low toxicity, are nonflammable, and are chemically and thermally stable. However, it has been pointed out that CFCs having such excellent characteristics, when released into the atmosphere, deplete the ozone layer in the stratosphere, and have a serious adverse effect on the earth's ecosystem including human beings. Its manufacturing was 1995
It was banned by an international treaty at the end of the year. Hydrochlorofluorocarbons (HCFCs) are CFCs.
It is decided that by 2020, its use and manufacture will be phased-limited, in order to deplete the ozone layer, although not as much as its impact.

In order to deal with such global environmental problems, it can be used as a refrigerant, a heat transfer medium, a foaming agent, a cleaning agent, a fire extinguishing agent, a reaction solvent, etc., which does not destroy the ozone layer even when it is released into the atmosphere. , CFCs and HCFCs are in demand. Examples of compounds that can meet this purpose include polyfluoroalkyl ethers having an oxygen atom as a hetero atom (Japanese Patent No. 2908033).
No. 3099964), and further, ketones having a polyfluoroalkyl group having improved decomposability by providing a double bond (Japanese Patent No. 2961).
No. 924, No. 2869432, No. 2952414, 31
41325). On the other hand, as the latter candidate compound of the ketone system, polyfluoroalkylketone having a nitrogen-containing perfluoroalkyl group in the molecule has a nitrogen atom inserted as a hetero atom in the perfluoroalkyl group, and therefore, is more suitable. It can be expected as a compound with degradability (that is, a property that is friendly to the global environment). Therefore, although this compound was considered as a raw material for a useful fluorine-containing product, a compound of this type has not been known so far.

[0004]

Under the circumstances, the present inventors have developed a novel fluorinated ketone compound that can be used as a material for the fluorinated product in view of the above-mentioned prior art. As a result of extensive research aiming to achieve the above, the nitrogen-containing perfluorocarboxylic acid fluoride, which can be easily synthesized in one step by the electrolytic fluorination reaction of the corresponding nitrogen-containing methyl carboxylate, was directly used as a raw material. The inventors have found that the intended object can be achieved by producing a novel perfluoroalkyl / alkylketone compound by reacting a corresponding organometallic compound, and have completed the present invention. That is, the present invention relates to raw materials and synthetic intermediates for fluorine-containing products such as surfactants, pesticides and pharmaceuticals, as well as CFCs and HCFCs.
It is an object of the present invention to provide a novel fluorine-containing ketone compound that can be used as a refrigerant, a heat transfer medium, a foaming agent, a cleaning agent, a fire extinguishing agent, a reaction solvent, etc. Another object of the present invention is to provide a method for efficiently producing the above novel fluorinated ketone compound.

[0005]

That is, the present invention provides the following general formula (1):

[0006]

[Chemical 3]

(In the formula, R represents a lower aliphatic alkyl group having 1 to 4 carbon atoms. R _F 1 and R _F 2 represent a lower aliphatic perfluoroalkyl group having 1 to 3 carbon atoms. , Which may form a 5-membered or 6-membered heterocycle with or without an oxygen atom).

The present invention is also a method for producing a novel fluorine-containing ketone compound represented by the above general formula (1), which comprises the following general formula (2)

[0009]

[Chemical 4]

(In the formula, R _F 1 and R _F 2 have a carbon number of 1 to
3 is a lower aliphatic perfluoroalkyl group of 3, which is a 5-membered ring or 6-membered with or without an oxygen atom.
A nitrogen-containing perfluorocarboxylic acid fluoride represented by (which may form a heterocycle of a member ring) and an organometallic compound having a lower aliphatic alkyl group are reacted in an aprotic polar solvent. A method for producing a fluorinated ketone.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail. As a general method for synthesizing perfluoroalkyl / alkylketone, for example, 1) a method of reacting 2 equivalents of a Grignard reagent or an organolithium compound with a fluorinated carboxylic acid [Organic Reactions Vol. 18, Chap
ter 1, MJ Jorgensen, "Preparation of Ketones fro
m the Reaction of Organolithium Reagents with Carbo
xylic Acids ", John Wiley & Sons (1970)], and 2) a method of reacting a fluorine-containing carboxylic acid chloride with an organometallic compound. In addition to the above two methods, a corresponding fluorine-containing carboxylic acid Condensation reactions of acid esters and ketoesters under base catalysis, followed by hydrolysis of the condensation products are widely known [AM Lovelace, DA Rausch and W. Postelnek, "Al.
iphaticFluorine Compounds ", ACS Monograph No. 138,
Reinhold Publishing Co. (1957), p.182].

Among the above-mentioned general synthetic methods, organozinc, organocadmium or copper ate complex is known as a metal compound used for the reaction of the acid chloride of the above 2). These reagents used in the reaction with the acid chloride include:
It is selective and the reagent does not react further with the ketone formed. As a method using a Grignard reagent having high reactivity, a method of dropping a limited amount of Grignard reagent into a solution of an acid chloride has been used to some extent, but an organolithium compound having higher reactivity than the Grignard reagent has been used. Almost no ketone was synthesized by the reaction of the acid chloride with the acid chloride. Also, from the perspective of the substrate,
No acid fluoride was used in place of the acid chloride.

According to the present invention, a nitrogen-containing perfluorocarboxylic acid fluoride which can be easily synthesized in one step by electrolytic fluorination reaction of a corresponding nitrogen-containing methyl carboxylate is used as a raw material as it is, and an organic compound corresponding to this is used. By reacting a metal compound, a novel perfluoroalkyl / alkylketone compound having a nitrogen-containing perfluoroalkyl group can be easily produced.

The nitrogen-containing perfluorocarboxylic acid fluoride used in the present invention can be easily synthesized in one step by the electrolytic fluorination reaction of the corresponding nitrogen-containing methyl carboxylate. For example, perfluoropyrrolidino acetyl fluoride, perfluoromorpholino acetyl fluoride,
And perfluoro [3- (N, N-dimethylamino) propionyl fluoride] are methyl pyrrolidinoacetate, methyl morpholinoacetate and methyl 3- (N, N-dimethylamino) propionate, respectively, in anhydrous hydrofluoric acid. It can be synthesized in good yield by electrolytic fluorination with [T. Abe, E. Hayashi, H. Baba, H. Fukaya,
J. Fluorine Chem., 48 (1990) 257-278; 50 (1990) 17
3-196]. In the fluorinated product separated from anhydrous hydrofluoric acid, with the target nitrogen-containing perfluorocarboxylic acid fluoride, various cleavage products are mixed, but omitting the purification step of perfluorocarboxylic acid fluoride, The mixture as it is can be used for the reaction with the organometallic compound.

In the present invention, examples of the organometallic compound include organolithium compounds such as butyllithium and methyllithium, Grignard reagents, organozinc compounds, organic cadmium compounds, and the like, with preference given to organic compounds such as butyllithium and methyllithium. Lithium compounds and Grignard reagents are used. In the method of the present invention, a solvent is used. In this case, ether, glyme,
It is preferable to use an aprotic polar solvent such as diglyme, triglyme, tetraglyme or tetrahydrofuran. Further, in this case, in order to improve the yield of the target fluorinated ketone, it is preferable to use a completely dehydrated solvent.

The amount of the organometallic compound used is not particularly limited when the reagent has selectivity such as an organozinc compound or a cadmium compound, and is preferably 1 to 5 mol, preferably 1 mol to 1 mol of a nitrogen-containing perfluorocarboxylic acid fluoride. Is 1 to 2 mol. On the other hand, when the reactivity is large and the selectivity is low, such as a lithium compound or a Grignard reagent, the yield of the obtained ketone is sensitively affected by the equivalent amount of the reagent used. In this case, an approximately equivalent amount of the reagent is preferably used with respect to the nitrogen-containing perfluorocarboxylic acid fluoride.

The reaction is carried out by dissolving or dispersing nitrogen-containing perfluorocarboxylic acid fluoride in a solvent and introducing an organometallic compound. The addition of the organometallic compound is
It is carried out by introducing continuously or intermittently during the reaction for controlling the reaction. The reaction temperature varies greatly depending on the type of the organometallic compound used and the reaction conditions (reagent dropping rate, reaction scale, etc.), but a temperature range of −110 ° C. to 100 ° C. is applied. When a Grignard reagent or an organolithium compound is used, the temperature range is relatively low (-
100 ° C. to 20 ° C. is used, and in the case of an organic zinc compound or an organic cadmium compound, a relatively high temperature range (0 ° C. to 50 ° C.) is preferably used because the reaction rate is slow. The reaction time cannot be unconditionally determined depending on the kind of the organometallic compound used and the reaction conditions, but it is several tens.
The reaction is almost complete in a few minutes to a few hours.

The novel fluorine-containing ketone compound synthesized by the above method is 1) a starting material for various fluorine-containing products,
It is useful as 2) its synthetic intermediate, and 3) a material that can substitute for CFC and HCFC. First, an example of the starting material of the above 1) will be specifically described.
When a reduction reaction is carried out using lithium aluminum hydride, sodium borohydride, etc.), the corresponding secondary alcohol useful as a raw material for a fluoropolymer or a nonionic fluorosurfactant can be obtained. In addition, since this compound is a fluorine-containing alcohol having an asymmetric carbon, it is used as a raw material for various products utilizing optical activity by optically resolving it.

[0019]

[Chemical 5]

Further, specifically explaining one example as the synthetic intermediate of the above 2), the corresponding fluorine-containing acrylic ester can be easily obtained by the reaction of the fluorine-containing alcohol and acrylic acid chloride. This serves as a monomer raw material for the fluorine-containing acrylic resin.

[0021]

[Chemical 6]

[0023] Further, specifically explaining one example as an alternative material of the above 3), methyl perfluoro (morpholinomethyl) ketone is a colorless substance having a boiling point of 123.97 ° C and a density of 1.6169 (23 ° C). A transparent liquid that can be used alone or in another solvent (eg,
By mixing with hydrocarbons, HCHCs, fluorine-containing ethers, etc.), these can be used as a draining agent or cleaning agent for precision parts made of metal or plastic, which have been used as CFC-based fluorine solvents. It can be used as an agent.

[0023]

EXAMPLES Next, the novel fluorine-containing ketone of the present invention and its
A manufacturing example will be specifically described with reference to Examples. Example 1 Perfluoromorpholino acetyl fluoride and organic lithium
Umium compound (n-C_Four H₉ N-but by reaction with Li)
Synthesis of chill perfluoro (morpholinomethyl) ketone Crude perfluoro (morpholino acetyl fluoride)
Transfer 75.7 g to a 500 mL four-necked flask and add 200
mL of dry ether was added. Then add n to the dropping funnel.
-Butyllithium solution 90 mL (about 0.133 mol)
After stirring, start stirring and add liquid nitrogen to the flask
Nessless wide-mouthed duer-pouring into a bottle and lowering the temperature of the flask
It was When the internal temperature has dropped to -100 ° C,
Start the dropping of the chilled lithium solution to the height of the cooling bath
Adjust the speed below to keep the internal temperature at about -100 ° C.
It was to so. It took 25 minutes for the dropping. Then about 2
After a long time, the internal temperature rose to 13 ° C, and then the reaction
The mixture was left for a few days and then hydrolyzed. Pasty insoluble matter
Interfered with the separation of the ether layer and the aquarium.
Removed by suction filtration. Separate the ether layer and remove the sulfate.
After drying with gnesium, depressurize after distilling off the ether layer.
Fractional distillation yields n-butyl perfluoro
(Morpholinomethyl) ketone, bp68 ℃ / 29mmH
g, 27.5 g (0.0753 mol) was obtained. Raw material
Since the ratio of the oxyfluoride in the product was 60%,
The amount of the fluoride in is 0.139 mol.
Based on n-butyl perfluoro (morpholino
The yield of methyl) ketone was 54%.

IR, ¹ H-NMR, ¹⁹ F-of the desired product
The NMR and MS data are shown below. IR (capillary film) (cm ^-1 ): 2
968ν (CH) (w), 2943ν (CH) (w),
2878ν (CH) (w), 1769ν [C (O)]
(Ms), 1467 (w), 1408 (w), 1333
(Ms), 1300 (vs), 1217 (vs), 11
64 (vs), 1145 (vs), 1083 (m), 1
016 (w), 970 (w), 927 (s), 817
(W), 754 (w), 657 (w).

[0025]¹ H-NMR (CDCl₃ ): Δ2.75
[2H, t, J = 7, -C (O) CH₂ ], Δ1,68
[2H, t-t, J = 7, J = 6, -C (O) CH₂ C
H₂ CH₂ CH₃ ], Δ1.38 [2H, q−t, J =
7, J = 7, -C (O) CH₂ CH₂ CH₂ CH₃ ],
δ 0.97 [3H, t, J = 7, CH₃ ].¹⁹ F-NMR (CFCl₃ ), Δ-85.6 [4F,
s, c-O (CF₂ CF₂ )₂ ], Δ-90.9 [4
F, t, J = 14, c-N (CF₂ CF₂ )₂ ], Δ−
88.8 [2F, quin, J = 14, NCF₂ ].

MS: m / e 280c-O (CF ₂ CF
₂ ) ₂ NCF ₂ ⁺ (2.8), 164C ₃ F ₆ N ⁺
(1.6), 119C ₂ F ₅ ⁺ (8.), 114C ₂ F
₄ N ⁺ (8.9), 100C ₂ F ₄ ⁺ (4.2), 85
C (O) C ₄ H ₉ ⁺ (28.1), 69CF ₃ ⁺ (5.
6), 57C ₄ H ₉ ⁺ (100), 41C ₃ H ₅ ⁺ (7
8.9).

Example 2 Synthesis of ethyl perfluoro (morpholinomethyl) ketone by reaction of perfluoro (morpholinoacetylfluoride) with Grignard reagent (C ₂ H ₅ MgBr) Almost the same as in Example 1, four 500 mL volumes were used. In a neck flask, 65.7 g of crude perfluoro (morpholinoacetyl fluoride) [41.4 g as a 63% content rate]
(Containing 0.126 mol)], ether 200
After adding mL, the mixture was mechanically stirred under an argon atmosphere, and the Grignard reagent (C ₂ H ₅ MgBr: 1.00) was added thereto.
Equivalent) was added dropwise. In this experiment, the internal temperature was kept at -50 ° C during the dropping. Gradually loosen the cooling, and when the internal temperature reaches 18 ℃, add 20m of water while stirring vigorously.
The reaction was stopped by adding L. Decant the ether solution.
It was separated from impurities by filtration, dried over magnesium sulfate, the ether was distilled off, and the residual liquid was subjected to fractional distillation under reduced pressure. Ethyl perfluoro (morpholinomethyl) ketone, bp 48 ° C / 44 mmHg, 25.8 g (0.08
mol) was obtained. Based on the amount of the acid fluoride contained in the raw material, the yield of ethyl perfluoro (morpholinomethyl) ketone was 63%.

IR, ¹ H-NMR, ¹⁹ F-of the desired product
The NMR and MS data are shown below. IR (capillary film) (cm ^-1 ): 2
995ν (CH) (w), 2943ν (CH) (w),
2878ν (CH) (w), 1771ν [C (O)]
(Ms), 1506 (w), 1412 (w), 1300
(Vs), 1215 (vs), 1170 to 1142 (v
s), 1083 (m), 1018 (w), 957
(W), 926 (s), 787 (w), 714 (w),
656 (w).

[0029]¹ H-NMR (CDCl₃ ): Δ2.79
[2H, t, J = 7, -C (O) CH₂ ], Δ 1.20
[3H, t, J = 7, CH₃ ].¹⁹ F-NMR (CFCl₃ ), Δ-85.7 [4F,
s, c-O (CF₂ CF₂ )₂ ], Δ-91.0 [4
F, t, J = 14, c-N (CF₂ CF₂ )₂ ], Δ−
88.7 [2F, quin, J = 14, NCF₂ ].

MS: m / e 280c-O (CF ₂ CF
₂ ) ₂ NCF ₂ ⁺ (9.3), 119C ₂ F ₅ (6.
3), 114C ₂ F ₄ ⁺ (10.0), 100C ₂ F ₄
⁺ (5.8), 69CF ₃ ⁺ (6.3), 57C (O)
^{_{C 2 H 5 + (8.4)}} , 41C 3 H 5 + (100).

Example 3 Synthesis of ethyl perfluoro (morpholinomethyl) ketone by reaction of perfluoro (morpholinoacetylfluoride) with diethylcadmium An experimental method was prepared by reacting cadmium chloride with Grignard reagent instead of Grignard reagent. The procedure was substantially the same as in Example 2 except that the diethyl cadmium prepared above was used. Crude diethyl cadmium was prepared by stirring a powder of cadmium chloride in ether in a 200 mL four-necked flask under a stream of argon gas, adding an ether solution of Grignard reagent, and then heating and refluxing for 1 hour. did. After the mixture was ice-cooled, a solution of 20 g of crude perfluoro (morpholinoacetyl fluoride) [containing 12.6 g (0.039 mol) as a 63% content] in 50 mL of dry ether was added thereto. ,
The mixture was heated under reflux for 5 hours. After the reaction, 5 mL of water was added to stop the reaction. The ether layer was separated, dried and fractionally distilled in the same manner as in Example 2. As a result, 6.9 g (0.02%) of ethyl perfluoro (morpholinomethyl) ketone was obtained.
1 mol) was obtained. Based on the amount of the acid fluoride contained in the raw material, the yield of ethyl perfluoro (morpholinomethyl) ketone was 53%.

Example 4 Perfluoro (morpholino acetyl fluoride) and green
Niall reagent (CH₃ Methyl by reaction with MgI)
Synthesis of perfluoro (morpholinomethyl) ketone The experimental method was ethyl bromide as Grignard reagent.
Instead of nesium, methylmagnesium iodide (CH
₃ Except for using (MgI), the same procedure as in Example 2 was performed.
It was. That is, crude perfluoro (morpholinoacetate
Tilfluoride) 104.8 g [63% as the content
Containing 66.0 g (0.201 mol) of acid fluoride
Yes] into the reaction flask and 250 mL of ether
And mechanically stir to keep the internal temperature at -100 ° C.
, Ether solution of methylmagnesium iodide 157 m
L (0.23 mol) was added over about 1 hour. cooling
Gradually loosen and become violent at around 0 ° C.
While stirring, add 25 mL of water to stop the reaction and
The ether separated by the
After drying with magnesium, ether was distilled off. Reduction of residual liquid
By pressure fractional distillation, methyl perfluoro (morphol
Nomethyl) ketone, bp35 ° C / 49mmHg, 35g
(0.108 mol) was obtained. The acid contained in the raw material
Based on the amount of fluoride, methyl perfluoro (mo
The yield of lufolinomethyl) ketone was 54%.

Physicochemical data of methyl perfluoro (morpholinomethyl) ketone obtained as a novel compound,
In addition, IR, ¹ H-NMR, ¹⁹ F-NMR and MS data are shown below. Boiling point: 123.97 ° C (measured at 760 mmHg), density: 1.6169 (measured at 23 ° C), vapor pressure: 12.4
mmHg (measured at 23 ° C).

IR (capillary film)
(Cm ⁻¹ ): 2928ν (CH) (w), 1774ν
[C (O)] (ms), 1425 (w), 1412
(W), 1337 (ms), 1300 (vs), 121
7 to 1142 (vs), 1082 (m), 1016
(W), 956 (w), 926 (s), 818 (w),
797 (w), 657 (w).

[0035]¹ H-NMR (CDCl₃ ): Δ2.45
[T, J = 1.3, -C (O) CH₃ ].¹⁹ F-NMR (CFCl₃ ), Δ-85.7 [4F,
s, O (CF₂ )₂ ], Δ-89.0 [2F, quin
tet, J = 14, NCF₂ ], Δ-91.7 [4F,
t, J = 14, N (CF₂ )₂ ].

MS: m / e 280c-O (CF ₂ C
F ₂ ) ₂ NCF ₂ ⁺ (1.3), 262 (3.3), 1
64C ₃ F ₆ N ⁺ (2.6), 119C ₂ F ₅ ⁺ (7.
9), 114C ₂ F ₄ N ⁺ (12.0), 100C ₂ F
₄ ⁺ (7.9), 69CF ₃ ⁺ (8.2), 50CF ₂
⁺ (3.1), 43C (O) CH ₃ ⁺ (100).

Example 5 Synthesis of methyl perfluoro (pyrrolidinomethyl) ketone by reaction of perfluoro (pyrrolidinoacetyl fluoride) with Grignard reagent (CH ₃ MgBr) 101 g of crude in a four-necked flask with a capacity of 500 mL. Perfluoro (pyrrolidinoacetyl fluoride) was taken and 250 mL of dry ether was added. A mechanical stirrer was attached to the center port of the flask, and a low temperature thermometer (-150 to + 30 ° C), a dropping funnel, and a Dimroth condenser introduced with argon gas from the top were attached to the side tubes. The reaction temperature was adjusted to −100 ° C. by cooling with liquid nitrogen contained in a stainless Dewar. Internal temperature is -1
When the temperature dropped to 00 ° C., it took 30 minutes to prepare an ether solution of methylmagnesium bromide (89 mL, 0.217 m).
ol) was added dropwise. During that time, the internal temperature was adjusted to -1 by adjusting the dropping rate of the reagent and the height of the Dewar bottle containing liquid nitrogen.
Keep between 10 ° C and -100 ° C. After dripping, stirring was continued to gradually raise the internal temperature, and after increasing to 0 ° C (after about 1 and a half hours), 25 mL of water was added, and a weak heat was generated, which was almost transparent with the jelly-like insoluble matter. A new ether solution formed.

The ether was separated by decantation, the insoluble matter was washed twice with a small amount of ether, the washings were combined into an ether solution, and the combined solution was dried over anhydrous magnesium sulfate. After the ether was distilled off, the residual liquid was fractionally distilled under reduced pressure to give methyl perfluoro (pyrrolidinomethyl) ketone, bp 37 ° C./39 mmHg, 31.8 g (0.10
2 mol) was obtained. Since the proportion of the oxyfluoride in the raw material was 56%, the amount of the fluoride in the raw material was 0.
182 mol, based on which the yield of methyl perfluoro (pyrrolidinomethyl) ketone was 56%. The physicochemical data of methyl perfluoro (pyrrolidinomethyl) ketone obtained as a new compound, and IR, ¹ H-NMR, ¹⁹ F-NMR and MS data are shown below. Boiling point: 115.1 ° C. (measured at 760 mmHg), density:
1.6103 (measured at 23 ° C), vapor pressure: 18.0 mm
Hg (measured at 23 ° C).

IR (capillary film)
(Cm ⁻¹ ): 2928ν (CH) (w), 1772ν
[C (O)] (ms), 1430 (w), 1402
(W), 1337 (vs), 1307 (ms), 127
4 (w), 1216 (vs), 1171 (s), 113
3 (s), 1083 (m), 1031 (m), 1007
(W), 872 (m), 804 (m), 639 (w),
602 (w).

[0040]¹ H-NMR (CDCl₃): Δ2.46
[T, J = 1.4, -C (O) CH₃ ].¹⁹ F-NMR (CFCl₃ ), Δ-90.7 [4F,
t, J = 9, c- (CF₂ CF₂ )₂ N], delta-91.
1 [2F, quintet, J = 9, NCF₂ ], Δ−
132.9 [4F, s, J = 14, c- (CF₂ CF
₂ )₂ N].

MS: m / e 264c- (CF ₂ CF ₂ ).
₂ NCF ₂ ⁺ (4.7), 246 (4.4), 214
(2.1), 145 (3.3), 114C ₂ F ₄ N ⁺
(6.6), 100C ₂ F ₄ ⁺ (4.3), 69CF ₃
⁺ (12.8), 50CF ₂ ⁺ (2.3), 43C
(O) CH ₃ ⁺ (100).

Example 6 Perfluoro (3-N, N-dimethylaminopropionyl fluoride) and Grignard reagent (CH ₃ MgBr)
A synthetic experimental method for synthesizing methyl perfluoro (2-N, N-dimethylaminoethyl) ketone by reaction with perfluoro (3-morpholinoacetylfluoride) was used as the raw material nitrogen-containing perfluorocarboxylic acid fluoride. The procedure of Example 4 was repeated, except that N, N-dimethylaminopropionyl fluoride) was used. That is, 100 g of a crude sample of perfluoro (3-N, N-dimethylaminopropionyl fluoride) (0.234 mol as 70% content) was placed in a flask, and ether 25
0 mL was added and stirred, 100 mL of a solution of methylmagnesium bromide (0.234 mol) was added over about 1 hour while maintaining an internal temperature of -100 ° C. Cooling was loosened, the internal temperature was raised to 0 ° C in 1 hour, and 25 mL of water was added with vigorous stirring. Impurities adhered to the inner wall of the flask, and almost clear ether solution could be separated by decantation. done. After drying over anhydrous magnesium sulfate, the ether was distilled off and the residual liquid was subjected to fractional distillation. As a result, methyl perfluoro (2-N, N-dimethylaminoethyl) ketone, bp 101-102 ° C, 3
1.1 g (0.105 mol) was obtained. Based on the amount of the acid fluoride contained in the raw material, the yield of methyl perfluoro (2-N, N-dimethylaminoethyl) ketone was 45%.

Methyl perf obtained as a novel compound
Of Luoro (2-N, N-dimethylaminoethyl) ketone
Physicochemical data, as well as their IR,¹ H-NM
R,¹⁹ F-NMR and MS data are shown below. Boiling point: 100.1 ° C. (measured at 760 mmHg), density:
1.5645 (measured at 25 ° C), vapor pressure: 34.1 mm
Hg (measured at 25 ° C).

IR (capillary film)
(Cm ^-1 ): 2935ν (CH) (w), 1763ν
[C (O)] (ms), 1425 (w), 1320-1
352 (vs), 1208 (vs), 1120 (m),
1044 (w), 883 (m), 834 (m), 763
(M), 728 (ms).

¹ H-NMR (CDCl ₃ ): δ2.46
_{[-C (O) CH 3]} . ¹⁹ F-NMR (CFCl ₃ ), δ-52.8 [6F, t
-T, J = 7.5, J = 15.0, (CF 3) 2 N],
δ-91.4 [2F, heptet, J = 15.0, N
CF ₂ CF ₂ ], δ-120.2 [2F, hepte
t, J = 7.3, NCF ₂ CF ₂ ].

MS: m / e143CF₂CF₂ NC
(O) CH₃ ⁺ (15.5), 119C₂ F_Five ⁺ (2.
4), 114C₂ F_Four N⁺ (8.2), 100C₂ F_Four 
⁺ (5.5), 69CF₃ ⁺ (30.7), 50CF₂ 
⁺ (2.0), 43C (O) CH₃ ⁺ (100).

[0047]

As described above in detail, the present invention relates to a novel fluorinated ketone compound and a method for producing the same. According to the present invention, a novel fluorinated ketone compound and a method for efficiently producing the same Methods are provided. This novel fluorinated ketone compound is used for surfactants, agricultural chemicals, pharmaceuticals,
It is useful as a raw material or a synthetic intermediate for various fluorine-containing products such as fluoropolymers, and as a refrigerant that can substitute for CFC and HCFC, a heat transfer medium, a foaming agent, a cleaning agent, a fire extinguishing agent, a reaction solvent, and the like.

   ─────────────────────────────────────────────────── ─── Continued front page    (71) Applicant 000157119             Kanto Denka Kogyo Co., Ltd.             1-2-1, Marunouchi, Chiyoda-ku, Tokyo (71) Applicant 000002004             Showa Denko Co., Ltd.             1-13-9 Shibadaimon, Minato-ku, Tokyo (71) Applicant 000002200             Central Glass Co., Ltd.             5253 Oki Ube, Oza, Ube City, Yamaguchi Prefecture (71) Applicant 000002853             Daikin Industries, Ltd.             2-4-12 Nakazaki-nishi, Kita-ku, Osaka-shi, Osaka Prefecture             Umeda Center Building (71) Applicant 000003034             Toagosei Co., Ltd.             1-14-1 Nishishimbashi, Minato-ku, Tokyo (71) Applicant 000174851             Mitsui DuPont Fluorochemical Co., Ltd.             1-5-18 Sarugakucho, Chiyoda-ku, Tokyo (72) Inventor Takashi Abe             1-1-1 Higashi 1-1-1 Tsukuba City, Ibaraki Prefecture             Human Resources Research Institute             Quality Control Technology Research Center (72) Inventor Kunio Okuhara             14-13 West Gotanda, Haguro, Inuyama, Aichi Prefecture (72) Inventor Yuji Kurokawa             Hongo Wakai Bi 2-40-17 Hongo, Bunkyo-ku, Tokyo             6th floor Global Environment Industrial Technology Research Machine             Construction of new refrigerant, etc. F-term (reference) 4C054 AA02 BB03 CC03 DD22 EE22                       FF22                 4C056 AA02 AB01 AC03 AD01 AE01                       AF04 EA01 EB02 EC07                 4C069 AA12                 4H006 AA01 AA02 AB84 BM10

Claims (2)

[Claims] 1. The following general formula (1): (In the formula, R represents a lower aliphatic alkyl group having 1 to 4 carbon atoms. R _F 1 and R _F 2 represent a lower aliphatic perfluoroalkyl group having 1 to 3 carbon atoms, and these are A fluorine-containing ketone represented by a 5- or 6-membered heterocycle may be formed with or without an oxygen atom. 2. A method for producing a fluorinated ketone represented by the above general formula (1), which comprises the following general formula (2): (In the formula, R _F 1 and R _F 2 represent a lower aliphatic perfluoroalkyl group having 1 to 3 carbon atoms, and these are 5-membered or 6-membered heterocycles with or without an oxygen atom. A nitrogen-containing perfluorocarboxylic acid fluoride represented by (may form a ring) and an organometallic compound having a lower aliphatic alkyl group are reacted in an aprotic polar solvent. Production method.